Roles of MnO₂ Colloids and Mn(III) during the Oxidation of Organic Contaminants by Permanganate

Although intermediate manganese species can be generated during the reactions of permanganate (Mn(VII)) with organic pollutants in water, the role of the in situ generated MnO₂ colloids in the Mn(VII) oxidation process remained controversial and the contribution of Mn(III) was largely neglected. This study showed that the apparent second-order rate constants (k_app) of Mn(VII) oxidation of methyl phenyl sulfoxide and carbamazepine remained constant with time. However, the degradation of four selected phenolic contaminants by Mn(VII) exhibited an autoaccelerating trend and a linear trend at pH 3.0-6.0 and pH 7.0-9.0, respectively. Multiple lines of evidence revealed that the occurrence of the autoaccelerating trend in the Mn(VII) oxidation process was ascribed to the oxidation of the phenolic organics by MnO₂ colloids. The influence of pyrophosphate on the oxidation of different organic contaminants by MnO₂ colloids suggests that Mn(III) was also responsible for the autoaccelerating oxidation of organic contaminants by Mn(VII) under specific reaction conditions. The kinetic models revealed that the overall contributions of MnO₂ colloids and Mn(III) ranged within 6.6-67.9% during the autoaccelerating oxidation of phenolic contaminants by Mn(VII). These findings advance the understanding of the roles of MnO₂ colloids and Mn(III) in the Mn(VII) oxidation process.