Byproducts produced when treating perfluorooctanoic acid (PFOA) and perfluorooctanesulfonate (PFOS) in water using a plasma treatment process intentionally operated to treat these compounds slowly to allow for byproduct accumulation were quantified. Several linear chain perfluoroalkyl carboxylic acids (PFCAs) (C4 to C7) were identified as byproducts of both PFOA and PFOS treatment. PFOA, perfluorohexanesulfonate (PFHxS), and perfluorobutanesulfonate (PFBS) were also found to be byproducts from PFOS degradation. Significant concentrations of fluoride ions, inorganic carbon, and smaller organic acids (trifluoroacetic acid, acetic acid, and formic acid) were also identified. In addition to PFCAs, PFHxS, and PFBS, trace amounts of 43 PFOA-related and 35 PFOS-related byproducts were also identified using a screening and search-based algorithm. Minor concentrations of gas-phase byproducts were also identified (<2.5% of the F originally associated with the parent molecules) some of which are reported for the first time in perfluoroalkyl substance degradation experiments including cyclic perfluoroalkanes (C₄F₈, C₅F₁₀, C₆F₁₂, C₇F₁₄, and C₈F₁₆). The short chain PFCAs detected suggest the occurrence of a stepwise reduction of the parent perfluoroalkyl substances (PFAS) molecule, followed by oxidation of intermediates, perfluoroalkyl radicals, and perfluoro alcohols/ketones. Using a fluorine mass balance, 77% of the fluorine associated with the parent PFOA and 58% of the fluorine associated with the parent PFOS were identified. The bulk of the remaining fluorine was determined to be sorbed to reactor walls and tubing using sorption experiments in which plasma was not generated.

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