Chemistry for Any Weather Greenpeace Tests Outdoor Clothes for Perfluorinated Toxins E D

Chemistry for any weather Greenpeace tests outdoor clothes for perfluorinated toxins e d

www reenpeace 02 1 03 Table of Contents

1 Summary 05

2 Sampling and methodology 07

2.1 What was tested? 07

2.2 How was testing done? 08

3 Results for perfluorinated and polyfluorinated compounds (PFCs) 13

3.1 Perfluorinated carboxylic acids (PFCAs) with perfluorooctanoic acid (PFOA) 14

3.2 Fluorotelomer alcohols (FTOHs) 15

3.3 Perfluorinated sulfonate (PFOS) 16

4 Results for other toxins 19

4.1 Alkylphenol ethoxylates 20

4.2 Phthalate plasticizers 20

4.3 Azo dyes 21

4.4 Organotin compounds 21

4.5 Antimony 21

4.6 Isocyanates 21

5 Alternatives to fluorocarbon coatings and finishes 25

6 Conclusions and recommendations 29

7 Appendix 31

7.1 Hazardous Substances in the Textile Industry 42

7.2 References 43

Imprint Publisher Greenpeace e. V., Große Elbstraße 39, 22767 Hamburg, T 040 . 3 06 18 - 0, F 040 . 3 06 18 - 100, mail @ greenpeace.de, www. greenpeace . de Political Representation Berlin Marienstr. 19 – 20, 10117 Berlin, T 030 . 30 88 99 - 0 V.i.S.d.P. Manfred Santen Authors Manfred Santen, Ulrike Kallee Editor Simone Miller Photo Titel: Bente Stachowske, Bente Stachowske (16), Marcus Meyer (9), alle © Greenpeace Picture Editorial Max Seiler Production Christiane Bluhm Artwork Klasse 3b, Hamburg 2 / 2013 04 1 1. Summary 05 Summary Greenpeace 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 often The Detox campaign works Hazardous chemicals must be used for advertising outdoor clothing. to improve the environmental removed from outdoor clothing But nature does not remain untouched balance of textile production production by the chemicals in weather-resistant In the context of the international Detox The findings from this product investigation fabrics. All over the world, from seclu- campaign, Greenpeace is calling on textile underline the urgent need to ban PFCs from ded mountain lakes and Arctic polar ice manufacturers to replace hazardous produc- outdoor wear production. PFC-free materi- to deep in the oceans, traces can be tion chemicals with harmless alternatives. als are already available today. The outdoor found of perfluorinated and polyfluori- Greenpeace is also calling on governments clothing industry must continue to develop nated compounds (PFCs), pollutants to regulate more chemicals that are hazar- safer alternatives and use them in proces- with properties that are harmful to the dous. PFCs are among the groups of sub- sing their products. environment and health. stances 1) on the Detox campaign’s priority list. Some PFCs are known to be endocrine The hazardous properties of well-researched Outdoor clothing is in close contact with a disruptors and are harmful to the repro- PFCs such as PFOS and PFOA and insuffi- whole range of chemicals before it is used ductive system. cient data on other PFCs call for much more for hiking or skiing. Yarns, fabrics and even stringent regulation to protect health and ready-made garments are treated with che- As early as 2011, Greenpeace proved that the environment. Greenpeace supports the mical substances to enhance functionality PFCs from the production of brand name initiative of Germany’s Federal Environment and make items easy to care for. Most brand textiles in China were discharged to rivers. 2) Agency to place PFOA on the Candidate name manufacturers use PFCs so that we This study proves that residues of PFCs and List of Substances of Very High Concern stay dry in our outdoor wear, inside and other chemicals are in the outdoor wear (SVHC) so that they are subject to further outside. These man-made compounds of made by well-known manufacturers. restriction through REACH 4). carbon and fluorine are so stable that they can hardly be removed from the environ- Commissioned by Greenpeace, two inde- In view of the hazardous properties of ment, if at all. pendent laboratories tested weatherproof C8 PFCs (PFOA and PFOS), and in view of jackets and pants between June and Sep- research findings indicating that other For the consumer, it is not clear which tember 2012. PFCs 3) were found in all 14 PFCs (C6) might possess similar hazardous chemicals have been used during the pro- samples; among them was the well-known properties, it is not enough to regulate only duction of outdoor clothing and which hazardous compound perfluorooctanoic single substances such as PFOA. Greenpeace harmful substances clothing may still acid (PFOA). In six samples, PFOA was demands that the entire group of PFCs contain. PFCs and other chemicals reach found in significant concentrations. is put under scrutiny for a possible regu- drinking water, food and ultimately human In addition, six samples had fluorotelomer lative ban. blood and breast milk from such various alcohols (FTOHs) in high concentrations. sources as manufacturing and household wastewater, dust, and the disposal of textiles. It is even possible to inhale them. Correction The current version of the Report “Chemistry for any weather” was updated in February 2013. According to the laboratories samples were switched during the analysis for perfluorinated chemicals. The concentrations of the Mammut jacket have to be corrected upwards: The PFOA concentration is now 4,7 µg/m2 instead of 0,6 µg/m2. The sum of perfluorinated carboxylic acids is now 46,8 µg/m2 instead of 5,4 µg/m2. The original version was published in October 2012.

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.pdf 3) 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. 2. Sampling and

06 2 methodology 07 Sampling and methodology 2.1 What was tested?

In the spring of 2012, Greenpeace pur cha s- Two jackets, one from Zimtstern (made for The products were either purchased in their ed 13 items of outdoor clothing bearing Greenpeace) and one from Fjällräven, were original packaging or put into an unconta- well-known outdoor brand names. These labeled as PFC-free. According to the labels, minated plastic bag immediately after included four jackets and one pair of pants eleven of the 14 products were made in purchase. The samples were registered at for children, and eight jackets for women. 5) China, and one each was made in Indone- Greenpeace and documented in photos. Nine jackets were purchased in Germany, sia, Vietnam and Ukraine. A sample of fabric measuring 20 x 20 cm two in Switzerland, and two in Austria. The was cut out of the back of each garment products were bought either in ﬂagship or where there was no printing or labeling. specialized stores, or ordered online. In ad- Samples were individually wrapped tightly dition to these purchased items, a rain jacket in aluminum foil and tested in two inde- made especially for Greenpeace activists pendent labs. (manufactured by Zimtstern) was also tested. These jackets are not available for sale.

Table 1: The outdoor clothing items that were tested

Brand Country of Product Name or Technology for Coating/Finish Environmental Store Name Production Description Label or Claim Purchased in Germany Zimtstern / China Light rain jacket Membrane: polyester (SympaTex), Bluesign Own product Greenpeace for women Dendrimer finish (Bionic finish ECO) Jack Wolfskin Indonesia Cloud Stream Jacket Membrane: Texapore AIR, Globetrotter (for children/boys) Outer shell: 100% polyamide Vaude China Kids Escape Jacket Membrane: Ceplex advanced, 100% PU GreenShape Vaude.de Outer shell: polyamide, PU-coating Bluesign Vaude Vietnam Escape Bike Jacket III Membrane: Ceplex advanced, 100% PU globetrotter.de (for women) Outer shell: polyamide, PU-coating North Face China Sutherland Jacket Membrane: PTFE(Gore-Tex), 100% globetrotter.de (for women) 100% polyester laminated Mountain Ukraine WMNS Firefox-Jacket Membrane: PTFE(Gore-Tex) Globetrotter Equipment Marmot China Boy’s Torrey Pant #64310 UPF / UV40: Globetrotter 96% Nylon, 4% Elastan Fjällräven China Eco-Trail Jacket Women Membrane: Eco-Shell Fluorcarbon-free Amazon.de (Trekking) 100% recycled polyester Sportausstatter Meinunger Patagonia China Piolet Jacket Lady Black Membrane: PTFE(Gore-Tex) Common Threats Backpacking ForEver (Modell 2012) Outer shell: 100% nylon Initiative Adidas China Terrex Feather Jacket Membrane: PTFE(Gore-Tex), Adidas.de (for women) 100% polyamide Purchased in Austria Northland China Basic Child Rain Poncho Membrane: 100% polyester Northland store in in train station, Vienna Seven China Tamina Kinder-Regenjacke Membrane: Ice Tech 5000 MM Intersport Eybl Summits (child’s rain jacket) 5000 MVP / polyamide Megastore, Vienna Purchased in Switzerlans Mammut China Fujiyama Jacket Women Membrane: PTFE(Gore-Tex) Mammut Store, Zurich Kaikkialla China Annuka Jacket Womens XS Membrane: Toray DermizaxEV Transa, Zurich

5) Only women’s jackets were purchased because they can be worn in small sizes by young teenagers. 08 2 09 2.2 How was testing done?

