Radium-based pore water fluxes of silica, alkalinity, manganese, DOC, and uranium: A decade of studies in the German Wadden Sea

A decade of studies of metal and nutrient inputs to the back-barrier area of Spiekeroog Island, NW German Wadden Sea, have concluded that pore water discharge provides a significant source of the enrichments of many components measured in the tidal channels during low tide. In this paper we add studies of radium isotopes to help quantify fluxes into and out of this system. Activities of radium isotopes in surface water from tidal channels in the back-barrier area exhibit pronounced changes in concert with the tide, with highest activities occurring near low tide. Other dissolved components: silica, total alkalinity (TA), manganese, and dissolved organic carbon (DOC) exhibit similar changes, with patterns matching the Ra isotopes. Uranium follows a reverse pattern with highest concentrations at high tide. Here we use radium isotope measurements in water column and pore water samples to estimate the fluxes of pore waters that enter the tidal channels during low tide. Using a flushing time of 4 days and the average activities of ²²⁴Ra, ²²³Ra, and ²²⁸Ra measured in the back-barrier surface and pore waters, we construct a balance of these isotopes, which is sustained by a deep pore water flux of (2-4) × 10⁸ L per tidal cycle. This flux transports Ra and the other enriched components to the tidal channels and causes the observed low tide enrichments. An independent estimate of pore water recharge is based on the depletion of U in the tidal channels. The U-based recharge is about two times greater than the Ra-based discharge; however, other sinks of U could reduce the recharge estimate. The pore waters have wide ranges of enrichment in silica, alkalinity, manganese, DOC, and depletion of U with depth. We estimate concentrations of these components in pore water from the depth expected to contribute the majority of the pore water flux, 3.5 m, to determine fluxes of these components to the tidal channels. Samples from this depth have minimum concentrations of silica, alkalinity, manganese, and DOC. We also estimate the exports of these components (and import of U) due to mixing based on average measured concentrations in the tidal creeks and the 4-day flushing time. A comparison of these estimates reveals that the exports (negative in the case of U) equal or exceed the pore water fluxes. By using values slightly higher than the minimum concentrations at 3.5 m to calculate inputs, the two estimates could be forced to match. We conclude that pore water drainage is the major factor regulating fluxes of Ra isotopes, silica, alkalinity, manganese, DOC, and uranium in this system.