Despite the prevalence of nitrate reduction in groundwater, the biotransformation of per- and polyfluoroalkyl substances (PFAS) under nitrate-reducing conditions remains mostly unknown compared with aerobic or strong reducing conditions. We constructed microcosms under nitrate-reducing conditions to simulate the biotransformation occurring at groundwater sites impacted by aqueous film-forming foams (AFFFs). We investigated the biotransformation of 6:2 fluorotelomer thioether amido sulfonate (6:2 FtTAoS), a principal PFAS constituent of several AFFF formulations using both quantitative liquid chromatography-tandem mass spectrometry (LC-MS/MS) and qualitative high-resolution mass spectrometry analyses. Our results reveal that the biotransformation rates of 6:2 FtTAoS under nitrate-reducing conditions were about 10 times slower than under aerobic conditions, but about 2.7 times faster than under sulfate-reducing conditions. Although minimal production of 6:2 fluorotelomer sulfonate and the terminal perfluoroalkyl carboxylate, perfluorohexanoate was observed, fluorotelomer thioether and sulfinyl compounds were identified in the aqueous samples. Evidence for the formation of volatile PFAS was obtained by mass balance analysis using the total oxidizable precursor assay and detection of 6:2 fluorotelomer thiol by gas chromatography-mass spectrometry. Our results underscore the complexity of PFAS biotransformation and the interactions between redox conditions and microbial biotransformation activities, contributing to the better elucidation of PFAS environmental fate and impact.
Keywords: Lodyne; anaerobic microcosms; aqueous film-forming foams (AFFFs); fluorotelomer biotransformation; mass spectrometry; microbial biotransformation; nitrate reduction; organothiol; per- and polyfluoroalkyl substances (PFAS).