The samples were sent to two laboratories The testing covered the PFCs that could be and tested for perfluorinated and polyfluo- extracted using solvents. The analysis of PFCs blood of umbilical cords and newborns exposure and adiposity (Thorhallur 2012), 1. Coatings and finishes rinated compounds and for other hazar dous PFCAs extracted with methanol was done Per- and Polyfluorinated chemicals (Fromme 2010). This is particularly worri- diminished fertility (Fei 2009), immune Fluorotelomer alcohols (FTOHs) are chemicals such as plasticizers (phthalates), using high-performance liquid chromato- (PFC)11) are chemical compounds in some because PFCs circulate through disorders (Grandjean 2012) and thyroid processed on a large scale into fluori- surfactants (nonylphenol ethoxylates), graphy combined with tandem mass spec- which the hydrogen atoms on a carbon the human body for a relatively long time. diseases (Melzer 2010). PFOA is currently nated polymers which are used to organotin compounds, and carcinogenic trometry (HPLC-MS/MS), and the FTOHs skeleton are replaced completely (per- The retention time for perfluorooctanoic not subject to legal regulation. Germany’s make textiles waterproof, dirt-repellent amines that can be released from azo dyes. extracted with methyl tertiary butyl ether fluorinated) or partially (polyfluorinated) acid (PFOA) is more than three years on Federal Environment Agency is working or grease-resistant. Many impregnating (MTBE) were analyzed using gas chroma- by fluorine atoms. PFCs do not occur average. PFCs have been found in breast to put PFOA on the REACH Candidate fabric care products also contain fluori- The first lab tested for a comprehensive tography coupled with mass spectrometry in nature. They have been made for milk (Fromme 2010). Although concentra- List of Substances of Very High Concern nated polymers. Finished products such list of perfluorinated and polyfluorinated (GC-MS). more than 50 years by fluorochemical tions are lower than in blood, they are (SVHC) (Vierke 2012). as outdoor jackets or impregnating compounds, among them perfluorinated manufacturers. The OECD (Organization nevertheless problematic because infants sprays can contain residues of FTOH. carboxylic acids such as PFOA and perfluo- The second lab tested the clothing for other for Economic Cooperation and Develop- are still developing and therefore are PFCs end up in the environment either Annual FTOH production is estimated rinated sulfonic acids such as PFOS. The toxins. The selection of substances for te- ment) lists a total of 853 different particularly sensitive. A study carried out directly – during production – or indirectly at 11,000 to 14,000 tons around the list also included, among other compounds, sting was determined by the nature of the fluorine compounds. in Germany showed that infants actually when products containing PFCs are used world. Since fluorotelomer alcohols are fluorotelomer alcohols (FTOHs)6); FTOHs fabrics. Among others, alkylphenol ethoxy- had higher PFC contaminations than their and disposed of. The apparel industry volatile compounds, they are thought to are the main starting product today in lates, plasticizers (phthalates), aromatic In the apparel industry, perfluorinated mothers (Fromme 2010). uses PFCs in particular for coating and play an important role in global sprea- the synthesis of fluorinated polymers.7) amines released from azo dyes, isocyanates, carboxylic acids (PFCAs) such as per- finishing outdoor garments or sporting ding. Air currents can transport them Polymers ensure the waterproofing and/or and organotin compounds were measured fluorooctanoic acid (PFOA), for instance, Animal testing has shown that some PFCs goods (1) or for the production of breatha- even to remote areas (Weinberg 2011), dirt-repellent properties of the PFC finish using GC-MS. Among the alkylphenol and the fluorotelomer alcohols (FTOHs) are harmful to reproduction. They can also ble membranes (2). and they can be inhaled and retained on outdoor textiles.8) To the best of our ethoxylates were nonylphenol ethoxylates play a role. Because the carbon-fluorine promote the growth of tumors (UBA 2009). in the body. These substances are pro- knowledge, very few studies so far have (NPEs), which have been discussed exten- bond is the most stable in organic There is growing evidence that PFOA in blematic because they can be conver- tested for such a comprehensive list of sively in earlier Greenpeace reports. 10) chemistry, PFCs are very persistent. particular does other harm, and it is sus- ted into perfluorinated carboxylic acids PFCs in outdoor clothing.9) Some samples were tested for antimony. Once they have been released to the pected of being an endocrine disruptor. (such as PFOA) in the environment and environment, they barely degrade and Recent epidemiological studies have in organisms. There are indications that A scanning electron microscope (SEM) remain there for long periods of time. suggested an association between PFOA during this conversion process, inter- was used in qualitative testing to detect the It is therefore not surprising that these mediate products form in the body that presence of fluorine. This testing indicates chemicals have been found around the Examples of PFCs and their chemical structure can actually be much more harmful whether a membrane or fabric contains globe. Scientists have found them in than the end product of perfluorinated Group12) E xa m p l e fo r a c o m p o u n d Chemical Structure the snow of the Alps and the waters of carboxylic acid (Rand und Mabury 2012). fluorine. Fluorine is not subject to official Perfluorinated sulfonic PFOS F F F F F F F F O the deep sea. Even the blood of Arctic acids Even the production of FTOHs is itself declaration. It is already a known fact that FC C C C C C C C S OH

Gore-Tex and Teﬂon membranes contain polar bears and the dung of penguins F F F F F F F F O a problem because PFOA can form as

ﬂuorine in the form of polytetraﬂuoroethy- on Tierra del Fuego are contaminated Perfluorinated PFOA F F F F F F F F an impurity. carboxylic acids O lene (PTFE). For other membranes, SEM with PFCs. FC C C C C C C C C O analysis provides valuable information on F F F F F F F F 2. Membranes Fluorotelomer alcohols 8:2 FTOH F F F F F F F H H the mode of production. PFCs accumulate mainly in blood. These Compounds containing fluorine are also F C C C C C C C C C OH chemicals enter the human body in food, used to produce outdoor membranes The Bremer Umweltinstitut [environmental insti- F F F F F F F H H tute] analyzed outdoor textiles for Greenpeace. air and drinking water. According to Fluorocarbon polymers Polytetrafluoroethylene (PTFE) (Gore-Tex, Teflon). Many of these mem- (Breathable membranes such as F F present knowledge, absorption through Gore-Tex) C C branes are made of polytetrafluoroethy-

the skin is rather low. The fact is that F F n lene (PTFE), for which PFOA is used PFCs are detectable in human blood Fluorinated polymers Perfluoroalkyl monomer as a process additive during manufac- (Waterproofing and dirt-repellent H OR H H F F F F F F F F F F around the world (Bonefeld-Jorgensen treatment of textiles) COCCC C C C C C C C C C C C F turing. This can be found again as an H 2011), and have even been found in the H H F F F F F F F F F F impurity in the finished product. Some manufacturers have therefore already switched to using other fluorine-contai- 6) 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). ning additives. But these are also per- 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) and Walters 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) sistent and therefore not environmentally 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. compatible. 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.pdf Berger U, Herzke D (2006). Per- and polyfluorinated alkyl substances (PFAS) extracted from textile samples. Poster presentation 10) http://www.greenpeace.org/international/en/publications/reports/Dirty-Laundry-2/ 11) References for text see Section 7.2 in the Appendix. 12) http://www.umweltdaten.de/publikationen/fpdf-l/3818.pdf 10 2 11

In the production and processing of texti les nation. Testing for PFCs in rainwear from The accumulation potential of these containing PFCs, chemicals are released Norway and Sweden also found residues substances in the body is lower than for into wastewater. Even private households of FTOHs and perfluorinated carboxylic PFOA. A study carried out in Sweden can be a source (UBA 2009) when, for acids (PFCAs) (Berger 2006). shows however that the contamination example, coated textiles are washed. How of blood with these substances has in- much PFC is released during washing It is not clear what happens to an outdoor creased significantly in the Swedish has not been investigated. Most PFCs do jacket when it is no longer worn and ends population in recent years (Berger 2012, not degrade in sewage treatment plants. up in the rubbish. Occasional air measure- presentation). Samples of breast milk Some of these chemicals are collected in ments at waste dumps have shown increa- from China and Sweden were also con- sewage sludge. The rest reaches rivers and sed PFC contamination in these locations taminated (Jensen 2008). Short-chain lakes in “clean” sewage water (UBA 2009) (Weinberg 2010). However, there are no PFCs are as persistent as PFOA. It is and disperses through waterways all data on the chemical behavior of materials also worrisome that short-chain PFCs around the globe. Due to its high nutrient containing PFCs when they are incinerated can reach groundwater more easily be- content, sewage sludge is often used as as waste. If combustion is incomplete, it cause they bond less well to particles. agricultural fertilizer. In this way, PFCs leach is conceivable that dioxin-like substan ces Compared to PFOA, short-chain PFCs into the soil and into groundwater, or accu- form. Here there is an urgent need for have been poorly investigated, a situa- mulate in plants which are processed into research. tion which must be addressed urgently food. A few years ago, the use of PFC- due to the increasing use and pervasive- contaminated sewage sludge around the Since the public debate on PFOA (eight ness of these compounds. Germany’s town of Arnsberg (in western Germany’s carbon atoms) is ongoing, the industry Federal Environment Agency does not Hochsauerland district) meant that drinking has also recently begun to use short-chain rate these chemicals as environmentally- water had become highly contaminated. PFCs (with four to six carbon atoms). friendly alternatives due to their high Tests in Arnsberg revealed that people who In 2006, eight major fluorochemical manu- stability and potential to contaminate had consumed contaminated drinking fac turers pledged to reduce their PFOA drinking water (UBA 2009). water had concentrations of up to eight emissions and residues in products by times more PFOA in their blood than those 95 percent by 2010. Samples taken in the who had not been exposed (UBA 2009). environment since then show an increasing contami nation with short-chain PFCs Scientists have found PFCs in fish, meat, in water (Möller 2010) and air (Weinberg milk products and plants, including in 2011). These short-chain alternatives grains grown on contaminated soils. PFCs have also been found in Antarctica (Llorca are in dust and indoor air. In fact, the in- 2012), in snow (Cai 2012), in drinking door air of houses, apartments and offices water (Dauchy 2012) and in rainwater is 30 to 570 times more contaminated than (Eschauzier 2010). outdoor air (UBA 2009). Air measurements taken inside two outdoor equipment stores in Germany showed particularly high concentrations of FTOHs (Langer 2010). Scientists suspect that PFCs evaporating from products such as impregnated clothing are the source of this contami- 3. Results for perfluorinated and polyfluorinated

12 3 compounds (PFCs) 13 Results for perfluorinated and polyfluorinated compounds (PFCs)

All 14 samples of outdoor clothing Significant levels of PFOA (> 1 μg/m2) 15) Perfluorooctane sulfonate (PFOS) was not contained extractable PFCs. This was were found in six of 14 samples, in the detected in any sample. The 2008 ban on regardless of whether the label indica- jackets made by Mammut, Jack Wolfskin, this substance is apparently effective. ted that the product was made with a The North Face, Patagonia and Kaikkialla, fluorine membrane such as Gore-Tex and the child’s pants from Marmot The findings of the PFC study are described or Teflon, or finished with a coating (see Figure 1). below according to the class of substance. containing fluorine compounds. The test results are listed in detail in Tables The lowest concentrations of PFOA 1 to 4 of the Appendix. Even the items of clothing for which pro- were found in jackets made by Mountain duction intentionally abstained from using Equipment, Vaude Women and Zimtstern fluorochemicals, such as the jackets from (manufactured for Greenpeace). In six Fjällräven and Zimtstern, contained a small of 14 samples, concentrations of PFOA amount of fluorine chemicals (see Table 3 were above the detection level but below in the Appendix). 13) The sources of these 0.3 μg/m2. Samples were from the brands low concentrations are unclear. PFCs are just named as well as from Adidas, persistent and – as a consequence of their Fjällräven and Seven Summits. industrial use – they are so widespread that it may be a real challenge to engage in clean The highest sums of all perfluorinated production in which chemicals and/or carboxylic acids (PFCAs) were found in production facilities are not contaminated jackets made by Mammut (46 μg/m2), by PFCs. 14) Kaikkialla (11 μg/m2) and Patagonia (8.5 μg/m2), and in the child’s pants from Marmot (6.3 μg/m2). Sums were lowest in the samples from Mountain Equipment, Seven Summits and Zimtstern (Greenpeace).

