Environment Research of the Federal Ministry for the Environment, Nature Conversation, Building and Nuclear Safety

Final report FKZ 3709 65 410

REACH: Test of substances of very high concern to prepare Annex XV Dossiers using perfluorinated compounds as example REACH: vertiefte Prüfung von besonders besorgniserregenden Stoffen zur Vorbereitung von Anhang XV Dossiers am Beispiel perfluorierter Verbindungen

Fraunhofer-Gesellschaft, München with the institutes: Fraunhofer Institute for Molecular Biology and Applied Ecology IME Division Applied Ecology Auf dem Aberg 1 57392 Schmallenberg Germany and Fraunhofer Institute for Process Engineering and Packaging IVV Giggenhauser Straße 35 85354 Freising Germany Project Management: Dr. Josef Müller, IME Responsible in IVV: Dr. Martin Schlummer

ON BEHALF OF THE FEDERAL ENVIRONMENT AGENCY

October 31, 2011

Berichtskennblatt Berichtsnummer

UBA-FB 00

Titel des Berichts

REACH: vertiefte Prüfung von besonders besorgniserregenden Stoffen zur Vorbereitung von Anhang XV Dossiers am Beispiel perfluorierter Verbindungen

Autor(en) (Name, Vorname)

Dr. Müller, Josef Dr. Schlummer, Martin

Durchführende Institution (Name, Anschrift)

Fraunhofer Institut für Molekularbiologie und Angewandte Oekologie IME Auf dem Aberg 1 57392 Schmallenberg

Fördernde Institution

Umweltbundesamt Postfach 14 06 06813 Dessau-Roßlau

Abschlussdatum

31. Oktober 2011

Forschungskennzahl (FKZ) Seitenzahl des Berichts

3709 65 410 115

Zusätzliche Angaben

Schlagwörter

FKZ 3709 65 410, Final Report

PFAA, PFAS, Perfluorierte und Polyfluorierte Chemikalien, PFOS, PFOA, Bedarfsgegenstände, Lebensmittel Kontakt Materialien, Outdoor-Textilien

page 2 of 115

Report Cover Sheet Report No.

UBA-FB 00

Report Title

REACH: Test of substances of very high concern to prepare Annex XV Dossiers using perfluorinated compounds as example

Author(s) (Family Name, First Name)

Dr. Müller, Josef Dr. Schlummer, Martin

Performing Organisation (Name, Address)

Fraunhofer Institute for Molecular Biology and Applied Ecology Auf dem Aberg 1 57392 Schmallenberg

Funding Agency

Umweltbundesamt Postfach 14 06 06813 Dessau-Roßlau

Report Date

October 31, 2011

Project No. (FKZ)

3709 65 410

No. of Pages

115

Supplementary Notes

Keywords

FKZ 3709 65 410, Final Report

PFAA, PFAS, Perfluorinated and Polyfluorinated Chemicals, PFOS, PFOA, Consumer Products, Food Contact Materials, Outdoor Textiles

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REACH: Test of substances of very high concern to prepare Annex XV Dossiers using perfluorinated compounds as example Content

Page

Abbreviations

6

1.

Summary

7

2.

Background and Objective

10

3.

Performance 3.1 General 3.2 Search for PFC relevant products and product groups 3.3 Selection of consumer products and samples 3.4 Selection of PFC target compounds 3.5 Extent of investigation

11 11 11 14 15 17

4.

Analytical Methods 4.1 General 4.2 Analysis of consumer products 4.2.1 Analysis of cleaning agents 4.2.2 Analysis of carpets 4.2.3 Analysis of impregnating sprays 4.2.4 Analysis of outdoor materials 4.2.5 Analysis of leather samples 4.2.6 Analysis of paper samples 4.2.7 Analysis of ski waxes 4.2.8 Analysis of wood glue and awning cloth 4.3 Sampling and analysis of indoor air 4.4 Sampling and analysis of product emissions 4.5 Quality assurance

21 21 21 21 22 22 23 24 24 24 25 25 26 26

5.

Results 5.1 PFCs in cleaning agents 5.1.1 Perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) in cleaning agents 5.1.2 Fluorotelomer alcohols in cleaning agents 5.1.3 Summary on PFCs in cleaning agents 5.2 PFCs in carpet samples 5.2.1 Perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) in carpet samples 5.2.2 Fluorotelomer alcohols in carpet samples 5.2.3 Summary on PFCs in carpets 5.3 PFCs in impregnating sprays

28 28

FKZ 3709 65 410, Final Report

28 29 30 30 30 32 33 34

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5.4

5.5

5.6 5.7 5.8 5.9

5.3.1 Perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) in impregnating spray samples 5.3.2 Fluorotelomer alcohols in impregnating sprays 5.3.3 Summary on PFCs in impregnating sprays PFCs in outdoor materials 5.4.1 Perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) in outdoor materials 5.4.2 Fluorotelomer alcohols in outdoor materials 5.4.3 Emissions of volatile PFCs from outdoor materials 5.4.4 Summary on PFCs in outdoor materials PFCs in paper samples 5.5.1 Perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) in paper samples 5.5.2 Fluorotelomer alcohols in mixed paper samples 5.5.3 Summary on PFCs in paper samples Perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) in leather samples Perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) in ski waxes Perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) in wood glue and awning cloth Fluorotelomer alcohols in indoor air samples

34 35 36 38 38 40 41 43 45 45 51 52 55 58 61 62

6.

Discussion 6.1 Results overview 6.2 Discussion of the results of product groups 6.2.1 Cleaning agents and impregnating sprays 6.2.2 Carpets 6.2.3 Outdoor materials 6.2.4 Leather samples 6.2.5 Baking and sandwich papers and paper baking forms 6.2.6 Ski waxes 6.2.7 Indoor air at work places 6.3 Discussion of the results regarding to current regulations 6.4 Environmental and human exposure resulting from product emissions

64 64 66 66 66 67 68 68 68 69 70 72

7.

Outlook

73

8.

References

76

Annex 1: Annex 2: Annex 3:

Analytical methods for the determination of Perfluoroalkyl carboxylic and Perfluoroalkane sulfonic acids (PFAAs) in consumer products

81

Analytical methods for the determination of Fluorotelomer alcohols (FTOHs) in air samples, impregnating sprays and solid samples

103

Screening methods for fluorinated coatings

112

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Abbreviations PFC* PFAS* PFAA* PFCA* PFSA* FTOH* PAP diPAP PTFE

Perfluorocarbons Perfluoroalkyl and polyfluoroalkyl substances Perfluoroalkyl acid Perfluoroalkyl carboxylic acid Perfluoroalkane sulfonic acid Fluorotelomer alcohol Polyfluoroalkyl phosphoric acid ester Polyfluoroalkyl phosphoric acid diester Polytetrafluorethylen

PFBA PFPA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA PFTrA PFTeA PFBS PFHxS PFHpS PFOS PFDS PFOSA 4:2 FTOH 6:2 FTOH 8:2 FTOH 10:2 FTOH

Perfluorobutanoic acid Perfluoropentanoic acid Perfluorohexanoic acid Perfluoroheptanoic acid Perfluorooctanoic acid Perfluorononanoic acid Perfluorodecanoic acid Perfluoroundecanoic acid Perfluorododecanoic acid Perfluorotridecanoic acid Perfluorotetradecanoic acid Perfluorobutanesulfonic acid Perfluorohexanesulfonic acid Perfluoroheptanesulfonic acid Perfluorooctanesulfonic acid Perfluorodecanesulfonic acid Perfluorooctanesulfonamide 4:2 Fluorotelomer alcohol 6:2 Fluorotelomer alcohol 8:2 Fluorotelomer alcohol 10:2 Fluorotelomer alcohol

CI GC HPLC MS UPLC P&T-GC-EPED

Chemical ionization Gaschromatography High Performance Liquid Chromatography Mass spectrometry Ultra Performance Liquid Chromatography Purge and trap gaschromatography coupled to plasma emission detector with an Echelle spectrometer Limit of Detection Limit of Quantification

LOD LOQ ECHA RAC REACH

Environmental Chemicals Agency Risk Assessment Committee Registration, Evaluation, Authorisation and Restriction of Chemicals (EU regulation no. 1907/2006)

* see Buck et al., 2011

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1.

