Low-Frequency Electrical Properties of Polycrystalline Saline Ice and Salt Hydrates

Abstract

We measured the 1 mHz-1 MHz electrical properties of ice-hydrate binary systems formed from solutions of NaCl, CaCl(2), and MgSO(4), with supplementary measurements of HCl. Below the eutectic temperature, electrical parameters are well described by mixing models in which hydrate is always the connected phase. Above the eutectic temperature, a salt concentration threshold of approximately 3 mM in the initial solution is required for the unfrozen brine fraction to form interconnected, electrically conductive networks. The dielectric relaxation frequency for saline ice increases with increasing impurity content until Cl(-) reaches saturation. Because there is insufficient H(3)O(+) for charge balance, salt cations must be accommodated interstitially in the ice. Dielectric relaxations near the ice signature were identified for CaCl(2).6H(2)O and MgSO(4).11H(2)O but not for NaCl.2H(2)O. Ionic and L-defect concentrations in salt hydrates up to approximately 10(-4) and 10(-3) per H(2)O molecule, respectively, follow from the electrical properties, Jaccard theory, and the assumption that protonic-defect mobilities are similar to ice. These high defect concentrations-up to a few orders of magnitude greater than saturation values in ice-indicate that intrinsic disruption of hydrogen bonding in salt hydrates is common.