Increased rates of dissimilatory nitrate reduction to ammonium (DNRA) under oxic conditions in a periodically hypoxic estuary

The Yarra River Estuary is a salt wedge estuary prone to hypoxia in the bottom waters during low flow periods. Rates of denitrification and dissimilatory nitrate reduction to ammonium (DNRA) were quantified using N-15 in relation to oxygen, nitrate and available reductants. Denitrification was the dominant nitrate reduction pathway under all oxygen conditions, however, DNRA increased from < 1% under hypoxic conditions (< 50 mu mol L-1 O-2) to similar to 18% of total nitrate reduction under oxygen saturation in the water column in intact core incubations. Microprofiles of nitrate reduction pathways in intact cores using diffusive equilibrium in thin layer (DET) gels showed significant rates of DNRA only occurred under oxic conditions in the presence of Fe2+. Cores incubated anoxically, developed free sulfide within the porewater, had very low concentrations of Fe2+ and low rates of DNRA. Slurry incubations with varying concentrations of NO3- showed that denitrifying bacteria had a higher affinity than nitrate ammonifying bacteria with K-m values of 49 and 86 mu mol L-1 for denitrification and DNRA, respectively, however, this could not explain the change in the rates of DNRA relative to denitrification observed. Further slurry incubations to investigate the relationship between DNRA and Fe2+ oxidation were inconclusive and complicated by very high backgrounds of sorbed (HCl extractable) Fe2+. Addition of Fe2+ to the slurry did not stimulate denitrification compared to a control (no Fe2+ addition), however, there was a significant decrease in the Fe2+ concentration over the period where DNRA occurred in the Fe2+ addition treatment, and no significant decrease in the control treatment. The ratio of DNRA to Fe2+ consumption was 15 +/- 6 and 7 +/- 3 for the Fe2+ and control treatments, respectively. We suggest reduced rates of DNRA under anoxic conditions can be explained by the binding of Fe2+ with free sulfides and the formation of FeS removing available Fe2+ for DNRA. (C) 2014 Elsevier Ltd. All rights reserved.