Accelerated Degradation of Perfluorosulfonates and Perfluorocarboxylates by UV/Sulfite + Iodide: Reaction Mechanisms and System Efficiencies

[Image: see text] The addition of iodide (I(–)) in the UV/sulfite system (UV/S) significantly accelerated the reductive degradation of perfluorosulfonates (PFSAs, C(n)F(2n+1)SO(3)(–)) and perfluorocarboxylates (PFCAs, C(n)F(2n+1)COO(–)). Using the highly recalcitrant perfluorobutane sulfonate (C(4)F(9)SO(3)(–)) as a probe, we optimized the UV/sulfite + iodide system (UV/S + I) to degrade n = 1–7 PFCAs and n = 4, 6, 8 PFSAs. In general, the kinetics of per- and polyfluoroalkyl substance (PFAS) decay, defluorination, and transformation product formations in UV/S + I were up to three times faster than those in UV/S. Both systems achieve a similar maximum defluorination. The enhanced reaction rates and optimized photoreactor settings lowered the EE/O for PFCA degradation below 1.5 kW h m(–3). The relatively high quantum yield of e(aq)(–) from I(–) made the availability of hydrated electrons (e(aq)(–)) in UV/S + I and UV/I two times greater than that in UV/S. Meanwhile, the rapid scavenging of reactive iodine species by SO(3)(2–) made the lifetime of e(aq)(–) in UV/S + I eight times longer than that in UV/I. The addition of I(–) also substantially enhanced SO(3)(2–) utilization in treating concentrated PFAS. The optimized UV/S + I system achieved >99.7% removal of most PFSAs and PFCAs and >90% overall defluorination in a synthetic solution of concentrated PFAS mixtures and NaCl. We extended the discussion over molecular transformation mechanisms, development of PFAS degradation technologies, and the fate of iodine species.