Enhancing ammonia oxidation mediated using different crystalline Mn-oxides in an anoxic environment

A recent study found that the nitrogen cycle in marine sediments can occur under oxygen-limited conditions, and this is associated with a reduction of Mn (IV). However, the effect of MnO2 mediated anoxic ammonia oxidation in different sediments field test results are controversial. In this study, based on the fact that the crystal form and morphology of MnO2 in marine sediments are affected by geochemistry, α-, β-, γ-MnO2 and amorphous MnO2 were prepared to explore the effect of the different MnO2 crystals on nitrogen removal under oxygen-limited conditions. The experimental results showed that the anoxic ammonia oxidation process was mediated by microorganisms, and the reaction was affected by pH and temperature. The optimal pH was 7 in the range of pH 4–9 and the optimal temperature was 25 °C in the range of 10 °C–40 °C. When the initial concentration of NH4+-N was 50 mg/L, the removal amounts of NH4+-N under an anoxic condition by α-, β-, γ-MnO2 and amorphous MnO2 were 18.97 mg/L/d, 6.12 mg/L/d, 10.68 mg/L/d and 24.89 mg/L/d, respectively. During the anoxic oxidation between MnO2 and NH4+-N, the adsorption process occurred. In addition, the oxidation process produced both NOx−-N (nitrification reaction) and gaseous nitrogen (ammonia oxidation reaction). The kinetic study showed that the NH4+-N removal process conformed to the pseudo-second-order rate model, and the removal rates were ranked as amorphous MnO2 > α- > γ- > β-MnO2. Together, these results showed that the amorphous MnO2 crystal structure was conducive to improve anoxic ammonia oxidation and nitrogen removal under oxygen-limited conditions. •Microbial mediated ammonia oxidation was improved in the presence of MnO2.•Anoxic ammonia oxidation was affected by different crystal forms of MnO2.•Amorphous MnO2 rapidly removed NH4+-N under anoxic conditions and reached 30 mg/L.•MnO2 mediated anoxic ammonia oxidation included adsorption and oxidation processes.