The Charge Distribution MUltiSite Ion Complexation or CD–MUSIC\ud modeling approach is used to describe the chemical structure of carbonate mineralaqueous\ud solution interfaces. The new model extends existing surface complexation\ud models of carbonate minerals, by including atomic scale information on the surface\ud lattice and the adsorbed water layer. In principle, the model can account for variable\ud proportions of face, edge and kink sites exposed at the mineral surface, and for the\ud formation of inner- and outer-sphere surface complexes. The model is used to\ud simulate the development of surface charges and surface potentials on divalent\ud carbonate minerals as a function of the aqueous solution composition. A comparison\ud of experimental data and model output indicates that the large variability in the\ud observed pH trends of the surface potential for calcite may in part reflect variable\ud degrees of thermodynamic disequilibrium between mineral, solution and, when present,\ud gas phase during the experiments. Sample preparation and non-stoichiometric surfaces\ud may introduce further artifacts that complicate the interpretation of electrokinetic\ud and surface titration measurements carried out with carbonate mineral suspensions.\ud The experimental artifacts, together with the high sensitivity of the model\ud toward parameters describing hydrogen bridging and bond lengths at the mineralwater\ud interface, currently limit the predictive application of the proposed CD–MUSIC\ud model. The results of this study emphasize the need for internally consistent experimental\ud data sets obtained with well-characterized mineral surfaces and in situ aqueous\ud solution compositions (that is, determined during the charge or potential measurements),\ud as well as for further molecular dynamic simulations of the carbonate\ud mineral-water interface to better constrain the bond lengths and the number plus\ud valence contribution of hydrogen bridges associated with different structural surface sites
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