A review of the occurrence and microbial transformation of per- and polyfluoroalkyl substances (PFAS) in aqueous film-forming foam (AFFF)-impacted environments

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Aqueous film-forming foams (AFFFs) have been extensively used for extinguishing hydrocarbon-fuel fires at military sites, airports, and fire-training areas. Despite being a significant source of per- and polyfluoroalkyl substances (PFAS), our understanding of PFAS occurrence in AFFF formulations and AFFF-impacted environments is limited, as is the impact of microbial transformation on the environment fate of AFFF-derived PFAS. This literature review compiles PFAS concentrations in electrochemical fluorination (ECF)- and fluorotelomer (FT)-based AFFFs and provides an overview of PFAS occurrence in AFFF-impacted environments. Our analysis reveals that AFFF use is a predominant point source of PFAS contamination, including primary precursors (polyfluoroalkyl substances as AFFF components), secondary precursors (polyfluoroalkyl transformation products of primary precursors), and perfluoroalkyl acids (PFAAs). Moreover, there are discrepancies between PFAS concentration profiles in AFFFs and those measured in AFFF-impacted media. For example, primary precursors constitute 52.6 % and 99.5 % of PFAS mass in ECF- and FT-based AFFFs, respectively, whereas they represent only 0.7 % total mass in AFFF-impacted groundwater. Conversely, secondary precursors, which constitute <1 % of PFAS in AFFFs, represent 4.0–27.8 % of PFAS in AFFF-impacted environments. The observed differences in PFAS levels between AFFFs and environmental samples are likely due to in-situ biotransformation processes. Biotransformation rates and pathways reported for AFFF-derived primary and secondary precursors varied among different classes of precursors, consistent with the PFAS occurrence in AFFF-impacted environments. For example, readily biodegradable primary precursors, N-dimethyl ammonio propyl perfluoroalkane sulfonamide (AmPr-FASA) and n:2 fluorotelomer thioether amido sulfonate (n:2 FtTAoS), were rarely detected in AFFF-impacted environments. In contrast, key secondary precursors, perfluoroalkane sulfonamides (FASAs) and n:2 fluorotelomer sulfonate (n:2 FTS), were widely detected, which was attributed to their resistance to biotransformation. Key knowledge gaps and future research priorities are presented to better understand the occurrence, fate, and transport of AFFF-derived PFAS in the environment and to design more effective remediation strategies.