Cycling of redox-sensitive trace metals in barrier island freshwater lenses

Freshwater lenses connect the terrestrial and marine realm via groundwater discharge at the edges of islands and serve as drinking water resources. We studied the redox-sensitive metals U, Mo, V, and Tl along the redox gradient of fresh groundwater lenses on Spiekeroog Island, northern Germany. Groundwater solute concentrations were linked to groundwater age and redox characteristics. We further quantified the contribution of precipitation, sea spray, and aquifer matrix to the groundwater metal concentrations and evaluated the sink and source function of the aquifer under oxic and reducing conditions. We found that biogeochemical processes altered the concentrations of the trace metals. In young, oxygen to nitrate reducing zones, the aquifer matrix represented the major metal source to the groundwater. For Tl, rain was an additional important (anthropogenic) source. Under manganese and iron oxide to sulfate reducing conditions, U and Tl were sensitive to redox dependent removal, whereas Mo and V were less affected by reductive precipitation/adsorption. In detail, 99% of dissolved Tl, 88% of U, 66% of Mo, and 44% of V were removed to the solid phase in comparison to values from less reducing zones. Large parts of the western freshwater lens on Spiekeroog were anoxic. For this reason, the delivery of aquifer derived metals to the ocean via fresh groundwater discharge appeared to be limited. Higher U, Mo, V, and Tl concentrations were observed in the presently developing young freshwater lens in the east of Spiekeroog Island. This suggests that less reducing groundwater lenses may be a source of these metals to the adjacent beach/coastal seawater. Especially for V, freshwater discharge from sandy coastal aquifers may be important, as groundwater concentrations exceeded seawater concentration under oxic as well as anoxic conditions. Regarding the suitability of the freshwater as drinking water, all measured trace metal concentrations were classified as uncritical.