The efficient degradation of diclofenac by ferrate and peroxymonosulfate: performances, mechanisms, and toxicity assessment

In this study, the degradation efficiency and reaction mechanisms of diclofenac (DCF), a nonsteroidal anti-inflammatory drug, by the combination of ferrate (Fe(VI) and peroxymonosulfate (PMS) (Fe(VI)/PMS) were systematically investigated. The higher degradation efficiency of DCF in Fe(VI)/PMS system can be obtained than that in alone persulfate (PS), Fe(VI), PMS, or the Fe(VI)/PS process at pH 6.0. DCF was efficiently removed in Fe(VI)/PMS process within a wide range of pH values from 4.0 to 8.0, with higher degradation efficiency in acidic conditions. The increasing reaction temperature (10 to 30 ℃), Fe(VI) dose (6.25 to 100 µM), or PMS concentration (50 to 1000 µM) significantly enhanced the DCF degradation. The existences of HCO 3 ¯, Cl¯, and humic acid (HA) obviously inhibited the DCF removal. Electron paramagnetic resonance (EPR), free radical quenching, and probing experiments confirmed the existence of sulfate radicals (SO 4 • ¯), hydroxyl radicals ( • OH), and Fe(V)/ Fe(IV), which are responsible for DCF degradation in Fe(VI)/PMS system. The variations of TOC removal ratio reveal that the adsorption of organics with ferric particles, formed in the reduction of Fe(VI), also were functioned in the removal process. Sixteen DCF transformation byproducts were identified by UPLC-QTOF/MS, and the toxicity variation was evaluated. Consequently, eight reaction pathways for DCF degradation were proposed. This study provides theoretical basis for the utilization of Fe(VI)/PMS process. Graphical abstract