Systematic determination of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in outdoor jackets

Chemosphere 160 (2016) 173e180

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Systematic determination of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in outdoor jackets € mel, Thomas P. Knepper* Christoph Gremmel, Tobias Fro Hochschule Fresenius, University of Applied Sciences, Limburger Straße 2, 65510, Idstein, Germany

h i g h l i g h t s
Quantitative methods for the determination of 23 PFASs in textile samples.
Re-analysis of selected jackets exhibited losses of FTOHs during storage of 3.5 years.
Developed methods were successfully applied to different outdoor and working jackets.

a r t i c l e i n f o

a b s t r a c t

Article history: Received 11 March 2016 Received in revised form 9 June 2016 Accepted 10 June 2016

Sixteen outdoor jackets were purchased in 2011/12 and analyzed for 23 different perfluoroalkyl and polyfluoroalkyl substances (PFASs). The jackets were selected based on their origin of production, price, market, and textile, such as polyester, nylon, polyamide, and content of poly(tetrafluoroethylene) membranes. Two robust analytical methods based on high pressure liquid chromatography combined with tandem mass spectrometry, as well as two liquid extractions, were developed enabling the analysis of PFASs with widely different physico-chemical properties. The jackets were found to contain PFASs in a range between 0.03 and 719 mg/m2. Perfluorooctanoic acid (PFOA) was omnipresent (0.02e171 mg/m2), although at lower concentrations compared to the precursors of perfluoroalkyl carboxylic acids (PFCAs), namely fluorotelomer alcohols (FTOHs) (<0.001 e698 mg/m2). Perfluoroalkane sulfonic acids and their putative precursors, in particular perfluoroalkane sulfonamides, were detected much less frequently at concentrations up to 5 mg/m2. To determine the effect of the volatility of FTOHs, four selected jackets were stored in a sealed bag in the dark at room temperature and re-analyzed after 3.5 years. Only 10%e20% of the initial concentration of 8:2-FTOH and 20%e50% of 10:2-FTOH were found, whereas the concentrations of PFOA and perfluorodecanoic acid increased significantly. This supports the hypothesis that PFAS concentrations in textiles are also strongly dependent on age, and conditions of transport and storage. © 2016 Elsevier Ltd. All rights reserved.

Handling Editor: I. Cousins Keywords: Perfluoroalkyl and polyfluoroalkyl substances (PFASs) Outdoor jackets Textile chemistry

1. Introduction Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are a class of chemicals where at least two aliphatic carbon atoms bear fluorine in place of hydrogen (Knepper and Lange, 2012). These have been manufactured in increasing quantities since the 1950s (Buck et al., 2011). With increasing chain length, the perfluoroalkyl moiety imparts surface-active, hydrophobic and oleophobic properties to the molecule. These properties have made them useful as industrial chemicals and in consumer products such as textiles, * Corresponding author. E-mail address: [email protected] (T.P. Knepper). http://dx.doi.org/10.1016/j.chemosphere.2016.06.043 0045-6535/© 2016 Elsevier Ltd. All rights reserved.

carpets and paper products which require treatment for water and grease repellency (Kissa, 2001). Fluorochemicals are the most commonly used repellents in the textile industry due to their added ability to repel oil and dirt (Lacasse and Baumann, 2004). These repellents are mainly copolymers of side-chain fluorinated polymers, such as polyfluoroalkyl acrylates and methacrylates. The functional groups attached to the co-monomers contain variations of alkyl groups which modify the physical properties and improve the performance of the polymers. To achieve best repellency with side-chain fluorinated polymers, at least four perfluorinated carbon atoms should be present and the end group should be trifluoromethyl. The side-chain fluorinated polymers are applied as a thin film on the fabric surface, usually in combination with other