Fluorotelomer alcohols were found in eight of 14 samples. Where FTOHs were found, their concentrations were signiﬁ- cantly higher than concentrations of per- ﬂuorinated carboxylic acids. The highest FTOH concentrations (> 400 μg/m2) were in the jackets made by Mammut and Vaude Kids. Likewise, high FTOH concentrations (> 100 μg/m2) were found in the samples from 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. 14 3 15 3.1 Perfluorinated carboxylic acids (PFCAs) with 3.2 Fluorotelomer alcohols (FTOHs) perfluorooctanoic acid (PFOA)

Among the PFCs found in every sample was In six of 14 samples, the PFOA concentra- Greenpeace believes that even minor FTOHs were found in eight of the 14 samp- item containing (considerably higher) Fluorotelomer alcohols, when used for perfluorooctanoic acid (PFOA), a substance tion was above the detection level but be- contamination during production should les. The highest concentration of fluorotelo - 352 μg/m2 of 6:2 FTOH. Long-chain C10 waterproof and dirt-repellent finishes, are with hazardous properties. Since there low 0.3 μg/m2. The lowest concentrations cease. To reach this objective, outdoor mer alcohols was found in the jacket from telomers were used in the products from supposed to ensure that fewer PFC inter- are no regulations for PFOA, the EU limit of PFOA were measured in the jackets made clothing producers and their material sup- Mammut (464 μg/m2). The child’s jacket Vaude, Patagonia, Mammut and Kaikkialla. mediates such as PFOS are formed. They value for perfluorooctane sulfonate (PFOS) by Mountain Equipment, Vaude Women, pliers, but also the chemicals industry, made by Vaude also had a high concentra- are divided into long-chain and short-chain of 1 μg/m2 (micrograms of PFOS per square Zimtstern (manufactured for Greenpeace), must work together and strictly control tion of FTOHs at 419 μg/m2 (see Figure 2). Next to the fluorotelomer alcohols, fluoro- compounds. Basically, the longer their meter of fabric) was used as the comparison Adidas, Fjällräven and Seven Summits. It which substances are used in production. telomer acrylates (FTAs), also known as chains, the more these toxic substances can value. PFOA’s hazardous properties are remains unclear where the contamination Greenpeace will work together with the Test results showed that some manufactu- polyfluorinated acrylates, were also detec- accumulate in an organism. The compound similar to those of PFOS – it is harmful for came from. It may be that factories produ- manufacturers of its activists’ jackets rers are already using C6 telomer alcohols, ted in some samples. These acrylates are 8:2 FTOH must be evaluated critically be- fertility (toxic to reproduction) and is sus- cing textiles containing fluorine compounds (not for sale) to investigate sources of PFC which were dominant in the jackets from intermediates in the production of fluori- cause it is converted into PFOA through pected of being an endocrine (hormonal) are not able to manufacture fabrics that contamination and take corrective action. Adidas und Fjällräven. The item from nated polymers. Like the C8 telomers, they oxidation in the atmosphere and in the disruptor. are completely free of PFCs. This would Adidas contained 99 μg/m2 of 6:2 FTOH. can be converted into PFOA through oxi- body. Some manufacturers therefore want necessitate textiles being manufactured Although the Fjällräven jacket was explici tly dation. Significant C8 FTA concentrations to switch from C8 to short-chain substances PFOA concentration of 1 μg/m2 was excee- in plants that completely exclude using labeled as PFC-free, it contained 52 μg/m2 were found in the items from Vaude, The such as 6:2 FTOH. But C6 and C4 PFCs, ded in six samples: the Mammut Fujiyama perfluorinated chemicals. But it is also of this substance. North Face, Marmot and Patagonia, as well used as alternatives, are also persistent and Jacket Women, the Jack Wolfskin child’s conceivable that contamination occurs in as in the Mammut and Kaikkialla items found in the environment and in humans jacket, the North Face woman’s jacket, transit, during storage or in the store. C6 telomer alcohols were also found in purchased in Switzerland. Lower concen- around the world. They can also oxidize the Marmot child’s pants, the Patagonia Even the process of sampling and testing the Northland child’s poncho purchased in trations of C8 FTA were found in the into their respective carboxylic acids, which woman’s jacket and the Kaikkialla can lead to contamination. Austria (17.6 μg/m2 of 6:2 FTOH) and in Jack Wolfskin, Mountain Equipment and are potentially hazardous to health. woman’s jacket (see Figure 1). the two jackets purchased in Switzerland, Adidas items, and the lowest concentration with the Kaikkialla article containing of C8-FTA was found in the Greenpeace So far, no regulation or value limits have 27.0 μg/m2 of 6:2 FTOH, and the Mammut (Zimtstern) jacket. been established for fluorotelomer alcohols. Figure 1: Concentrations of perfluorinated carboxylic acids (PFCAs) in 14 samples of outdoor clothing

2 PFOA concentration in μg/m Figure 2: Concentrations of fluorotelomer alcohols (FTOHs) in 14 samples of outdoor clothing Sum PFCA 46,8 – 12 concentration in μg/m2 8:2 FTOH 6:2 FTOH 11,0 – 11 Sum FTOH Sum FTA – 10 – 500

– 9 – 450 8,5 – 8 – 400

– 7 – 350 6,3 – 6 – 300 5,1 5,0 – 5 – 250 4,7 – 4 – 200 3,4

2,8 – 3 – 150 2,3 2,2 2,0 – 2 – 100 1,6 1,2 1,2 1,2 1,0 0,7 0,6 0,7 – 1 – 50 0,6 0,4 0,3 0,2 0,2 0,3 0,3 0,3 – 0 – 0 Zimtstern / Jack Vaude Vaude North Face Mountain Marmot Fjällräven Patagonia adidas Northland Seven Mammut Kaikkialla Zimtstern / Jack Vaude Vaude North Face Mountain Marmot Fjällräven Patagonia adidas Northland Seven Mammut Kaikkialla Greenpeace Wolfskin Child’s Woman’s Woman’s Equipement Child’s Woman’s Woman’s Woman’s Child’s Summits Woman’s Woman’s Greenpeace Wolfskin Child’s Woman’s Woman’s Equipement Child’s Woman’s Woman’s Woman’s Child’s Summits Woman’s Woman’s Light Child’s Jacket Jacket Jacket Woman’s Pants Jacketn Jacket Jacket Poncho Child’s Jacket Jacket Light Child’s Jacket Jacket Jacket Woman’s Pants Jacket Jacket Jacket Poncho Child’s Jacket Jacket Jacket Jacket Jacket Jacket Jacket Jacket Jacket Jacket 16 3 17 3.3 Perfluorinated sulfonate (PFOS)

No perﬂuorooctane sulfonate (PFOS) was PFOS has been covered by the Stockholm found in the investigation. PFOS is rated as Convention since 2009. A permissible limit a PBT substance (Persistent, Bioaccumula- was set for PFOS of 1 µg/m2 (one micro- tive, Toxic). The use and marketing of PFOS gram of PFOS per 1 square meter of fabric) has been banned in the EU since 2008, for textiles and coatings. This value also with a few exceptions. Evidently the ban applies to imported products such as on PFOS has been effective. textiles. 18 4 4. Results for other toxins 19 Results for other toxins

All samples of outdoor clothing were tested Other chemicals used in textile production, for alkylphenol ethoxylates, which are used itemized on Greenpeace’s Detox List,16) as tensides or surfactants in wet processes were not investi gated if there was no im- in textile production. All samples were also mediate suspicion of their presence. tested for the phthalate group of substances which are used as plasticizers. The ﬁndings of the test series and the methodology applied are explained in detail Depending on the nature of the textiles in in Tables 5 and 6 of the Appendix. Here is question, some samples were additionally an overview of the most important results. screened for other toxins. Testing was done for aromatic compounds released from azo dyes, organotin compounds and antimony. The specialist laboratory itself selected which products to test for these harmful substances.

Table 2: Results for other harmful substances

Brand Country of Product Name or Nonylphenol Phthalate Organotins Antimony Isocyanates Name Production Description Ethoxylate17) (Sum)18) mg/kg mg/kg mg/kg mg/kg mg/kg Purchased in gekauft Zimtstern / China Light rain jacket for women 15 3 Greenpeace Jack Wolfskin Indonesia Cloud Stream Jacket (for children/boys) 9 Vaude China Kids Escape Jacket 13 3 30 23 (TDI22)) Vaude Vietnam Escape Bike Jacket III (for women) 10 13 (MOT19)) 10 16 4,8 (DOT20)) North Face China Sutherland Jacket (for women) 5 40 Mountain Ukraine WMNS Firefox-Jacket 11 Equipment Marmot China Boy’s Torrey Pant #64310 5 Fjällräven China Eco-Trail Jacket Women (Trekking) 19 (NP; 8) 16 120 Patagonia China Piolet Jacket Lady Black (Modell 2012) 4 35 Adidas China Terrex Feather Jacket (for women) 20 (NP; 8) 16* Purchased in Austria Northland China Basic Child Rain Poncho 5700 10 Seven Summits China Tamina Kinder-Regenjacke 320 270 (child’s rain jacket) Purchased in Switzerland Mammut China Fujiyama Jacket Women 88* 1 Kaikkialla China Annuka Jacket Womens XS 9 22* 2,3 / 0,55 / 5,8 / 2 5,6 / 0,18 21)

16) 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) Monooctyltin 20) Dioctyltin 21) Monobutytin MBT, Monooctyltin MOT, Dibutyltin DBT, Dioctyltin DOT, Tetraethyltin TeEtT 22) Toluylene diisocyanate 20 4 21 4.1 Alkylphenol ethoxylates 4.3 Azo dyes 4.4 Organotin compounds

Nonylphenol ethoxylates (NPEs) were found contained 320 mg/kg of NPE. Other signi- All of these items were manufactured in Testing was also done for carcinogenic The use of organotin compounds is already 18 mg/kg of tetraethyltin (TeET), 2.3 mg/kg in five of the 14 samples. NPEs belong to ficant concentrations were found in the China. In 2011, Greenpeace proved that aromatic amines that can be released from heavily restricted due to the toxicity of these of monobutyltin (MBT), 0.55 mg/kg of MOT, the substance group of alkylphenol ethoxy- jackets from Vaude (NPE 13 mg/kg), nonylphenol from the textile industry azo dyes. They were not detected in any chemicals. The GOTS standard allows no and 5.8 mg/kg of dibutyltin (DBT). lates, are very harmful to the environment Fjällräven (NPE 19 mg/kg, plus NP 8 mg/kg) con stitutes a serious problem of water of the samples tested, which were from the more than 0.05 mg/kg of tributyltin (TBT), and should not be detectable because and Adidas (NPE 20 mg/kg). The Kaikkialla pollution in China. 24) NPEs are used in the products made by Vaude, The North Face, and the OEKO-TEX standard for textiles sets Organic tin compounds are used as bio- they degrade to nonylphenol (NP). NP is jacket purchased in Switzerland contained dyeing process. Their effect is similar Adidas, Seven Summits, Mammut and a limit of 0.5 mg/kg for TBT and 1.0 mg/kg cides and anti-fungal agents. They have persistent, bioaccumulative and toxic, an NPE concentration of 9 mg/kg. 23) to that of estrogen and they can disrupt Kaikkialla. Some azo dyes used in the for dioctyltin (DOT). The samples from an antibacterial effect on socks, shoes and and can disrupt the endocrine (hormonal) the development of reproductive organs textile industry can cause cancer when Vaude, Mammut and Kaikkialla were tested. sportswear and are supposed to prevent systems of animals and humans. Lower levels of NPEs do not necessarily in fish and other aquatic animals. Since they release cancerogenic amines. Both standards’ limits were significantly odors. They are also used in PU as an acce- indicate that NPEs were used in lower January 2005, textiles containing more exceeded in the Vaude jacket for women; lerator. If tributyltin (TBT) is released into The highest concentration of NPEs was amounts during manufacturing. Greenpeace than 0.1 percent of NPs or NPEs are not the value for DOT was 4.8 kg/mg and for the environment, it can accumulate in the found in the Seven Summits child’s rain reported in 2012 that NPE residues can marketable. monooctyltin (MOT) 13 mg/kg. The Kaik- body where it disrupts the immune system jacket purchased in Austria. This sample be washed out in just a few washes. kialla jacket contained 5.6 mg/kg of DOT, and diminishes fertility.

