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A novel "ferrate/percarbonate (Fe(VI)/SPC) co-oxidation process" was used to treat ciprofloxacin (CIP) and various micropollutants (MPs), which owned better performance than mixture of Fe(VI), Na 2 CO 3 and H 2 O 2. The mechanism investigation found that the low-concentration H 2 O 2 (1–2 µM) released by SPC can promote the high-valent iron intermediates (Fe(IV)/Fe(V)) of Fe(VI) to the MP oxidation, and Fe(VI) products can also activate SPC to produce hydroxyl radical (·OH). The interactive activation of Fe(VI) and SPC was realized, which retained the high selectivity of Fe(VI) to electron-rich pollutants, and also made up the oxidation of electron-deficient pollutants through •OH, improving the degradation effect of various MPs by 20–30%, and the rate constant was increased by 1 to 3 times. Moreover, non-purgeable organic carbon (NPOC) determination confirmed that •OH participation reduced the NPOC value of CIP from 5.43 mg/L to 4.37 mg/L. The transformation pathway of CIP showed that Fe(VI)/SPC resulted in more hydroxylation intermediates of CIP than Fe(VI) alone. Acute toxicity assays found that the photoinhibition rate of CIP treated with Fe(VI) alone was 14.5%, while the sample treated with Fe(VI)/SPC showed no significant photoinhibition effect, which proved that the new process had good detoxification properties for CIP. [Display omitted] • The interaction between SPC and Fe(VI) formed both·OH and Fe(IV)/Fe(V). • Low-concentration H 2 O 2 released by SPC improved the electron utilization of Fe(VI). • The·OH enables CIP to generate hydroxylation products possessing reduced toxicity. • SPC/Fe(VI) process is suitable for oxidation of electron rich and electron deficient pollutants. [ABSTRACT FROM AUTHOR]