Catalytic oxidation of Mn(II) in the co-presence of Fe(II) by free chlorine: significance of in situ formed Mn(II)-doped Fe(III) oxides

Fe(II) and Mn(II) are abundant in groundwater and require operationally simple and efficient method to remove in drinking water treatment. The rapid oxidation of Mn(II) is essential in water treatment. This study investigates the efficiency of Mn(II) oxidation by free chlorine in the presence of Fe(II). The results demonstrate that the presence of Fe(II) significantly accelerates the oxidation rate of Mn(II) by free chlorine under neutral and alkaline conditions. The rapid oxidation of Fe(II) by free chlorine and the presence of Mn(II) promote the formation of in situ Mn(II)-doped ferrihydrite. Kinetic modeling and characterization of Fe(III) oxides confirm that the heterogeneous catalytic effect of the Mn(II)-doped ferrihydrite, rather than manganese oxides or their coupled catalytic effect, is responsible for the enhanced oxidation rates. The doped Mn(II) substitutes the tetrahedral Fe(III) ions in the ferrihydrite, introducing additional negative charges at the doped sites. The increased charge enhances Mn(II) adsorption and lowers its redox potential, thereby accelerating Mn(II) oxidation rate through direct electron transfer with adjacent free chlorine. Additionally, the lepidocrocite formed by the reaction between Fe(II) and dissolved oxygen significantly impedes the catalytic performance. These findings provide new insights into the catalytic co-oxidation mechanism of Fe(II) and Mn(II), and help the optimization of water treatment engineering practices.