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Polyfluorinated surfactants (PFS) in paper and board coatings for food packaging

Abstract

Introduction

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.

Results

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.

Conclusion

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.

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Acknowledgement

Donation of industrial blends and synthesised standards by Wuhan Fengfan Chemical Co. Ltd., China, The Danish Veterinary and Food Administration and by ISPRA/The EU Commission is much appreciated. The environmental research school RECETO, Food-DTU and KU-LIFE funded the Ph.D. study, and Lundbeck and the Cowi foundations funded the UPLC system. Thanks to Karen Hjorth, M.Sc. for work on the migration/extractions of food packaging materials and to Giorgio Tomasi and Nikoline Juul Nielsen for the work on the Matlab figures using in-house routines.

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Correspondence to Xenia Trier.

Additional information

Responsible editor: Ake Bergman

Electronic supplementary materials

Detailed method information

Supporting information 1

DOC 69.5 kb

MSMS spectra of two peaks in FF10 (PDF 63.9 KB)

Table S1

Precursor and product ions of a selection of PFS (DOCX 15.2 kb)

Table S2

Method performance parameters of the UPLC-ESI--QTOF MS method for diPAPS, PFOA and PFOS (DOCX 11.8 kb)

Table S3

LC retention times and MS parameters for the HPLC-ESI--QqQ MS method for diPAPS and S-diPAPS (DOCX 11.4 kb)

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Trier, X., Granby, K. & Christensen, J.H. Polyfluorinated surfactants (PFS) in paper and board coatings for food packaging. Environ Sci Pollut Res 18, 1108–1120 (2011). https://doi.org/10.1007/s11356-010-0439-3

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Keywords

  • Fluorinated surfactants
  • Screening
  • Identification
  • Accurate mass spectrometry
  • UPLC-ESI-QTOF
  • Food contact materials
  • Migration