Summary Available data on perfluorocarbons (PFCs) in consumer products are scarce to date and more information is needed in order to get an overview on recent PFC loads. More data are also necessary to evaluate if they implicate further measures against PFOA with respect to a regulation according to REACH. Therefore, the Federal Environment Agency of Germany initiated an analytical screening project to determine the PFC load of selected consumer products. Perfluoroalkyl carboxylic (C4–C14-PFCA), perfluoroalkane sulfonic acids (C4, C6-C8, C10PFSA) and fluorotelomer alcohols (4:2, 6:2; 8:2 and 10:2 FTOH) were analysed in 118 consumer products including textiles (outdoor materials), carpets, cleaning and impregnating agents, leather samples, baking and sandwich papers, paper baking forms and ski waxes. PFCAs and PFSAs (= perfluoroalkyl acids PFAAs) were analysed by HPLC-MS-MS, whereas FTOH were detected by GC-CI-MS. In addition the exposure by volatile fluorotelomer alcohols in presumably polluted indoor air was measured. In spite of the restricted number of materials and samples the investigation shows, that PFCs are present in a variety of consumer products. Though they were found in most of the tested product groups the study can only yield examples for possible PFC expositions, further investigations should follow. The PFC load of the investigated consumer products differed between product groups and inside the groups. In addition considerable differences between the levels of PFAAs and FTOHs were observed. While the PFAA contents in the examined cleaning agents was negligible (< 0.5 µg/kg) their FTOH level were very high (up to 73 000 µg/kg 8:2 FTOH). In outdoor textiles the FTOH levels ranged till 180 µg/m2 and the PFOS levels till 10 µg/m2. Very high PFAA contents with values up to 2 000 µg/kg PFOA were detected in some ski waxes. The highest concentrations found were measured for FTOHs in impregnating sprays (up to 719 000 µg/kg 8:2 FTOH). In rooms with elevated amounts of PFC loaded products like in outdoor or sports outfitters shops increased FTOH levels in the indoor air were detected (till 250 ng/m3) accordingly. Inside group differences are demonstrated for example for the PFOA concentrations which varied from 0.4 to 19 µg/m2 for outdoor materials, from 7.9 to 24.8 µg/kg for impregnating sprays and from 0.6 to 502 µg/kg for paper baking form samples. In leather samples the PFOA range was 0.8 to 11.2 µg/m2 while PFBA ranged from 1.4 to 228 µg/m2. The PFC spectrum found varied also considerably. Ski waxes showed nearly the complete spectrum and other samples were dominated by individual compounds (like e.g. short chain PFCAs in leather samples). Some paper baking forms (muffin forms) originating from private stocks of coworkers showed high PFAA contaminations with PFOA loads up to 500 µg/kg. In contrast new bought samples did not confirm these high loads (0.8 to ~ 5 µg/kg PFOA).

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The sources of the PFC pollution of low contaminated samples and products remain unclear. They may be caused by contamination processes during production, transport, storage or by the packaging. But even low contaminated products may contribute significantly to the human PFC burden if they are produced in high amounts and are widely used. The results show that there are consumer products with low or negligible PFSA- and PFCA-contents, such as the cleaning agents or baking and sandwich papers tested. On the other hand, high PFC levels were identified in ski waxes, leather samples, outdoor textiles and some baking papers. Moreover, the PFOS concentrations in carpet samples (up to 1.9 µg/m2), leather samples (up to 5 µg/m2) and outdoor materials (up to 10 µg/m2) exceeded the regulatory threshold value of 1 µg/m2 PFOS according to the European PFOS regulation.

Zusammenfassung Daten über perfluorierte Chemikalien (PFCs) in Verbraucherprodukten sind zur Zeit noch selten und mehr Informationen sind nötig, um einen Überblick über die aktuellen PFC-Belastungen erhalten. Sie sind auch nötig zur Abschätzung, ob im Rahmen von REACH Anwendungsbeschränkungen, z.B. für PFOA, nötig sind. Deshalb hat das Umweltbundesamt ein analytisches Screeningprogramm initiiert, um die PFC-Belastung von ausgewählten Verbraucherprodukten zu ermitteln. Perfluorierte Alkansulfonsäuren (C4, C6-C8, C10-PFSA), Alkylcarbonsäuren (C4–C14PFCA) und Fluortelomeralkohole (4:2, 6:2; 8:2 und 10:2 FTOH) wurden in 118 Verbraucherprodukten analysiert. Dazu gehörten Textilien (Outdoormaterialien), Teppiche, Reinigungs- und Imprägniermittel, Lederproben, Back- und Butterbrotpapiere, Papierbackformen sowie Skiwachse. PFCAs und PFSAs (= Perfluoroalkyl acids PFAAs) wurden mit HPLC-MS-MS und FTOHs mit GC-CI-MS analysiert. Außerdem wurden Gehalte an Fluortelomeralkoholen in der Luft vermutlich belasteter Innenräume gemessen. Trotz der eingeschränkten Anzahl der Materialien und Proben zeigt diese Untersuchung, dass perfluorierte Verbindungen in einer Vielzahl von Verbraucherprodukten vorkommen. Obwohl sie in den meisten untersuchten Produktgruppen gefunden wurden, kann diese Studie dennoch nur exemplarische Beispiele zur PFCBelastung liefern, weitere Untersuchungen sind auf jeden Fall zu empfehlen. Die PFC-Belastung der untersuchten Verbraucherprodukte variierte zwischen und innerhalb der untersuchten Produktgruppen. Außerdem gab es beträchtliche Unterschiede zwischen den PFAA und den FTOH-Gehalten. Während z.B. die PFAAGehalte in den untersuchten Reinigungsmitteln vernachlässigbar waren (< 0.5 µg/kg), war die FTOH-belastung sehr hoch (bis zu 73 000 µg/kg 8:2 FTOH). In Outdoortextilien fanden sich FTOHs bis 180 µg/m2 und PFOS bis zu 10 µg/m2. Sehr hohe PFAA-gehalte mit Werten bis 2 000 µg/kg PFOA wurden für einige Skiwachse ermittelt. Die höchsten Gehalte wurden für FTOHs in Imprägniermitteln gemessen (bis zu 719 000 µg/kg 8:2 FTOH).

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In Innenräumen, in denen belastete Produkte vermehrt anzutreffen sind, wie z.B. in Outdoor- und Sportgeschäften, wurden dementsprechend in der Raumluft auch erhöhte FTOH-Gehalte nachgewiesen (bis zu 250 ng/m3) Unterschiede innerhalb von Gruppen ergaben sich z.B. für die PFOA-Konzentrationen innerhalb der Outdoormaterialien (0.4 bis 19 µg/m2), der Imprägniermittel (7.9 bis 24.8 µg/kg) oder der Papierbackformen (0.6 bis 502 µg/kg). Die PFOA-Gehalte in Lederproben reichten von 0.8 bis 11.2 µg/m2 während die PFBA-Gehalte von 1.4 bis 228 µg/m2 schwankten. Das gefundene PFC-Spektrum schwankte ebenfalls beträchtlich. In den Skiwachsen wurde nahezu das gesamte Spektrum gefunden, in anderen Produkten dominierten einzelne Verbindungen, z.B. kurzkettige PFCs in den Lederproben. Einige Papierbackformen (Muffinformen) aus dem privaten Vorrat von Mitarbeitern zeigten besonders hohe PFC-Belastungen, besonders an PFOA (bis zu 500 µg/kg). Im Gegensatz dazu konnten diese hohen Gehalte in neu gekauften Proben nicht bestätigt werden (0.8 bis ~ 5 µg/kg PFOA). Die Ursachen der PFC-Belastung schwach belasteter Produkte bleibt unklar. Sie können z.B. auch in Verunreinigungen liegen, die während Produktion, Transport, Lagerung oder durch die Verpackung erfolgt sind. Auch wenn Produkte nur schwach belastet sein sollten, können sie möglicherweise einen signifikanten Belastungspfad darstellen, z.B. wenn es sich um weit verbreitete Produkte handelt. Die Ergebnisse zeigen, dass einige Verbraucherprodukte nur gering bzw. vernachlässigbare PFSA- und PFCA-gehalte aufweisen. Hierzu gehören z.B. die untersuchten Reinigungsmittel oder die Back- und Butterbrotpapiere. Andererseits wurden wurden hohe PFC-Gehalte in Skiwachsen, Lederproben, Outdoortextilien und einigen Backformen ermittelt. Außerdem zeigte sich, dass die PFOS-Konzentrationen in Teppichproben (Gehalte bis zu 1.9 µg/m2), Lederproben (bis zu 5 µg/m2) und Outdoortextilien (bis zu 10 µg/m2) den Grenzwert von 1 µg/m2 entsprechend der Europäischen PFOS-Gesetzgebung überschritten.

