Abstract
A new analytical method for the determination of 22 perfluoroalkylated (carboxylic and sulfonic) acids in water samples is presented. The method’s objective was to achieve the simultaneous quantification of compounds with different chain lengths (from C1 to C18). To this end, 500 mL of water were extracted with Oasis WAX solid-phase extraction cartridges and eluted with 3 mL of 5% ammonia in methanol. After evaporation to dryness, extracts were reconstituted in methanol:ultrapure water (1:1) and analyzed by mixed-mode liquid chromatography-tandem mass spectrometry (MMLC-MS/MS) using a weak anion exchange/reversed-phase column. The method provided good results, with limits of quantification lower than 1 ng/L in river water for most of compounds, except the two perfluorocarboxylic acids with the longest alkyl chain (>C14) and trifluoroacetic acid, for which a blank contamination problem was observed. The method proved good trueness and precision in both ultrapure and river water (R ≥ 81%, RSD ≤ 15%). After validation, the method was applied to the analysis of nine water samples where nine perfluoroalkylated acids were quantified. Seven of them were ultrashort- (C1-C4) and short-chain (C4-C8) perfluoroalkylated acids, pointing out the importance of developing methods capable to target such substances for further monitoring.
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Acknowledgments
Special thanks go to Dr. Leo Yeung (former member of University of Toronto and currently at Örebro University) and Prof. Thomas Knepper and Dr. Daniel Zahn (Hochschule Fresenius) for providing us standards of perfluoroethane sulfonic acid, perfluoropropane sulfonic acid, and perfluoromethane sulfonic acid, respectively.
Funding
This work was supported by the Water Challenges for a Changing World Joint Program Initiative (Water JPI) Pilot Call (ref. WATERJPI2013 – PROMOTE), the Spanish Ministry of Economy and Competitiveness/Spanish Agencia Estatal de Investigación (refs. JPIW2013-117 and CTM2017-84763-C3-2-R), the Galician Council of Culture, Education and Universities (ref. ED431C2017/36) and FEDER/EDRF funding.
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Published in the topical collection Persistent and Mobile Organic Compounds – An Environmental Challenge with guest editors Torsten C. Schmidt, Thomas P. Knepper, and Thorsten Reemtsma.
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Montes, R., Rodil, R., Placer, L. et al. Applicability of mixed-mode chromatography for the simultaneous analysis of C1-C18 perfluoroalkylated substances. Anal Bioanal Chem 412, 4849–4856 (2020). https://doi.org/10.1007/s00216-020-02434-w
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DOI: https://doi.org/10.1007/s00216-020-02434-w