Mn­(VI) and Mn­(V) (Mn­(VI/V)) were reported to be reactive to organic contaminants containing electron-rich moieties and some inorganic contaminants. It remained unclear whether Mn­(VI/V) contributed to contaminant abatement by Mn­(VII). This study developed two methods (methanol method and kinetics method) to identify the contributions of Mn­(VI/V) during contaminant oxidation by Mn­(VII). It was verified that methanol was a suitable probe for Mn­(VI/V), and HCHO was the major oxidizing product of methanol. By determining the influence of methanol on the stoichiometric ratio of contaminant to Mn­(VII) and the generation of HCHO, Mn­(VI/V) were found to play a remarkable role during the abatement of As­(III), methyl phenyl sulfoxide (MPSO), 2,2′-azino-bis­(3-ethylbenzothiazoline-6-sulfonate), and phenol by Mn­(VII). However, Mn­(VI/V) scarcely contributed to carbamazepine degradation by Mn­(VII). The difference between the apparent second-order rate constant of MPSO oxidation by Mn­(VII) determined in the presence of excess MPSO and that determined in the presence of excess Mn­(VII) further verified the contributions of Mn­(VI/V) during MPSO degradation by Mn­(VII). Natural organic matter in real water samples could also induce the generation of Mn­(VI/V) and thus accelerate MPSO abatement by Mn­(VII). This study gained deep insights into the overlooked role of Mn­(VI/V) in contaminant abatement during the Mn­(VII) oxidation process.

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