Determination of transformation products of per- and polyfluoroalkyl substances at trace levels in agricultural plants.

Per- and polyfluoroalkyl substances (PFASs) are ubiquitous in the environment. However, only a limited number of predominantly persistent perfluoroalkyl acids (PFAAs) have been analyzed in edible plants so far. We present a generic trace analytical method that allows for quantification of 16 intermediate fluorotelomer alcohol (FTOH)- or perfluoroalkane sulfonamidoethanol (FASE)-based transformation products as well as 18 PFAAs in plants. Additionally, 36 suspected intermediate PFAS transformation products were qualitatively analyzed. The ultrasound-assisted solid-liquid extraction of wheat and maize grain, maize leaves, Jerusalem artichoke and ryegrass (1-5 g plant sample intake) was followed by a clean-up with dispersive solid-phase extraction using graphitized carbon adsorbent (5-10 mg per sample) and chemical analysis by reversed phase liquid chromatography-tandem mass spectrometry. The method was based on matrix matched and extracted calibration and displayed good precision with relative standard deviations in triplicate analyses typically below 15% for all quantified analytes and matrices. An average deviation of 12% between quantified concentrations obtained by matrix matched and extracted calibration and a method based on isotopically labelled internal standards underlines the good trueness of the method. The method quantification limits for the majority of analytes in all plant samples were in the low ng/kg concentration range on a dry weight basis. Plant matrices were analyzed from crops grown on agricultural fields that have been contaminated with PFASs. FTOH- and/or FASE-based intermediate transformation products were detected in all samples with N-ethyl perfluorooctane sulfonamidoacetic acid (EtFOSAA) and perfluorooctane sulfonamide (FOSA) as the prevailing compounds in concentrations up to several hundred ng/kg in maize leaves. The 9:3 Acid (a transformation product of 10:2 FTOH) was tentatively identified. In accordance with these findings, the final degradation products perfluorooctane sulfonic acid (PFOS) and perfluorodecanoic acid (PFDA) were frequently detected. For perfluoroalkyl carboxylic acids (PFCAs), according to earlier findings, short chain homologues generally displayed the highest levels (up to 98 µg/kg for perfluorobutanoic acid (PFBA) in maize leaves). However, maize grain was an exception showing the highest concentrations for long chain PFCAs, whereas PFBA was not detected. The uptake of high levels of PFASs into plants is of concern since these may be used as animal feed or represent a direct exposure medium for humans.

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