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finishing auxiliaries, by a pad-dry-cure process. In this process, the dry fabric is passed through a bath of the aqueous dispersion and then squeezed under high pressure between pads to remove excess material, followed by drying and curing in the oven at temperatures up to 180  C. The term “drying” is used for the evaporation of the solvent, whereas “curing” is a synonym for the polymerization of the individual monomers. Curing is needed to achieve cross-linking (Lacasse and Baumann, 2004; Fischer et al., 2006). The dispersions used for the textile finishing contain fluoroacrylates and other co-monomers, such as epoxides for hardening and other auxiliaries. Fluorocarbons mostly contain longchain fatty alcohol acrylates (see Fig. 1) which increase water repellency. Other frequently used co-monomers to increase soil repellency are vinyl and vinylidene chloride, methyl methacrylate, and acrylonitrile. During the finishing process, the side-chain fluorinated polymers are fixed at 0.2 to 0.5 wt% and bound to the fiber. This results in a typical total fluorine concentration on the fabric ranging between 0.04 and 0.25% (Fischer et al., 2006). Outdoor jackets, mainly durable water resistant (DWR) jackets

treated with fluorinated side chain polymers can release fluorotelomer alcohols (FTOHs) and perfluoroalkyl carboxylic acids (PFCAs) (Posner, 2012). Exposure of humans and the environment to PFASs related to outdoor jackets may occur directly during the production process, during use, and after disposal. The approach to estimate this exposure is based on the Scenario-Based Risk Assessment model previously used by Trudel et al. (2008) and includes inhalation, dermal uptake, hand-to-mouth transfer and ingestion of indoor dust. Due to the availability of data, the compounds considered for the calculation of exposure were the PFCAs C6-C12 and the FTOHs (6:2-, 8:2- and 10:2-). The comparison of the exposure related to DWR jackets estimated with average dietary intake showed that the average dietary exposure (estimated average dietary intake from Sweden) was higher by a factor of 3e10 than the intermediate exposure scenario for consumer product related exposure (Vestergren et al., 2012). The occupational exposure, of the population e.g. working in outdoor stores, could be a more important exposure pathway compared to exposure via dietary intake (Langer et al., 2010).

Fig. 1. Schematic examples of the synthesis and transformation of C8-based fluorochemical repellents used for textile finishing and the role of precursors for the formation of relevant PFASs, e.g. PFOA and PFOS a) Fluorotelomer acrylate-based polymer; R1, R2, and R3 can be different side groups such as non-fluorinated alkyl chains; b) Perfluorooctane sulfonamide-based polymer (Lacasse and Baumann, 2004). Note that the structures shown are typical segments of the polymer.

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PFASs, such as FTOHs, can be transformed to persistent PFCAs under various conditions (Ellis et al., 2004; Martin et al., 2005; €mel and Wang et al., 2005; De Silva and Mabury, 2006; Fro Knepper, 2010). Thus an additional source for the ubiquitously detectable PFASs in humans and the environment comes from the transformation of different polyfluorinated precursors. These might be the polyfluorinated intermediates or raw materials used for the production of side-chain fluorinated polymers, or even residues from the breakdown of the polymer itself (Washington et al., 2009). It is estimated that 85% of indirect emissions of PFASs is a result of losses from consumer products during production, use and disposal (3M, 2000). Fluorotelomer and perfluoroalkane sulfonyl-based side-chain fluorinated polymers have been in use for over half a century and have been incorporated into a vast array of products. In Fig. 1, the proposed life cycle of two different C8-based side-chain fluorinated polymers is schematically drawn. Particular attention has been directed to non-polymeric PFASs, namely to PFCAs and perfluoroalkane sulfonic acids (PFSAs) belonging to the class of the perfluoroalkyl acids (PFAAs), to FTOHs, N-alkyl perfluoroalkane sulfonamides (FASAs) and N-alkyl perfluoroalkane sulfonamidoethanols (FASEs). In particular, PFSAs and PFCAs have been found to be globally present in the environment (Prevedouros et al., 2006), in wildlife (Giesy and Kannan, 2001) and human serum samples (Hansen et al., 2001; Houde et al., 2006). These compounds are also associated with a range of toxicological effects in animal models (Lau et al., 2007). Due to the bioaccumulative and toxic properties, perfluorooctane sulfonic acid (PFOS) was banned by the Stockholm Convention on Persistent Organic Pollutants (2010) and PFOA as well as C11-C14 PFCAs were added to the Candidate List of Substances of Very High Concern within REACH regulation (ECHA, 2015). Volatile PFASs, e.g. 6:2-, 8:2- and 10:2-FTOH (vapor pressure at 25  C: 145.2 Pa, 45.9 Pa and 13.3 Pa, respectively (Lei et al., 2004)), can be emitted into the air, whereas water-soluble PFASs, e.g. PFOA (water solubility 3.4 g/L (USEPA, 2013)), can be introduced into the water system either by rain or during laundry washing. As FTOHs have a relatively high volatility and vapor pressure, they can be found in the atmosphere (Martin et al., 2002) and in indoor air samples (Jahnke et al., 2007; Shoeib et al., 2011; Schlummer et al., 2013). Since 8:2-FTOH can be transformed both in the atmosphere (Wallington et al., 2005) and in soil and waste water (Wang et al., 2005; Ahrens et al., 2011) to form PFOA, an indirect exposure to PFOA via these routes is possible. The present study was undertaken to determine the extent by which PFASs from outdoor jackets, such as hardshell, softshell, and rain jackets, are degraded and released into the environment. However, since the various producers, especially in case of “noname-products”, do not use those terminologies in a stringent way and not in all cases water repellency values are indicated on the product tag, a differentiation among the individual jackets was not a goal of this study. Even if named as apparel or DWR textile, it does not automatically provide information about the chemistry of these textiles. Despite this lack of a clear definition we have grouped all garments as outdoor jackets, except one obvious exemption, which was a working gear jacket. The 24 target analytes within this study were PFCAs (C4-C14), PFSAs (C4, C6, C7, C8, C10), perfluorooctane sulfonamides (FOSAs: FOSA, N-MeFOSA and N-EtFOSA), perfluorooctane sulfonamidoethanols (FOSEs: N-MeFOSE and NEtFOSE) and FTOHs (6:2-, 8:2-, 10:2-FTOH). 2. Experimental 2.1. Samples Sixteen outdoor jackets (15 outdoor jackets, labeled J0-J14, and

