Effects of crystallographic orientation on calcite dissolution under alkaline conditions

Abstract

This study investigates the dissolution of calcite’s (104) and (100) surfaces under alkaline conditions (pH 8.8–13.1) using vertical scanning interferometry under flow-through conditions. The dissolution rate of (100) surfaces decreases with increasing pH. For example, the dissolution rate at pH 8.8 is more than 20 times higher than that at pH 13.1. In contrast, the dissolution rate of (104) surfaces is far less sensitive to pH. We explain these observations as being on account of the preferential adsorption of [OH−] on (100) surfaces, inhibiting their dissolution. Particularly, this is because Ca-surface sites on (100) surfaces are less coordinated and have a stronger tendency for [OH−] adsorption. As a result, (100) surfaces dissolve nearly twice as fast as (104) surfaces at pH 8.8, whereas (104) surfaces dissolved ∼4.5 times faster than (100) surfaces at pH 13.1; indicating an inversion in dissolution behavior. The dissolution rate of (104) surfaces at pH 13.1 is 60 % of the rate at pH 10–12 because of the formation of slow dissolving microfacets of other orientations. The rhombohedral dissolution etch-pits formed on (104) surfaces, at lower pH’s, disappeared upon exposure to solutions with pH > 12 and were replaced by protrusions. The addition of up to 4 m (molality) NaCl enhances the dissolution of (104) surfaces at pH 8.8–13.1 and (100) surfaces at pH 8.8–11.0, and inhibited the dissolution of (100) surfaces at pH = 12.0–13.1. In addition, the competing adsorption between OH− and CO32− species mitigates the inhibition effects of CO32− on both surfaces at pH 13.1 compared to pH 11, and the dissolution of (100) surfaces is far less affected by CO32− than (104) surfaces. These results provide new insights into the rates and mechanisms of how crystallographic orientations affect calcite’s dissolution at alkaline pH conditions.