International audienceThe induced polarization model developed recently by Revil and Florsch to understand the complex conductivity of fully saturated granular materials has been extended to partial saturation conditions. It is an improvement over previous models like the Vinegar and Waxman model, which do not account explicitly for the effect of frequency. The Vinegar and Waxman model can be considered as a limiting case of the Revil and Florsch model in the limit where the distribution of relaxation times is very broad. The extended model is applied to the case of unconsolidated sands partially saturated with oil and water. Laboratory experiments were performed to investigate the influence of oil saturation, frequency, grain size, and conductivity of the pore water upon the complex resistivity response of oil-bearing sands. The low-frequency polarization (below 100 Hz) is dominated by the polarization of the Stern layer (the inner part of the electrical double layer coating the surface of the grains in contact with water). The phase exhibits a well-defined relaxation peak with a peak frequency that is dependent on the mean grain diameter as predicted by the model. Both the resistivity and the magnitude of the phase increase with the relative saturation of the oil. The imaginary (quadrature) component of the complex conductivity is observed to decrease with the oil saturation. All these observations are reproduced by the new model
[1] Two sets of experiments were designed to understand the change in induced polarization associated with the sorption of copper and sodium, exhibiting distinct sorption behavior on a silica sand. A sand column experiment was first performed to see the change in the complex conductivity during the advective transport of a copper sulfate solution. A second set of experiments was done with the sand at equilibrium with various solutions of NaCl and CuSO 4 . In the first experiment, the copper sulfate solution replaced a sodium chloride solution, keeping the electrical conductivity of the solution nearly constant. During the passage of the copper sulfate solution, the apparent phase angle decreased from 3 6 0.2 to 0.5 6 0.2 mrad, while the magnitude of the conductivity of the sand remained nearly constant. A quantitative model is proposed to explain the change in the complex conductivity as a function of the chemistry assuming a polarization mechanism associated with the Stern layer (the inner part of the electrical double layer coating the water-mineral interface). The Stern layer polarization is combined with a complexation model describing the competitive sorption of copper and sodium at the pore water interface. The change of the phase lag is directly associated with the ion exchange between sodium and copper at the surface of the silica grains. The explanation of the observed phase differences between Na and Cu relies on their different complexation behaviors, with Na being loosely absorbed, while Cu forms relatively strong complexation with both inner (monodentate) and outer sphere (bidentate) complexes. The replacement of Cu 2þ by Na þ is less favorable; therefore, the kinetics of such a replacement is much slower than for the opposite replacement (Na þ by Cu 2þ ). We were able to reproduce the changes in the phase lags at thermodynamic equilibrium near the relaxation frequency and in the frequency domain. These measurements and modeling results open the door to the quantitative interpretation of spectral induced polarization data in the field in terms of quantification of the sorption processes.Citation: Vaudelet, P., A. Revil, M. Schmutz, M. Franceschi, and P. Bégassat (2011), Induced polarization signatures of cations exhibiting differential sorption behaviors in saturated sands, Water Resour. Res., 47, W02526,
6p.International audienceIn electrolyte-saturated sands, the storage of electrical charges under an alternating electrical field (called "induced polarization") is responsible for a phase lag between the applied current and the resulting electrical field. Because a variety of polarization mechanisms exists in porous materials, the underlying physics of induced polarization is somehow unclear and the field data difficult to interpret quantitatively. Measurements at various pHs and salinities can be used to discriminate between different competing mechanisms at low frequencies (1 mHz-1 kHz) in porous media in the absence of electronic conductors. New experimental data point out that, in addition to the polarization of the Stern layer (the inner part of the electrical double layer coating the surface of the silica grains), there is another polarization mechanism possibly associated with a hopping process of the protons on the silica surface. We propose that such a process could follow a Grotthuss cooperation mechanism (as in ice) involving the bound water of the silica surface. Our data also rule out a mechanism based on the diffuse layer. The new polarization mechanism may be applied to quantifying induced-polarization data collected over acidic contaminant plumes
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