Cited by 321Calcium Carbonate Crystallization and InhibitionGeochemistry and Elemental AnalysisCO2 Sequestration and Geologic Interactions

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Mechanisms of classical crystal growth theory explain quartz and silicate dissolution behavior

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Dove, Patricia M., Han, Nizhou, De Yoreo, James J.·2005·Proceedings of the National Academy of Sciences

DOI 10.1073/pnas.0507777102PMC PMC1266142

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Abstract

The central control of mineral weathering rates on biogeochemical systems has motivated studies of dissolution for more than 50 years. A complete physical picture that explains widely observed variations in dissolution behavior is lacking, and some data show apparent serious inconsistencies that cannot be explained by the largely empirical kinetic “laws.” Here, we show that mineral dissolution can, in fact, be understood through the same mechanistic theory of nucleation developed for mineral growth. In principle, this theory should describe dissolution but has never been tested. By generalizing nucleation rate equations to include dissolution, we arrive at a model that predicts how quartz dissolution processes change with undersaturation from step retreat, to defect-driven and homogeneous etch pit formation. This finding reveals that the “salt effect,” recognized almost 100 years ago, arises from a crossover in dominant nucleation mechanism to greatly increase step density. The theory also explains the dissolution kinetics of major weathering aluminosilicates, kaolinite and K-feldspar. In doing so, it provides a sensible origin of discrepancies reported for the dependence of kaolinite dissolution and growth rates on saturation state by invoking a temperature-activated transition in the nucleation process. Although dissolution by nucleation processes was previously unknown for oxides or silicates, our mechanism-based findings are consistent with recent observations of dissolution (i.e., demineralization) in biological minerals. Nucleation theory may be the missing link to unifying mineral growth and dissolution into a mechanistic and quantitative framework across the continuum of driving force.

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Authors: Dove, P. M., Han, N., & De Yoreo, J. J.
Affiliations: Lawrence Livermore National Laboratory (US)
Department of Geosciences, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061; and Department of Chemistry and Materials Science, Lawrence Livermore National Laboratory, Livermore, CA 94551
ORCID: Dove, Patricia M.
Venue: Proceedings of the National Academy of Sciences
Publisher: National Academy of Sciences
Published: 2005-10-17
Volume: 102
Issue: 43
Pages: 15357-15362
ISSN: 0027-8424 (ISSN-L)
1091-6490
DOI: 10.1073/pnas.0507777102
PMC: PMC1266142
OpenAlex: W2067608390
Semantic Scholar: faa91f435979732efe4fcf3edba2ec4d06672cb5
Cited by: 321
References: 24
Citations by year: 2026: 14 · 2025: 19 · 2024: 16 · 2023: 25 · 2022: 16 · 2021: 15 · 2020: 23 · 2019: 16 · 2018: 18 · 2017: 11 · 2016: 18 · 2015: 18 · 2014: 11 · 2013: 15 · 2012: 14
FWCI: 5.11
Type: journal article
Language: en
Open access: bronze
doi.org
Locations: Proceedings of the National Academy of Sciences (publishedVersion)
Europe PMC (PubMed Central) (publishedVersion)
PubMed Central (publishedVersion)
PubMed (publishedVersion)
Funders: National Science Foundation (0083173, 9903349)
U.S. Department of Energy (W-7405, FG0200ER15112, -7405-ENG-48)
Lawrence Livermore National Laboratory (W-7405-ENG 48, -7405-Eng-48)
Topics: Physical Sciences › Materials Science › Biomaterials › Calcium Carbonate Crystallization and Inhibition
Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Geochemistry and Elemental Analysis
Physical Sciences › Environmental Science › Environmental Engineering › CO2 Sequestration and Geologic Interactions
Keywords: mineral dissolution, nucleation theory, quartz dissolution, silicate dissolution, mineral weathering, kaolinite, K-feldspar, aluminosilicates, salt effects, etch pits, undersaturation, dissolution kinetics, saturation state

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Mechanisms of classical crystal growth theory explain quartz and silicate dissolution behavior

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