PMID- 37223990 OWN - NLM STAT- MEDLINE DCOM- 20231129 LR - 20240224 IS - 1520-5851 (Electronic) IS - 0013-936X (Print) IS - 0013-936X (Linking) VI - 57 IP - 47 DP - 2023 Nov 28 TI - Oxidation of Per- and Polyfluoroalkyl Ether Acids and Other Per- and Polyfluoroalkyl Substances by Sulfate and Hydroxyl Radicals: Kinetic Insights from Experiments and Models. PG - 18970-18980 LID - 10.1021/acs.est.3c00947 [doi] AB - Per- and polyfluoroalkyl substances (PFAS) are widely used anthropogenic chemicals. Because of the strength of the carbon-fluorine bond, PFAS are not destroyed in typical water treatment processes. Sulfate (SO(4)(*-)) and hydroxyl ((*)OH) radicals can oxidize some PFAS, but the behavior of per- and polyfluoroalkyl ether acids (PFEAs) in processes involving SO(4)(*-) and (*)OH is poorly understood. In this study, we determined second-order rate constants (k) describing the oxidation of 18 PFAS, including 15 novel PFEAs, by SO(4)(*-) and (*)OH. Among the studied PFAS, 6:2 fluorotelomer sulfonate reacted most readily with (*)OH [k(*OH) = (1.1-1.2) x 10(7) M(-1) s(-1)], while polyfluoroalkyl ether acids containing an -O-CFH- moiety reacted more slowly [k(*OH) = (0.5-1.0) x 10(6) M(-1) s(-1)]. In the presence of SO(4)(*-), polyfluoroalkyl ether acids with an -O-CFH- moiety reacted more rapidly [k(SO4)(*-) = (0.89-4.6) x 10(6) M(-1) s(-1)] than perfluoroalkyl ether carboxylic acids (PFECAs) and a chloro-perfluoro-polyether carboxylic acid (ClPFPECA) [k(SO4)(*-) = (0.85-9.5) x 10(4) M(-1) s(-1)]. For homologous series of perfluoroalkyl carboxylic acids, linear and branched monoether PFECAs, and multiether PFECAs, PFAS chain length had little impact on second-order rate constants. SO(4)(*-) reacted with the carboxylic acid headgroup of perfluoroalkyl carboxylic acids and PFECAs. In contrast, for polyfluoroalkyl ether carboxylic and sulfonic acids with an -O-CFH- moiety, the site of SO(4)(*-) attack was the -O-CFH- moiety. Perfluoroalkyl ether sulfonic acids were not oxidized by SO(4)(*-) and (*)OH under the conditions evaluated in this study. FAU - Zhang, Chuhui AU - Zhang C AUID- ORCID: 0000-0001-9686-0416 AD - Department of Civil, Construction, and Environmental Engineering, North Carolina State University, Raleigh, North Carolina 27695, United States. FAU - Tang, Tiffany AU - Tang T AD - Department of Civil, Construction, and Environmental Engineering, North Carolina State University, Raleigh, North Carolina 27695, United States. FAU - Knappe, Detlef R U AU - Knappe DRU AUID- ORCID: 0000-0003-1315-1791 AD - Department of Civil, Construction, and Environmental Engineering, North Carolina State University, Raleigh, North Carolina 27695, United States. AD - Center for Human Health and the Environment, North Carolina State University, Raleigh, North Carolina 27695, United States. LA - eng GR - P42 ES031009/ES/NIEHS NIH HHS/United States PT - Journal Article DEP - 20230524 PL - United States TA - Environ Sci Technol JT - Environmental science & technology JID - 0213155 RN - 0 (ammonium 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)-propanoate) RN - 0F5N573A2Y (Ether) RN - 0 (fluorotelomer sulfonic acids) RN - 3352-57-6 (Hydroxyl Radical) RN - 0 (Sulfates) RN - 0 (Fluorocarbons) RN - 0 (Ethers) RN - 0 (Sulfonic Acids) RN - 0 (Carboxylic Acids) RN - 0 (Water Pollutants, Chemical) SB - IM MH - Ether MH - Hydroxyl Radical MH - Sulfates MH - *Fluorocarbons/analysis MH - Ethers MH - Sulfonic Acids MH - Carboxylic Acids MH - *Water Pollutants, Chemical/analysis PMC - PMC10667564 MID - NIHMS1929684 OTO - NOTNLM OT - GenX OT - Nafion byproduct 2 OT - PFAS destruction OT - fluoroethers OT - photolysis EDAT- 2023/05/24 19:13 MHDA- 2023/11/29 06:42 PMCR- 2024/02/23 CRDT- 2023/05/24 12:04 PHST- 2023/11/29 06:42 [medline] PHST- 2023/05/24 19:13 [pubmed] PHST- 2023/05/24 12:04 [entrez] PHST- 2024/02/23 00:00 [pmc-release] AID - 10.1021/acs.est.3c00947 [doi] PST - ppublish SO - Environ Sci Technol. 2023 Nov 28;57(47):18970-18980. doi: 10.1021/acs.est.3c00947. Epub 2023 May 24.