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

The ζ 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 KCl solution with a resistivity of 400 Ω m is -40 ± 5 mV, where the error is dominated by sample to sample variations. The sensitivity of the ζ potential to the electrolyte resistivity for KCl is given experimentally by ρ_f^0.23±0.014, where ρ_f is the electrolyte resistivity. The point of zero charge (pzc) is observed for pH = 2.5 ± 0.1, and the ζ potential is positive for pH < pzc and negative for pH > pzc. For pH > 5 the variations of the ζ potential with pH can be approximated by ζ(pH)/ζ(5.7) = 1 + (0.068 ± 0.004)(pH - 5.7) for ρ_f = 100 Ω m. The ζ 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 ζ potential to the rock minerals has also been studied. The ζ 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 ζ potential to the ζ potential measured for KCl. This chemical efficiency is measured to be ∼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.