Streaming potential measurements 1. Properties of the electrical double layer from crushed rock samples

The zeta potential has been inferred from streaming potential measurements with crushed rock samples as a function of pH and electrolyte concentration for various salts. The value obtained for crushed Fontainebleau sandstone at pH = 5.7 and a KCI solution with a resistivity of 400 Omega m is -40 +/- 5 mV, where the error is dominated by sample to sample variations. The sensitivity of the zeta potential to the electrolyte resistivity for KCI is given experimentally by rho(f)(0.23+/-0.014), where rho(f) is the electrolyte resistivity. The point of zero charge (pzc) is observed for pH = 2.5 +/- 0.1, and the zeta potential is positive for pH < pzc and negative for pH > pzc. For pH > 5 the variations of the zeta potential with pH can be approximated by zeta(pH)/zeta(5.7) = 1 + (0.068 +/- 0.004)(pH - 5.7) for rho(f) = 100 Omega m. The zeta potential has been observed to be sensitive to the valence of the ions and is approximately reduced by the charge of the cation, unless specific adsorption takes place like in the case of Al3+. The experimental results are well accounted for by a three-layer numerical model of the electrical double layer, and the parameters of this model can be evaluated from the experimental data. The sensitivity of the zeta potential to the rock minerals has also been studied. The zeta potential obtained for granitic rocks is comparable to that obtained for Fontainebleau sandstone but can be reduced by a factor of 2-4 for sandstones containing significant fractions of carbonates or clay. To take into account the effect of the chemical composition of the electrolyte, a chemical efficiency is defined as the ratio of the zeta potential to the zeta potential measured for KCl. This chemical efficiency is measured to be similar to 80% for typical groundwater but can be as low as 40% for a water with a high dissolved carbonate content. The set of empirical laws derived from our measurements can be used to assess the magnitude of the streaming potentials expected in natural geophysical systems.