25) GOTS: Global Organic Textile Standard: http://tilth.org/files/certification/GOTSStandard.pdf 4.5 Antimony 4.6 Isocyanates Illustration 1: Soxhlet solvent extraction 4.2 Phthalate plasticizers Illustration 2: Textile sample in a separating funnel (GC-MS) Illustration 3: Analysis in the gas chromatograph Plasticizers in the phthalate group of with high market shares, especially in These concentrations indicate that phtha- Antimony is used in the production of Isocyanates are used in polyurethane (PU) Illustration 4: Inserting samples into the scanning substances were detected in every sample. China and South America. lates were probably not used intentionally polyester; its toxicity is often compared to production. They can trigger allergies and electron microscope (SEM) 26) The highest concentration, 5,700 mg/kg, as plasticizers, but are contaminants. that of arsenic. Antimony should not be in cause severe irritation to the respiratory Illustration 5: Analysis of clothing samples was in the Northland child’s rain poncho. The Seven Summits child’s jacket pur chas- children’s clothing. Because antimony is tract; they can also damage the lungs and in the SEM The di-2-ethylhexyl phthalate (DEHP) found ed in Austria also contained signiﬁcant Phthalates are used as plasticizers, for used to manufacture polyester, all jackets cause asthma. Some of them are suspected Illustration 6: Analysis of polyester membrane is considered to be particularly harmful. concentrations of phthalates (270 mg/kg, instance to soften the rigid plastic PVC. with a polyester membrane were tested. of being carcinogenic; one such compound at a magnification of 70 dominated by 260 ppm of DiNP). In com- In the textile industry they are used for These were from Vaude, The North Face, is toluene diisocyanate. In comparison, the currently valid EU parison, the sum of phthalates in textiles artiﬁcial leather, rubber and for printing Fjällräven, Northland, Patagonia, Mammut guideline for toys or objects that children manufactured in compliance with the (plastisol or dyes). Phthalates can severely and Kaikkialla. Polyurethane thermal insulation and PU can put into their mouths prescribes a GOTS standard 25) is not allowed to be more disrupt the endocrine system and lead membranes come into question as sources permissible limit of 1,000 mg/kg (equivalent than 100mg/kg. to infertility and adiposity. According The highest concentration was found in the of isocyanates. The membranes of both to 0.1 percent by mass). Because the pro- to the EU chemicals regulation REACH Fjällräven jacket (120 mg/kg). The North Vaude jackets were made either of PU or duct tested is a rain poncho for children, In the other twelve samples, phthalate con- (Registration, Evaluation, and Authorisation Face jacket contained 40 mg/kg, and the of polyester laminated with PU, and iso- the concentration found is unacceptable. centrations were lower than 100mg/kg, and of CHemicals), some compounds in this jacket from Patagonia contained 35 mg/kg cyanates were detected in both. The Kids Northland is an Austrian outdoor brand in six samples they were below 10mg/kg. group will be banned from 2015. of antimony. Much lower concentrations Escape Jacket contained 23 mg/kg of toluene were detected in the jackets from Northland diisocyanate, and the Escape Bike Jacket (10 mg/kg), Mammut (1 mg/kg), Kaikkialla for women contained 16 mg/kg of this

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 NPEs (2 mg/kg) and Zimtstern (manufactured substance. Testing was done in a VOC from the fabric prior to sale. Such washing would only have further contributed to inputs of NPEs/NP into the environment during the manufacturing stage. for Greenpeace, 3 mg/kg). screening process. 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.pdf 25) GOTS: Global Organic Textile Standard: http://tilth.org/files/certification/GOTSStandard.pdf 26) 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. 22 4 23

The outdoor industry – China still not trailblazers in protecting the environment China is Germany’s largest import The outdoor industry stands for cutting Advertising uses pictures of daring skiers trade partner for textiles. Some loose and being close to nature. This po- plunging through deep snow and fear- 30 percent of total annual imports of sitive image has brought strong double- less climbers scaling dizzying heights – textiles and apparel come from the digit growth in recent years to the sup- although most customers are not excep- People’s Republic. Textile production pliers of weather clothing. The European tional athletes but city dwellers looking steps for 95 percent of the textiles market in 2010 was worth about 4.5 billion to stay warm and dry during a bike ride available on the German market are euros. Germany, with a turnover of 1.02 or a walk in the rain. Nevertheless, the partially or wholly outsourced abroad. billion euros, is the leader in Europe, fol- industry has started a veritable arms race This makes it particularly difficult lowed by Great Britain, Ireland and France. so that outdoor clothing can withstand to control the use of substances ever more extreme weather conditions – that are harmful to the environment Jackets and pants are the most popular and this has been accompanied by a and health. items (50 percent), followed by shoes steady increase in chemical pollution, (25 percent), and backpacks (6 percent). especially from controversial PFCs. Consumers often pay several hundred euros for an extra warm deluxe anorak The latest novelties can be admired at the and – unlike in the fast fashion industry – OutDoor show in Friedrichshafen, where do not haggle over every cent. Profits of in July 2012 more than 900 businesses the VF Corporation, to which the world’s and manufacturers exhibited their pro- largest outdoor wear supplier The North ducts. But the hazards of the substances Face belongs as a brand, rose between used for production are kept secret from 2007 and 2011 from 24 to 36 million nature-conscious clientele. Instead, the dollars. talk is about natural fibers made of corn, coconut, hemp and merino wool. The Brands like The North Face, Patagonia, industry has made real progress in en- Vaude or Jack Wolfskin have long since vironmental protection elsewhere, but become household names, not only for here it has been criminally careless, mountain climbers and hikers. The indus- neglecting to replace the problematic try has gone from being a specialist chemical compounds used in membranes, supplier to a producer of trendy everyday coatings and finishings. Greenpeace’s clothes. Every city’s downtown area Detox campaign is now stirring this up. boasts brand name stores. Jack Wolfskin (from Idstein in Germany) alone has 200 of its own stores between the North Sea and the Alps, and in China it sells its products in more than 300 stores. 5. Alternatives to fluorocarbon

24 5 coatings and finishes 25 Alternatives to fluorocarbon coatings and finishes

Fluorine-free technologies are becoming Whether an item of clothing is waterproof Regarding oil repellency, however, the increasingly available on the market. An and can withstand even a strong downpour products containing controversial PFCs investigative research project at the Berlin is not governed by the outer coating or are superior to fluorine-free alternatives. University of Applied Sciences (HTW) finish. Waterproofing, windproofing, air There is still no replacement product with attested to the performance of these alter- permeability and breathability depend oil-repelling qualities. Here research is natives to fluorine products. 27) chiefly on the membrane on the inside of needed. But experience has shown that the jacket. Here lab testing showed that effective products are ready for the market Fabrics for apparel with wind and weather the fluorine-free SympaTex membrane and available as soon as outdoor clothing protection are generally impregnated on could withstand high water pressure and manufacturers specify a deadline by which the outside and have a membrane on the its performance was in fact as good, if not time they want to completely stop using inside. Alternatives to fluorine membranes better, than that of Gore-Tex. Over and hazardous chemicals. based on PTFE (such as Gore-Tex®) are above that, fluorine-free membranes are membranes made from polyester (such very breathable and allow perspiration For the consumer, oil repellency is generally as SympaTex®) or polyurethane (PU). to evaporate to the outside. Testing also not a relevant criterion – the decisive factor Alternatives to fluorocarbon finishes and showed another advantage – the alterna- is optimal water repellency. Functional coatings are waxes, paraffins (such as tives’ windproofing qualities were as good clothing is supposed to keep the wearer ecorepel®), polyurethane (such as Purtex®), as those of conventional membranes dry, inside and outside. The research study dendrimers (such as BIONIC-FINISH®ECO) containing fluorine compounds. explains that good workmanship on jackets and silicones. and pants is also essential for the wearer’s The additional coating or finishing of an comfort. Good quality means that zippers Three fluorine-free coatings and finishes article’s outside surface is there to repel are covered and seams are glued so that and one fluorine-free membrane were water, dirt and oily substances. Testing water and air cannot penetrate through. tested in the laboratory to compare their showed that fluorine-free alternatives were performance to that of conventional fluoro - just as waterproof and that water beaded Marijke Schöttmer’s research findings carbon products. Testing investigated off these materials just as well. Only the provided evidence that the outdoor clothing properties such as oil repellency, water PU finish demonstrated less of the water- industry can go without using PFC and repellency, waterproofing, resistance to beading effect, but the wearer remained nevertheless manufacture items that meet abrasion, windproofing, and breathability. dry. The protective finishing of fluorine-free most customers’ demands for functionality. alternatives can be reactivated by refresh- Before being used, alternatives need to be ing it with PFC-free agents. For the longe- checked for hazardousness to health and vity of outdoor clothing, it is important environment. that the coating is resistant to abrasion. The BIONIC-FINISH ECO made by the Rudolf company shows particularly high abrasion resistance, even after 10,000 abrasion cycles. In fact, it performs better than conventional finishes containing fluorine compounds.

