Efficient Reductive Decomposition of Perfluorooctanesulfonate in a High Photon Flux UV/Sulfite System

Hydrated electron (e_aq^-) induced reduction techniques are promising for decomposing recalcitrant organic pollutants. However, its vigorous reactivity with copresent scavenging species and the difficulty in minimizing the competitive reactions make the proportion of e_aq^- participating in pollutant decomposition low, reflecting by slow decomposition kinetics. In this study, a high photon flux UV/sulfite system was employed to promote e_aq^- production. Its feasibility in enhancing a notorious recalcitrant pollutant, PFOS, decomposition was investigated. The effective photon flux utilized for producing e_aq^- was 9.93 × 10^-8 einstein/cm²·s. At initial solution pH 9.2, with DO about 5 mg/L, and at around 25 °C, 98% PFOS was decomposed within 30 min from its initial concentration of 32 μM. The k_obs of PFOS decomposition was 0.118 min^-1 (7.08 h^-1), and about 8-400 folds faster than those obtained in other reductive approaches. In this system, PFOS decomposition showed can tolerate copresent 7 mg N/L of NO₃^-. Suggested by molecular orbitals and thermodynamic analyses, the mechanisms responsible for PFOS decomposition involve defluorination, desulfonation, and centermost C-C bond scission. By demonstrating a more practical relevant treatment process, the outcomes of this study would be helpful for facilitating future applications of e_aq^- induced reduction techniques for efficient recalcitrant pollutants decomposition.