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2.

Background and Objective The European Parliament regulation no. 1907/2006 concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) was published in the Official Journal of the EU on 30th December 2006 [EU 2007]. It is intended to assure a high level of consumer health and environmental protection. The REACH regulation is based on the precautionary principle. If chemicals show a need for action on community level, the evaluation of the chemical data will be carried out by the authorities. For risk minimization there are two different instruments available: authorization and restriction. For both, the EC Member States and the European Chemicals Agency (ECHA) can provide proposals for substances. Per- and polyfluoroalkyl substances (PFASs) including perfluorocarbons (PFCs) have inimitable properties. They are very stable, e.g. are resistant to biotic and abiotic breakdown, and are water and grease repellent. Therefore, they are used as detergents or impregnating agents in numerous industrial applications, such as paperand packaging as well as textile industry. The manufacture, use, and disposal of consumer products are important sources for exposure into the environment. The persistence of PFCs, however, is problematic for the environment. A number of PFCs can be found ubiquitously in the environment [Ahrens et al., 2011; Holmström and Berger, 2008; Landesamt für Natur, Umwelt und Verbraucherschutz NordrheinWestfalen 2011; Rüdel et al., 2010; Rüdel et al., 2011; Theobald et al., 2007; Umweltbundesamt Dessau 2009a; Verreault and Berger, 2007]. Findings in remote regions [Dietz et al., 2008; Butt et al., 2007; Reiner et al., 2011] in human blood [Umweltbundesamt Dessau 2009b; Brede et al., 2010; Eriksen et al. 2011; Hölzer et al., 2011; Inoue et al., 2004; Kärrmann et al., 2007; Olsen et al., 2011] and breast milk [Fromme et al., 2010; Thomsen et al., 2010; Kato et al., 2011] are of very high concern. The most frequently detected PFCs are perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). Both of these compounds are persistent, toxic and bioaccumulative. While the marketing and use of PFOS is prohibited with few exceptions in the EU since June 27, 2008 [EU 2006, EU 2009, EU 2010] there is no substance specific regulation for PFOA. As PFOA shows an impairment of fertility (category 2) the requirements for a regulation according to REACH are actually fulfilled. A proposal for the harmonized classification and labeling has been prepared by Norway and is currently under the revision of the Risk Assessment Committee (RAC) of the Environmental Chemicals Agency (ECHA).

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Available data on PFCs in consumer products are scarce to date. Therefore, the Federal Environment Agency of Germany initiated an analytical screening project in 2009. The goals of this project are the determination of PFCs in selected consumer products in order to get an overview of the PFC loads. Analyses of perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids as well as precursor substances like fluorotelomer alcohols and volatile and short chain PFCs were required . In addition the exposure of short chain PFCs in indoor air were quantified.

3.

Performance

3.1

General Consumer products of different groups were analysed for their PFAA and FTOH contents. In addition volatile PFCs (e.g. PFOA precursor substances like fluorotelomer alcohols) were measured in indoor air of rooms with high expected exposure levels. The investigation of sewage waters which was included in the original description of services of the project was not carried out as it would have exceeded the scope of the work. The analyses were carried out in the institutes Fraunhofer IME in Schmallenberg and Fraunhofer IVV in Freising. Fraunhofer IME analysed the perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids and Fraunhofer IVV the volatile PFCs (fluorotelomer alcohols). Air sampling and analyses of air samples were carried out in Fraunhofer IVV, too. Only a limited number of identical samples was analysed in both institutes. In general each institute procured and investigated its own set of samples mainly due to distance reasons.

3.2

Search for PFC relevant products and product groups Preliminary considerations and a pre-selection of relevant consumer products were carried out at the kick-off meeting of the project in the Federal Environment Agency of Germany (UBA) on 27.11.2009. Firstly, the available information from publications was evaluated. The results are shortly discussed in the following: Washburn et al. (2005) analysed and assessed several consumer products like carpets, carpet-care solution, treated apparel, treated upholstery, treated home and technical textiles, stone, tile, and wood sealants, industrial floor waxes and wax removers, latex paint, home and office cleaners, nonstick cookware and others for their fluorotelomers or fluoropolymers contents. Finally, the authors conclude that exposures of PFCs during consumer use of the investigated articles are not expected to cause adverse human health effects nor result in quantifiable PFC levels in human serum. The authors admit that there are considerable uncertainties in their assessment. Maybe, analytical possibilities in 2005 were very restricted, compared to today’s standards.

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Two studies of the Danish Ministry of the Environment dealing with the use of fluorinated compounds and their assessment were evaluated [Jensen et al., 2008; Feilberg et al., 2008]. Though, the studies relate only to registered products of per- and polyfluorinated compounds they give a good overview of the fields of use in Denmark. The study of Jensen et al. (2008) identified 92 fluorinated substances in the Danish Product Register. This number ‘includes all reported uses of fluorinated substances in Denmark, including industrial uses, which may not be consumer relevant’. However products for industrial use may end up in consumer products. The identified compounds in the Danish Product Register amount to about 16.5 t in total in the year 2006. But it has to be considered that for 48 substances (of the 92) an annual use of 0.00 t was registered, as the many companies reported the use of substances but did not report the used amounts. This means that the amounts of about one half of the registered PFCs were not registered. The identified compounds were classified according to their fields of use. The most important use areas are releasing agents (42 %), paints and lacquers (21 %), glues (15%), surface active substances (6 %), and galvanotechnical products (6 %). They account for about 90 % of total reported uses of 16.5 t/a. The remaining amount of 10 % is used in the areas polish and care products, impregnating agents, cleaning agents and surface active substances (non-metal, e.g. for paper and cardboard). The amounts of fluorinated chemicals used in these areas of use are most likely higher, as only chemical products labeled as dangerous have to be registered in the Danish Product Register. The OECD survey on the production, use, and release of PFCs in industry [OECD 2010] provides an overview of the fields of use of PFCs and their amounts, too. In the year 2009 27 companies worldwide were surveyed (the data refer to the year 2008). Responses were obtained for 9 nine companies. Most of the manufactures in OECD member states completed the survey while no responses were obtained from companies in non-OECD member states. The amount of fluorinated chemicals surveyed was about 65 t/a. The survey shows ‘that perfluorinated chemicals continue to have a wide range of uses’. The main quantities are used for raw materials for surface treatment agents (~ 25 % = 16 t/a) and water/oil repellent systems (~ 25 % = 16 t/a). Further main use areas are coatings / additives (~ 14 %), AFFF agents / surfactants / surface protectants (~ 6 %) and anti reflective coatings (ARCs) for photolithography processes (~ 6 %). The study clearly showed that PFOA and related substances are more broadly used than PFOS, PFAS or PFCA and their related substances. The study of Herzke et al. (2009) was performed for the Norwegian Pollution Control Authority (SFT) and aimed at the identification and quantification of the exposition of the Norwegian population to PFCs by industrial materials and consumer products. The study shows that only five of the 34 analysed products were free of polyfluorinated substances. It is noted that PFOS was found in leather and carpet products though its use was banned in the EU since 2006 [EU 2006].

