Polyfluorinated surfactants (PFS) in paper and board coatings for food packaging
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In this study, we explore the identity of a range of polyfluorinated surfactants (PFS) used for food contact materials, primarily to impart oil and water repellency on paper and board. PFS are of interest, as they can be precursors of poly- and perfluorinated alkyl substances (PFAS), of which several are persistent and are found worldwide in human blood and in the environment.
Materials and methods
To determine the elemental composition of PFS, we combined information from patents, chemical suppliers and analyses of industrial blends using ultra performance liquid chromatography-negative electrospray ionisation quadrupole time-of-flight mass spectrometry.
At a high pH of 9.7, both non-ionic and anionic PFS were ionised and were recognised by negative mass defects of exact masses, and neutral fragment losses of n × 20 or n × 100 Da. More than 115 molecular structures were found in industrial blends from the EU, US and China, belonging to the groups of polyfluoroalkyl-mono- and di-ester phosphates (monoPAPS, diPAPS and S-diPAPS), -ethoxylates, -acrylates, -amino acids, -sulfonamide phosphates and -thio acids, together with residuals and synthesis byproducts. In addition, a number of starting materials such as perfluorooctane sulfonamide N-alkyl esters were analysed. Di- and trialkylated PAPS and S-diPAPS were found in migrates from European food contact materials.
This study highlights the need to monitor for more types of PFS in order to map the sources of PFAS in humans and the environment.
KeywordsFluorinated surfactants Screening Identification Accurate mass spectrometry UPLC-ESI-QTOF Food contact materials Migration
- BfR (2009) Standard XXXVI. Paper and board for food contact. Federal Institute for Risk Assessment, Germany. Available from: http://bfr.zadi.de/kse/faces/resources/pdf/360-english.pdf;jsessionid=E5B3AC7FF5657548764CF8E20472A52D. Accessed on 23 June 2010
- CEN (2002). TC194.standard: EN 1186-1 to 15:2002, Materials and articles in contact with foodstuffs–plastics, and EN 13130–1:2004: Materials and articles in contact with foodstuffs—plastics substances subject to limitation–part 1. Available from: http://www.cen.eu/. Accessed on 12 May 2010.
- Ciba (BASF) (2000–2010). Available from: http://www.ciba.com/ind-pap-eff-bar-lodyne.htm. Accessed on 2 April 2010.
- Dupont de Nemours EI (2010). DuPontTM Zonyl Fluorosurfactants (2001, (4/01) P-200125.8, No. H-49731-3. Printed in USA), and DuPontTM Zonyl Fluorochemical Intermediates (2001, (8/02) P-200125.8, No. H-49730-4, Printed in USA) and DuPont Foraperle. Available from: http://www2.dupont.com/. Accessed on 14 May 2010.
- Düsseldorf Landeshauptstadt Umweltsamt (2010) Available from: http://www.duesseldorf.de/umweltamt/altlast/pft_grundwasserverunreinigung.shtml. Accessed on 24 June 2010
- EU Commission (2002) Plastics Directive: 2002/72/EC Commission Directive of 6 August 2002 relating to plastic materials and articles intended to come into contact with foodstuffs. (Plastics: unofficial consolidated version including 2002/72/EC, 2004/1/EC, 2004/19/EC, 2005/79/EC, 2007/19/EC, 2008/39/EC)Google Scholar
- EU Commission (2004) Framework Regulation: Regulation (EC) No 1935/2004 of the European Parliament and of the Council of 27 October 2004 on materials and articles intended to come into contact with food and repealing Directives 80/590/EEC and 89/109/EEC (L338/4)Google Scholar
- EU Commission (2010) COMMISSION RECOMMENDATION of 17 March 2010 on the monitoring of perfluoroalkylated substances in food, 2010/161/EU, L 68/22–23, Official Journal of the European Union 18.3.2010Google Scholar
- European Food Safety Authority (EFSA) (2008) Food contact materials: note for guidance for petitioners presenting an application for the safety assessment of a substance to be used in food contact materials prior to its authorisation, p. 25. http://www.efsa.europa.eu/cs/BlobServer/Scientific_Document/CEF_note_for_guidance_FCM_evaluation_2008.08.07.pdf. Accessed on 30 July 2008.
- Forrest MJ (2007) Coatings and inks for food contact materials. Smithers Rapra Techology, report no. 186, ISSN: 0889-3144 or ISBN 1 84735 079 8Google Scholar
- Frömel T, Knepper T (2008) Mass spectrometry as an indispensable tool for studies of biodegradation of surfactants. Trac 27(11):1091–1106Google Scholar
- Guo J, Resnick P, Efimenko K, Genzer J, De Simonoe JM (2008) Alternative fluoropolymers to avoid the challenges associated with perfluorooctanoic acid. Ind. Eng. Chem. Res. 47:502–508Google Scholar
- Hjorth K, Christensen JH, Trier X (2008) Migration of fluorochemicals from food contact paper into food simulants—analysed by LC-MS-MS and D-PLS. Master thesis, Dept. of Basic Sciences and Environment, Faculty of Life Science. Copenhagen UniversityGoogle Scholar
- Iengo B, Pavazotti P (2007) Use of carboxylic perfluoropolyethers for the oleo-repellent paper sizing. European Patent EP 1 484 445 B1, published in Bulletin 2007/28. Available from: http://www.freepatentsonline.com/EP1484445.html. Accessed on 9 May 2010.
