Growth rates of monolayer-height steps on the {1014} 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.
Mineral growth and dissolution are often treated as occurring via a single reversible process that governs the rate of reaction. We show that multiple distinct intermediate states can occur during both growth and dissolution. Specifically, we used metadynamics, a method for efficiently exploring the free-energy landscape of a system, coupled to umbrella sampling and reactive flux calculations to examine the mechanism and rates of attachment and detachment of a barium ion onto a stepped barite (BaSO(4)) surface. The activation energies calculated for the rate-limiting reactions, which are different for attachment and detachment, precisely match those measured experimentally during both growth and dissolution. These results can potentially explain anomalous non-steady-state mineral reaction rates observed experimentally and will enable the design of more efficient growth inhibitors and facilitate an understanding of the effect of impurities.
Geologic storage of CO(2) requires that the caprock sealing the storage rock is highly impermeable to CO(2). Swelling clays, which are important components of caprocks, may interact with CO(2) leading to volume change and potentially impacting the seal quality. The interactions of supercritical (sc) CO(2) with Na saturated montmorillonite clay containing a subsingle layer of water in the interlayer region have been studied by sorption and neutron diffraction techniques. The excess sorption isotherms show maxima at bulk CO(2) densities of ≈ 0.15 g/cm(3), followed by an approximately linear decrease of excess sorption to zero and negative values with increasing CO(2) bulk density. Neutron diffraction experiments on the same clay sample measured interlayer spacing and composition. The results show that limited amounts of CO(2) are sorbed into the interlayer region, leading to depression of the interlayer peak intensity and an increase of the d(001) spacing by ca. 0.5 Å. The density of CO(2) in the clay pores is relatively stable over a wide range of CO(2) pressures at a given temperature, indicating the formation of a clay-CO(2) phase. At the excess sorption maximum, increasing CO(2) sorption with decreasing temperature is observed while the high-pressure sorption properties exhibit weak temperature dependence.
Using in situ atomic force microscopy, the growth rates of the obtuse and acute step orientations on the {101̅ 4} calcite surface were measured at two saturation indices as a function of the aqueous calcium-to-carbonate ratio and aqueous strontium concentration. The amount of strontium required to inhibit growth was found to correlate with the aqueous calcium concentration, but did not correlate with carbonate, suggesting that strontium inhibits attachment of calcium ions to reactive sites on the calcite surface. Strontium/ calcium cation exchange selectivity coefficients, K ex , are estimated at 1.09 ± 0.09 and 1.44 ± 0.19 for reactive sites on the obtuse and acute step orientations, respectively. The implication of this work is that, to avoid poisoning calcite growth, the concentration of calcium should be higher than the quotient of the strontium concentration and K ex , regardless of the saturation index. Previous analytical models of nucleation of kink sites on steps are expanded to include growth rates at multiple saturation indices and the effect of strontium. The rate constants for calcium attachment are found to be similar for the two step orientations, but those of carbonate vary significantly. This work will have implications for natural or engineered calcite growth, such as to sequester subsurface strontium contamination.
The three-dimensional structure of the barite (001)−water interface was studied using in situ specular and nonspecular X-ray reflectivity (XR). Displacements of the barium and sulfate ions in the surface of a barite crystal and the interfacial water structure were defined in the analyses. The largest relaxations (0.13 Å lateral and 0.08 Å vertical) were observed for the barium and sulfate ions in the topmost unit cell layer, which diminished rapidly with depth. The best fit structure identified four distinct adsorbed species, which in comparison with molecular dynamics (MD) simulations reveals that they are associated with positions of adsorbed water, each of which coordinates one or two surface ions (either barium, sulfate, or both). These water molecules also adsorb in positions consistent with those of bariums and sulfates in the bulk crystal lattice. These results demonstrate the importance of combining highresolution XR with MD simulations to fully describe the atomic structure of the hydrated mineral surface. The agreement between the results indicates both the uniqueness of the structural model obtained from the XR analysis and the accuracy of the force field used in the simulations.
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