Chemical nitrite oxidation in acid solutions as a consequence of microbial ammonium oxidation

In long-term experiments with membrane aerated biofilm reactors we observed complete nitrite oxidation in highly concentrated ammonium nitrite solutions with a contaminant pH decrease to values below 3. The maximum initial concentration for ammonium was 42 mM and for nitrite was 41 mM. We hypothesized that (1) acid-tolerant ammonium oxidizing bacteria were responsible for the pH decrease, and (2) chemical processes caused complete nitrite oxidation at low pH values. To test this hypothesis we set up a mechanistic computer model based on kinetic data from literature and we validated the model with additional experiments. The simulations fitted the measurements very well. Additionally, an experiment with the inhibitor allylthiourea showed that ammonium-oxidizing bacteria were active at pH values far below 5.5. Experiments in a sterile reactor confirmed the chemical nitrite oxidation to nitrate. Nitrogen balances revealed that 8 +/- 4% of the initial nitrogen (ammonium, nitrite, and nitrate) were lost during the cycles. On the basis of measurements and simulations we concluded that volatilization was responsible for the significant nitrogen loss. We estimated that about half of the lost nitrogen volatilized as nitrous acid HNO2. The rest mainly volatilized as dinitrogen N2 and nitrous oxide N2O.