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Considering these information in a first stage of this project the following products / product groups were selected as potential examination candidates (Table 1). Table 1:

Consumer products / product groups with PFC-relevance

Product group

Products

Carpets

- with different impregnating agents - of different carpet stores

Textiles

- outdoor -jackets - stain repellent clothing - crease resistant clothing - functional textiles - shoes

Cleaning agents

- household cleaning agents - glass cleaning agents - carpet cleaning agents - oven cleaning agents - bathroom cleaning agents - dry cleaning agents - windscreen washer liquid

Care and impregnating agents

- shoe care products - textile care products - tent impregnating agents - furniture care products - bathroom care products - wash basin impregnation - shower curtain impregnation - car care materials

Home textiles

- table cloth - curtains - shower curtain - upholstery (e.g. in household, car, train) - ironing board cover - awning - sun protective textiles

Food

- ’worst-case’ mixed samples from kitchen waste papers - baking papers - release paper - grease resistant papers - baking forms - ‘non-stick’ foodware

Others

- ski waxes ® ® - Teflon sources (iron, kitchen boards, Teflon tape) - paints, lacquers - glues - ball point pens, inks - impregnated ski glasses - flame retardants - pesticides

Wipe samples

- wipe samples of oven ventilation slit - windows

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3.3

Product group

Products

Indoor air

- garage, car interior - carpet store - shoe shop - sports and outdoor shops - hunting shop, camping shop - new office rooms - automotive paint shop - Selling of home textiles - production of car upholstery - kitchen after use oven or microwave oven

Effluents

- from dry cleaning - from laundries - from car wash - from ‚Easy-to-clean‘ ceramics - dripping water from awnings - washing tests using PFC containing textiles

Selection of consumer products and samples The consumer products and samples to be analysed in this project were selected considering the preselected PFC relevant product groups shown in Table 1. The number of samples that could be analysed was restricted by the financial situation of the project. It was planned to analyse about ten different groups of consumer products with 10 samples each resulting in a total number of about 100 samples. The consumer product groups selected and the number of analysed samples are shown in Table 2. In order to improve the expressiveness of the study and to generate a data pool being as meaningful as possible the number of products groups and the number of samples analysed were extended. In total 270 samples (136 different samples) of 12 product groups were analysed (see Table 2). Table 2:

Overview over consumer product groups and number of samples analysed

Consumer product group

Number of samples

Cleaning agents Carpets Impregnating sprays Outdoor materials Leather Baking and sandwich papers Paper baking forms Mixed paper samples Ski waxes Other Product emission samples Air samples

9 14 16 11 13 19 14 7 13 2 7 11

Total

136

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The individual samples to be analysed were bought from local retailers or collected by co-workers of the institute or local clubs (e.g. ski waxes from local skiing club). The selection of the samples occurred randomly for the most part. This means that the selection was mostly governed by the supply of the shops. Information on the individual samples is given in the result section (chapter 0) . 3.4

Selection of PFC target compounds The OECD survey on production, use and release of PFCs in industry [OECD 2010, see also chapter 3.2] deals with 73 perfluorinated substances. The survey results indicate ‘that 42 of the 73 perfluorinated chemicals surveyed were manufactured and formulated into products in 2008 at an estimated total volume of 61 tonnes’. The compounds most used were PFOA (perfluorooctanoic acid ammonium salt) with an estimated amount of 19 t and 8:2 fluorotelomer alcohol with an amount of 14 t. The 8:2 fluorotelomer alcohol and further fluorotelomers like 8:2 iodide, 8:2 acrylate and 8:2 methacrylate play important roles as PFOA precursors as they can be transferred to PFOA under suitable conditions. The transfer can occur for example by abiotic reactions in the atmosphere [Ellis et al., 2004] or by biodegradation [Dinglasan et al., 2004]). The PFCs examined in this project are shown in Table 3. The selection was made considering the analytical possibilities and the fact that the compounds were already examined in previous studies. The selection of analytes was agreed with the UBA (interim report from 31.01.2010).

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Table 3: Acronym

PFC target compounds analysed Analyte name

CAS number*

Molecular formula

Analytica l method

Perfluoroalkyl carboxylic acids (PFCAs) PFBA

Perfluorobutanoic acid

375-22-4

C3F7COOH

HPLC-MS

PFPA

Perfluoropentanoic acid

2706-90-3

C4F9COOH

HPLC-MS

PFHxA

Perfluorohexanoic acid

307-24-4

C5F11COOH

HPLC-MS

PFHpA

Perfluoroheptanoic acid

375-85-9

C6F13COOH

HPLC-MS

PFOA

Perfluorooctanoic acid

335-67-1

C7F15COOH

HPLC-MS

PFNA

Perfluorononanoic acid

375-95-1

C8F17COOH

HPLC-MS

PFDA

Perfluorodecanoic acid

335-76-2

C9F19COOH

HPLC-MS

PFUnA

Perfluoroundecanoic acid

4234-23-5

C10F21COOH

HPLC-MS

PFDoA

Perfluorododecanoic acid

307-55-1

C11F23COOH

HPLC-MS

PFTrA

Perfluorotridecanoic acid

72629-94-8

C12F25COOH

HPLC-MS

PFTeA

Perfluorotetradecanoic acid

376-06-7

C13F27COOH

HPLC-MS

Perfluoroalkane sulfonic acids (PFSAs) PFBS

Perfluorobutanesulfonic acid

59933-66-3

C4F9SO3H

HPLC-MS

PFHxS

Perfluorohexanesulfonic acid

355-46-4

C6F13SO3H

HPLC-MS

PFHpS

Perfluoroheptanesulfonic acid

n.a.

C7F15 SO3H

HPLC-MS

PFOS

Perfluorooctanesulfonic acid

1763-23-1

C8F17SO3H

HPLC-MS

PFDS

Perfluorodecanesulfonic acid

335-77-3

C10F21SO3H

HPLC-MS

Fluorotelomer alcohols (FTOHs) 4:2 FTOH

4:2 Fluorotelomer alcohol

2043-47-2

C4F9C2H4OH

GC-MS

6:2 FTOH

6:2 Fluorotelomer alcohol

647-42-7

C6F13C2H4OH

GC-MS

8:2 FTOH

8:2 Fluorotelomer alcohol

678-39-7

C8F17C2H4OH

GC-MS

10:2 FTOH

10:2 Fluorotelomer alcohol

865-86-1

C10F21C2H4OH

GC-MS

Perfluorooctanesulfonamide

754-91-6

C8F17SO2NH2

HPLC-MS

Others PFOSA

* Salts of the analytes have different CAS numbers n.a. not available

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3.5

Extent of investigation Table 4:

Sample-ID

Sample overview PFC-Spectrum A = Perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) PFC-Spectrum B = Fluorotelomer alcohols (FTOHs) PFC-Spectrum C = FTOH emissions from products) Description

Cleaning agents RM-01 Backofenspray, Point, Aldi (oven spray) RM-02 Hochglanz Politur Metallic, DEA (furniture care product) RM-03 Hochglanz Politur Metallic, Sonax (furniture care product) RM-04 Cockpit Spray, W5, free of silicon, Lidl RM-05 Badreiniger, W5, Lidl (bathroom cleaning agent) RM-06 Glasreiniger, W5, Lidl (glass cleaning agent) RM-07 Flecken Sil (stain remover) RM-08 Viss Bad und Dusche (bathroom cleaner) RM-09 Clean Care Backofen Reiniger (oven spray) Carpet samples T-01 Baramundi, Casanova (Polyamide, Scotchgard® finishing) T-02 Estoril, Casanova (Polyamide, Scotchgard® finishing) T-03 Favorit, Casanova (Polyamide, Antron® finishing) T-04 Event, Casanova (Polyamide, Antron® finishing) T-05 Discovery, Casanova (Polyamide, no information on finishing) T-06 Timeless, Casanova (Polyamide, no information on finishing) T-07 TOUCH duraAir (Polyamide, no information on finishing) T-08 Noblesse (new wool, no information on finishing) T-09 Object Carpet (Polyamide, no information on finishing) T-10 Pearl duraAir (Polyamide, antistatic) T-11 Piano (Polyacryl, no information on finishing) T-12 Borneo (new wool, no information on finishing) T-13 NIRIS (new wool, no information on finishing) T-14 Minos duraAir (Polyamide, no information on finishing) Impregnating sprays IS-01 Nanospray, Quickschuh (shoe care product) IS-02 Imprägnol Langzeit Imprägnierer (shoe care product) IS-03 Erdal Dauer Imprägnierer (shoe care product) IS-04 Collonil Boots (shoe care product) IS-05 Toko Proof (shoe care product) IS-06 Salamander Combi Proper (shoe care product) IS-07 Salamander Universal SMS (shoe care product) IS-08 Erdal Nanotec (shoe care product) IS-09 Reno Imprägnierspray (shoe care product) IS-10 Wetterschutz Imprägnierspray (shoe care product)

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PFC-Spectrum A B C X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X

