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Enhanced perfluorooctanoic acid (PFOA) degradation by electrochemical activation of peroxydisulfate (PDS) during electrooxidation for water treatment

MetadataDetails
Publication Date2024-06-04
JournalThe Science of The Total Environment
AuthorsMelvin S. Samuel, K. Govindan, Donald R. Ryan, Sean T. McBeath, Brooke K. Mayer
InstitutionsMarquette University, University of Massachusetts Amherst
Citations29

Improved treatment of per- and polyfluoroalkyl substances (PFAS) in water is critically important in light of the proposed United States Environmental Protection Agency (USEPA) drinking water regulations at ng L<sup>-1</sup> levels. The addition of peroxymonosulfate (PMS) during electrooxidation (EO) can remove and destroy PFAS, but ng L<sup>-1</sup> levels have not been tested, and PMS itself can be toxic. The objective of this research was to test peroxydisulfate (PDS, an alternative to PMS) activation by boron-doped diamond (BDD) electrodes for perfluorooctanoic acid (PFOA) degradation. The influence of PDS concentration, temperature, and environmental water matrix effects, and PFOA concentration on PDS-EO performance were systematically examined. Batch reactor experiments revealed that 99 % of PFOA was degraded and 69 % defluorination was achieved, confirming PFOA mineralization. Scavenging experiments implied that sulfate radicals (SO<sub>4</sub><sup>-</sup>) and hydroxyl radicals (HO) played a more important role for PFOA degradation than <sup>1</sup>O<sub>2</sub> or electrons (e<sup>-</sup>). Further identification of PFOA degradation and transformation products by liquid chromatography-mass spectrometry (LC-MS) analysis established plausible PFOA degradation pathways. The analysis corroborates that direct electron transfers at the electrode initiate PFOA oxidation and SO<sub>4</sub><sup>-</sup> improves overall treatment by cleaving the CC bond between the C<sub>7</sub>F<sub>15</sub> and COOH moieties in PFOA, leading to possible products such as C<sub>7</sub>F<sub>15</sub> and F<sup>-</sup>. The perfluoroalkyl radicals can be oxidized by SO<sub>4</sub><sup>-</sup> and HO, resulting in the formation of shorter chain perfluorocarboxylic acids (e.g., perfluorobutanoic acid [PFBA]), with eventual mineralization to CO<sub>2</sub> and F<sup>-</sup>. At an environmentally relevant low initial concentration of 100 ng L<sup>-1</sup> PFOA, 99 % degradation was achieved. The degradation of PFOA was slightly affected by the water matrix as less removal was observed in an environmental river water sample (91 %) compared to tests conducted in Milli-Q water (99 %). Overall, EO with PDS provided a destructive approach for the elimination of PFOA.

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