Magnesium Coprecipitation with Calcite at Low Supersaturation: Implications for Mg-Enriched Water in Calcareous Soils

The concentrations of magnesium (Mg) and calcium (Ca) in natural aqueous environments are controlled by sorption and dissolution-precipitation reactions. Ca binding in calcareous soils depends on the degree of solution saturation with respect to CaCO3. Mg may be bound in precipitating calcite. Here, we investigated Mg incorporation into calcite via the recrystallization of vaterite, which simulates a very low supersaturation in a wide range of Mg to Ca ratios and pH conditions. Increasing the Mg to Ca ratios (0.2 to 10) decreased the partition coefficient of Mg in calcite from 0.03 to 0.005. An approximate thermodynamic mixing parameter (Guggenheim a(0) = 3.3 +/- 0.2), that is valid for dilute systems was derived from the experiments at the lowest initial Mg to Ca ratio (i.e., 0.2). At elevated Mg to Ca ratios, aragonite was preferentially formed, indicating kinetic controls on Mg partitioning into Mg-calcite. Scanning electron microscopy (SEM-EDX) analyses indicated that Mg is not incorporated into aragonite. The thermodynamic mixing model suggests that at elevated Mg to Ca ratio (i.e., >= 1) Mg-calcite becomes unstable relative to pure aragonite. Finally, our results suggest that the abiotic incorporation of Mg into calcite is only effective for the removal of Mg from aqueous environments like calcareous soil solution, if the initial Mg to Ca ratio is already low.

Automated summary

The concentrations of magnesium and calcium in natural aqueous environments are controlled by sorption and dissolution-precipitation reactions. Magnesium can bind in precipitating calcite, but at high magnesium to calcium ratios, aragonite is preferentially formed. Thermodynamic and kinetic controls may be at play at low magnesium to calcium ratios.