27) Marijke Schöttmer, master’s thesis: Investigation of Alternatives to Fluorocarbon Finishes for Textiles. Berlin University of Applied Sciences, 2012. 26 5 27

Figure 3: Fluorine-free alternatives under the electron microscope Tips for consumers

Necessity or desire? Buy classic pieces. Empty out your closet. For which purpose do you need outdoor Select items of clothing that are not Are there clothes in your closet that you clothing? For an expedition to the Arctic outdated after one season. Clothing never wear? Get rid of them! Give them or for an autumn walk? For normal rainy or worn for a long time is truly ecological. to friends, donate them to charities, slushy weather your jacket does not need sell them, auction them off, or throw a to withstand a 50,000 mm water column. Buy green. clothing-swap party. Selective buying helps outdoor clothing If you do need new functional clothing, manufacturers phase out their high- select items that are largely free of PFCs. Return outdoor articles to the store. performance rat race that calls for using There are outdoor brands that use only Some manufacturers such as Patagonia ever more chemicals. fluorine-free membranes. There is very take back worn-out clothes and shoes Sample 1: Sample 1: little difference in price. in their stores. ® ® SympaTex : membrane at a magnification of 220 SympaTex finish at a magnification of 130 Beware of textile labels. Illustration 1 – membrane Illustration 2 – fabric with finish Certifications and textile labels indicate Buy quality. Become active. that materials are free of hazardous Check the workmanship of the article. Check with your favorite brand or ask at substances, which is not always true. It’s better to leave it on the rack if it your favorite store whether they imple- In spite of known risks to health and the doesn’t pass inspection for quality work ment ecological and socially responsible environment, products coated with on zippers and seams. policies and find out how they manage fluorine compounds can still be awarded their chemicals. Let salespeople know the OEKO-TEX Standard 100 or the Do laundry in an environmentally- that you like the clothing but that you bluesign standard that is popular with friendly way. want to see improvements in production. outdoor clothing manufacturers. There is A large share of the environmental life an urgent need to raise these standards. cycle assessment of clothing is attributed Join campaigns. to laundering. Make sure your washer is Tell your family, friends, and colleagues Buy secondhand items. filled to capacity. Most electricity is used about these problems in the textile indus- In thrift shops, at flea markets and on the to heat water. Use low temperatures – try. To sensitize this issue, Greenpeace is Sample 2: Sample 4: Internet, there are masses of clothing in fact, washing normally soiled clothes putting pressure on the textile industry – ® Schoeller Ecorepel at a magnification of 130 Freudenberg at a magnification of 130 that others no longer wear. This is where at 30 degrees centigrade will get them for a toxin-free future. Illustration 1 – fabric with finish Illustration 1 – fabric with finish you can sometimes find items that be- clean. come long-time favorites. 6. Conclusions

28 6 and recommendations 29 Conclusions and recommendations

The outdoor clothing industry presents Our investigation also tested for other a very flattering image of itself and ex- substances hazardous to health such as What must happen next presses commitment to environmental plasticizers and alkylphenol ethoxylates. The outdoor clothing industry is called protection in numerous publications Our findings emphasize the urgent on to ban hazardous substances such and promotional activities. However, need to ban dangerous chemicals from as PFCs from its production processes the Greenpeace investigation described outdoor clothing production. and immediately switch to safe functional here points out a mismatch between alternatives wherever possible. The in- assertion and action. The industry is still Outdoor clothing brands make the consu- dustry must immediately take steps to far from reducing its use of hazardous mers of their products unwitting assistants further develop safer alternatives and use chemicals to zero and thereby ending its in releasing perfluorinated compounds them in production. Greenpeace calls pollution of waters and drinking water. to the environment. Even if the amount on all manufacturers of outdoor clothing Water is a scarce and threatened re- of PFC is low in single items of clothing to immediately address this issue and source in many regions of the world. tested, the total amount released from the begin phasing out the entire group of massive volume of clothing sold today PFC compounds from production. Since 2011, Greenpeace activists have can be substantial. Greenpeace is working been working around the world in the on instituting a register of hazardous The key elements for a toxin-free Detox campaign for the production of substance emissions in China. Only in future are: textiles free from harmful substances. By this way can local residents find out which testing samples of wastewater and textiles, chemicals have contaminated the waste- The phaseout of PFC chemistry Greenpeace has revealed that the textile water from “their” textile factory. and authentic commitment to industry releases chemical compounds this endeavor. that are harmful to the environment and Next to this analytical investigation of All dangerous chemicals must be banned health. Eleven groups of substances are hazardous substances, Greenpeace also from manufacturing processes and their named which must be phased out of textile helped to see through a research project on products. The findings from this product production due to their hazardous pro- “Alternatives to Fluorocarbon Finishes investigation underline the urgent need to perties. Among these groups are the per- for Textiles” carried out at the Berlin Uni- ban PFCs from outdoor wear produc tion. fluorinated chemical compounds (PFCs). versity of Applied Sciences in 2012. In this PFC-free materials are already available Some PFCs are known to be endocrine context, fluorine-free alternative fabrics today. The outdoor clothing industry must (hormone system) disruptors and harmful were physically tested for their capabilities continue to develop safer alternatives and to the reproductive system. and chemically tested for hazardous sub- use them in processing their products. 28) stances. The project proved that fluorine- This study identified per- and polyfluori- free materials are already on the market Precaution. nated chemicals in outdoor articles manu- that largely meet expectations for outdoor The hazardous properties of well-re- factured for major brands and drew con- clothing and that can be used in their searched PFCs such as PFOS and PFOA clusions about environmental risks and production. and insufficient data on other PFCs call the safety of consumers. Although some for much more stringent regulation to outdoor clothing manufacturers have protect health and the environment. In switched to using short-chain alternatives view of the hazardous properties of in their production, Greenpeace’s test series C8 PFCs (PFOA and PFOS) and in view has shown that the use of C8 fluorotelomer of research findings indicating that other alcohols is still common practice. Textiles PFCs (C6) possess similar hazardous are free of PFOS, but still contain PFOA properties, it is not enough to regulate as an impurity or degraded product. only single substances such as PFOA. The entire group of PFCs has to be under scrutiny for a possible regulative ban.

It’s time to act. Now. www.greenpeace.de/detox

28) http://www.ipe.org.cn/En/pollution/ 30 7 7. Appendix 31 Appendix Results for perfluorinated and polyfluorinated compounds

Table 1: PFCs (perfluorinated compounds) in outdoor clothing purchased in Germany Key steps to Detox our clothes The need for government action Material Country of PFOA PFCA PFS FTA 8:2 FTOH FTOH To effectively stop the pollution of our Governments need to do their share as Production (Sum) (Sum) (Sum) (Sum) waters with hazardous chemicals, brands well and adopt political commitment to the μg/m2 μg/m2 μg/m2 μg/m2 μg/m2 μg/m2 should: zero discharge of all hazardous chemi- Greenpeace in Germany, jacket China 0,27 0,70 n.d. 1,4 n.d. n.d. cals within one generation, based on the Jack Wolfskin, child’s jacket Indonesia 2,01 5,11 n.d. 10,1 n.d. n.d. credibly commit to phasing out the precautionary principle and including Vaude, child’s outdoor jacket China 0,58 2,78 n.d. n.d. 230 418,5 use of all toxic chemicals in their global a preventative approach by avoiding Vaude, woman’s jacket Vietnam 0,24 1,21 n.d. 19,5 n.d. n.d. supply chains and in all products by the production and use, and therefore, The North Face, woman’s jacket China 1,58 3,37 n.d. 23,8 n.d. n.d. 1 January 2020. exposure to hazardous chemicals. Mountain Equipment, woman’s jacket Ukraine 0,20 0,58 n.d. 6,1 n.d. n.d. Marmot, boys rain pants China 2,31 6,29 n.d. 25,6 n.d. n.d. Credible commitment means that three This commitment must be matched with Fjällräven, woman’s jacket China 0,29 1,17 n.d. 20,8 n.d. 52,0 fundamental principles are unambiguously an implementation plan containing inter- Patagonia, outdoor-jacket China 2,16 8,48 n.d. 65,0 30 123,0 adopted – precaution 29), comprehensive mediate short-term targets, a dynamic list Adidas, outdoor-jacket China 0,29 1,04 n.d. 5,6 n.d. 99,0 and complete elimination (including zero of priority hazardous substances requiring discharges) 30), and the right to know 31). immediate action based on the substi- tution principle, and a publicly available walk the talk by committing to rapid register of data on discharge emissions Table 2: PFCs (perfluorinated compounds) in outdoor clothing purchased and full public disclosure of the use and and losses of hazardous substances, in Austria (AT) and Switzerland (CH) release of toxic chemicals in and from such as a Pollutant Release and Transfer suppliers’ facilities. This information must Register (PRTR). Material Country of PFOA PFCA PFS FTA 8:2 FTOH FTOH be precise and comprehensive, and it Production (Sum) (Sum) (Sum) (Sum) must be updated at regular and relevant Governments must adopt comprehensive μg/m2 μg/m2 μg/m2 μg/m2 μg/m2 μg/m2 intervals (at least once a year), especially chemicals management policies and Northland, child’s poncho China 0,45 1,20 n.d. n.d. n.d. 17,6 with regard to local/national inhabitants. regulations in order to: Seven Summits, child’s jacket China 0,30 0,66 n.d. n.d. 40,6 40,6 32) Credible public information platforms ) level the playing field and make leading Mammut, woman’s jacket China 4,69 46,34 0,46 57,2 78,1 464,2 should be used for this purpose. Clear and brands’ actions a reality throughout the Kaikkialla, woman’s jacket China 4,98 10,96 n.d. 78,3 87,8 175,5 ambitious deadlines must be set for the entire sector and beyond, as many of the elimination of priority substances such hazardous chemicals used in textiles are as APEs, and a new sectoral blacklist of also in use in other sectors; hazardous chemicals to be eliminated give industry a clear direction by showing must be drawn up which is based on and that hazardous chemicals have no place takes into account the intrinsic properties in a sustainable society, which will in already identified in other hazardous turn drive innovation towards safer alter- chemicals. natives; and prevent ongoing releases into the environment that may require future clean-up and have serious impact on the environment and on people’s health and liveli- hoods, 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/ 32 7 33 2 2

EV EV 58,1 87,8 27,0 20,3 60,8 0,173 0,647 0,475 0,559 0,446 0,238 Toray Toray Toray Toray 1,485 4,982 1,958 <6,75 <4,05 <4,05 <4,05 <4,05 <4,05 μg/m μg/m jacket <0,112 <0,112 <0,112 <0,112 <0,170 <0,170 <0,170 <0,170 <0,170 <0,225 <0,225 <0,225 <0,225 Jacket Dermizax Dermizax Dermizax Dermizax woman’s woman’s Kaikkialla Kaikkialla Kaikkialla Kaikkialla Membrane: Membrane: Membrane: Membrane: 2 2 4,7 7,3 0,4 2,3 0,5 0,5 0,2 1,2 1,0 1,9 352 <11 34,1 78,1 17,6 39,6 26,9 <5,5 <5,5 <5,5 <5,5 <5,5 PTFE PTFE μg/m μg/m jacket <0,163 <0,163 <0,163 <0,244 <0,244 <0,244 <0,244 Jacket <0,326 <0,326 <0,326 <0,326 Mammut Mammut Mammut woman’s woman’s Fujiyama Fujiyama (Gore Tex) (Gore Tex) 2 2 <35 <5,6 <5,6 <5,6 <5,6 <5,6 <5,6 <5,6 5000 5000 5000 5000 0,363 0,296 <11,9 40,60 100% 100% <23,8 μg/m μg/m Seven Seven jacket <0,112 <0,112 <0,112 <0,112 <0,112 <0,112 <0,112 <0,112 <0,112 <0,112 <0,112 <0,168 <0,168 <0,168 <0,168 <0,224 <0,224 <0,224 <0,224 <0,224 child’s child’s Jacket Ice Tech Ice Tech Summits Summits polyamide polyamide 2 2

land land 0,097 17,60 0,094 0,446 0,083 0,280 0,200 <3,19 <1,59 <1,59 <1,59 <1,59 <1,59 <1,59 <1,59 <8,79 100% <5,59 100% μg/m μg/m North- North- <0,115 <0,115 <0,115 <0,115 <0,153 <0,153 <0,153 <0,153 <0,153 <0,077 <0,077 <0,077 <0,077 <0,077 <0,077 <0,077 shild’s child’s poncho poncho polyester polyester 2 2

