Growth rate of calcite steps as a function of aqueous calcium-to-carbonate ratio: Independent attachment and detachment of calcium and carbonate ions

Growth rates of monolayer-height steps on the {101̄4} calcite surface have been measured as a function of the aqueous calcium-to-carbonate ratio. The maximum growth rates of the two common crystallographic orientations were found to deviate from the ideal stoichiometric ratio of 1:1, and dissolution features were observed under supersaturated solutions containing high calcium-to-carbonate ratios. To explain these phenomena, a theory is applied that treats the rates of attachment and detachment of aqueous calcium and carbonate ions separately. The resultant attachment rate constants are 1-3 orders of magnitude smaller than the water exchange rate of the constituent aqueous ions, suggesting that ligand-exchange processes may directly drive attachment. The broader implication is that the saturation state alone is not adequate to fully describe the rates of the multiple, independent reactions that occur on mineral surfaces under these conditions.