Effects of crystallographic orientation on calcite dissolution under alkaline conditions

Min, Yujia; Chen, Xin; La Plante, Erika Callagon; Sant, Gaurav

doi:10.1016/j.gca.2023.01.019

Effects of crystallographic orientation on calcite dissolution under alkaline conditions

Journal Article · Thu Jan 26 23:00:00 EST 2023 · Geochimica et Cosmochimica Acta

DOI:https://doi.org/10.1016/j.gca.2023.01.019· OSTI ID:2418343

^[1]; ^[2]; La Plante, Erika Callagon ^[3]; Sant, Gaurav ^[2]

Univ. of California, Los Angeles, CA (United States); OSTI
Univ. of California, Los Angeles, CA (United States)
Univ. of California, Los Angeles, CA (United States); Univ. of Texas, Arlington, TX (United States)

Here, 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 4m (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 CO₃^2– species mitigates the inhibition effects of CO₃^2– on both surfaces at pH 13.1 compared to pH 11, and the dissolution of (100) surfaces is far less affected by CO₃^2– 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.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE), Nuclear Energy University Program (NEUP)

Grant/Contract Number:: NE0008882

OSTI ID:: 2418343

Alternate ID(s):: OSTI ID: 1957699

Journal Information:: Geochimica et Cosmochimica Acta, Journal Name: Geochimica et Cosmochimica Acta Vol. 346; ISSN 0016-7037

Publisher:: Elsevier; The Geochemical Society; The Meteoritical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Effects of crystallographic orientation on calcite dissolution under alkaline conditions

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