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one working jacket J15) were acquired during the period from August 2011 to March 2012. A detailed description of the jackets, regarding price, market, and textile, such as e.g. polyester, nylon, polyamide, content of poly(tetrafluoroethylene) membranes is given in Table 11 in the Supplement Information (SI). Initially, the authors were aiming to include jackets from EU and Asia in the analysis. However, it was almost impossible to find outdoor jackets being produced completely in Germany and the EU, respectively. Upon arrival in the laboratory, all acquired outdoor jackets were labeled and documented. Besides the working jacket J15, the jacket J4 (arrived unpacked in shop and had been on sale for 4 weeks) and J14 (on sale since February 2010) all jackets were new and packed in a plastic shell. In order to avoid contamination, the jackets were stored in a separate room and handled exclusively with gloves. In April and May 2012, these jackets were analyzed regarding their PFASs concentrations in order to obtain information of possible correlation regarding origin of production as well as price and fabrics. Four jackets which had high concentrations of FTOHs were re-analyzed after three and a half years. The outdoor jackets J2, J8 and J10 were stored in the original delivered plastic shell over the three and a half years and J14 was stored in a new plastic shell. All samples were stored at room temperature in the dark. 2.2. Chemicals and reagents The individual standards of PFCAs (C4-C14) and FTOHs (6:2-, 8:2, 10:2-FTOH) were purchased from Neochema (Bodenheim, Germany). The individual standards of PFSAs (C4, C6, C7, C8, C10), FOSEs (N-MeFOSE and N-EtFOSE), FOSAs, (FOSA, N-MeFOSA and NEtFOSA) and the 2H-, 13C- and 18O- (M) labeled internal standards perfluoro-n-[13C4]butanoic acid (MPFBA), perfluoro-n-[1,2-13C2] hexanoic acid (MPFHxA), perfluoro-n-[1,2,3,4e13C4]octanoic acid (MPFOA), perfluoro-n-[1,2,3,4,5-13C5]nonanoic acid (MPFNA), perfluoro-n-[1,2-13C2]decanoic acid (MPFDA), perfluoro-n-[1,2e13C2] undecanoic acid (MPFUnDA), perfluoro-n-[1,2-13C2]dodecanoic acid (MPFDoDA), perfluoro-1-hexane[18O2]sulfonate (MPFHxS), perfluoro-1-[1,2,3,4-13C4]octanesulfonate (MPFOS) and 2Perfluorooctyl-[1,1,-2H2]-[1,2-13C2]-ethanol (M-8:2-FTOH) were obtained from Wellington Laboratories, Inc. (Guelph, Canada). All individual and labeled standards had a chemical purity 98%, except PFUnDA (96%), PFDoDA, PFTrDA and PFTeDA (97%). SupraSolv® (99.8%) acetone, acetonitrile (ACN,  99.8%), methanol (MeOH,  99.8%) and n-hexane (99.8%) were obtained from Merck (Darmstadt, Germany) and ammonium acetate (99.0%) from Sigma-Aldrich (Buchs, Switzerland). Aqueous solutions were prepared in Milli-Q-water (Millipore direct-Q3 system, Millipore, Milford USA). The standard solutions were prepared in SupraSolv® MeOH and stored in glass vials protected from light at 18  C. During all steps of the preparation and storage, contact of all solutions and samples with perfluorinated materials, such as polytetrafluoroethylene (PTFE), was avoided in order to prevent contamination. 2.3. PFAS analysis A list of structural formulae of investigated substances is given in Table 1. Three different methods were developed to extract the PFAS from outdoor jackets and determine the concentration of PFASs by LC-MS/MS. The first method, with the abbreviation PFASa, includes PFCAs and PFSAs, and the 13C- and 18O- (M) labeled internal standards MPFBA, MPFHxA, MPFOA, MPFNA, MPFDA, MPFUnDA, MPFDoDA, MPFHxS, and MPFOS. The second method, with the label PFAS-n, includes FTOHs and FOSEs utilizing 13C- and 2 H-labeled M-8:2-FTOH as internal standard. The third method, with the acronym PFAS-f includes the FOSA derivatives. The whole

