Chemical Flux Associated with Spatially and Temporally Variable Submarine Groundwater Discharge, and Chemical Modification in the Subterranean Estuary at Gloucester Point, VA (USA)


Submarine groundwater discharge represents a major but poorly constrained component of coastal marine chemical budgets. In the current study, the geochemical behavior of 224Ra, inorganic nitrogen species, and Fe in shallow coastal groundwater was characterized to improve estimates of chemical flux via submarine groundwater discharge (SGD) at a site in the York River estuary, VA (USA). Directly measured SGD rates varied between 3.9 ± 1.2 cm day−1 offshore, and 8.9 ± 2.6 cm day−1 close to shore. A clear inverse relationship was observed between SGD and tidal height, reflecting the hydraulic gradient between groundwater and surface water. Discharge rates varied spatially in conjunction with the subterranean estuary location, and there was a strong inverse correlation between seepage rates and seepage salinity. Dissolved 224Ra activity in the mixing zone reached levels up to 6 dpm L−1 and co-varied with salinity in the groundwater but not in the surface water or seepage water. Instead, a consistent sigmoidal trend of Ra with pH was observed, which matched previous laboratory experiment results. Dissolved NH4 + reached concentrations up to 120 μM in the groundwater and appeared to mix conservatively with respect to salinity in the subterranean estuary. In contrast, NOx (NO2 − + NO3 −) was low in both fresh groundwater and surface water and showed non-conservative enrichment (up to 23 μM) within the subterranean estuary. Dissolved Fe also showed non-conservative excess in the subterranean estuary, reaching concentrations up to 50 μM. SGD-derived chemical fluxes were estimated using several different commonly used approaches: average groundwater concentrations, pore water constituent-salinity trends coupled with directly collected seepage salinity, constituent concentrations in directly collected seepage, and concentrations in shallowest groundwater samples. Different flux estimates were compared with a “variable endmember” approach based on the observed geochemical distribution and inferred behavior.

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Estuaries and Coasts



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