Nontarget and Suspect Screening of Fluorinated Ionic Liquids and PFAS in European Wastewaters Using Supercritical Fluid Chromatography

Per- and polyfluoroalkyl substances (PFAS) and fluorinated ionic liquids were investigated in municipal effluents from 30 wastewater treatment plants (WWTPs) across 15 European countries using supercritical fluid chromatography–high-resolution mass spectrometry (SFC-HRMS) for nontarget screening. Bis-perfluoroalkyl sulfonimide (bis-FASI) ionic liquids were detected as bis(trifluoromethanesulfonyl)imide (NTf₂^–), two rarely reported homologues (±2 CF₂, namely FSI^– and BETI^–), and two previously unreported homologues (±1 CF₂, namely FTFSI^– and FTNTf₂^–). Bis-FASIs were present in 85% of samples and were more abundant in effluents from larger WWTPs. The fluorinated anion PF₆^–, commonly used in ionic liquids, was found in all samples (≤3 μg/L). Hexafluoroarsenate (AsF₆^–), reported here for the first time in municipal wastewater, was detected in 32% of samples in eight countries. PF₆^– and AsF₆^– concentrations exceeded those of traditional PFSAs and PFCAs in 97% of the samples. No removal was detected for perfluorinated compounds, inorganic anions, and low-fluorinated pharmaceuticals and pesticides. Low-fluorinated substances were detected in 90% of samples (>100 ng/L), yet PF₆^– alone surpassed the combined concentration of all low-fluorinated substances in 27 out of 30 samples. These results reveal the significance of unconventional fluorinated substances for the overall fluorine load in wastewater, highlighting the need to extend monitoring strategies beyond legacy PFAS.