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Table 1 List of investigated substances and mass labeled standards. Compound class

Acronym

Perfluoroalkyl carboxylic acids

PFCAs

Chemical structure O F CF2

Perfluoroalkane sulfonic acids

O S OH

n

O CF 2

n

S

NH

FASEs

O F

CF 2

n

S O

Fluorotelomer alcohols

FTOHs

F CF2

n

PFAS-a

4 (4,6,8,10)

2 (6, 8)

PFAS-a

3 (8), R ¼ H, Me, Et

/

PFAS-a

2 (8), R ¼ Me, Et

/

PFAS-n

3 (6,8,10)

1 (8)

PFAS-n

R

O

Perfluoroalkane sulfonamidoethanols

LC-MS/MS method

7 (3,5,7-11)

O

FASAs F

No. mass labeled (n)

11 (3-13)

OH

PFSAs F CF2

Perfluoroalkane sulfonamides

n

C

No. native (n)

CH 2 CH 2 N

OH R

CH2 CH2 OH

set of certified compounds is listed in Table 3 in the supplement information as well as detailed information regarding instrumental parameters and assignment of internal standards (Tables 4e7). Due to the lack of internal standards, the results of PFTrDa, PFTeDA, PFBS, PFHpS, PFDS, FOSAs and FOSEs should be considered semi-quantitative. 2.3.1. HPLC-MS/MS methods The instrumental setup was based on a high pressure liquid chromatograph (Perkin Elmer Series 200, Norwalk, CT, USA) combined with a triple quadrupole mass spectrometer (QqQ-MS) Q Trap 3200 (Applied Biosystems, Foster City, CA, USA, software Analyst, version 1.5.1) equipped with electrospray ionization (ESI) source in negative ion mode (V ¼ 4.5 kV). A reversedphase C18 column (MZ-Aqua Perfect, C18, 50  2.1 mm, 5 mm, MZ Analysentechnik, Mainz, Germany) with pre-column (MZAqua Perfect, C18, 10  2.1 mm, 5 mm) was used for chromatographic separation. Eluents consisted of A: H2O/MeOH (95:5 v:v) and B: H2O/MeOH (5:95 v:v) both containing 5 mM ammonium acetate. Two HPLC-MS/MS methods were used to determine the concentration of PFASs in the samples analyzed. The PFAS-a HPLC-MS/ MS method was used to analyze PFCAs (C4-C14), PFSAs (C4, C6, C7, C8, C10) within the PFAS-a method and for the determination of FOSA derivatives (FOSA, N-MeFOSA and N-EtFOSA) during the PFAS-f method. The PFAS-n HPLC-MS/MS method was used to analyze FTOHs (6:2-, 8:2-, 10:2-FTOH) and FOSE derivatives (N-MeFOSE and N-EtFOSE) with the PFAS-n method. Injection volume for both methods was 50 mL at a flow rate of 300 mL/min (PFAS-a) and 200 mL/min (PFAS-n), respectively. The solvent gradient of the HPLC methods is given in Tables 4 and 5 in the SI. 2.3.2. Sample preparation and extraction of PFAS-a Two individual squares of 5  10 cm from the lower backside of each jacket (including membrane and lining) were cut out with a pair of scissors and were analyzed in duplicate. The squares were weighed and cut to small pieces. Each sample was spiked with a mixture of internal standards. Five spots of 10 mL internal standard solution each were placed on the outer shell of the sample. The internal standard mixture contained MPFBA, MPFHxA, MPFOA, MPFNA, MPFDA, MPFUnDA, MPFDoDA, MPFHxS, and MPFOS with a concentration of 0.02 ng/mL dissolved in MeOH resulting in a total

