Journal
JOURNAL OF PHYSICAL CHEMISTRY B
Volume 114, Issue 18, Pages 6065-6073Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp9070778
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The low-frequency electrical properties of mixtures of silicates and saline H(2)O were measured over broad ranges of temperature and frequency to assess the subfreezing interactions between these materials synoptically, particularly the effects of adsorbed, unfrozen water. Adsorbed water content was determined using nuclear magnetic resonance. Materials were chosen to control effects of grain size and mineralogical complexity, and the initial salt content was also specified. The temperature-dependent DC conductivity of a sand-salt-H(2)O mixture was found to be described well by Archie's law, with either brine or salt hydrate (above and below the eutectic, respectively) as the conductive and partially saturating phase. For materials with pore sizes less than a few micrometers, the brine/hydrate channels become disconnected, and the DC conductivity is controlled by the surrounding ice. High DC conductivity in a montmorillonite-H(2)O mixture is attributed to proton mobility in interlayer adsorbed water. The ice content of the sand mixture was recovered from the static dielectric permittivity using a power-law mixing model. Ice relaxation frequencies were higher than those observed in defect-saturated saline ice, indicating that additional defects are able to form in proximity to silicate surfaces. Five dielectric relaxations related to H(2)O were identified: two orientation polarizations (ice and adsorbed water), two Maxwell-Wagner interfacial polarizations (because of the conductivity differences between hydrate and silicate and adsorbed water and ice, respectively), and a low-frequency dispersion, probably caused by charge hopping. Thicknesses of a few H(2)O monolayers and the preference of hydronium for surface sites, making adsorbed water slightly acidic, favor protons as the mobile charges responsible for these adsorbed-water interfacial polarizations.
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