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HPLC–MS/MS methods for the determination of 52 perfluoroalkyl and polyfluoroalkyl substances in aqueous samples

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Abstract

Two quantitative methods using high-performance liquid chromatography (HPLC) combined with triple quadrupole tandem mass spectrometry (MS/MS) were developed to determine perfluoroalkyl and polyfluoroalkyl substances (PFASs) in aqueous samples. The first HPLC–MS/MS method was applied to 47 PFASs of 12 different substance classes with acidic characteristics such as perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkane sulfonic acids (PFSAs), as well as precursor substances and biotransformation intermediates (e.g., unsaturated fluorotelomer carboxylic acids). In addition, 25 13C-, 18O-, and 2H-labeled PFASs were used as internal standards in this method. The second HPLC–MS/MS method was applied to fluorotelomer alcohols (FTOHs) and perfluorooctane sulfonamidoethanols as these compounds have physicochemical properties different from those of the previous ones. Accuracy between 82% and 110% and a standard deviation in the range from 2% to 22% depending on the substances were determined during the evaluation of repeatability and precision. The method quantification limit after solid-phase extraction ranged from 0.3 to 199 ng/L depending on the analyte and matrix. The HPLC–MS/MS methods developed were suitable for the determination of PFASs in aqueous samples (e.g., wastewater treatment plant effluents or influents after solid-phase extraction). These methods will be helpful in monitoring campaigns to evaluate the relevance of precursor substances as indirect sources of perfluorinated substances in the environment. In one exemplary application in an industrial wastewater treatment plant, FTOHs were found to be the major substance class in the influent; in particular, 6:2-FTOH was the predominant compound in the industrial samples and accounted for 74% of the total PFAS concentration. The increase in the concentration of the transformation products of FTOHs in the corresponding effluent, such as fluorotelomer carboxylic acids, unsaturated fluorotelomer carboxylic acids, n:3 polyfluorinated saturated carboxylic acids (n indicates the number of nonfluorinated carbon atoms), and PFCAs, indicated biotransformation of FTOHs or their derivatives during wastewater treatment. However, only 33 mol% of the total amount of PFASs present in the influent was quantified in the corresponding effluent.

Method development of an HPLC-MS/MS multi-method for the determination of PFASs in aqueos samples

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Acknowledgements

We thank the German Environment Agency (Dessau, Germany) for financial support of the research project “Investigations on the presence and behavior of precursors to perfluoroalkyl substances in the environment as a preparation of regulatory measures” (FKZ 3712 65 415/01); PFC_EXPO. We thank Lena Vierke and Annegret Biegel-Engler of the German Environment Agency for helpful discussions. We also like thank the operators of the wastewater treatment plant for their support during the planning and realization of the sampling campaigns. We are very thankful to Robert Buck and Ning Wang from DuPont for providing the reference material for n:3-acids as well as the isotopically labeled standards used in the HPLC–MS/MS-n method.

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  1. Hochschule Fresenius University of Applied Sciences, Limburger Straße 2, 65510, Idstein, Germany

    Christoph Gremmel, Tobias Frömel & Thomas P. Knepper

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  1. Christoph Gremmel
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Correspondence to Thomas P. Knepper.

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Gremmel, C., Frömel, T. & Knepper, T.P. HPLC–MS/MS methods for the determination of 52 perfluoroalkyl and polyfluoroalkyl substances in aqueous samples. Anal Bioanal Chem 409, 1643–1655 (2017). https://doi.org/10.1007/s00216-016-0110-z

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