Stability of Nitrogen-Containing Polyfluoroalkyl Substances in Aerobic Soils.

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Zwitterionic per- and polyfluoroalkyl substances (PFASs) used in aqueous film-forming foams (AFFFs) could face diverse environmental fates once released at military bases, airports, fire-training areas, and accidental release sites. Here, we studied for the first time the transformation potential of four electrochemical fluorination (ECF)-based PFAS zwitterions (two carboxyl betaines and two tertiary amines) in aerobic soils. The two perfluoroalkyl sulfonamide derivatives were precursors to perfluorooctanesulfonate (PFOS), while the amide derivatives were precursors to perfluorooctane carboxylate (PFOA). These zwitterions and four other previously reported zwitterions or cations were compared for their transformation pathways and kinetics. Structural differences, especially the nitrogen head groups, largely influenced the persistence of these compounds in aerobic soils. The perfluoroalkyl sulfonamide-based compounds showed higher microbial stability than the corresponding perfluoroalkyl amide-based ones. Their stability in aerobic soils is ranked based on the magnitude of DT50 (time for 50% of substance to disappear): quaternary ammonium ≈ carboxyl betaine ≫ tertiary amine > amine oxide. The PFASs containing quaternary ammonium or betaine groups showed high stability in soils, with the longest DT50 likely to be years or decades, while those with tertiary amine or amine oxide groups showed DT50 of weeks or months. These eight ECF-based precursors provide insights into the degradation pathways and persistence in surface soils of other perfluoroalkyl cations and zwitterions present in AFFFs.