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Sample-ID

Description

IS-11 Luhns Leder Textil (leather care product) IS-12 Hey Sport Impa (textile care product) IS-13 Hey Sport TEX (textile care product) IS-14 EMO Imprägnierspray (shoe care product) IS-15 Solitaire Effekt Leder Spray (leather care product) IS-16 Deichmann HITech Pflege Schaum (shoe care product) Outdoor materials OM-01 Rain wear (pants and jacket Norton) OM-02 Outdoor Trousers, Children rain pants OM-03 Outdoor jacket Escursione GTX OM-04 Gloves Astro GX OM-05 Gloves OM-06 Children gloves Lisbo GT OM-07 Outdoor Jacket, Resulte Performance OM-08 Outdoor Trousers, Resulte Performance OM-09 Outdoor jacket, H&M OM-10 Outdoor jacket, CraneSports OM-11 Outdoor jacket, outer jacket, Jack Wolfskin OM-12 Outdoor jacket, inner jacket, Jack Wolfskin Leather samples L-01 Z 66/22, Wi-Schi L-02 Vivre Caramel, Polinova L-03 29 comfort pfirsich, Himolla L-04 R 9250 961 Kiwi, Arco L-05 Aura creme, Kaniza L-06 5119/97, Weco L-07 137-72 aprico hell, Elastog. L-08 L130-Fb.63 mammu, E-Schli. L-09 16/2904, Gepade L-10 Nobile viola, Koinot L-11 Broco 71, K+W L-12 IL 10 Traminji 104 G, Italsofa L-13 Punch creme Ol, Steinpol/Poco Baking and sandwich papers BP-01 Folia, Aldi BP-02 Toppits BP-03 Plus BP-04 Markant BP-05 Selex Selection BP-06 Toppits Cross & Frit BP-07 Aromata, Lidl BP-08 Paclan, HIT BP-09 Quickpack, Kaufpark

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PFC-Spectrum A B C X X X X X X X X X X X X

X X

X X X

X X X X X X X X X X X X X X X X X X X X X X

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X X

X X X X X X

Sample-ID

Description

BP-10 Rewe BP-11 PAPSTAR, Art.-Nr. 18306, Zuschnitte "Springform" BP-12 Gut & Günstig, Edeka BP-13 Quickpack, MacGeiz BP-14 Rubin, Rossmann BP-15 Pergafin, BfR BuP-01 Sandwich paper, Gut & Günstig, Edeka BuP-02 Sandwich paper, neoten, MacGeiz BuP-03 Sandwich paper, Rubin, Rossmann BuP-04 Sandwich paper, JA, Rewe Paper baking forms BF-01 Moderne Kueche, Rewe BF-02 a la casa, Rewe BF-03 Lidl BF-04 kik BF-05 kik, coloured BF-06 kik, small (for pralines, chocolates) BF-07 Kaiser BF-08 Kaiser, small (for pralines, chocolates) BF-09 Wenco, Edeka BF-10 Bacher and Demmler, MacGeiz BF-11 Rubin, Rossmann BF-12 Kathi, Edeka BF-13 Dr. Oetker, Edeka (baking mixture) BF-14 Quick Burgers Mixed paper samples PM-01 Cardboard folded box (packaging for deep frozen food) (2 brands) Muffin and baking papera (5 brands: Gloria, Kathi, Weltgold PM-02 Zenker Fackelmann, Toppits) PM-03 Confectionary packaging PM-04 corrugated cardboard (non-food) PM-05 Cheese packaging (4 products) PM-06 Egg packaging (3 brands) PM-07 Others (teafilter, tea bag packaging, paper towels) Ski waxes SW-01 Racing Wax Alpin, Nordic, Powerpack Wax-Additiv SI, Holmenkol SW-02 Power Pack Nordic, Base-Wax Graphit schwarz, 4/65, Holmenkol SW-03 Medium Additive, B3Orange, 0°C/-3°C Briko s.r.l., Italy SW-04 Racing Wax Nordic, Powerpack Base-Wax Gelb; -6°C, Holmenkol SW-05 Toko Nordic, Dibloc Thermo Wax Yellow, 0°C/-4°C, Toko AG SW-06 Basis und Rennwax, K1; +2°C/-5°C, HWK Wachsservice SW-07 SM 15 Fluor; +15°C/-1°C, HWK Wachsservice SW-08 SP6 X; +4°C/-12°C, HWK Wachsservice SW-09 Medium Additive, GR B 3Yellow, -1°C/-5°C, Briko s.r.l., Italy

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PFC-Spectrum A B C X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X

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Sample-ID SW-10 SW-11 SW-12 SW-13 Others Wood glue Awning cloth Air samples LP-01 LP-02 LP-03 LP-04 LP-05 LP-06 LP-07 LP-08 LP-09 LP-10 LP-11

Description Basis und Rennwax, F1; +10°C/-2°C, HWK Wachsservice Racing und Basiswax, P1; -2°C/-20°C, HWK Wachsservice High-Fluor-Paraffin, HFW2; +2°C/-6°C, HWK Wachsservice 3

ALPIN Skiwachs, P3 Creme, Holmenkol

PFC-Spectrum A B C X X X X X X

Office 1 Office 2 Kitchen Workshop 1, Metal processing Workshop 2, Automotive paint shop Sports outfitters 1, Swimwear Sports outfitters 2, Football shoes + tricots Outdoor shop 1, Outdoor jackets Outdoor shop 2, Outdoor jackets, bags, sleeping bags Carpet shop Car interior, French car, 9 months old

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X X X X X X X X X X X

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4.

Analytical Methods

4.1

General This section gives an overview of the analytical methods used. Detailed information on the methods are presented in the annexes 1 to 3. Validated analytical methods for the determination of PFCs in water, sewage sludge, sediments, blood, breast milk, biota (like mussels, fish, bird eggs) and food are in use in both Fraunhofer institutes (IME and IVV). Depending on the matrices procedures using ion pair extraction, acidic-alkaline sequential extraction or solid phase extraction (SPE) with weak anion exchangers are applied. Partly preceding solvent extraction and/or extraction of fats is used. The instrumental analysis of the perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) was carried out by HPLC-MS-MS while the fluorotelomer alcohols (FTOHs) were analysed by GC-CI-MS. The methods applied differed in sample preparation, clean up including selection of solvents and the type of instrumental measurement (GC-MS and HPLC-MS-MS). The PFCs analysed represent the amounts of the compounds which are extractable by the used methods. After the collection of the consumer products the analytical procedures were checked for their suitability for PFC determination in the different matrices and adjusted accordingly. Basic developments were carried out for the air sampling and analysis of fluorotelomer alcohols. Results are given in the Annex.

4.2

Analysis of consumer products Sample preparation and cleanup was performed as described in the chapter. Generally after evaporation of the extracts, reconstitution in methanol-water and filtration the concentration of the perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) were determined by HPLC-MS-MS using 13C- resp. 18O-labelled internal standards for quantification. The fluorotelomer alcohols and related compounds were transferred into dichloromethane or hexane and subsequently analysed by gaschromatography with mass spectrometric detection (GC-MS) after positive chemical ionisation.

4.2.1 Analysis of cleaning agents Perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) Spray samples: Maximal 1 g of the sample is sprayed into a 15 mL polypropylen (PP) centrifuge tube. Liquid samples: 1 g of the sample is transferred into a 15 mL polypropylen (PP) centrifuge tube. Then 100 µL of internal standard solution (9 internal standards, 100 ng/mL each) and 2 mL of 0.25 M Na2CO3 / NaHCO3 buffer, 1 mL of 0.5 M tetrabutylammonium hydrogensulfate (TBA) and 5 mL of methyl-t-butyl-ether (MTBE) is added (for the preparation of the Na2CO3 / NaHCO3 buffer and the TBA solution see Annex 1). FKZ 3709 65 410, Final Report

