Influence of calcite on uranium(VI) reactive transport in the groundwater–river mixing zone

• Calcite may be depleted in the groundwater–river mixing zone at Hanford 300 Area.
• Calcite distribution affects water composition and U(VI) reactive transport.
• Effect of calcite distribution on field-scale U(VI) reactive transport is complex.
• Calcite distribution should be accounted for in U(VI) reactive transport model.

Calcite is an important, relatively soluble mineral phase that can affect uranium reactive transport in subsurface sediments. This study was conducted to investigate the distribution of calcite and its influence on uranium adsorption and reactive transport in the groundwater–river mixing zone of the Hanford 300A site, Washington State. Simulations using a two-dimensional (2D) reactive transport model under field-relevant hydrological and hydrogeochemical conditions revealed the development of a calcite reaction front through the mixing zone as a result of dynamic groundwater–river interactions. The calcite concentration distribution, in turn, affected the concentrations of aqueous carbonate and calcium, and pH through dissolution, as river waters intruded and receded from the site at different velocities in response to stage changes. The composition variations in groundwater subsequently influenced uranium mobility and discharge rates into the river in a complex fashion. The results implied that calcite distribution and concentration are important variables that need to be quantified for accurate reactive transport predictions of uranium, especially in dynamic groundwater–river mixing zones.