Nature and extent of carbonate precipitation during aquifer thermal energy storage

Heating of calcite-saturated groundwater induces no precipitation to thermodynamic equilibrium with respect to end-member Ca-carbonates. Column experiments, using native groundwater and aquifer sediment, were performed to study the controlling factors in the kinetics of carbonate precipitation for a natural system by injection of groundwater in a sediment core at 90°C. The temperature increase induced a fast precipitation of a CaFe-carbonate, containing Mn and phosphate, and a CaMgFe-carbonate, containing Mn, within at most 10 h. Both precipitates varied in composition and were partly amorphic, partly crystalline. Prolonged precipitation, after almost all Fe[II] had been removed, was extremely slow despite a twelve-fold supersaturation with respect to end-member calcite. The resulting supersaturation cannot be explained by either calcite precipitation kinetics, Mg-inhibition, Mg-calcite solubility control, or Ca-organic acid complexing, because these factors may explain a two-fold supersaturation at most. The maintenance of supersaturation is attributed to inhibition of precipitation by phosphate and/or organic acids. The influence of secondary reactions, as cation-exchange and silicate weathering, is of minor importance on the carbonate chemistry. Cation-exchange was observed in the initial stages of heated water injection. Potassium, NH₄ and Fe become desorbed upon temperature increase. Related Ca-adsorption is insufficient to avoid Ca-carbonate precipitation. Weathering of silicates occurs continuously and leads to the release of Na, Ca and Mg.