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Non-target screening (NTS) based on high-resolution mass spectrometry (HRMS) is necessary to comprehensively characterize per- and polyfluoroalkyl substances (PFAS) in environmental, biological, and technical samples due to the very limited availability of authentic PFAS reference standards. Since in trace analysis, MS/MS information is not always achievable and only selected PFAS are present in homologous series, further techniques to prioritize measured HRMS data (features) according to their likelihood of being PFAS are highly desired due to the importance of efficient data reduction during NTS. Kaufmann et al. (J AOAC Int, 2022) presented a very promising approach to separate selected PFAS from sample matrix features by plotting the mass defect (MD) normalized to the number of carbons (MD/C) vs. mass normalized to the number of C (m/C). We systematically evaluated the advantages and limitations of this approach by using ~ 490,000 chemical formulas of organic chemicals (~ 210,000 PFAS, ~ 160,000 organic contaminants, and 125,000 natural organic matter compounds) and calculating how efficiently, and especially which, PFAS can be prioritized. While PFAS with high fluorine content (approximately: F/C > 0.8, H/F 55%) can be separated well, partially fluorinated PFAS with a high hydrogen content are more difficult to prioritize, which we discuss for selected PFAS. In the MD/C-m/C approach, even compounds with highly positive MDs above 0.5 Da and hence incorrectly assigned to negative MDs can still be separated from true negative mass defect features by the normalized mass (m/C). Furthermore, based on the position in the MD/C-m/C plot, we propose the estimation of the fluorine fraction in molecules for selected PFAS classes. The promising MD/C-m/C approach can be widely used in PFAS research and routine analysis. The concept is also applicable to other compound classes like iodinated compounds. Graphical Abstract

The limited availability of analytical reference standards makes non-target screening approaches based on high-resolution mass spectrometry increasingly important for the efficient identification of unknown PFAS (per- and polyfluoroalkyl substances) and their TPs. We developed and optimized a vendor-independent open-source Python-based algorithm (FindPFΔS = FindPolyFluoroDeltas) to search for distinct fragment mass differences in MS/MS raw data (.ms2-files). Optimization with PFAS standards, two pre-characterized paper and soil samples (iterative data-dependent acquisition), revealed Δ(CF

Polyfluoroalkyl phosphate diesters (diPAPs) are widely used for paper and cardboard impregnation and discharged via waste streams from production processes and consumer products. To improve the knowledge about the environmental fate of diPAPs, electrochemical oxidation (EO) was used to characterize the transformation pathways and reaction kinetics. 6:2 diPAP was transformed electrochemically to perfluorocarboxylic acids (C5-C7 PFCAs) and two intermediates (6:2 fluorotelomer carboxylic acid, FTCA, and 6:2 fluorotelomer unsaturated carboxylic acid, FTUCA). EO of potential intermediates 6:2 monoPAP and 6:2 fluorotelomer alcohol (FTOH) showed similar transformation products but with different ratios. We show that 6:2 diPAP is initiated by OH radical (•OH) reactions, as evidenced by the measured steady-state concentrations of •OH with the probe molecule terephthalic acid, quenching experiments, and pH dependency of the reaction. PFHpA was the main product of 6:2 diPAP oxidation, and it was formed in a pseudo-first-order reaction for which a bimolecular rate constant was estimated to be kO•H,diPAPformPFHpA = 9.4(±1.4) × 107 M-1 s-1 by an initial rate approach. This can be utilized to estimate the environmental half-life of 6:2 diPAP for the reaction with •OH and the formation kinetics of persistent PFCAs.

High per- and polyfluorinated alkyl substance (PFAS) concentrations have been detected in agricultural soils in Southwest Germany. Discharges of PFAS-contaminated paper sludge and compost are suspected to be the cause of the contamination. Perfluorinated carboxylic acids (PFCAs) have been detected also in groundwater, drinking water, and plants in this area. Recently, previously unknown compounds have been identified by high-resolution mass spectrometry (HRMS). Major contaminants were polyfluorinated dialkylated phosphate esters (diPAPs) and N-ethyl perfluorooctane sulfonamide ethanol–based phosphate diester (diSAmPAP). In this study, HRMS screening for PFAS was applied to 14 soil samples from the contaminated area and 14 impregnated paper samples which were from a similar period than the contamination. The paper samples were characterized by diPAPs (from 4:2/6:2 to 12:2/12:2), fluorotelomer mercapto alkyl phosphates (FTMAPs; 6:2/6:2 to 10:2/10:2), and diSAmPAP. In soil samples, diPAPs and their transformation products (TPs) were the major contaminants, but also FTMAPs, diSAmPAP, and their TPs occurred. The distribution patterns of the carbon chain lengths of the precursor PFAS in soil samples were shown to resemble those in paper samples. This supports the hypothesis that paper sludge is a major source of contamination. The presence of major degradation products like PFCAs, FTSAs, or PFOS and their distribution of carbon chain lengths indicate the activity of biotic or abiotic degradation processes and selective leaching processes from the upper soil horizons. Graphical abstract Supplementary Information The online version contains supplementary material available at 10.1007/s00216-021-03463-9.

The application of contaminated paper sludge on arable land in southwest Germany caused the occurrence of a broad range of poly- and perfluoroalkyl substances (PFASs) on soil. Recently, the dead-end transformation products (TPs) perfluorooctanoic acid and perfluorooctanesulfonic acid were detected in groundwater and drinking water. The precursors and other transformation products mostly remained unknown. Therefore, HRMS screening by Kendrick mass analysis and assignment of homologous series in combination with suspect screening were applied to identify original PFASs and their TPs in four different soil samples from sites where contaminated paper sludge was applied. In total, twelve compound classes comprising more than 61 PFASs could be fully or tentatively identified. The data reveal that contamination mainly originates from polyfluorinated dialkylated phosphate esters (from 4:2/6:2 to 12:2/14:2), N-ethyl perfluorooctane sulfonamide ethanol–based phosphate diesters (only C8/C8) and transformation products of these precursors. Contamination patterns can be attributed to PFASs used for paper impregnation and can vary slightly from site to site. Graphical abstract Electronic supplementary material The online version of this article (10.1007/s00216-019-02358-0) contains supplementary material, which is available to authorized users.