Per- and polyfluoroalkyl substances (PFASs) have been a focal point of environmental chemistry and chemical regulation in recent years, culminating in a shift from individual PFAS regulation toward a PFAS group regulatory approach in Europe. PFASs are a highly diverse group of substances, and knowledge about this group is still scarce beyond the well-studied, legacy long-chain, and short-chain perfluorocarboxylates (PFCAs) and perfluorosulfonates (PFSAs). Herein, quantitative and semiquantitative data for 43 legacy short-chain and ultra-short-chain PFASs (≤2 perfluorocarbon atoms for PFCAs, ≤3 for PFSAs and other PFASs) in 46 water samples collected from 13 different sources of German drinking water are presented. The PFASs considered include novel compounds like hexafluoroisopropanol, bis­(trifluoromethylsulfonyl)­imide, and tris­(pentafluoroethyl)­trifluorophosphate. The ultra-short-chain PFASs trifluoroacetate, perfluoropropanoate, and trifluoromethanesulfonate were ubiquitous and present at the highest concentrations (98% of sum target PFAS concentrations). “PFAS total” parameters like the adsorbable organic fluorine (AOF) and total oxidizable precursor (TOP) assay were found to provide only an incomplete picture of PFAS contamination in these water samples by not capturing these highly prevalent ultra-short-chain PFASs. These ultra-short-chain PFASs represent a major challenge for drinking water production and show that regulation in the form of preventive measures is required to manage them.

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Fragmentation flagging (FF), a high-resolution mass spectrometric screening variant that utilizes intentionally produced indicative in-source fragments, was used to screen for per-and polyfluoroalkyl substances (PFASs) in surface waters. Besides expected legacy PFAS, FF enabled the detection of some rarely investigated representatives, such as trifluoromethanesulfonic acid (TFMSA). Additionally, a novel PFAS was detected and identified as tris(pentafluoroethyl)trifluorophosphate (FAP) via MS/MS experiments and confirmed with a reference standard. The first monitoring of FAP in 20 different surface waters revealed a localized contamination affecting three connected rivers with peak concentrations of up to 3.4 μg/L. To the best of our knowledge, this is the first time FAP has been detected in environmental water samples. The detection of FAP, which is exclusively used as a constituent of ionic liquids (ILs), raises questions about the environmental relevance of ILs in general and particularly fluorinated ILs. A following comprehensive literature search revealed that ILs have already been intensely discussed as potential environmental contaminants, but findings reporting ILs in environmental (water) samples are almost non-existent. Furthermore, we address the relevance of ILs in the context of persistent, mobile, and toxic chemicals, which are at present gaining increasing scientific and regulatory interest, and as part of the PFAS "dark matter" that represents the gap between the amount of fluorine originating from known PFAS and the total adsorbable organically bound fluorine. Keywords (Fluorinated) ionic liquids . PFAS . HRMS . Fragmentation flagging . PM(T) substances Published in the topical collection Persistent and Mobile Organic Compounds -An Environmental Challenge with guest editors Torsten C.

Persistent, mobile, and toxic (PMT) and very persistent and very mobile (vPvM) substances have been recognized as a threat to both the aquatic environment and to drinking water resources. These substances are currently prioritized for regulatory action by the European Commission, whereby a proposal for the inclusion of hazard classes for PMT and vPvM substances has been put forward. Comprehensive monitoring data for many PMT/vPvM substances in drinking water sources are scarce. Herein, we analyze 34 PMT/vPvM substances in 46 surface water, groundwater, bank filtrate, and raw water samples taken throughout Germany. Results of the sampling campaign demonstrated that known PMT/vPvM substances such as 1Hbenzotriazole, melamine, cyanuric acid, and 1,4-dioxane are responsible for substantial contamination in the sources of German drinking water. In addition, the results revealed the widespread presence of the emerging substances 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and diphenylguanidine (DPG). A correlation analysis showed a pronounced co-occurrence of PMT/vPvM substances associated predominantly with consumer or professional uses and also demonstrated an inhomogeneous co-occurrence for substances associated mainly with industrial use. These data were used to test the hypothesis that most PMT/vPvM substances pass bank filtration without significant concentration reduction, which is one of the main reasons for introducing PMT/vPvM as a hazard class within Europe.