Coupling Key Transport and Reaction Kinetics to Evaluate the Nitrate Source-Sink Function of Groundwater-Surface Water Environments

Groundwater-surface water exchange environments, including groundwater discharge to coastal ecosystems, are characterized by strong hydrological and biogeochemical gradients. These gradients control the fate and transport of important ecosystem solutes, such as biologically-available nitrogen (N) and carbon. However, it is difficult to quantify the spatiotemporal coupling of these physical and biogeochemical gradients. Our recent investigations of N in groundwater-surface water environments (GSEs) help determine the relative role of these physical and biogeochemical controls across a range of temporal and spatial scales. For example, we used an advection, dispersion, and residence time model coupled with multiple Monod kinetic models to simulate the GSE concentrations of oxygen (O2), ammonium (NH4), nitrate (NO3), and dissolved organic carbon (DOC). This modeling showed how physical transport and biogeochemical reaction kinetics couple in GSEs to control the fate of NO3. Further, we examined coupled nitrification-denitrification (N source-sink) dynamics across many scales of transport and reaction conditions with global Monte Carlo sensitivity analyses and a nondimensional form of the models. Results demonstrated that the residence time of water in the GSE and the uptake rate of O2 from either respiration and/or nitrification determined whether the GSE was a source or a sink of NO3 to the surface waters. We further show that whether the GSE is a net NO3 source or net NO3 sink is determined by the ratio of the characteristic transport time to the characteristic reaction time of O2 (i.e., the Damköhler number, DaO2), where GSEs with DaO2 < 1 will be net nitrification environments and GSEs with DaO2 >> 1 will be net denitrification environments. Previous investigations of N dynamics variously identified stream GSEs as either a net source or sink of NO3. Our coupling of the hydrological and biogeochemical limitations of N transformations across different temporal and spatial scales within the GSE of streams allows us to explain the mechanisms behind these widely contrasting results. Our modeling results suggest that only estimates of residence times and O2 uptake rates are necessary to predict this nitrification-denitrification threshold in many types of GSE systems. Ultimately, the DaO2 approach could be an elegant method for determining if freshwater and coastal GSEs will function as either a net source or sink of NO3.