Isotopic evidence for alteration of nitrous oxide emissions and producing pathways contribution under nitrifying conditions

Abstract. Nitrous oxide (N2O) emissions by a nitrifying biofilm reactor were investigated with N2O isotopocules. The site preference of N2O (15N-SP) indicated the contribution of producing and consuming pathways in response to changes in oxygenation level (from 0 to 21 % O2 in the gas mix), temperature (from 13.5 to 22.3 °C), and ammonium concentrations (from 6.2 to 62.1 mg N L−1). Nitrite reduction, either nitrifier-denitrification or heterotrophic denitrification, was the main N2O producing pathway under the tested conditions. Nitrite oxidation rates decreased as compared to ammonium oxidation rates at temperatures above 20 °C and sub-optimal oxygen levels, increasing N2O production by the nitrite reduction pathway. Below 20 °C, a difference in temperature sensitivity between hydroxylamine and ammonium oxidation rates is most likely responsible for an increase in the N2O production via the hydroxylamine oxidation pathway (nitrification). A negative correlation between the reaction kinetics and the apparent isotope fractionation was additionally shown from the variations of δ15N and δ18O values of N2O produced from ammonium.