5,58 <5,4 <5,4 <5,4 <5,4 <5,4 <5,4 <9,9 0,204 0,543 99,00 0,293 <29,7 <19,8 100% 100% μg/m μg/m jacket <0,138 <0,138 <0,138 <0,138 <0,138 <0,138 <0,138 <0,138 <0,138 <0,138 <0,277 <0,277 <0,277 <0,277 <0,277 <0,208 <0,208 <0,208 <0,208 adidas adidas adidas adidas Jacket GoreTex, GoreTex, Pro Shell, Pro Shell, woman’s woman’s polyamide polyamide 2 2

<4 <4 <4 <4 <4 <8 2,157 3,211 0,155 0,103 0,891 nylon nylon 0,667 21,00 0,554 0,644 0,098 35,00 30,00 30,00 72,00 100% 100% μg/m μg/m jacket <0,145 <0,145 <0,145 <0,145 <0,194 <0,194 <0,194 <0,194 <0,194 <0,096 <0,096 <0,096 <0,096 Jacket GoreTex, GoreTex, woman’s woman’s outer shell: outer shell: Patagonia Patagonia Patagonia Patagonia 2 2

<6,5 <6,5 <6,5 <6,5 <6,5 <6,5 0,581 52,00 0,295 0,294 20,80 <14,3 <42,9 <28,6 μg/m μg/m jacket <0,118 <0,118 <0,118 <0,118 <0,118 <0,118 <0,118 <0,118 <0,118 <0,118 <0,178 <0,178 <0,178 <0,178 <0,237 <0,237 <0,237 <0,237 <0,237 Jacket PFC-free, PFC-free, polyester polyester woman’s woman’s Eco-Shell, Eco-Shell, 100% rec. 100% rec. Fjällräven Fjällräven Fjällräven Fjällräven 2 2

4% 4% 96% 96% 2,312 2,261 0,877 0,842 nylon, nylon, 25,60 <11,2 <11,2 <11,2 <11,2 <11,2 <11,2 <22,4 <44,8 <65,6 <65,6 pants pants μg/m μg/m <1,207 <1,207 <1,207 <1,207 <1,609 <1,609 <1,609 <1,609 <1,609 <0,804 <0,804 <0,804 <0,804 <0,804 <0,804 <0,804 <0,804 <0,804 child’s child's elastan Marmot Marmot elastane ) ² 2 2 <21 <21 6,09 0,373 0,202 <3,15 <3,15 <7,35 <3,15 <3,15 <3,15 <3,15 <13,6 100% 100% μg/m μg/m jacket <0,148 <0,148 <0,148 <0,148 <0,198 <0,198 <0,198 <0,198 <0,198 <0,098 <0,098 <0,098 <0,098 <0,098 <0,098 <0,098 <0,098 <0,098 <0,098 <0,098 Jacket GoreTex, GoreTex, woman’s woman’s Mountain Mountain Mountain Mountain polyamide polyamide outer shell: outer shell: Equipment Equipment ) ² 2 2 0,111 Face Face 0,138 0,312 23,75 0,092 0,644 1,575 0,433 0,066 <4,75 <4,75 <4,75 <4,75 <4,75 <4,75 PTFE- PTFE- <10,4 <30,4 <30,4 <20,9 North North μg/m μg/m jacket <0,103 <0,051 <0,051 <0,051 <0,051 <0,051 <0,051 <0,077 <0,077 <0,077 <0,077 <0,077 <0,077 <0,077 Jacket laminate laminate polyester polyester (GoreTex) (GoreTex) woman’s woman’s 2 2

<7,8 <3,9 <3,9 <3,9 <3,9 <3,9 <3,9 0,242 0,082 0,684 <22,1 <22,1 0,200 19,50 <14,3 μg/m μg/m jacket jacket Vaude Vaude Vaude Vaude <0,128 <0,064 <0,064 <0,064 <0,064 <0,064 <0,064 <0,064 <0,064 <0,064 <0,064 <0,096 <0,096 <0,096 <0,096 <0,096 <0,096 <0,096 woman’s woman’s 100% PU, 100% PU, Ceplex ad, Ceplex ad, polyamide polyamide + PU coating + PU coating 2 2

0,197 <179 0,142 0,576 0,232 0,359 0,366 0,909 <29,7 <29,7 <29,7 <29,7 <29,7 <29,7 <29,7 <59,4 μg/m μg/m jacket jacket Vaude Vaude Vaude Vaude 229,50 <0,134 <0,134 <0,134 <0,134 <0,134 <0,134 189,00 <0,201 <0,201 <0,201 <0,201 <0,268 <0,268 <0,268 <0,268 <0,268 child’s child’s 100% PU, 100% PU, Ceplex ad, Ceplex ad, polyamide polyamide + PU coating + PU coating 2 2 Air, Air, 0,177 0,170 Jack Jack 2,014 0,081 10,13 0,470 0,218 <10,1 1,015 0,462 0,244 0,255 <15,2 <15,2 100% <2,53 <2,53 <2,53 <2,53 <2,53 <2,53 100% <5,06 μg/m μg/m jacket jacket <0,121 child’s child’s <0,090 <0,090 <0,090 <0,060 <0,090 <0,060 <0,090 <0,090 <0,090 <0,060 <0,060 Wolfskin Wolfskin Wolfskin Wolfskin Texapore Texapore Texapore Texapore polyamide polyamide 2 2 Eco Eco 1,36 <6,8 <6,8 0,077 0,273 0,084 0,266 <4,25 <2,55 <0,85 <0,85 <0,85 <0,85 <0,85 <0,85 μg/m μg/m jacket jacket <0,042 <0,042 <0,042 <0,042 <0,042 <0,042 <0,042 <0,042 <0,042 <0,085 <0,064 <0,064 <0,064 <0,064 <0,064 <0,064 <0,064 <0,064 Polyester Polyester activist’s activist’s SympaTex, SympaTex, Zimtstern / Zimtstern / Bionic-Finish Bionic-Finish Greenpeace Greenpeace

PFPA PFBA PFDA PFHp PFBS conc. conc. PFDS PFNA PFOA PFOS PFTrA PFTeA DMOA PFHxS PF-3,7- PFHxA PFDoA PFUnA PFHpA PFOSA 6:2 FTS 6:2 FTA 8:2 FTA EtFOSE EtFOSA H2PFDA HPFHpA H4PFOS; MeFOSE 10:2 FTA MeFOSA 6:2 FTOH 8:2 FTOH 4:2 FTOH H4PFUnA 10:2 FTOH FASE 1-

cane

fluor- fluor- fluor- fluoro-1- fluoro-1- fluoro-1- fluoro-1-

Perfluor- dimethyloc- decane decane Concentrations are given in micrograms of PFC per square meter of fabric (µg/m Method of testing for PFCAs and PFSAs: extraction with methanol in a Soxhlet extractor, separation,HPLC-MS/MS identification (high-performance and quantification liquid chromatographywith an internal standard combined using with tandem triple-quadrupole mass spectrometry). Concentrations are given in micrograms of PFC per square meter of material/fabric (µg/mMethod of testing for FTOHs: extraction with MTBE (methyl tertiary butyl ether) in anusing ultrasonic GC-MS (gas bath, chromatography separation, identification coupled with mass and spectrometry), quantification verification with an internal using standard HPLC-MS/MS. carboxylate Perfluorohexane sulfonate Perfluorohexane sulfonate Perfluoroheptane sulfonate Perfluorooctane carboxylate Perfluoropentane carboxylate Perfluoroheptane carboxylate Perfluorooctane ooctylacrylat 1H,1H,2H,2H-Per odecylacrylat 1H,1H,2H,2H-Per ododecylacrylat 1H,1H,2H,2H-Per hexanol 1H,1H,2H,2H-Per oktanol 1H,1H,2H,2H-Per decanol 1H,1H,2H,2H-Per dodecanol 2-(N-methylperfluoro- octanesulfonamido)-ethanol 2-(N-ethylperfluoro-1- octanesulfonamido)-ethanol N-methylperfluoro-1- Table 3: PFC concentrations 3: PFC Table (perfluorinated of PFCAs carboxylic acids) andPFSAs (perfluorinated sulfonic acids) in outdoor clothing Perfluorobutane sulfonate Perfluorodecane sulfonate Perfluorooctane sulfonate P1H,1H,2H,2H Perfluorooctane sulfonate Perfluorobutane carboxylate Perfluorononane carboxylate Perfluorodecane carboxylate Perfluoroundecane carboxylate Perfluorododecane carboxylate Perfluorotridecane carboxylate Perfluorotetra carboxylate concentrations 4: PFC Table (perfluorinated of PFCAs carboxylic acids),PFSAs (perfluorinated sulfonic acids) and fluorotelomer alcohols (FTOHs) in outdoor clothing Perfluoro-3,7- tane carboxylate 7H-Dodecanefluoroheptane carboxylate 2H,2H-Perfluorode carboxylate 2H,2H,3H,3H- carboxylate oundecane 1H,1H,2H,2H-Per octansulfonamide N-ethylperfluoro-1- octanesulfonamide 34 7 35 Children’s clothing (sum PFCA in μg/m2) Results: Perfluorinated and

PFOA concentration in μg/m2 polyfluorinated compounds of separate brands Sum PFCA and PFS – 6

– Greenpeace Jack Wolfskin Vaude

– 5

–

– 4

– PFBA

–3 PFOA

–

– 2 Sum Sum Sum 8:2 FTA extractable PFC: 8:2 FTA extractable PFC: PFDA 10:2 FTOH extractable PFC: 8:2 FTOH – 2 μg/m2 PFOA 15 μg/m2 421 μg/m2 – 1

–

– 0 Seven Summits Northland Vaude Jack Wolfskin Marmot child’s jacket child’s poncho child’s jacket child’s jacket child’s pants

Perfluorinated compounds in children’s clothes

Woman’s jacket (sum PFCA in μg/m2) PFC PFC PFC 2 2 2 PFOA concentration in μg/m2 concentration/amount μg/m % concentration/amount μg/m % concentration/amount μg/m % Sum PFCA and PFS 46,8 PFBA 0,3 13 PFBA 0,2 1 PFBA 0,9 0 – 12 PFHxA 0,1 4 PFPA 0,2 1 PFPA 0,4 0 PFHpA 0,1 4 PFHxA 0,5 3 PFHxA 0,4 0 – 11 PFOA 0,3 13 PFHpA 0,2 2 PFHpA 0,2 0 – 10 8:2 FTA 1,4 66 PFOA 2,0 13 PFOA 0,6 0 PFNA 0,3 2 PFDA 0,2 0 – 9 concentration in μg/m2 PFDA 1,0 7 PFUnA 0,1 0 amount PFC in % – 8 PFUnA 0,1 1 8:2 FTOH 229,5 54 – 7 PFDoA 0,5 3 10:2 FTOH 189,0 45 H4PFUnA 0,2 1 concentration in μg/m2 – 6 8:2 FTA 10,1 66 amount PFC in % – 5 concentration in μg/m2 – 4 amount PFC in %