amount of 1 ng internal standard in each sample. The pieces were transferred into 15 mL polypropylene vials after the solvent of the standard mixture was evaporated at ambient conditions. 10 mL of acetone/acetonitrile (80:20 v:v) were added to the vials and sonicated for 1 h. Following the extraction step, the solution was pipetted into a 24 mL glass vial with screw cap and the small textile pieces were washed with 5 mL acetone/acetonitrile (80:20 v:v). Each sample was mixed 1 min by using a vortex mixer during the washing. This 5 mL were transferred into the same 24 mL glass vial. The resulting 15 mL of solvent were evaporated with a gentle nitrogen flow at 50  C. The residue was dissolved in 500 mL MeOH/H2O (50:50 v:v) and mixed for 2 min by using a vortex mixer. The solutions were filtered with a syringe cellulose filter (pore size of 0.45 mm, bore of 13 mm, supplier: Schleicher & Schuell, Dassel, Germany) and finally transferred into a 500 mL polypropylene HPLC vial and measured with the LC-MS/MS system using the PFAS-a HPLC-MS/MS method. A series of standards in a range from 0.05 ng/mL to 40 ng/mL (corresponding to 10 ng/m2e8 mg/m2) with 14 concentration levels was prepared in MeOH/H2O (50:50 v:v) and measured five times, respectively. Only the results with accuracy of ±30% and at least three of five measurements for each concentration level with a signal to noise ratio >5 were included in the calibration curve.

2.3.3. Sample preparation and extraction of PFAS-n Two individual squares of 5  10 cm from the lower backside of each jacket (including membrane and lining) were cut out with a pair of scissors and were prepared as duplicate. The squares were weighed and cut to small pieces, transferred into 15 mL polypropylene vials and 10 mL n-hexane was added. An internal standard solution with a concentration of 5 mg/mL M8:2-FTOH in MeOH was prepared and due to the volatility of FTOHs, 24 mL was pipetted directly into the extraction solvent, resulting in a concentration of 120 ng M-8:2-FTOH in each sample. After sonication for 1 h, the 10 mL n-hexane was transferred into a 24 mL glass vial. The small textile pieces were washed with 5 mL n-hexane using a vortex mixer for 2 min and the solution was transferred into the same glass vial. Subsequently, solid phase extraction (SPE) was applied in order to eliminate matrix compound and to concentrate the sample. A silica cartridge (Bond Elut® Si, 40 mm, 1 g sorbent mass, 6 mL

Three different analytical methods, PFAS-a for the PFCAs (C4C14) and PFSAs (C4, C6, C7, C8, C10), the PFAS-n for the FTOHs (6:2-, 8:2-, 10:2-FTOH) and FOSE derivatives (N-MeFOSE, N-EtFOSE) and PFAS-f for the FOSA-derivatives (FOSA; N-MeFOSA and N-EtFOSA) were developed. The recovery rates of analytes indicate repeatable and accurate quantification methods. The resulting coefficients of determination of calibration curves are shown in the SI and ranged from 0.9914 to

