Roothaan-Hartree-Fock molecular orbital methods were applied to investigate the ground-state structural, energetic properties, and bonding relationships of the hydrated (10.4) calcite surface. The adsorption of water molecules was modeled at the 6-31G(d,p) level of theory using Ca(n)(CO(3))(n) slab cluster models (4

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The characterization of the proton sorptive properties of calcite in aqueous solutions at 25 +/- 1 degrees C over a relatively wide range of chemical conditions (7.16 [triple bond]Ca(HCO3)2(exc) + CaCO3(s). Accordingly, reliable predictions of aqueous speciation in natural or engineered calcite-containing systems at variable pCO(2) conditions must consider this exchange reaction and the associated K(ex). The postulated proton/calcium exchange may have far-reaching implications on the interpretation of kinetic and equilibrium data and can partly explain the anomalous solution chemistry observed in some field and laboratory carbonate studies.

Gaspeite is a low reactivity, rhombohedral carbonate mineral and a suitable surrogate to investigate the surface properties of other more ubiquitous carbonate minerals, such as calcite, in aqueous solutions. In this study, the acid-base properties of the gaspeite surface were investigated over a pH range of 5 to 10 in NaCl solutions (0.001, 0.01, and 0.1 M) at near ambient conditions (25 +/- 3 degrees C and 1 atm) by means of conventional acidimetric and alkalimetric titration techniques and microelectrophoresis. Over the entire experimental pH range, surface protonation and electrokinetic mobility are strongly affected by the background electrolyte, leading to a significant decrease of the pH of zero net proton charge (PZNPC) and the pH of isoelectric point (pH(iep)) at increasing NaCl concentrations. This challenges the conventional idea that carbonate mineral surfaces are chemically inert to background electrolyte ions. Multiple sets of surface complexation reactions (i.e., ionization and ion adsorption) were formulated within the framework of three electrostatic models (CCM, BSM, and TLM) and their ability to simulate proton adsorption and electrokinetic data was evaluated. A one-site, 3-pK, constant capacitance surface complexation model (SCM) reproduces the proton adsorption data at all ionic strengths and qualitatively predicts the electrokinetic behavior of gaspeite suspensions. Nevertheless, the strong ionic strength dependence exhibited by the optimized SCM parameters reveals that the influence of the background electrolyte on the surface reactivity of gaspeite is not fully accounted for by conventional electrostatic and surface complexation models and suggests that future refinements to the underlying theories are warranted.