Monitoring contamination from per- and polyfluoroalkyl substances (PFASs) in water systems impacted by aqueous film-forming foams (AFFFs) typically addresses a few known PFAS groups. Given the diversity of PFASs present in AFFFs, current analytical approaches do not comprehensively address the range of PFASs present in these systems. A suspect-screening and nontarget analysis (NTA) approach was developed and applied to identify novel PFASs in groundwater samples contaminated from historic AFFF use. A total of 88 PFASs were identified in both passive samplers and grab samples, and these were dominated by sulfonate derivatives and sulfonamide-derived precursors. Several ultrashort-chain (USC) PFASs (≤C3) were detected, 11 reported for the first time in Australian groundwater. Several transformation products were identified, including perfluoroalkane sulfonamides (FASAs) and perfluoroalkane sulfinates (PFASis). Two new PFASs were reported (((perfluorohexyl)sulfonyl)sulfamic acid; m/z 477.9068 and (E)-1,1,2,2,3,3,4,5,6,7,8,8,8-tridecafluorooct-6-ene-1-sulfonic acid; m/z 424.9482). This study highlights that several PFASs are overlooked using standard target analysis, and therefore, the potential risk from all PFASs present is likely to be underestimated.
Keywords: groundwater; high-resolution mass spectrometry; passive sampling; ultrashort-chain PFAS.