1.52 4.23 14.7 171 27.7 85.3 20.3 80.9 3.70 20.5 430
J15 J14a

0.10 0.17 0.36 6.81 3.30 9.24 2.17 2.69 0.60 0.97 28.4
J14 J13

n.d. n.d. 0.03 0.10 0.03
J12 J11

0.28 0.46 0.37 2.31 1.05 0.58 0.36 n.d. n.d. n.d. 5.42
J10a J10

n.d. n.d. 0.02 0.23 0.05 0.12 n.d. n.d. n.d. n.d. 0.42
J9 J8a


J8 J7

n.d.
J6 J5

n.d. n.d. 0.01 0.13 0.05
J4 J3 J2a

n.d.
J2 J1

n.d.
3. Results

J0

2.3.5. Quality assurance of analytical procedures For the determination of PFASs in the jackets, two samples of each jacket were prepared with the sample preparation of the three methods PFAS-a, PFAS-n and PFAS-f, extracted and measured using the corresponding LC-MS/MS method. The limit of detection (LOD) was determined with the signal to noise ratio > 3 and the limit of quantification (LOQ) with a signal to noise ratio > 9. During all sample preparations, a reference without textile sample (blank) was treated simultaneously in order to detect possible cross-contaminations. During all LC-MS/MS analysis, standard solutions were measured to validate the HPLC and the MS/ MS methods. A pre-column (Phenomenex® Aqua, C18, 50  2.0 mm, 5 mm) was inserted before the injector in the HPLC system to exclude contaminations of PFASs in the eluent and HPLC system. During each step of the sample preparation, all devices were washed at least three times with acetone and the protection gloves were changed during the different preparation steps as well in order to prevent the samples from contaminations. All polypropylene vials and the weighing pans were used only once. The results obtained during the different steps of the method development, as well as the quality assurance experiments, such as blank concentrations and recovery rates of internal standards in the samples, are given either in the results section or in the SI.

PFBA PFPeA PFHxA PFOA PFNA PFDA PFUnDA PFDoDA PFTrDA PFTeDA Sum PFCAs 6:2-FTOH 8:2-FTOH 10:2-FTOH Sum FTOHs PFBS PFHxS PFHpS PFOS PFDS FOSA N-MeFOSA N-EtFOSA N-MeFOSE N-EtFOSE Sum PFASs

2.3.4. Sample preparation and extraction of PFAS-f To determine the concentration of FOSA and FOSA-derivatives (FOSA, N-MeFOSA and N-EtFOSA) the PFAS-n extraction method was combined with the PFAS-a HPLC-MS/MS method. 240 mL eluate of the PFAS-n extraction method was spiked with 10 mL internal standard solution of the PFAS-a method with a concentration of 0.2 ng/mL and mixed with 250 mL H2O, resulting in a total concentration of 1 ng internal standard (MPFDoDA) per sample. A series of standards in a range from 0.05 ng/mL to 50 ng/mL (corresponding to 10 ng/m2 e10 mg/m2) with ten concentration levels was prepared in MeOH/H2O (50:50 v:v) and measured. Only the standards with accuracy of ±30% were implemented in the calibration curve and at least three of five measurements for each concentration level with a signal to noise ratio >5 were implemented in the calibration curve.

177

PFASs

volume, Agilent Technologies, Waldbronn, Germany) was used for the SPE. Agilent Bond Elut® Si (1 g, 6 mL) normal phase cartridges were conditioned with 3 mL acetone, and twice 3 mL n-hexane. The samples were enriched and after drying the cartridges for 3 min by compressed air, analytes were eluted with 2  1.5 mL MeOH. Eluates were mixed with a vortex mixer, filtered with a syringe filter and directly measured by the PFAS-n HPLC-MS/MS method. A series of standards in a range from 0.05 ng/mL to 50 ng/mL (corresponding to 10 ng/m2e10 mg/m2) with ten concentration levels was prepared in MeOH and measured five times. Only the standards with accuracy of ±30% and at least three of five measurements for each concentration level with a signal to noise ratio >5 were implemented in the calibration curve.

Table 2 Mean concentration of PFASs in analyzed outdoor jackets in mg/m2; Jacket No; the jackets were analyzed in April and May 2012; ‘a’ refers to the re-analyzed jackets (measured in December 2015); n.d. ¼ not detected; n.a. ¼ not analyzed; n ¼ 2.

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Fig. 2. Comparison of detected PFASs concentrations and ratios in DWR jackets; top: full scale, bottom: cut-out.

