Zeta potential in sandpacks: Effect of temperature, electrolyte pH, ionic strength and divalent cations

Rocks in many subsurface settings are at elevated temperature and are saturated with brines of high ionic strength (high salinity) containing divalent ions. Yet most laboratory measurements of zeta potential in earth materials are obtained at room temperature using simple monovalent electrolytes at low ionic strength. Consequently, the zeta potential at conditions relevant to many subsurface settings is not known. We report experimental measurements of the temperature dependence of the zeta potential in well characterised, natural quartz sandpacks over the temperature range 23–120 °C saturated with electrolytes containing divalent ions at a range of concentrations relevant to natural systems. We find that the key control on zeta potential in these unbuffered experiments is pH, which varies in response to temperature and electrolyte composition. The zeta potential is negative irrespective of sample or electrolyte, but its magnitude is strongly correlated to pH, which varies both with temperature and the concentration of divalent ions. The pH decreases with increasing temperature at low ionic strength, but is independent of temperature at high ionic strength. The pH is also typically lower in the presence of divalent ions, irrespective of the total ionic strength. The zeta potential increases in magnitude with increasing pH. Different relationships between zeta potential, temperature and concentration of divalent ions could be obtained in buffered experiments where the pH is fixed at a given value.