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After vortexing for 60 min the mixture is centrifuged at 4000 rpm for 10 min. The clear supernatant is transferred into a further 15 mL PP tube. The solvent is evaporated by a stream of nitrogen to dryness. The residue is solved in 1 mL of methanol-water (50+50, v/v, 5 min ultrasonic bath) and the liquid filtered using a 0.45 µm RC Filter. The clear filtrate is transferred into an autosampler vial and measured by HPLC-MS-MS. PFOSA could not be determined by this method, as fortification tests resulted in recoveries of < 10 %. Fluorotelomer alcohols (FTOHs) Liquid samples containing potentially FTOHs like impregnating sprays were transferred into glass vials. After dilution with acetone (1:10000) 5 µL of the internal standard solution was added. Recoveries tests were not employed as the samples were analysed directly by GC-MS without further processing steps. 4.2.2 Analysis of carpets Perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) The samples are stamped out of the carpet using a hole punch (d=25 mm). Two stamps are used for one analytical sample und put into a 15 mL polypropylen (PP) centrifuge tube. Then 100 µL of internal standard solution (9 internal standards, 100 ng/mL each) and 10 mL of acetone is added. After 30 min of ultrasonic treatment the mixture is vortexed for about 30 min. Then the extract is transferred into a further 15 mL PP tube and the solvent evaporated by a stream of nitrogen to dryness. The residue is solved in 1 mL of methanol-water (50+50, v/v, 5 min ultrasonic bath) and the liquid filtered using a 0.45 µm RC Filter. The clear filtrate is transferred into an autosampler vial and measured by HPLC-MS-MS. Fluorotelomer alcohols (FTOHs) Solid samples were doted by the internal standards (13C-labelled) and extracted with an apolar solvent (hexane) in an ultrasonic bath for 15 min. Then extracts were centrifuged if needed and the solvent evaporated. If necessary the further silica cleanup steps following the procedure of Szostek et al. (2004) were carried out. The silica columns were conditioned with 2 mL of acetone and 2 mL of hexane. After addition of the extract the column was washed with 6 mL of hexane. The elution of the FTOHs was carried out using 1 mL of isopropanol. For the determination of the recovery the eluate was fortified with 4 µL injection standard. 4.2.3 Analysis of impregnating sprays Perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) Maximal 1 g of sample is sprayed into a 15 mL polypropylen (PP) centrifuge tube. Then 100 µL of internal standard solution (9 internal standards, 100 ng/mL each) and 2 mL of 0.25 M Na2CO3 / NaHCO3 buffer, 1 mL of 0.5 M tetrabutylammonium hydrogensulfate (TBA) and 5 mL of methyl-t-butyl-ether (MTBE) is added (for the preparation of the Na2CO3 / NaHCO3 buffer and the TBA solution see Annex 1).

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After vortexing for 60 min the mixture is centrifuged at 4000 rpm for 10 min. The clear supernatant is transferred into a further 15 mL PP tube. The solvent is evaporated by a stream of nitrogen to dryness. The residue is solved in 1 mL of methanol-water (50+50, v/v, 5 min ultrasonic bath) and the liquid filtered using a 0.45 µm RC Filter. The clear filtrate is transferred into an autosampler vial and measured by HPLC-MS-MS. Fluorotelomer alcohols (FTOHs) Liquid samples containing potentially FTOHs like impregnating sprays were transferred into glass vials. After dilution with acetone (1:10000) 5 µL of the internal standard solution was added. Recoveries tests were not employed as the samples were analysed directly by GC-MS without further processing steps. In addition a screening method based on headspace GC with a plasma emission detector (HS-GC-EPED) was used for the detection of precursor compounds. Therefore samples were sprayed on a sheet of paper, which was then allowed to dry at room temperature. A blank sample (paper without impregnating spray) as well as the impregnated paper sheets were placed in head space vials and analysed by HS-GCEPED. 4.2.4 Analysis of outdoor materials Perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) 4 cm2 of the outdoor materials were put into a 15 mL polypropylen (PP) centrifuge tube. Then 100 µL of internal standard solution (9 internal standards, 100 ng/mL each) and 2 mL of 0.25 M Na2CO3 / NaHCO3 buffer, 1 mL of 0.5 M tetrabutylammonium hydrogensulfate (TBA) and 5 mL of methyl-t-butyl-ether (MTBE) is added (for the preparation of the Na2CO3 / NaHCO3 buffer and the TBA solution see Annex 1). After vortexing for 60 min the mixture is centrifuged at 4000 rpm for 10 min. The clear supernatant is transferred into a further 15 mL PP tube. The solvent is evaporated by a stream of nitrogen to dryness. The residue is solved in 1 mL of methanol-water (50+50, v/v, 5 min ultrasonic bath) and the liquid filtered using a 0.45 µm RC Filter. The clear filtrate is transferred into an autosampler vial and measured by HPLC-MS-MS. PFOSA could not be determined by this method, as fortification tests resulted in recoveries < 10 %. Fluorotelomer alcohols (FTOHs) Solid samples were doted by the internal standards (13C-labelled) and extracted with an apolar solvent (hexane) in an ultrasonic bath for 15 min. Then extracts were centrifuged if needed and the solvent evaporated. If necessary the further silica cleanup steps following the procedure of Szostek et al. (2004) were carried out. The silica columns were conditioned with 2 mL of acetone and 2 mL of hexane. After addition of the extract the column was washed with 6 mL of hexane. The elution of the FTOHs was carried out using 1 mL of isopropanol. For the determination of the recovery the eluate was fortified with 4 µL injection standard.

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4.2.5 Analysis of leather samples Perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) The analytical sample is stamped out of the leather using a hole punch (d=25 mm) und put into a 15 mL polypropylen (PP) centrifuge tube. Then 100 µL of internal standard solution (9 internal standards, 100 ng/mL each) and 10 mL of acetone is added. After 30 min of ultrasonic treatment the mixture is vortexed for about 30 min. Then the extract is transferred into a further 15 mL PP tube and the solvent evaporated by a stream of nitrogen to dryness. The residue is solved in 1 mL of methanol-water (50+50, v/v, 5 min ultrasonic bath) and the liquid filtered using a 0.45 µm RC Filter. The clear filtrate is transferred into an autosampler vial and measured by HPLC-MS-MS. 4.2.6 Analysis of paper samples Perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) 100 cm2 baking paper resp. 1 baking form is chopped and put into a 15 mL polypropylen (PP) centrifuge tube. Then 100 µL of internal standard solution (9 internal standards, 100 ng/mL each) and 10 - 15 mL of acetone is added. After 10 min of ultrasonic treatment the mixture is vortexed for about 60 min. Then the extract is transferred into a further 15 mL PP tube and the solvent evaporated by a stream of nitrogen to dryness. The residue is solved in 1 mL of methanol-water (50+50, v/v, 5 min ultrasonic bath) and the liquid filtered using a 0.45 µm RC Filter. The clear filtrate is transferred into an autosampler vial and measured by HPLC-MS-MS. Fluorotelomer alcohols (FTOHs) Solid samples were doted by the internal standards (13C-labelled) and extracted with an apolar solvent (hexane) in an ultrasonic bath for 15 min. Then extracts were centrifuged if needed and the solvent evaporated. If necessary the further silica cleanup steps following the procedure of Szostek et al. (2004) were carried out. The silica columns were conditioned with 2 mL of acetone and 2 mL of hexane. After addition of the extract the column was washed with 6 mL of hexane. The elution of the FTOHs was carried out using 1 mL of isopropanol. For the determination of the recovery the eluate was fortified with 4 µL injection standard. 4.2.7 Analysis of ski waxes Perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) About 0.1 to 0.3 g of the ski wax is weighed accurately and transferred into a 15 mL polypropylen (PP) centrifuge tube. Then 100 µL of internal standard solution (9 internal standards, 100 ng/mL each) and 5 mL of hexane is added. After vortexing for 30 min 1 mL of methanol is added and the vortexing continued for further 30 min. Then the mixture is centrifuged at 4000 rpm at 10°C for 10 min and the lower methanolic phase is transferred into a further 15 mL PP tube. The solvent is evaporated by a stream of nitrogen to dryness. The residue is solved in 1 mL of methanol-water (50+50, v/v, 5 min ultrasonic bath) and the liquid filtered using a 0.45 µm RC Filter. The clear filtrate is transferred into an autosampler vial and measured by HPLC-MS-MS.

