Hydrologic and Organic Carbon Quality Controls on Nitrous Oxide Dynamics Across a Variably Confined Karst Aquifer

Atmospheric concentrations of the potent greenhouse gas nitrous oxide (N2O) have increased approximately 20% since the pre-industrial era. Riverine systems represent an important atmospheric source of N2O however, the influence of varying hydrogeological conditions and dissolved organic carbon (DOC) quantity and quality on N2O dynamics remains poorly understood. We investigate effects of these processes on N2O dynamics in the Santa Fe River watershed in north-central Florida, USA where a gradient in DOC quantity and quality is caused by varying surface water-groundwater exchange. The watershed is underlain by the karstic Floridan aquifer, which is confined in the headwaters and contains terrigenous recalcitrant DOC, while the unconfined lower reaches contain protein-like labile DOC substrates. Where extensive surface water-groundwater exchange occurs at the boundary between the confined and unconfined aquifer, incomplete denitrification raises N2O concentration to 6.1 mu g N-N2O L-1, approximately 20 times greater than the concentration expected from equilibration with atmospheric N2O. These elevated concentrations create average local fluxes reaching similar to 950 mu g N-N2O m(-2) hr(-1) within the mixing zone. Summation of spatially explicit emission estimates for upstream, mixing zone, and downstream river sections yield a total average emission rate of similar to 3,758 kg N-N2O yr(-1). Despite having the smallest surface area across the river transect (similar to 8%), emissions from the mixing zone account for 26% of the total river emission rate. These findings highlight the potential contributions from karst landscapes to N2O cycling caused by varying redox conditions during surface water-groundwater exchange, which creates hotspots of N2O production and emissions.