Analysis of fluorotelomer alcohols and perfluorinated sulfonamides in biotic samples by liquid chromatography-atmospheric pressure photoionization mass spectrometry

A quantitative analytical method was developed to simultaneously detect fluorotelomer alcohols (6:2 FTOH, 8:2 FTOH and 10:2 FTOH) and polyfluorinated sulfonamides (perfluoro-1-octanesulfonamide (FOSA) and N-methylperfluoro-1-octanesulfonamide (NMeFOSA)) in biotic samples with liquid chromatography-atmospheric pressure photoionization mass spectrometry (LC-APPI-MS/MS). APPI mass spectra for FOSA and NMeFOSA showed that the major ionization mechanism was not photoionization, whereas for the FTOHs it was photoionization. For FTOHs, a [M+O-2](-) ion was generated with a similar response as the deprotonated molecular ion [M-H](-). We demonstrated that FTOHs, FOSA and NMeFOSA can be measured in various biota samples using APPI with a minimized matrix effect. Using APPI, the linear response range for the FTOHs was 0-1000 ng/mL (r(2) > 0.9997), and for FOSA and NMeFOSA ranged from 0 to 250 ng/mL (r(2) > 0.995). The instrument and method detect limits ranged from 0.16 to 0.63 pg and below 1 ng/g wet weight (w.w.), respectively. For the overall method applied to the test matrices, recovery efficiencies ranged from 73 to 102% for egg homogenate and 89-100% for liver tissue. The present study demonstrates for the first time that a far more response and sensitive approach for the detection and quantification of FTOHs and polyfluorinated sulfonamides is possible using APPI as opposed to electrospray ionization. Crown Copyright (C) 2008 Published by Elsevier B.V. All rights reserved.