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4.2.8 Analysis of wood glue and awning cloth Perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) The wood glue and the awning cloth were analysed as the outdoor materials. About 0.5 g of the glue and 4 cm2 of the awning cloth were used. The analysis of PFOSA was possible in the awning cloth (in contrast to the matrix outdoors materials). 4.3

Sampling and analysis of indoor air The air volumes to be sampled are set to 5 – 50 m³ using a maximal sampling time of 48 hours. These values resulted from the expected FTOH concentrations and the sampling outside of working hours. Table 5 shows the materials tested as possible adsorber media for FTOHs. They are based on a polystyren-divinylbenzen copolymer (PVDB). Table 5:

Adsorber materials tested for the air sampling of FTOHs

Adsorber

Mass in cartridge [mg]

Volume [mL]

Article number

Manufacturer

OASIS WAX

150

6

186002493

Waters

ISOLUTE ENV+

200

6

915-0020-L

Separtis

Strata-X

500

6

8B-S100-HCH-TN

Phenomenex

Supelclean ENVI-Carb

500

6

57242

Sigma-Aldrich

Atoll Columns Xtream Capacity

500

6

XC-70-9313

Interchim

Strata Phenyl

1000

6

8B-S006-JCH

Phenomenex

HyperSep Ratain PEP

1000

25

60107-215

Thermo Scienfitic

ISOLTUE ENV+

1000

25

915-0100-E

Biotage

The FTOH elution from the adsorber cartridges was carried out following Jahnke et al., 2007a and 2007b. The procedure was optimized by the exchange of the elution solvent methanol by dichloromethane and addition of ethylacetate as keeper as evaporation of methanol eluates resulted in increased losses of analytes. The optimal sorption material was selected considering the recoveries and the blank values of breakthrough und reproducibility tests. The recovery was the main criterion for the selection. The adsorbers OASIS WAX (150 mg) and ISOLUTE ENV+ (2x200 mg) exhibited the highest percentage recoveries. The adsorber ISOLUTE ENV+ (1000 mg) performed well also with a mean recovery of about 71 %. The recoveries of the other adsorption materials are clearly lower (e.g. < 50 %) or show breakdowns for the different analytes. Therefore they were not used as sorption materials in the air sampling of FTOHs. The materials OASIS WAX (150 mg) and ISOLUTE ENV+ (2x200 mg) were not used because of their low bed mass in the available sorption cartridges. Therefore the adsorber material ISOLTUE ENV+ (1000 mg) was finally used.

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4.4

Sampling and analysis of product emissions There were financial restrictions for the purchase or collection of sufficient amounts of some sample materials (especially clothing/textiles) for conventional analyses which require destructive sample preparations. For such samples the determination of the FTOH emissions was carried out. The emissions were determined by placing the product into a 10 L desiccator equipped with an air in- and outlet. Through the outlet air was sucked over an SPE adsorber tube using a MZ C2 Synchor pump. The pressure in the desiccator was balanced via the air inlet. The emissions of the consumer products were determined over a time period of 3 h at 25 °C. The air volume sampled was 3 m³ and the air exchange rate was about 100. Blank experiments were performed with an empty desiccator and the same set of parameters (3 h, 25 °C, 3 m³). The processing of the SPE sampling tubes was identical to the processing of the air samples.

4.5

Quality assurance Quality assurance included the use of mass labeled internal standards, use of multiple mass transitions for quantitation and identification (if possible), recovery and precision tests (if possible) and the measurement of control standards (independent from calibration solutions) and blanks in every analytical series. LOQs differed for the different sample types and are presented in Table 8 and in Table 52 in Annex 1. LOQs are given in terms of mass of analyte per mass of sample and - if feasible - in terms of mass of analyte per area of sample. The following tables give an overview of the quality assurance results. Further details are presented in the Annexes 1 and 2. Table 6:

Repeatability (precison) in the analysis of perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) in consumer products

Product group

number of samples

number of replicates

Relative standard deviation of multiple measurements [%]

Cleaning agents

6

2-3

- (all samples < LOQ)

Carpets

6

3

6.2 - 52

Impregnating sprays

3

3

3.5 – 41

Outdoor materials

6

3

1.4 - 46

Leather

13

2

1.8 – 36

Papers

33

2 - 12

4 - 75

Ski waxes

13

2

0.1 - 59

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Table 7:

Recoveries of mass labelled internal standards in the analysis of perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) in consumer products

Product group

Recoveries MPFOA [%]

MPFOS [%]

other standards [%]

Cleaning agents

40 – 65

49 – 59

31 – 55

Carpets

51 – 64

46 – 70

42 – 73

Impregnating sprays

45 – 67

40 – 60

30 – 63

Outdoor materials

73 – 84

39 – 87

65 – 95

Leather

39 – 61

42 – 72

35 – 78

Papers

61 – 89

65 – 108

75 – 95

Ski waxes

37 – 69

51 – 67

50 – 82

Table 8:

2

Limits of quantification in µg/kg and µg/m (Analysis of perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) in consumer products)

Product Group

Limit of Quantification (LOQ) 2

[µg/kg]

[µg/m ]

Cleaning agents

0.5

‘-

Carpets

0.5

0.5

Impregnating sprays

0.5

‘-

Outdoor materials

0.5

0.3

Leather

0.5

0.5

Baking and sandwich papers

0.5

0.02

Paper baking forms

0.5

0.02

Ski waxes

0.5

‘-

Table 9:

Blanks and control samples in the analysis of perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) in consumer products

Product Group

Instrumental and procedural blanks [µg/kg]

Recovery of control samples [%]

Cleaning agents

< 0.5

85 – 112

Carpets

< 0.5

74 – 119

Impregnating sprays

< 0.5

73 – 84

Outdoor materials

< 0.5

69 – 117

Leather

< 0.5

70 – 119

Baking and sandwich papers

< 0.5

69 – 121

Paper baking forms

< 0.5

72 – 113

Ski waxes

< 0.5

74 – 116

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5.

Results This chapter presents the results of the determinations of PFCs in consumer products. The column ‘n’ in the result tables gives the number of individual analyses. For data below the limit of quantification (LOQ) the measured values are reported and are given in red colour and in parentheses. For data below the limit of detection (LOD) the symbol ‘(0.0)’ is used. The analytical methods including the results of the quality assurance measures (like repeatabilities, recoveries, LOQs, blanks and controls) are described in Annex 1 and Annex 2.

5.1

PFCs in cleaning agents

5.1.1 Perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) in cleaning agents The cleaning agent samples analysed for PFAAs by HPLC-MS-MS are shown in Table 10. The samples were purchased randomly in local shops in the first quarter of the year 2010. No information was available on the use of PFCs in the products.

Table 10:

Cleaning agent samples analysed for PFAAs by HPLC-MS-MS

Sample-ID

Description

RM-01

Backofenspray, Point, Aldi (oven spray)

RM-02

Hochglanz Politur Metallic, DEA (furniture care product)

RM-03

Hochglanz Politur Metallic, Sonax (furniture care product)

RM-04

Cockpit Spray, W5, free of silicon, Lidl

RM-05

Badreiniger, W5, Lidl (bathroom cleaning agent)

RM-06

Glasreiniger, W5, Lidl (glass cleaning agent)

RM-07

Flecken Sil (stain remover)

RM-08

Viss Bad und Dusche (bathroom cleaner)

RM-09

Clean Care Backofen Reiniger (oven spray)

The PFAA concentrations in cleaning agents are shown in Table 11. All results are below the limit of quantification (LOQ) of 0.5 µg/kg or even below the limit of detection (LOD) of 0.1 µg/kg. This is indicated by the values given in red colour and in parenthesis as described at the beginning of chapter 0.

