Importance of nitrate reduction in benthic carbon mineralization in two eutrophic estuaries Modeling, observations and laboratory experiments

Estuaries are important nutrient filters between rivers and coastal zones. However, the quantification of the nutrient mitigation capacity related to benthic diagenesis is still poorly quantified. In this paper, we investigated carbon mineralization and the contribution of benthic nitrate reduction in two macrotidal eutrophic estuaries (Elorn and Aulne, Brittany, France) during winter and spring. These anthropized estuaries exhibited large variations of bottom water nitrate concentrations from very high values in upstream waters (up to 500 ?M) to low values downstream (andlt; 10 ?M). Bottom water oxygen concentrations presented small gradients compared to nitrate concentrations gradients resulting in large variation in nitrate to oxygen ratios NOx ?/O2 between downstream and upstream (0.03–1.6). We combined the use of diagenesis modeling with field data (porosity, organic carbon and nitrogen, pore water profiles of dissolved oxygen, nitrogen, iron, manganese and sulfide concentrations, published in Khalil et al., 2013) and experimentally-determined nitrate reduction rates, in order to investigate the different organic carbon mineralization pathways in these estuarine sediments including denitrification and the contribution of benthic nitrate reduction to the estuarine N budget. Overall a good agreement between pore water data (organic carbon, oxygen, nitrate and ammonium) and model simulations was observed. The modeled organic matter mineralization rates were high in the upstream estuary and low in the saline estuary for the two estuaries Aulne and Elorn. This decrease may be related to the dilution and the trapping of allochtonous organic matter in estuarine sediments and its subsequent recycling in the upper estuary. Organic carbon mineralization rates were higher in the Elorn than in the Aulne estuary, which is most likely related to the labile character of the organic matter from urban origin exported from the Elorn watershed. The contribution of nitrate reduction to the total mineralization was generally high in upstream sediments (15–35%) of both Aulne and Elorn estuaries and decreased consistently downstream to 5–10%. The relative large contribution of nitrate reduction to organic matter degradation was to a large extent related to high bottom water nitrate concentrations that fueled 37–78% of total nitrate reduction in the upstream part of the estuaries. Overall, the reduction of bottom water nitrate by denitrification to N2 represented 3–13% of the river flux of nitrate in these estuaries in winter and spring, and could reach ~ 50% during summer. These results highlight that nitrate reduction in the sediment attenuate the high river nitrate flux, despite the huge quantities of anthropogenic nitrate discharged by the two rivers to the estuaries.