0.9986 (Table 9). The software Analyst 1.5.1 (AB Sciex, Toronto, Canada) was used for the calculation with a weighting by 1/x. The limits of quantification ranged from 10 to 400 ng/m2, depending on the compound (see supplement information Table 8). The differences in LOQs are largely attributed to different ionization and fragmentation efficiencies during MS analysis. With the developed analytical methods, it was possible to analyze 23 PFASs, differing extremely in both, polarity and volatility in the complex textile matrix. The application of a broad set of labeled internal standards was crucial to compensate matrix effects during the analysis. Blanks were below LODs for all substances except for PFHpA, which showed noticeable method blank levels, which led to exclusion of PFHpA from all quantitative determinations. The individual results for all analyzed jackets are summarized in Table 2. The results are calculated as concentration per meter square and mass per kg (see SI). The entire set of values, including the deviations between the duplicates, are given in the SI in Table 10. In all analyzed jackets, PFASs were determined, varying in a range from 0.03 to 719 mg/m2. Despite these high sum concentrations, analytes of the class of PFSA could only be detected a few times in concentrations up to 0.5 mg/m2. The regulated PFOS was detected in only five jackets in a range from 0.01 to 0.54 mg/m2. Concentrations of potential PFOS precursors, such as FOSA- and FOSE-derivatives were, when detectable, almost always below the LOQ.

PFOA was detected in jackets in a concentration range of 0.02e4.59 mg/m2. Thereby no correlation could be established with respect to the individual textile, membranes and quality of the jacket. The concentration of PFOA in the working jacket (J15) analyzed was with a value of 171 mg/m2 almost fortyfold above the so far highest value measured within this study. Except for FTOH, all other detected PFASs in this jacket exhibited the highest concentration compared to the other jackets analyzed. The PFASs subgroup with the highest concentrations determined was by far the FTOHs, with sum concentrations of a factor of several dozens above the PFCAs. However, for J0 and J15, this was not the case. The FTOH concentration in J15 was low compared to total PFASs concentration of this jacket. In one single jacket (J14), which had been bought from an older collection and had been on sale since 2010, by far the highest PFASs concentrations were quantified. The concentrations of 8:2-FTOH in the four re-analyzed outdoor jackets (J2, J8, J10 and J14) were in the range from 9% to 18% after storage for three and a half years, compared to the concentrations determined at the beginning of this study. The concentrations of 10:2-FTOH, determined during the re-analysis also decreased after the three year storage and ranged from 23% to 47% of the initial concentrations in the four jackets. Despite the significant loss of 8:2-FTOH in the re-analyzed jacket J2 (only 10% 8:2-FTOH compared to the previously analyzed sample), no increase of PFOA could be determined. The concentration of PFOA in J8, J10 and

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J14 increased between 46% and 90% and perfluorodecanoic acid (PFDA) was detected in a concentration from 9 to 106% higher compared to the previous analysis. 4. Discussion The developed methods were suitable for the extraction and determination of PFASs in the textile samples analyzed. Since all the analyzed jackets consisted of different materials, colors, number and kind of layers, these factors influenced the matrix effects during the LC-MS/MS analysis. The extracted constituent parts of the matrix have an important influence, both on the chromatographic separation and the MS/MS analysis. Additionally, the amount of PFASs being used as cocktail during the finishing process might have varied depending on the different textile pieces of the jackets analyzed and therefore in the individual samples. However, through the application of 2H-, 13C- and 18O-labeled internal standards, the quantitative results of this study are reliable. The low deviations of the samples being prepared and analyzed in duplicate show that this variation did not seem to play an important role during the analyses. The results of the analysis, where no analog mass labeled standard was available should be considered as semiquantitative. Even the jacket having a label of fluorine-free impregnation gave a concentration of 20 ng/m2 PFOA. Three samples from the lower backside of the jacket were analyzed and each sample measured for PFOA. The use of PFOA-containing substances as repellent agent during the finishing of the textile cannot be ruled out considering this result. Contamination during the production of the textile is also possible. Whether the regulated PFOS detected in five jackets stem from contamination during transport and storage, or were introduced during the production of the textiles is not clear so far. The first analytical study on PFASs conducted with various textiles were published by Berger and Herzke (2006). Among other clothing items, the authors analyzed a rain and outdoor jacket, a sailing jacket, impregnated cotton textiles, Gore Tex® textiles, as well as various outdoor jackets from various brands. The methods used were ethyl acetate extraction with GC-MS analysis for FTOHs and other neutral PFASs as well as methanol extraction and subsequent LC-MS detection for PFAA quantification. Very high PFASs concentrations of 8:2-FTOH above 90% were detected in the rain and outdoor jacket and the sailing jacket with sum concentrations above 10,000 and 1000 mg/m2, respectively. Also high PFASs concentrations were detected in the cotton T-shirt, where PFOA (>400 mg/m2) was predominantly detected. From the other investigated jackets only the sum PFASs concentration in the Gore Tex® jacket and a further jacket were above 200 mg/m2 with an 8:2-FTOH share below 50% and PFOA concentrations above 30 mg/m2 (Berger and Herzke, 2006). All other determined total PFASs concentrations were below 200 mg/m2 with a share of 8:2-FTOH between 50 and 90% of the total PFAS amount and PFOA concentrations below 10 mg/m2. These concentrations are consistent with most of the values obtained in the present study (Fig. 2). Only two “outliers” could be detected, where the sum PFASs values were either above 700 mg/m2 or the PFOA concentration was close to 200 mg/m2, related to a jacket from an “older” production batch (presumably manufactured before 2011) and a working gear jacket. The decreased concentration of the volatile FTOHs, determined in the four re-analyzed outdoor jackets showed the release of these substances into the environment over time. The fact that almost no 6:2-FTOH was detected in the analyzed jackets indicates that the predicted phase-out of the PFASs-C8 chemistry had not been initiated at the time the jackets were bought. Individual queries at the manufacturers support this

