Simultaneously promoted reactive manganese species and hydroxyl radical generation by electro-permanganate with low additive ozone

•Electrolysis, permanganate, and O3 showed a satisfactory synergistic effect for various organics degradation.•Reactive manganese species (RMnS) and ·OH were the dominant reactive species in E-PM-O3 process.•1 mg L − 1 gaseous ozone dramatically promoted generating both RMnS and ·OH with even lower energy consumption.•In situ formed MnO2 played a critical role for generating both RMnS and ·OH.•·OH generated by O3 catalysis transfer colloid MnO2 to free mn (Ⅴ) and mn (Ⅵ) in the E-PM-O3 process. A novel water treatment process combining electrolysis, permanganate and ozone was tested in the laboratory. The combination showed synergistic effects in degrading various organic contaminants (like diclofenac, sulfamethoxazole, carbamazepine, etc.). A small amount of O3 (1 mg L−1, 60 mL min−1) significantly improved the oxidation and mineralization ability of an electro-permanganate process by generating more reactive manganese species and hydroxyl radicals. The combination required less energy consumption than comparable processes. Mechanism experiments showed that the ·OH involved was mainly generated by cathode reduction, homogeneous manganese catalysis, and heterogeneous manganese catalysis of O3 decomposition. Reactive Mn species were generated by electro-reduction, ·OH oxidation or/and O3 activation. In situ generated Mn (Ⅳ)s plays a vital role in generating ·OH and reactive Mn species. ·OH generated by O3 catalysis could transfer colloid Mn (Ⅳ)s to free Mn (Ⅴ)aq and Mn (Ⅵ) aq. And both the ·OH and RMnS played the dominant role for DCF removal. Increasing permanganate dosage, O3 concentration, the current density, Cl−, or humic acid, and decreasing the pH all enhanced the degradation of diclofenac, but the presence of PO43− or HCO3− inhibited it. Supplementing electrolysis with permanganate and O3 might be a practical, sustainable, and economical technology for treating refractory organics in natural waters. [Display omitted]