Impact of dissolved O₂ on phenol oxidation by δ-MnO₂

Although redox reactions of organic contaminants with manganese oxides have been extensively studied, the role of dissolved O2 in these processes has largely been overlooked. In this study, the oxidative degradation of phenol by δ-MnO2 was investigated under both oxic and anoxic conditions. Dissolved O2 inhibited phenol degradation due to its promoting role in the reoxidation and precipitation of reduced Mn(ii) to Mn(iii) on the δ-MnO2 surface, resulting in partial transformation of δ-MnO2 to "c-disordered" H+-birnessite at pH 5.5 and feitknechtite, manganite, and hausmannite at pH 7.0 and 8.5. The reformed Mn(iii) phases could reduce phenol oxidation by blocking reactive sites of δ-MnO2. In addition, dissolved O2 caused a higher degree of particle agglomeration and a more severe specific surface area decrease, and hence lower reactivity of δ-MnO2. These findings revealed that after reductive dissolution by phenol and reoxidation by dissolved O2 throughout continuous redox cycling, δ-MnO2 became less reactive rather than being regenerated. These results can provide new insights into the understanding of the oxidation of organic contaminants by manganese oxides in the natural environment.