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observation. In the meantime, analysis of the new series of DWR jackets showed some changes of chemical formulations used for DWR jackets. 6:2-FTOH can be found more frequently in DWR jackets analyzed during the last six months (data not shown), suggesting the start of the phase-out of the PFAS-C8 chemistry. All of the results showed only the concentration of extractable PFASs and cannot give the total concentration of PFASs used during manufacture. The covalently bound PFASs moieties are assumed not to be measureable by the described approach due to the fact that no hydrolysis takes place under the applied extraction methods. 5. Conclusion A decline of the amount of PFASs used for textile finishing can be detected by the comparison of these results with the study of Berger and Herzke (2006). A link between PFAS concentrations with the manufacturer of the jackets or the textile materials could not be found. However, the present results show only the concentration of extractable PFASs and not the total concentration of PFASs in the textile samples. Analysis of polymeric PFASs remains still a tremendous analytical challenge. The re-analysis of four selected jackets after three and a half years of storage underlines our hypothesis that detected PFAS concentrations in textiles are strongly depended on the age and conditions following production, transport and storage. Since these factors are highly variable and not possible to retrieve, we recommend analysis of PFASs and further textile contaminants during and immediately after production. Thus all reported values, including those given in the literature, can only be understood as confirmation of the presence of PFASs in outdoor textiles. It has been shown that outdoor jackets emit PFASs to the environment, namely into the air as well as into water during the washing process (Knepper et al., 2014). The environmental load of the different PFASs from outdoor jackets is low, but surely contributes as one source to the overall PFASs burden. Thus outdoor jackets, and presumably those jackets being DWR based on PFASschemistry, are one source among many others of PFASs. Acknowledgement We thank the Federal Environmental Agency (UBA, Dessau, Germany) for financial support of the research project: Evaluation of exposure pathways of per- and polyfluorinated chemicals (PFC) through use of products containing PFCs-assessment of risk to humans and the environment (FKZ: 3711 63 418); PFC_EXPO. Annegret Biegel-Engler and Lena Vierke, UBA, Dessau, Germany for helpful discussions. Appendix A. Supplementary data Supplementary data related to this article can be found at http:// dx.doi.org/10.1016/j.chemosphere.2016.06.043. References 3M, 2000. POSF Life Cycle Waste Stream Estimates. Ahrens, L., Shoeib, M., Harner, T., Lee, S.C., Guo, R., Reiner, E.J., 2011. Wastewater treatment plant and landfills as sources of polyfluoroalkyl compounds to the atmospherey. Environ. Sci. Technol. 45, 8098e8105. Berger, U., Herzke, D., 2006. Per and polyfluorinated alkyl substances (PFAS) extracted from textile samples. Organohalog. Compd. 68, 2023e2026. Buck, R.C., Franklin, J., Berger, U., Conder, J.M., Cousins, I.T., de Voogt, P., Jensen, A.A., Kannan, K., Mabury, S.A., van Leeuwen, S.P.J., 2011. Perfluoroalkyl and polyfluoroalkyl substances in the environment: terminology, classification, and origins. Integr. Environ. Assess. Manag. 7, 513e541.

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