Alteration of birnessite reactivity in dynamic anoxic/oxic environments

Abstract

Although the oxidative capacity of manganese oxides has been widely investigated, potential changes of the surface reactivity in dynamic anoxic/oxic environments have been often overlooked. In this study, we showed that the reactivity of layer structured manganese oxide (birnessite) was highly sensitive to variable redox conditions within environmentally relevant ranges of pH (4.0 - 8.0), ionic strength (0-100 mM NaCl) and Mn(II)/MnO₂ molar ratio (0-0.58) using ofloxacine (OFL), a typical antibiotic, as a target contaminant. In oxic conditions, OFL removal was enhanced relative to anoxic environments under alkaline conditions. Surface-catalyzed oxidation of Mn(II) enabled the formation of more reactive Mn(III) sites for OFL oxidation. However, an increase in Mn(II)/MnO₂ molar ratio suppressed MnO₂ reactivity, probably because of competitive binding between Mn(II) and OFL and/or modification in MnO₂ surface charge. Monovalent cations (e.g., Na⁺) may compensate the charge deficiency caused by the presence of Mn(III), and affect the aggregation of MnO₂ particles, particularly under oxic conditions. An enhancement in the removal efficiency of OFL was then confirmed in the dynamic two-step anoxic/oxic process, which emulates oscillating redox conditions in environmental settings. These findings call for a thorough examination of the reactivity changes at environmental mineral surfaces (e.g., MnO₂) in natural systems that may be subjected to alternation between anaerobic and oxygenated conditions.

Keywords: Antibiotics; Manganese oxide; Oxidation; Redox; Removal.