Constraining the temporal variations of Ra isotopes and Rn in the groundwater end-member: Implications for derived SGD estimates

Submarine groundwater discharge (SGD) has been recognized as an important supplier of chemical compounds to the ocean that may influence coastal geochemical cycles. Radium isotopes (²²³Ra, ²²⁴Ra, ²²⁶Ra ²²⁸Ra) and radon (²²²Rn) have been widely applied as tracers of SGD. Their application requires the appropriate characterization of both the concentrations of tracers in the discharging groundwater and their distribution in the coastal water column. This study evaluates the temporal evolution of Ra isotopes and ²²²Rn concentrations in a dynamic subterranean estuary of a microtidal Mediterranean coastal aquifer that experiences large displacements of the fresh-saltwater interface as a necessary initial step in evaluating the influence of SGD in coastal waters. We show that changes in groundwater salinities due to the seaward displacement of the fresh-saltwater interface produced large variations in Ra activities in groundwater (by a factor of ~ 19, ~ 14, ~ 6, and ~ 11 for ²²³Ra, ²²⁴Ra, ²²⁶Ra and ²²⁸Ra, respectively), most importantly during rainfall events. In contrast, the ²²²Rn activities in groundwater oscillated only by a factor of 3 during these rainy periods. The large temporal variability in Ra activities hampers the characterization of the SGD end-member when using Ra isotopes as tracers, and thus presents a challenge for obtaining accurate SGD estimates. This study emphasizes the need to understand the hydrodynamics of coastal aquifers to appropriately constrain the Ra isotopes and ²²²Rn concentrations in groundwater and when applying both tracers in dynamic microtidal coastal systems.