Porewater nitrate profiles in sandy sediments hosting submarine groundwater discharge described by an advection-dispersion-reaction model

In order to separate the effects of reaction from those of transport on vertical porewater concentration profiles of nitrate at an intertidal groundwater seepage site (Ria Formosa, Portugal), a free-boundary solution of an Advection-Dispersion-Reaction (ADR) model was used to describe the shape of NO concentration profiles collected in situ. The model includes three sequential reaction layers, postulated with basis on the local distribution of the benthic organic C:N ratio and major identifiable changes in concentration gradients with depth. The advective nature of the system was used to propose a mass balance simplification to the constitutive equations permitting a free-boundary solution, which in turn allowed prediction of sediment-water fluxes of NO. Sensitivity analysis confirmed that in similarly advective-dominated environments, both the porewater concentration distribution and the interfacial fluxes are strongly dependant on seepage rate and benthic reactivity. The model fitted the measured profiles with high correlation (usually higher than 90%), and model-derived sediment-water NO fluxes were in good agreement to fluxes measured in situ with Lee-type seepage meters (0. 9948 slope, R = 0.8672, n = 8). Nitrate oxidation and reduction rates extracted from model fits to the data (10-10 mmol m h) agreed with literature values. Because dispersive effects are not included in direct mass balances based on the porewater concentrations, the model presented here increases the accuracy of apparent reaction rate estimates and geochemical zonation at Submarine Groundwater Discharge (SGD) sites. The results establish the importance of sandy sediments as reactive interfaces, able to modulate mass transfer of continental-derived contaminants into coastal ecosystems. We suggest that tools such as the one described here might be used to advantage in preparing further experimental studies to elucidate how benthic reactivity affects nitrate distribution and fluxes in sediments affected by SGD. © 2010 Springer Science+Business Media B.V.