Using 3H and 14C to constrain the degree of closed-system dissolution of calcite in groundwater

This study uses 3H concentrations, 14C activities (a14C), 87Sr/86Sr ratios, and δ13C values to constrain calcite dissolution in groundwater from the Ovens catchment SE Australia. Taken in isolation, the δ13C values of dissolved organic C (DIC) and 87Sr/86Sr ratios in the Ovens groundwater imply that there has been significant calcite dissolution. However, the covariance of 3H and 14C and the calculated initial 14C activities (a014C) imply that most groundwater cannot have dissolved more than 20% of 14C-free calcite under closed-system conditions. Rather, calcite dissolution must have been partially an open-system process allowing 13C and 14C to re-equilibrate with CO2 in the unsaturated zone. Recognising that open-system calcite dissolution has occurred is important for dating deeper groundwater that is removed from its recharge area in this and other basins. The study is one of the first to use 14C and 3H to constrain the degree of calcite dissolution and illustrates that it is a valuable tool for assessing geochemical processes in recharge areas.