– 3

– 2

– 1

– 0 Zimtstern / Mountain adidas Fjällräven Vaude North Face Mammut Patagonia Kaikkialla Greenpeace Equipement woman’s jacket woman’s jacket woman’s jacket woman’s jacket woman’s jacket woman’s jacket woman’s jacket light jacket woman’s jacket

Perfluorinated compounds in woman’s jackets Zimtstern / Greenpeace | activist’s jacket Jack Wolfskin | child's jacket Vaude | child’s Jacket 36 7 37

Vaude North Face Mountain Equipment Marmot Fjällräven Patagonia

PFOA PFBA PFBA 10:2 FTOH

PFOA 8:2 FTA 6:2 FTA

8:2 FTOH

Sum Sum Sum Sum Sum Sum 8:2 FTA extractable PFC: 8:2 FTA extractable PFC: 8:2 FTA extractable PFC: 8:2 FTA extractable PFC: 6:2 FTOH extractable PFC: extractable PFC: 2 2 2 2 2 2 21 μg/m 27 μg/m 7 μg/m 32 μg/m 74 μg/m 196 μg/m 10:2 FTA

6:2 FTOH

PFC PFC PFC PFC PFC PFC concentration/amount μg/m2 % concentration/amount μg/m2 % concentration/amount μg/m2 % concentration/amount μg/m2 % concentration/amount μg/m2 % concentration/amount μg/m2 % PFBA 0,2 1 PFBA 0,3 1 PFBA 0,4 6 PFBA 2,3 7 PFBA 0,6 1 PFBA 0,9 0 PFOA 0,2 1 PFHxA 0,6 2 PFOA 0,2 3 PFHpA 0,8 3 PFHxA 0,3 0 PFPA 0,6 0 PFDA 0,1 0 PFHpA 0,1 0 8:2 FTA 6,1 91 PFOA 2,3 7 PFOA 0,3 0 PFHxA 3,2 2 H4PFUnA 0,7 3 PFOA 1,6 6 PFDA 0,9 3 6:2 FTA 20,8 28 PFHpA 0,6 0 concentration in μg/m2 8:2 FTA 19,5 94 PFNA 0,1 0 8:2 FTA 25,6 80 6:2 FTOH 52,0 70 PFOA 2,2 1 amount PFC in % PFDA 0,4 2 PFNA 0,1 0 concentration in μg/m2 concentration in μg/m2 concentration in μg/m2 PFDoA 0,1 0 PFDA 0,7 0 amount PFC in % amount PFC in % amount PFC in % H4PFUnA 0,1 1 PFUnA 0,1 0 8:2 FTA 23,8 88 PFDoA 0,2 0 8:2 FTA 35,0 18 concentration in μg/m2 10:2 FTA 30,0 15 amount PFC in % 6:2 FTOH 72,0 37 8:2 FTOH 30,0 15 10:2 FTOH 21,0 11

concentration in μg/m2 amount PFC in %

Adidas Northland Seven Summits Mammut Fujiyama Kaikkialla

8:2 FTA 10:2 FTOH

8:2 FTA 10:2 FTOH 8:2 FTOH 8:2 FTA

Sum Sum Sum Sum Sum extractable PFC: 6:2 FTOH 6:2 FTOH extractable PFC: 6:2 FTOH extractable PFC: 8:2 FTOH extractable PFC: extractable PFC: 2 106 μg/m2 19 μg/m2 41 μg/m2 568 μg/m 265 μg/m2 10:2 FTA

6:2 FTOH 8:2 FTOH

PFC PFC PFC PFC PFC concentration/amount μg/m2 % concentration/amount μg/m2 % concentration/amount μg/m2 % concentration/amount μg/m2 % concentration/amount μg/m2 % PFBA 0,5 1 PFBA 0,3 1 PFBA 0,4 1 PFBA 1,0 0 PFBA 0,6 0 PFHxA 0,2 0 PFOA 0,4 2 PFOA 0,3 1 PFPA 2,3 0 PFPA 0,2 0 PFOA 0,3 0 PFNA 0,1 0 8:2 FTOH 40,6 98 PFHxA 26,9 5 PFHxA 1,5 1 8:2 FTA 5,6 5 PFDA 0,2 1 PFHpA 7,3 1 PFHpA 0,5 0 concentration in μg/m2 6:2 FTOH 99,0 94 PFUnA 0,1 0 PFOA 4,7 1 PFOA 5,0 2 amount PFC in % PFDoA 0,1 1 PFNA 1,2 0 PFNA 0,4 0 concentration in μg/m2 6:2 FTOH 17,6 94 PFDA 1,9 0 PFDA 2,0 1 amount PFC in % PFUnA 0,4 0 PFUnA 0,2 0 concentration in μg/m2 PFDoA 0,5 0 PFDoA 0,6 0 amount PFC in % PFTrA 0,2 0 8:2 FTA 58,1 22 8:2 FTA 39,6 7 10:2 FTA 20,3 8 10:2 FTA 17,6 3 6:2 FTOH 27,0 10 6:2 FTOH 352,0 62 8:2 FTOH 87,8 33 8:2 FTOH 78,1 14 10:2 FTOH 60,8 23 10:2 FTOH 34,1 6 concentration in μg/m2 H4PFOS 0,5 0 amount PFC in % concentration in μg/m2 amount PFC in %

17 <1 <1 <1 <1 22* EV EV <5 <5 <2 <2 <2 <3 <3 2,3 5,6 5,8 n.n. <15 <15 0,18 0,55 Toray Toray Toray Toray jacket jacket mg/kg mg/kg <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 Dermizax Dermizax Dermizax Dermizax women’s women’s Kaikkialla Kaikkialla Kaikkialla Kaikkialla detectable Membrane: Membrane: Membrane: Membrane: 2 1 1 85 <1 <1 <1 <1 88* <5 <5 <5 <2 <2 <2 <3 <3 n.n. <15 <15 PTFE PTFE jacket jacket mg/kg mg/kg <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 Mammut Mammut Mammut Mammut women’s women’s Fujiyama Fujiyama (Gore Tex) (Gore Tex) detectable 6 4 <1 <1 <1 <1 <1 <5 <5 <2 <2 <2 <3 <3 n.n. n.n. 270 320 260 <15 5000 5000 5000 5000 100% 100% Seven Seven jacket jacket mg/kg mg/kg child’s child’s Ice Tech Ice Tech Summits Summits polyamide polyamide 2

10 <1 <1 <1 <1 <5 <5 <5 <2 <2 <2 <3 <3 n.n. <15 <15 land land 5706 5700 100% 100% North- North- mg/kg mg/kg child’s child's poncho poncho polyester polyester 2 8 7 7

20 <1 <1 <1 <1 <5 <5 16* <2 <2 <2 <3 n.n. n.n. <15 <15 100% 100% jacket jacket mg/kg mg/kg adidas adidas adidas adidas GoreTex, GoreTex, Pro Shell, Pro Shell, women’s women’s polyamide polyamide

1 1

4 35 <1 <1 <1 <1 <5 <5 <5 <2 <2 <2 <3 <3 <15 <15 nylon nylon 100% 100% jacket jacket mg/kg mg/kg GoreTex, GoreTex, women’s women’s outer shell: outer shell: detectable Patagonia Patagonia Patagonia Patagonia 2 8

4 16 19 10 <1 <1 <1 <1 <5 <5 <2 <2 <2 <3 120 <15 <15 100% jacket jacket mg/kg mg/kg Rec.PES PFC-free, PFC-free, polyester Eco Shell, Eco Shell, women’s women’s 100% rec. Fjällräven Fjällräven Fjällräven Fjällräven detectable 5 3 1 1

<1 <1 <1 <1 <5 <5 <5 <2 <2 <2 <3 <3 4% 4% <15 <15 96% 96% nylon, nylon, pants pants mg/kg mg/kg child’s child's elastan elastan Marmot Marmot detectable

3 4 4 11 <1 <1 <1 <1 <5 <5 <5 <2 <2 <2 <3 <3 <15 <15 100% 100% jacket jacket mg/kg mg/kg GoreTex, GoreTex, women’s women’s Mountain Mountain Mountain Mountain polyamide polyamide detectable outer shell: outer shell: Equipment Equipment 5 1 4 40 <1 <1 <1 <1 <1 <5 <5 <5 <2 <2 <2 <3 <3 n.n. <15 <15 Face Face PTFE- PTFE- North North jacket jacket mg/kg mg/kg laminate laminate polyester polyester (GoreTex) (GoreTex) women’s women’s detectable 5 2 3

13 10 10 <1 <1 <1 <1 <5 <5 <5 <2 <2 <2 <3 <3 n.n 4,8 n.n. <15 <15 jacket jacket Vaude Vaude Vaude Vaude mg/kg mg/kg <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 women’s women’s 100% PU, 100% PU, Ceplex ad, Ceplex ad, polyamide polyamide Isocyanate + PU coating + PU coating 3 3

30 13 <1 <1 <1 <1 <1 <1 <5 <5 <2 <2 <2 <3 <3 n.n. <15 <15 jackej jacket Vaude Vaude Vaude Vaude mg/kg mg/kg <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 <0,025 child’s child’s 100% PU, 100% PU, Ceplex ad, Ceplex ad, polyamide polyamide Isocyanate + PU coating + PU coating 5 9 3 1 <1 <1 <1 <1 <5 <5 <5 <2 <2 <2 <3 <3 Air, Air, <15 <15 Jack Jack Boys Boys 100% 100% jacket mg/kg mg/kg child’s Jacket Polyamid Wolfskin Wolfskin Wolfskin Wolfskin Texapore Texapore Texapore Texapore polyamide detectable 8 3 7 <1 <1 <1 <1 <1 15* <5 <5 <5 <2 <2 <2 <3 <3 n.n. Eco Eco <15 <15 jacket jacket mg/kg mg/kg Polyester Polyester activist’s activist’s SympaTex, SympaTex, Zimtstern / Zimtstern / Bionic-Finish Bionic-Finish Greenpeace Greenpeace F

Sb NP OP TPT TBT DBT TOT DEP DOT NPE BBP DBP OPE MBT TcyT MOT DMP DiBP DiDP DiNP TPhT TeBT DPhT conc. conc. TeEtT DnDP DnNP DEHP DnOP DMEP DEHIP

amines Concentrations are given in milligrams of toxin per kilogram of fabric (mg/kg = ppm). Values

Berger U, Herzke D (2006). Jensen A & Leffers H (2008). Per- and polyfluorinated alkyl substan ces (PFAS) extracted from Emerging endocrine disrupters: perfluoroalkyaled substances. Hazardous substances in the textile industry – 11 groups of chemicals textile samples. Poster presentation International Journal of Andrology 31: 161-169.

