Analytical and Bioanalytical Chemistry

, Volume 406, Issue 5, pp 1471–1480 | Cite as

A targeted/non-targeted screening method for perfluoroalkyl carboxylic acids and sulfonates in whole fish using quadrupole time-of-flight mass spectrometry and MSe

  • Bernard S. CrimminsEmail author
  • Xiaoyan Xia
  • Philip K. Hopke
  • Thomas M. Holsen
Research Paper


A new method for measuring perfluoroalkyl contaminants (PFCs) in biological matrices has been developed. An ultra-high pressure liquid chromatograph equipped with a quadrupole time-of-flight mass spectrometer (UPLC-QToF) was optimized using a continuous precursor/product ion monitoring mode. Unlike traditional targeted studies that isolate precursor/product ion pairs, the current method alternates between two ionization energy channels to continuously capture standard electrospray ionization (low energy) and collision induced dissociation (high energy) spectra. The result is the indiscriminant acquisition of paired low and high energy spectra for all constituents eluting from the chromatographic system. This technique was evaluated for the routine analysis of perfluoroalkyl species. Using this technique, linear perfluoroalkyl carboxylic acids (C4 to C14) and perfluoroalkyl sulfonates (C4, C6, C8 and C10) exhibited a linear range spanning over three orders of magnitude and were detectable at levels less than 1 pg on column with a root mean squared signal to noise ratio of 5 to 20. Lake trout (Salvelinus namaycush) and National Institutes of Standards and Technology Standard Reference Material 1946 were used to evaluate matrix effects and the accuracy of this method when applied to a whole fish extract. The current method was also evaluated as a diagnostic tool to identify unknown PFCs using experimental fragmentation patterns, mass defect filtering and Kendrick plots.


The future of toxics analysis in biological media: cataloging spectral fingerprints at targeted analysis sensitivity.


PFOS QToF MSe Lake trout Perfluorinated sulfonates Perfluorinated acids 



Collision induced dissociation




Electrospray ionization


Full width at half maximum


Low energy (no collision energy) scan using MSe mode


High energy (ramped collision energy) scan using MSe mode


Fourier transform ion cyclotron resonance mass spectrometer


Gas chromatography


Great Lakes Fish Monitoring and Surveillance Program


Kendrick mass defect


Lake Michigan


Mass defect


Perfluoro-n-[13C4]butanoic acid


Perfluoro-n-[1,2-13C2]decanoic acid


Perfluoro-n-[1,2-13C2]dodecanoic acid




Perfluoro-n-[1,2-13C2]hexanoic acid


Perfluoro-n-[1,2,3,4,5-13C5]nonanoic acid


Perfluoro-n-[1,2,3,4-13C4]octanoic acid


Perfluoro-1-[1,2,3,4-13C4]octane sulfonate


Perfluoro-n-[1,2-13C2] undecanoic acid


Continuous low/high energy mass spectrometry


Multiple reaction monitoring


Precursor/product mass spectrometry


National Institutes of Standards and Technology (USA)


Perfluoroalkyl carboxylic acids


Perfluoroalkyl sulfonates


Perfluoro-n-butanoic acid




Perfluordecanoic acid


Perfluoro-n-dodecanoic acid


Perfluoro-n-decane sulfonate


Perfluoro-n-heptanoic acid


Perfluoro-n-heptane sulfonate


Perfluoro-n-hexanoic acid


Perfluoro-n-hexane sulfonate


Perfluoro-n-nonanoic acid


Perfluoro-n-octanoic acid


Perfluoro-n-octane sulfonate


Perfluoro-n-pentanoic acid



The U.S. Environmental Protection Agency Great Lakes Fish Monitoring and Surveillance Program supported this project under contract GL-96594201-1. Also we wish to thank the Program Manager Elizabeth Murphy and many people who assisted in sample collection and processing. Although the research described in this article has been funded wholly or in part by the United States Environmental Protection Agency, it has not been subjected to the Agency’s required peer and policy review and therefore, does not necessarily reflect the views of the Agency and no official endorsement should be inferred.

Supplementary material

216_2013_7519_MOESM1_ESM.pdf (843 kb)
ESM 1 (PDF 843 KB)


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Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  • Bernard S. Crimmins
    • 1
    Email author
  • Xiaoyan Xia
    • 2
  • Philip K. Hopke
    • 2
  • Thomas M. Holsen
    • 1
  1. 1.Department of Civil and Environmental EngineeringClarkson UniversityPotsdamUSA
  2. 2.Center for Air Resources Engineering and ScienceClarkson UniversityPotsdamUSA

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