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Table 11:

Concentration of PFAAs in cleaning agents (results in µg/kg; sample ID: see Table 10; LOQ = 0.5 µg/kg)

Sample ID

n

PFBA

PFPA PFHxA PFHpA

PFOA

PFNA PFDA

PFUnA

RM-01

3

(0.0)

(0.0)

(0.0)

(0.0)

(0.7)

(0.1)

(0.0)

(0.0)

RM-02

2

(0.0)

(0.0)

(0.0)

(0.0)

(0.1)

(0.0)

(0.0)

(0.0)

RM-03

2

(0.0)

(0.0)

(0.0)

(0.0)

(0.9)

(0.0)

(0.0)

(0.0)

RM-04

2

(0.0)

(0.0)

(0.0)

(0.0)

(0.5)

(0.0)

(0.0)

(0.0)

RM-05

2

(0.0)

(0.0)

(0.0)

(0.0)

(0.2)

(0.0)

(0.0)

(0.0)

RM-06

2

(0.0)

(0.0)

(0.0)

(0.0)

(0.9)

(0.0)

(0.0)

(0.0)

Sample ID

n

PFDoA

PFTrA

PFTeA

PFBS

PFHxS

PFHpS PFOS

PFDS

RM-01

3

(0.1)

(0.2)

(0.5)

(0.0)

(0.0)

(0.0)

1.1

(0.0)

RM-02

2

(0.0)

(0.2)

(0.1)

(0.0)

(0.0)

(0.0)

(0.7)

(0.0)

RM-03

2

(0.2)

(0.2)

(0.0)

(0.0)

(0.0)

(0.0)

(0.6)

(0.0)

RM-04

2

(0.0)

(0.2)

(0.1)

(0.0)

(0.0)

(0.0)

(0.8)

(0.0)

RM-05

2

(0.0)

(0.2)

(0.0)

(0.0)

(0.0)

(0.0)

(0.0)

(0.0)

RM-06

2

(0.0)

(0.2)

(0.1)

(0.0)

(0.0)

(0.0)

(0.9)

(0.0)

5.1.2 Fluorotelomer alcohols in cleaning agents The cleaning agent samples analysed for fluorotelomer alcohols (FTOHs) by GC-CI-MS are shown inTable 12. The samples were purchased randomly in local shops in the first quarter of the year 2010. No information was available on the use of PFCs in the products.

Table 12:

Cleaning agent samples, analysed for FTOHs by GC-CI-MS

Sample-ID

Description

RM-07

Flecken Sil (stain remover)

RM-08

Viss Bad und Dusche (bathroom cleaner)

RM-09

Clean Care Backofen Reiniger (oven spray)

Table 13 shows the FTOH concentrations in cleaning agents. In all cases 8:2 FTOH is the dominant FTOH.

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Table 13:

Concentration of FTOHs in cleaning agents (results in µg/kg, sample ID: see Table 12, LOQ = 20000 µg/kg)

Sample

4:2 FTOH

6:2 FTOH

8:2 FTOH

10:2 FTOH

RM-07

< 20000

38000

47000

37000

RM-08

< 20000

38000

73000

23000

RM-09

< 20000

39000

63000

20000

5.1.3 Summary on PFCs in cleaning agents The concentrations of PFAAs in the cleaning agents analysed are not relevant as all measured concentrations were below the limit of quantification (LOQ) of 0.5 µg/kg. FTOH results show remarkably high values in the µg/kg range. Application of these sprays is therefore a significant source of FTOH and – following atmospheric degradation – presumably of PFOA. Figure 1 shows the concentrations of FTOHs in the cleaning agent samples analysed. 80.000 70.000

4:2 FTOH

µg/kg

6:2 FTOH

60.000

8:2 FTOH

50.000

10:2 FTOH

40.000 30.000 20.000 10.000 0

RM-07

RM-08

RM-09

Sample ID

Figure 1:

5.2

FTOHs in cleaning agent samples

PFCs in carpet samples

5.2.1 Perfluoroalkyl carboxylic and perfluoroalkane sulfonic acids (PFAAs) in carpet samples The carpet samples analysed for PFAAs by HPLC-MS-MS are shown in Table 14. They are samples of the product line of a local industrial carpet enterprise and were collected in the first quarter of the year 2010.

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All carpet samples consist of polyamide fibers but are different in the fiber finishing. The samples T-01 and T-02 contain a Scotchgard® finishing, the samples T-03 and T-04 an Antron® finishing and for samples T-05 and T-06 no information regarding the finishing was available. Scotchgard® contained PFOS and PFOSA as key ingredients in former times. PFOS was replaced in 2003 mainly by PFBS [Renner 2006]. Antron® is the trade name of a carpet fibre with a ‘Teflon® carpet protector.

Table 14:

Carpet samples analysed for PFAAs by HPLC-MS-MS

Sample-ID

Description ®

T-01

Baramundi, Casanova

Polyamide, Scotchgard finishing

T-02

Estoril, Casanova

Polyamide, Scotchgard finishing

T-03

Favorit, Casanova

Polyamide, Antron finishing

T-04

Event, Casanova

Polyamide, Antron finishing

T-05

Discovery, Casanova

Polyamide, no information on finishing

T-06

Timeless, Casanova

Polyamide, no information on finishing

®

® ®

The results of the analysis of carpet samples are shown in Table 15.

Table 15:

Concentration of PFAAs in carpet samples 2 2 (results in µg/m ; sample ID: see Table 14; LOQ = 0.5 µg/m )

Sample ID

n

PFBA

PFOA

PFNA

PFDA

PFUnA

PFDoA

T-01

3

7.5

2.0

0.8

(0.1)

0.9

(0.5)

(0.3)

(0.1)

(0.4)

T-02

3

12.1

3.8

0.7

(0.1)

(0.4)

(0.2)

(0.1)

(0.1)

(0.2)

T-03

3

(0.2)

T-04

3

(0.2)

1.3

(0.1)

(0.1)

(0.2)

(0.3)

(0.1)

(0.1)

(0.1)

0.9

(0.1)

(0.1)

(0.3)

(0.2)

(0.2)

(0.2)

(0.3)

T-05

3

(0.4)

1.5

(0.2)

(0.2)

(0.4)

(0.3)

(0.2)

(0.2)

(0.3)

T-06

3

3.5

1.2

(0.5)

1.2

0.8

0.7

0.9

(0.5)

1.1

Sample ID

n

PFTrA

PFTeA

PFBS

PFHxS PFHpS

PFOS

PFDS

PFOSA

T-01

3

(0.1)

(0.5)

9.2

(0.1)

(0.0)

1.1

(0.0)

(0.1)

T-02

3

(0.1)

0.5

19.5

(0.0)

(0.0)

1.6

(0.0)

(0.1)

T-03

3

(0.2)

(0.2)

(0.0)

(0.0)

(0.0)

1.9

(0.0)

(0.0)

T-04

3

(0.2)

(0.4)

(0.1)

(0.1)

(0.0)

0.8

(0.1)

(0.0)

T-05

3

(0.4)

(0.3)

(0.3)

(0.1)

(0.0)

1.6

(0.0)

(0.1)

T-06

3

(0.4)

0.8

15.1

(0.1)

(0.0)

1.0

(0.0)

(0.0)

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PFPA PFHxA PFHpA

page 31 of 115

The samples with Scotchgard® finishing (T-01, T-02) contained PFBS as expected and in addition short chain perfluoroalkyl carboxylates like PFBA and PFPA. The same counts for sample T-06 which therefore has most likely also a Scotchgard® finishing. The concentrations are relatively high, for sample T-02 12.1 µg/m2 PFBA; 3.8 µg/m2 PFPA and 19.5 µg/m2 PFBS were determined. These values correspond to 11,5 µg/kg PFBA, 3,7 µg/kg PFPA and 18,5 µg/kg PFBS. The order of magnitude is 10-7 % which is well below the value of 0.1 % demanded by the EU legislation (see [EU 2010] and chapter 6.3). The Antron® fiber carpets (T-03, T-04) did not contain PFBS. Only PFOS and PFPA were detected. The concentrations of other PFCs were low. The results of sample T-05 are comparable. The values of PFOS however were in one sample nearby and in all other samples higher than the limit value of 1 µg/m2 according to the current European PFOS regulation [EU 2010]. 5.2.2 Fluorotelomer alcohols in carpet samples Eight carpet samples were analysed for fluorotelomer alcohols by GC-CI-MS. Samples listed in Table 16 origin a carpet store, in which the presence of FTOH congeners was proofed by indoor air measurements (compare Chapter 5.9). The selling stuff could not provide information on the possible application of fluorinated compounds in these carpets. A later recherché of the chosen products in public available data bases did not reveal these information also.

Table 16:

Carpet samples analysed for FTOHs by GC-CI-MS

Sample-ID

Description

T-07

TOUCH duraAir

Polyamide, no information on finishing

T-08

Noblesse

new wool, no information on finishing

T-09

Object Carpet

Polyamide, no information on finishing

T-10

Pearl duraAir

Polyamide, antistatic

T-11

Piano

Polyacryl, no information on finishing

T-12

Borneo

new wool, no information on finishing

T-13

NIRIS

new wool, no information on finishing

T-14

Minos duraAir

Polyamide, no information on finishing

FKZ 3709 65 410, Final Report

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FTOH levels in carpet samples (Table 17) were in the lower ppb range (