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The environmental fate of per- and polyfluoroalkyl substances (PFAS) in aqueous film-forming foams (AFFFs), especially those synthesized by electrochemical fluorination (ECF) processes, remains largely unknown. This study evaluated the transformation of AFFF-derived ECF-based precursors in aerobic soil microcosms amended with a historically used AFFF formulation (3M Light Water). Fifteen classes of PFAS, including AFFF components and transformation products, were identified or tentatively identified by suspect screening/nontargeted analysis (SSA/NTA) throughout a 308-day incubation. This study demonstrates that AFFF-derived ECF-based precursors serve as sources of perfluoroalkane sulfonamides (FASAs) and perfluoroalkyl acids (PFAAs), which are commonly detected at AFFF-impacted sites. Temporal sampling provided evidence for biotransformation of multiple precursors including tri- or dimethyl ammonio propyl perfluoroalkane sulfonamides. Additionally, the environmental stability (i.e., resistance to transformation) of ECF-based precursors was found to depend upon structural characteristics, including perfluoroalkyl chain length, presence of sulfonamide or carboxamide groups, and functional groups (e.g., a branch of carboxyalkyl group) attached to the nitrogen atoms. These findings provide insights into the transformation pathways of AFFF-derived PFAS and other structurally similar ECF-based PFAS, which will support the management and remediation of PFAS contamination at legacy AFFF-impacted sites.
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http://dx.doi.org/10.1021/acs.est.4c08665 | DOI Listing |
Environ Sci Technol
December 2024
Department of Biological and Environmental Engineering, Cornell University, Ithaca, New York 14853, United States.
The environmental fate of per- and polyfluoroalkyl substances (PFAS) in aqueous film-forming foams (AFFFs), especially those synthesized by electrochemical fluorination (ECF) processes, remains largely unknown. This study evaluated the transformation of AFFF-derived ECF-based precursors in aerobic soil microcosms amended with a historically used AFFF formulation (3M Light Water). Fifteen classes of PFAS, including AFFF components and transformation products, were identified or tentatively identified by suspect screening/nontargeted analysis (SSA/NTA) throughout a 308-day incubation.
View Article and Find Full Text PDFEnviron Sci Technol
November 2022
Department of Civil and Environmental Engineering, University of California, Berkeley, California 94720, United States.
Sites impacted by aqueous film-forming foam (AFFF) contain co-contaminants that can stimulate biotransformation of polyfluoroalkyl substances. Here, we compare how microbial enrichments from AFFF-impacted soil amended with diethyl glycol monobutyl ether (found in AFFF), aromatic hydrocarbons (present in co-released fuels), acetate, and methane (substrates used or formed during bioremediation) impact the aerobic biotransformation of an AFFF-derived six-carbon electrochemical fluorination (ECF) precursor -dimethyl ammonio propyl perfluorohexane sulfonamide (AmPr-FHxSA). We found that methane- and acetate-oxidizing cultures resulted in the highest yields of identifiable products (38 and 30%, respectively), including perfluorohexane sulfonamide (FHxSA) and perfluorohexane sulfonic acid (PFHxS).
View Article and Find Full Text PDFEnviron Sci Technol
April 2021
Department of Civil Engineering, McGill University, Montreal, QC H3A 0C3, Canada.
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).
View Article and Find Full Text PDFAnal Bioanal Chem
February 2016
Department of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA, 02139, USA.