The zetapotential of calcite in contact with aqueous solutions of varying composition is determined for pre-equilibrated suspensions by means of electrophoretic measurements and for non-equilibrium solutions by means of streaming potential measurements. Carbonate and calcium are identified as charge determining ions. Studies of the equilibrium solutions show a shift of isoelectric point with changing CO2 partial pressure. Changes in pH have only a weak effect in non-equilibrium solutions. The surface structure of (1 0 4)-faces of single crystal calcite in contact to solutions corresponding to those of the zetapotential investigations is determined from surface diffraction measurements. The results reveal no direct indication of calcium or carbonate inner-sphere surface species. The surface ions are found to relax only slightly from their bulk positions; the most significant relaxation is a similar to 4 degrees tilt of the surface carbonate ions towards the surface. Two ordered layers of water molecules are identified, the first at 2.35 +/- 0.05 angstrom above surface calcium ions and the second layer at 3.24 +/- 0.06 angstrom above the surface associated with surface carbonate ions. A Basic-Stern surface complexation model is developed to model observed zetapotentials, while only considering outer-sphere complexes of ions other than protons and hydroxide. The Basic-Stern SCM successfully reproduces the zetapotential data and gives reasonable values for the inner Helmholtz capacitance, which are in line with the Stern layer thickness estimated from surface diffraction results. (C) 2010 Elsevier Inc. All rights reserved.