Nitrogen biogeochemistry of submarine groundwater discharge

To investigate the role of the seepage zone in transport, chemical speciation, and attenuation of nitrogen loads carried by submarine groundwater discharge, we collected nearshore groundwater samples (n = 328) and examined the distribution and isotopic signature (δ¹⁵N) of nitrate and ammonium. In addition, we estimated nutrient fluxes from terrestrial and marine groundwater sources. We discuss our results in the context of three aquifer zones: a fresh groundwater zone, a shallow salinity transition zone (STZ), and a deep STZ. Groundwater plumes containing nitrate and ammonium occurred in the freshwater zone, whereas the deep STZ carried almost exclusively ammonium. The distributions of redox-cycled elements were consistent with theoretical thermodynamic stability of chemical species, with sharp interfaces between water masses of distinct oxidation : reduction potential, suggesting that microbial transformations of nitrogen were rapid relative to dispersive mixing. In limited locations in which overlap occurs between distribution of nitrate with that of ammonium and dissolved Fe²⁺, changes in concentration and in δ¹⁵N suggest loss of all species. Concurrent removal of NO₃⁻ and NH₄⁺, both in freshwater and the deep STZ, might occur through a range of mechanisms, including heterotrophic or autotrophic denitrification, coupled nitrfication : denitrification, anammox, or Mn oxidation of NH₄⁺. Loss of nitrogen was not apparent in the shallow STZ, perhaps because of short water residence time. Despite organic Cpoor conditions, the nearshore aquifer and subterranean estuary are biogeochemically active zones, where attenuation of N loads can occur. Extent of attenuation is controlled by the degree of mixing of biogeochemically dissimilar water masses, highlighting the critical role of hydrogeology in N biogeochemistry. Mixing is related in part to thinning of the freshwater lens before discharge and to dispersion at the fresh : saline groundwater interface, features common to all submarine groundwater discharge zones.