- Joensen UN, Bossi R, Leffers H, Jensen AA, Skakkebæk NE, Jørgensen N (2009) Do perfluoroalkyl compounds impair human semen quality? Environ Health Perspect 117(6):923–927Google Scholar
- Kissa E (2002) Fluorinated surfactants, 2nd edn. Marcel Dekker, New YorkGoogle Scholar
- Knepper T, de Voogt P, Barceló D (2005) Analysis and fate of surfactants in the aquatic environment, Amsterdam, The NertherlandsGoogle Scholar
- Lange FT, Schmidt C, Brauch H-J (2006) Perfluoroalkylcarboxylates and sulfonates. Emerging contaminants for drinking water supplies? Association of River Waterworks–RIWA. Available from: www.riwa-rijn.org/e_publikaties/137_ptfe_report.PDF. Accessed on 12 June 2010
- Larsen BL, Stchur P, Szostek B, Bachmura SF, Rowand RC, Prickett KB, Korzeniowski SH, Buck RC (2006) Method development for the determination of residual fluorotelomer raw materials and perflurooctanoate in fluorotelomer-based products by gas chromatography and liquid chromatography mass spectrometry. J Chromatogr A 1110(1–2):117–124CrossRefGoogle Scholar
- Mason Surfactants (2010) Available from: http://www.masonsurfactants.com—search for fluorinated surfactants. Accessed on 14 April 2010.
- Piringer OG, Baner AL (2008) Plastic packaging: interactions with food and pharmaceuticals, 2nd edn. Wiley, WeinheimGoogle Scholar
- prEN 15519:2007: E, European Committee for standardization (2007) Paper and board intended to come into contact with foodstruffs—preparation of an organic solvent extract. CEN, BrusselsGoogle Scholar
- Ringman-Beck J (2010) Food contact: time for the industry to take the lead. Food Packag Bull 19(4&5):16–18Google Scholar
- Schröder HF, Meesters RJW (2005) Stability of fluorinated surfactants in advanced oxidation processes—a follow up of degradation products using flow injection–mass spectrometry, liquid chromatography–mass spectrometry and liquid chromatography–multiple stage mass spectrometry. J Chromatogr A 1082:110–119CrossRefGoogle Scholar
- Schröder HF, Knepper TP, Barceló D, Voogt Pd (eds) (2003) Analysis and fate of surfactants in the aquatic environment, 1st edn. Elsevier Science BV. Wilson & Wilsons Comprehensive Analytical Chemistry, AmsterdamGoogle Scholar
- Solvay Solexis (2010) April 21st. Available from: http://www.solvaysolexis.com/. Accessed on 12 May 2010.
- Tentschert J, Kappenstein O, Richter S, Luch A, Pfaff K (2010) Development of a screening method for perfluorinated compounds. Presented as poster at the 2nd Fluoro Surfactant workshop, 17–19 June 2010, Idstein, GermanyGoogle Scholar
- Tittlemier SA, Pepper K, Seymour C, Moisey J, Bronson R, Cao XL, Dabeka R (2007) Dietary exposure of Canadians to perfluorinated carboxylates and perfluorooctane sulfonate via consumption of meat, fish, fast foods, and food items prepared in their packaging. J Agric Food Chem 55(8):3203–3210CrossRefGoogle Scholar
- Trier X, Nielsen NJ, Christensen JH (2010) Mass spectrometric detection of structural isomers of polyfluorinated di- and tri-alkylated phosphate ester surfactants in coatings for food paper and board. Submitted to ESPR, June 2010Google Scholar
- US EPA (2010) http://epa.gov/oppt/pfoa/pubs/stewardship/index.html. Accessed on 10 Dec 2010
- US FDA (2010a) April 30th. Available from: http://www.accessdata.fda.gov/scripts/fcn/fcnNavigation.cfm?rpt=fcsListing&page=12. Accessed on 14 May 2010
- US FDA (2010b) regulations 176.160 and 176.170 and effective food-contact-notifications (FCN’s) website: FDA http://www.fda.gov/Food/FoodIngredientsPackaging/FoodContactSubstancesFCS/ucm116567.htm. Accessed on 26 Nov 2010
- van der Putte I, Murin M, van Velthoven N, Affourtit F (2010) Analysis of the risks arising from the industrial use of perfuorooctanoic acid (PFOA) and ammonium perfluorooctanoate (APFO) and from their use in consumer articles. Evaluation of the risk reduction measures for potential restrictions on the manufacture, placing on the market and use of PFOA and APFO. European Commision DG-Enterprise, Final report of Contract 30-CE-0230115/00-70 implementing Framework Contract 30-CE-0220929/00-38Google Scholar
- Wuhan Fengfan (2010) Chem. Co. Available from: http://fengfan-chem.diytrade.com. Accessed on 6 May 2010.