Novel solar-driven ferrate(VI) activation system for micropollutant degradation: Elucidating the role of Fe(IV) and Fe(V)

This paper presents a novel process of solar-ferrate(VI) [Fe(VI)] for micropollutant degradation. The solar-Fe(VI) process promoted micropollutant degradation compared with Fe(VI) alone and solar. The radical scavenging and probing experiment results suggested that Fe(V) and Fe(IV) but not reactive oxygen species were most likely involved in the solar-Fe(VI) process. Through building a kinetic model, Fe(IV) and Fe(V) were observed to play an equally significant role in the solar-Fe(VI) process. Afterward, the reaction mechanism of the photochemistry of Fe(VI) was elaborated. Fe(IV) formed from Fe(VI) photolysis and then decomposed to Fe(II) which reacted with Fe(VI) to form Fe(V). Furthermore, the effect of pH on carbamazepine (CBZ) degradation was studied and the quantum yields of Fe(VI) were determined, with (1.98 ± 0.16)× 10⁻³ mol∙einstein⁻¹, (5.90 ± 0.27)× 10⁻⁴ mol∙einstein⁻¹, and (1.66 ± 0.14)× 10⁻⁴ mol∙einstein⁻¹ at pH 7.0, 8.0, and 9.0, respectively. Inorganic ions, including Cl^-, HCO₃^-, and Br^- displayed negligible influence on the CBZ degradation, whereas humic acid inhibited the CBZ degradation. Finally, the solar-Fe(VI) process exhibited good applicability in authentic waters and under different irradiation (natural sunlight, ultraviolet light, and visible light from solar cut-off emission). Overall, this study provides a new routine for efficient micropollutant elimination and reveals the photochemistry of Fe(VI).