Environmental Science and Pollution Research

, Volume 18, Issue 8, pp 1422–1432

Structural isomers of polyfluorinated di- and tri-alkylated phosphate ester surfactants present in industrial blends and in microwave popcorn bags

  • Xenia Trier
  • Nikoline Juul Nielsen
  • Jan H. Christensen
Research Article

DOI: 10.1007/s11356-011-0488-2

Cite this article as:
Trier, X., Nielsen, N.J. & Christensen, J.H. Environ Sci Pollut Res (2011) 18: 1422. doi:10.1007/s11356-011-0488-2



In this study, we provide strategies for detecting and quantifying the structural isomers of polyfluorinated di- and tri-alkyl surfactants (PFAS) by mass spectrometry (MS). We specifically investigate polyfluorinated dialkylated phosphate ester surfactants (x:2/y:2 diPAPS, (F(CF2)xCH2CH2O-P(O)(O)-OCH2CH2(CF2)yF)) and their thioether analogues (x:2/y:2 S-diPAPS, F(CF2)xCH2CH2SCH2-C[CH2O)2P(O)(O)]-CH2SCH2CH2(CF2)yF), which are used for industrial applications, such as oil- and water-repellent coatings on paper and board. DiPAPS have been found in human blood and are metabolised to the persistent perfluoroalkyl carboxylic acids (PFCA) in rats.

Materials and methods

A microwave popcorn bag extract was analysed by ultrahigh-pressure liquid chromatography coupled to a negative electrospray ionisation-quadrupole time-of-flight MS.

Results and discussion

The extract contained S-diPAPS, diPAPS and trialkylated (triPAPS) impurities. TriPAPS were also present in industrial and synthetic diPAPS standards, and were verified with an 8:2/8:2/8:2 triPAPS standard. The eight elemental compositions (m/z’s) of diPAPS in the extract represent 19 precursor ion structures, and the six S-diPAPS m/z’s represent at least 13 structures. The diPAPS had [M-H] precursor ions of m/z 789, 889,…1,489 and the S-diPAPS of m/z 921, 1,021,…1,421, corresponding to fluorinated chains from C6–18. Each m/z appeared as one to three chromatographic peaks of structural isomers, where, e.g. m/z 1,189 was present as 10:2/10:2, 8:2/12:2 and 6:2/14:2 diPAPS. The isomers formed different products ions, thus only half of the m/z 1,189 diPAPS concentration was measured with one precursor ion > product ion transition.


In general, knowledge about structural isomers of poly-alkylated PFAS is needed for the estimation of types and amounts of perfluorinated degradation products, such as PFCA from diPAPS.


FluorinatedSurfactantsIsomersMass spectrometryQuantificationIdentification pointsLC-MSdiPAPSS-diPAPStriPAPSPaper and boardMigrationFood contact material

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Xenia Trier
    • 1
    • 2
  • Nikoline Juul Nielsen
    • 1
  • Jan H. Christensen
    • 1
  1. 1.Department of Basic Sciences and Environment, Faculty of Life SciencesUniversity of CopenhagenFrederiksbergDenmark
  2. 2.Technical University of DenmarkNational Food InstituteSøborgDenmark