These eleven groups of chemicals are Phthalates: Organotin compounds: Chlorinated solvents: Berger U (Oral Prasentation). Langer V, Dreyer A, Ebinghaus R (2010). Perfluoroalkyl acids in blood serum from first time mothers from Polyfluorinated compounds in residential and nonresidential used extensively in the textile industry. Phthalates are used as plasticizers, for Organic tin compounds are used as Chlorinated solvents such as trichloro- Uppsala, Sweden: temporal trends 1996-2010 and serial samples indoor air. Environ Sci Technol 2010, 44:8075-8081. Once released, many of them accu- instance to soften the rigid plastic PVC. biocides and anti-fungal agents in many ethylene (TCE) are used to remove during pregnancy and nursing, 6th SETAC World Congress / SETAC Europe 22nd Annual Meeting, Berlin, 20-24 Mai 2012 Llorca M, Farré M, Tavano MS, Alonso B, Koremblit G, mulate in the environment – in rivers, In the textile industry they are used for products. They have an antibacterial chemical residues from textiles and to Barceló D (2012). the oceans, in the soil and in plants. artificial leather, rubber and in dyes. effect on socks, shoes and sportswear clean them. TCE is damaging to the Bonefeld-Jorgensen EC, Long M, Bossi R, Ayotte P, Fate of a broad spectrum of perfluorinated compounds in soils Asmund G, Krüger T, Ghisari M, Mulvad G, Kern P, Nzulumiki P, and biota from Tierra del Fuego and Antarctica. Environ Pollut. These substances are transported to Specifically, di-2-ethylhexyl phthalate and are supposed to prevent odors. ozone layer. Moreover, it can damage Dewailly E (2011). 163:158-66. a certain extent around the world and (DEHP) and dibutyl phthalate (DBP) are If tributyltin (TBT) is released into the en- the central nervous system, the liver Perfluorinated compounds are related to breast cancer risk in greenlandic inuit: A case control study Environ Health. 10:88 Melzer D, Rice N, Depledge MH, Henley WE, Galloway TS (2010). contaminate ecosystems far from considered hazardous because they vironment, it can accumulate in the bodies and kidneys in humans and animals. Association between serum perfluorooctanoic acid (PFOA) where they were initially introduced inhibit the development of reproductive of humans and animals and disrupt the Since 2008, TCE has been allowed only Cai M, Yang H, Xie Z, Zhao Z, Wang F, Lu Z, Sturm R, and thyroid disease in the U.S. National Health and Nutrition Ebinghaus R (2012). Examination Survey. Environ Health Perspect. 118(5): 686–692. to the environment. They are defined organs in mammals. Since 2005, four immune system and reduce fertility. limited use in the EU. Per- and polyfluoroalkyl substances in snow, lake, surface run-off as persistent. Some substances are phthalates (DBP, BBP, DEHP and DIBP) water and coastal seawater in Fildes Peninsula, King George Möller A, Ahrens L, Surm R, Westerveld J, van der Wielen F, Island, Antarctica. J Hazard Mater. 209-210:335-42. Ebinghaus R, de Voogt P (2010). bioaccumulative, meaning they can have been on the REACH Candidate List Perfluorinated compounds (PFCs): Chlorophenols: Distribution and sources of polyfluoroalkyl substances (PFAS) accumulate in the blood, organs of Substances of Very High Concern PFCs are used to make textiles and Chlorophenols are used as biocides in Dauchy X, Boiteux V, Rosin C, Munoz JF (2012). in the River Rhine watershed. Environ Pollut. 158(10):3243-50. Relationship between industrial discharges and contamination and tissues of living organisms and for Authorisation. [REACH (Registration, leather products water-repellent and the textile industry. Pentachlorophenol of raw water resources by perfluorinated compounds. Rand AA, Mabury SA. damage health. Evaluation, and Authorisation of CHemi- dirt-repellent. They are persistent and (PCP) in particular is highly toxic to Part I: case study of a fluoropolymer manufacturing plant. In vitro interactions of biological nucleophiles with fluorotelomer Bull Environ Contam Toxicol. 2012 89(3):525-30. unsaturated acids and aldehydes: fate and consequences. cals) is the main general European Union some PFCs accumulate in human tissue aquatic organisms and can damage Environ Sci Technol. 46(13):7398-406. Alkylphenols: chemicals regulation]. This means they and blood. They can damage the liver and human organs and the central nervous Eschauzier C, Haftka J, Stuyfzand PJ, de Voogt P (2010). Perfluorinated compounds in infiltrated river Rhine water and Schöttmer M. (2012). The alkylphenols include nonylphenol and are subject to severe restriction criteria. disrupt the body’s endocrine (hormonal) system. The production and use of infiltrated rainwater in coastal dunes. Environ Sci Technol. Investigation of Alternatives to Fluorocarbon Finishes for Textiles. octylphenol. They are released from their system. Perfluorooctane sulfonate (PFOS) PCP has been banned in the European 44(19):7450-5. Berlin University of Applied Sciences, master thesis

ethoxylates. In this way, nonylphenols Brominated and chlorinated is restricted around the world by the Union since 1991. Fei C, McLaughlin JK, Lipworth L, Olsen J (2009). Thorhallur IH, Rytter D, Småstuen Haug L, Hammer Bech B, (NPs) are a product of nonylphenol etho- flame retardants: Stockholm Convention and is on the Maternal levels of perfluorinated chemicals and subfecundity. Danielsen I, Becher G, Brink Henriksen T, Olsen SF (2012). Hum Reprod. 24(5):1200-5. Prenatal Exposure to Perfluorooctanoate and Risk of Overweight xylates (NPEs). NPEs are frequently used Many brominated flame retardants (BFRs) Candidate List of Substances of Very High Short-chain chlorinated paraffins at 20 Years of Age: A Prospective Cohort Study. Environ Health in the textile industry to wash materials accumulate in the environment and can Concern for Authorisation (SVHC). It is (SCCPs): Friends of the Earth Norway (2006). Perspect. 120(5): 668–673. Fluorinated pollutants in all-weather clothing: during the dyeing process. The NPs ge- now be found everywhere. These chemi- banned in Europe for certain applications. Short-chain chlorinated paraffins are http://www.snf.se/pdf/rap-hmv-allvadersklader-eng.pdf UBA (2009). nerated in wastewater from NPEs behave cals are used for fire control, in textiles Germany’s Federal Environment Agency used in the textile industry as flame Perfluorinated compounds: Avoid inputs – protect the environment, Fromme H, Mosch C, Morovitz M, Alba-Alejandre I, Boehmer S, http://www.umweltdaten.de/publikationen/fpdf-l/3818.pdf similarly to estrogen and can disrupt the too. Specifically, polybrominated diphenyl has proposed putting perfluorooctanoic retardants and to finish textiles and Kiranoglu M, Faber F, Hannibal I, Genzel-Boroviczény O, (9/2012), http://www.umweltdaten.de/publikationen/fpdf-l/3812.pdf development of the reproductive organs ethers (PBDEs) are considered “particu- acid (PFOA) on the SVHC list as well. leather. They are considered toxic to Koletzko B, Völkel W (2010). Pre- and postnatal exposure to perfluorinated compounds (PFCs). Vierke L, Staude C, Biegel-Engler A, Drost W, Schulte C (2012). of fish and other aquatic animals. The larly hazardous” according to EU water aquatic organisms and accumulate in Environ Sci Technol. 44(18):7123-9. Perfluorooctanoic acid (PFOA) — main concerns and regulatory sale of products containing more than legislation. They are hormonally active and Chlorobenzenes: living organisms. Their use has been developments in Europe from an environmental point of view. GOTS – Global Organic Textile Standard (2011). Environmental Sciences Europe 24:16. 0.1 percent of nonylphenols or nonyl- can damage the growth and development Chlorobenzenes are used as biocides restricted in the EU since 2004. Global Organic Textile Standard (GOTS) Version 3.0, phenol ethoxylates has been severely re- of reproductive organs. Their use in the and solvents in textile production. Some http://tilth.org/files/certification/GOTSStandard.pdf Walters A, Santillo D, Johnston P. An Overview of Textiles Processing and Related Environmental stricted in the European Union since 2005. European Union is subject to tight restric- of them damage the liver, the thyroid Heavy metals: Grandjean P, Andersen EW, Budtz-Jørgensen E, Nielsen F, Concerns, http://www.greenpeace.org/seasia/th/Global/seasia/ tions in order to protect surface waters. and the central nervous system. Hexa- Heavy metals like cadmium, lead and Mølbak K, Weihe P, Heilmann C. (2012). report/2008/5/textile-processing.pdf Serum vaccine antibody concentrations in children exposed to chlorobenzene (HCB) is persistent and copper are in dyes and pigments. They perfluorinated compounds. JAMA. 307(4):391-7. Walters A, Santillo D. Azo dyes: hormonally active. Like the polychlorina- can accumulate in the body and damage Uses of Perfluorinated Substances, Greenpeace Research Greenpeace (2011). Dirty Laundry. Laboratories Technical Note 06/2006, http://www.greenpeace.to/ Azo dyes are widely used in the textile ted biphenyls (PCBs), their use is severely organs as well as the central nervous Unraveling the corporate connections to toxic water pollution in greenpeace/wp-content/uploads/2011/05/uses-of-perfluorinated- industry. Some azo dyes release aro- restricted by the Stockholm Convention. system. Chromium is used for tanning China. Greenpeace International, 2011. http://www. greenpeace. chemicals.pdf org/dirtylaundryreport matic amines, of which some such as leather. As chromium VI, it is a potent Weinberg I, Dreyer A, Ebinghaus R. (2011). 3.3'-dimethoxybenzidine (also known environmental toxin even at low con- Greenpeace (2011). Dirty Laundry 2. Waste water treatment plants as sources of polyfluorinated Hung Out to Dry. Unravelling the toxic trail from pipes to products. compounds, polybrominated diphenyl ethers and musk as o-dianisidine dihydrochloride), can centrations. Chromium VI, mercury and Greenpeace International, 2011. http://www.greenpeace.org/in- fragrances to ambient air, Environ Pollut. 59(1):125-32. cause skin cancer. According to EU cadmium can cause cancer. The use of ternational/en/publications/reports/Dirty-Laundry-2 these heavy metals in the EU is subject regulations, 22 azo dyes may no longer Greenpeace (2012). Dirty Laundry. be used for textiles worn directly on the to strict conditions. Reloaded How big brands are making consumers unwitting ac- skin. A similar regulation exists in China. complices in the toxic water cycle. Greenpeace International, 2012. http://www.greenpeace.org/international/en/publications/ Campaign-reports/Toxics-reports/Dirty-Laundry-Reloaded No money from industry and state Greenpeace is an independent global campaigning organisation that acts to change attitudes and behaviour, to protect and conserve the environment and to promote peace.