Despite the broad range of interest and applications, controls on calcite surface charge in aqueous solution, especially at conditions relevant to natural systems, remain poorly understood. The primary data source to understand calcite surface charge comprises measurements of zeta potential. Here we collate and review previous measurements of zeta potential on natural and artificial calcite and carbonate as a resource for future studies, compare and contrast the results of these studies to determine key controls on zeta potential and where uncertainties remain, and report new measurements of zeta potential relevant to natural subsurface systems. The results show that the potential determining ions (PDIs) for the carbonate mineral surface are the lattice ions Ca2+, Mg2+ and CO32-. The zeta potential is controlled by the concentration-dependent adsorption of these ions within the Stern layer, primarily at the Outer Helmholtz Plane (OHP). Given this, the Iso-Electric Point (IEP) at which the zeta potential is zero should be expressed as pCa (or pMg). It should not be reported as pH, similar to most metal oxides. The pH does not directly control the zeta potential. Varying the pH whilst holding pCa constant yields constant zeta potential. The pH affects the zeta potential only by moderating the equilibrium pCa for a given CO2 partial pressure (pCO2). Experimental studies that appear to yield a systematic relationship between pH and zeta potential are most likely observing the relationship between pCa and zeta potential, with pCa responding to the change in pH. New data presented here show a consistent linear relationship between equilibrium pH and equilibrium pCa or pMg irrespective of sample used or solution ionic strength. The surface charge of calcite is weakly dependent on pH, through protonation and deprotonation reactions that occur within a hydrolysis layer immediately adjacent to the mineral surface. The Point of Zero Charge (PZC) at which the surface charge is zero could be expressed as pH, but surface complexation models suggest the surface is negatively charged over the pH range 5.5-11. Several studies have suggested that SO42- is also a PDI for the calcite surface, but new data presented here indicate that the value of pSO4 may affect zeta potential only by moderating the equilibrium pCa. Natural carbonate typically yields a more negative zeta potential than synthetic calcite, most likely due to the presence of impurities including clays, organic matter, apatite, anhydrite or quartz, that yield a more negative zeta potential than pure calcite. New data presented here show that apparently identical natural carbonates display differing zeta potential behaviour, most likely due to the presence of small volumes of these impurities. It is important to ensure equilibrium, defined in terms of the concentration of PDIs, has been reached prior to taking measurements. Inconsistent values of zeta potential obtained in some studies may reflect a lack of equilibration. The data collated and reported here have broad application in engineering processes including the manufacture of paper and cement, the geologic storage of nuclear waste and CO2, and the production of oil and gas.

Laboratory experiments and field trials have shown that oil recovery from carbonate reservoirs can be increased by modifying the brine composition injected during recovery in a process termed controlled salinity water-flooding (CSW). However, CSW remains poorly understood and there is no method to predict the optimum CSW composition. This work demonstrates for the first time that improved oil recovery (IOR) during CSW is strongly correlated to changes in zeta potential at both the mineral-water and oil-water interfaces. We report experiments in which IOR during CSW occurs only when the change in brine composition induces a repulsive electrostatic force between the oil-brine and mineral-brine interfaces. The polarity of the zeta potential at both interfaces must be determined when designing the optimum CSW composition. A new experimental method is presented that allows this. Results also show for the first time that the zeta potential at the oil-water interface may be positive at conditions relevant to carbonate reservoirs. A key challenge for any model of CSW is to explain why IOR is not always observed. Here we suggest that failures using the conventional (dilution) approach to CSW may have been caused by a positively charged oil-water interface that had not been identified.

Acknowledgements TOTAL are thanked for partial supporting Jackson through the TOTAL Chairs programme at Imperial College London, for supporting Vinogradov through the TOTAL Laboratory for Reservoir Physics at Imperial College London, and for granting permission to publish this work.Peer reviewedPostprin

We present measurements of the streaming potential coupling coefficient in intact sandstone samples saturated with NaCl brines at concentrations up to 5.5 molL⁻¹. The values we record at low salinity are consistent with those reported previously. As brine salinity increases, the coupling coefficient decreases in magnitude, but is still measureable up to the saturated concentration limit. The magnitude of the zeta potential also decreases with increasing salinity, but approaches a constant value at high salinity. This behaviour is not captured by current models of the electrical double layer. Our results suggest that streaming potential measurements may be used to monitor flow in saline subsurface environments such as deep saline aquifers and hydrocarbon reservoirs. However, they were obtained at laboratory temperature. Future work will focus on the effect of elevated temperatures at high salinity.

We report experimental measurements of the streaming potential coupling coefficient in sandstones saturated with NaCl‐dominated artificial and natural brines up to 5.5 M (321.4 g L⁻¹ of NaCl; electrical conductivity of 23 S m⁻¹). We find that the magnitude of the coupling coefficient decreases with increasing brine salinity, as observed in previous experimental studies and predicted by models of the electrical double layer. However, the magnitude of the coupling coefficient remains greater than zero up to the saturated brine salinity. The magnitude of the zeta potential we interpret from our measurements also decreases with increasing brine salinity in the low‐salinity domain (0.4 M). We hypothesize that the constant value of zeta potential observed at high salinity reflects the maximum packing of counterions in the diffuse part of the electrical double layer. Our hypothesis predicts that the zeta potential becomes independent of brine salinity when the diffuse layer thickness is similar to the diameter of the hydrated counterion. This prediction is confirmed by our experimental data and also by published measurements on alumina in KCl brine. At high salinity (>0.4 M), values of the streaming potential coupling coefficient and the corresponding zeta potential are the same within experimental error regardless of sample mineralogy and texture and the composition of the brine.