4.8 Article

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

Journal

ENVIRONMENTAL SCIENCE & TECHNOLOGY
Volume 57, Issue 2, Pages 997-1005

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.est.2c07399

Keywords

Intermediate manganese species; Autoaccelerating trend; Linear trend; Oxidation kinetics; Permanganate

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This study investigates the role of MnO2 colloids and Mn(III) in the oxidation process of Mn(VII) with organic pollutants. The results show that the oxidation of phenolic contaminants by Mn(VII) exhibits an autoaccelerating trend, which is attributed to the oxidation of the organics by MnO2 colloids. The influence of pyrophosphate suggests that Mn(III) is also responsible for the autoaccelerating oxidation under specific conditions. The overall contribution of MnO2 colloids and Mn(III) ranges from 6.6% to 67.9% during the oxidation process.
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 (kapp) 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.

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