Quantifying the influence of the type and arrangement of conductive phases on the electrical properties of rocks using impedance spectroscopy

We have employed impedance spectroscopy to investigate the impact of chemical composition and microstructure on the electrical properties of geological samples. Our study focused on a metapelite sample containing graphite, extracted from a depth of 530 meters in borehole DT-1B as part of the DIVE (Drilling the Ivrea-Verbano zonE) project in Ornavasso, Italy. Additionally, we examined the electrical properties of synthetic mineral assemblages. These were created by combining quartz powders with variable amounts of graphite (1% and 5% by weight), muscovite (5% by weight), and biotite (5% by weight). The goal was to identify which conductive or semiconductive phases predominantly influenced the electrical behavior of the metapelite. Measurements were conducted using a Solartron-1260 Impedance/Gain-Phase Analyzer within a piston cylinder apparatus. The experiments were carried out at a pressure of 500 MPa, temperatures ranging from 22 to 1000 °C, nominally dry conditions, and across a frequency range from 0.1 Hz to 200 kHz.

All samples exhibited high electrical resistance (R > 10⁶ Ω.m), low electrical conductivity (< 10^-6 S/m) and behaved as capacitors, with a phase angle magnitude exceeding 70° for most frequency ranges at temperatures below 200 °C. A representative impedance spectrum (Nyquist plot) illustrates this behavior through a partial semicircular arc originating from the origin. An inverse relationship between electrical conductivity and temperature was observed in almost all samples when temperatures increased from 300 to 500 °C. This phenomenon is attributed to the presence of open grain boundaries in the samples, leading to electrical charge scattering. Notable variations in electrical behavior were observed at temperatures exceeding 600 °C, including a linear increase in electrical conductivity, changes in Nyquist plots such as a reduction in prominence of the ‘grain interior arc’ and an increase in significance of the ‘grain boundary arc’, a decrease in sample capacitance, and a significant decline in the phase angle's frequency dependency. Microstructural analysis reveals that these changes were associated with dehydration melting of mica in mica-bearing samples and the growth and interconnection of graphite grains in graphite-bearing samples. Variations in activation enthalpy with temperature suggested that impurity conduction and small polaron hopping played a crucial role at lower temperatures, while the diffusion of H and alkali ions (in mica-bearing samples) or carbon (in graphite-bearing samples) along grain boundaries became significant at higher temperatures.

The natural metapelite sample exhibited electrical conductivities similar to the quartz + 5% graphite sample at high temperatures, reaching 10^-1.5 S/m at 1000°C. This is comparable to the conductivity levels typically measured by magneto-telluric (MT) surveys in Earth's crust.