ALBERT

Description: Submarine groundwater discharge (SGD) is an important component of chemical fluxes in the coastal ocean. The composition of SGD is influenced by biogeochemical reactions that take place within the subterranean estuary (STE), the subsurface mixing zone of fresh and saline groundwaters. The STE is characterized by redox gradients that affect the speciation and mobility of redox-sensitive elements (RSEs). We examined the distributions and behavior of the RSEs Mo, U, V, and Cr within the larger redox framework of a shallow STE and evaluated the source-sink function of the STE for these elements. We found that the advection of water through the STE and the apparent respiration of organic matter drives the formation of a “classic” redox sequence typically observed in diffusion-dominated fine-grained sediments. High concentrations of dissolved organic matter (up to 2.9 mM) lead to extensive sulfide production (up to 1.8 mM) within 3 m of the surface. Both Mo and U are quantitatively removed as oxic surface waters mix into ferruginous and sulfidic zones. Molybdenum removal appears to occur where sulfide concentrations exceed ~ 11 μM, a previously reported threshold for quantitative formation of highly particle-reactive thiomolybdate species. Uranium removal apparently occurs via reduction and formation of insoluble phases or sorption to sediments. It is not clear how readily sequestered metals may be returned to solution, but SGD may be an important sink in the marine budget for both Mo and U. In contrast, both V and Cr show non-conservative addition across the salinity mixing gradient. Increases in pH appear to promote dissolution of V from minerals within the shallow aquifer, and mobilization may also be associated with dissolved organic matter. Chromium enrichment is associated with higher dissolved organic matter and is likely due to the formation of soluble Cr-organic complexes. Fluxes of these elements were constrained using SGD volume fluxes, determined using radium isotopes as well as direct discharge measurements by Lee-type seepage meters, and concentrations in directly-sampled seepage (Mo: − 0.21 to − 7.7 μmol m− 2 day− 1; U: − 0.02 to − 0.6 μmol m− 2 day− 1; V: 0.05 to 2.0 μmol m− 2 day− 1; Cr: 0.12 to 4.4 μmol m− 2 day− 1).

Description: Brackish coastal groundwater is enriched in Ra, which is transported to surface waters via submarine groundwater discharge (SGD). The Ra activity of the SGD end-member is influenced by a variety of environmental factors including salinity, pH, and isotope half-life. In the York River estuary (YRE), 223Ra, 224Ra, and 226Ra were measured in surface water and shallow groundwater across a range of salinities and additional Ra sources quantified (desorption and diffusion from sediments, input from tidal marshes). The Ra budget of the estuary indicated a major source of Ra that could only be satisfied by SGD. The apparent Ra flux was combined with groundwater Ra end-member activity to estimate SGD volume fluxes of 5–178 L m− 2 d− 1. Each isotope exhibited a different seasonal pattern, with significantly higher 224Ra flux during summer than winter, lower 226Ra SGD flux during summer than winter, and no seasonal differences in 223Ra SGD flux. However, the SGD 224Ra end-member activity varied with seasonal pore water salinity fluctuations, indicating end-member control on seasonal 224Ra flux. Each Ra isotope suggested a different SGD volume flux, indicating that different nuclide regeneration rates may respond to and reflect different flow mechanisms in the subterranean estuary. This work indicates that volume fluxes estimated using geochemical tracers are sensitive to SGD end-member variations and end-member variability must be well-characterized for reliable SGD flux estimates.