Sulfite

Sulfonic acid

Inorganic chemistry

Perfluorooctanoic acid

Organic chemistry

Environmental chemistry

Aqueous solution

Chemistry

Environmental Science & Technology

Ultraviolet photochemical reaction of sulfite (SO32–) photosensitizer generates strongly reducing hydrated electrons (eaq–; NHE = −2.9 V) that have been shown to effectively degrade individual per- and polyfluoroalkyl substances (PFASs), including perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). However, treatment of complex PFAS mixtures in aqueous film-forming foam (AFFF) remains largely unknown. Here, UV-sulfite was applied to a diluted AFFF to characterize eaq– reactions with 15 PFASs identified by liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) targeted analysis. Results show that reactivity varies widely among PFASs, but reaction rates observed for individual PFASs in AFFF are similar to rates observed in single-solute experiments. While some structures, including long-chain perfluoroalkyl sulfonic acids (PFSAs) and perfluoroalkyl carboxylic acids (PFCAs) were readily degraded, other structures, most notably short-chain PFSAs and fluorotelomer sulfonic acids (FTSs), were more recalcitrant. This finding is consistent with results showing incomplete fluoride ion release (up to 53% of the F content in AFFF) during reactions. Furthermore, results show that selected PFSAs, PFCAs, and FTSs can form as transient intermediates or unreactive end-products via eaq– reactions with precursor structures in AFFF. These results indicate that while UV-sulfite treatment can be effective for treating PFOS and PFOA to meet health advisory levels, remediation of the wider range of PFASs in AFFF will prove more challenging.

Destruction of Per- and Polyfluoroalkyl Substances (PFASs) in Aqueous Film-Forming Foam (AFFF) with UV-Sulfite Photoreductive Treatment