The Relative Importance of Saturated Silica Sand Interfacial and Pore Fluid Geochemistry on the Spectral Induced Polarization Response

Adsorption at the solid-pore fluid interface is a key mechanism controlling the mobility of nutrients and contaminants in subsurface soils and sediments. The spectral induced polarization (SIP) method has been shown to be sensitive to the quantity and type of adsorbed ions. Extending previous results, we investigated the relevance of pH, solution conductivity, and ion type on the SIP response of saturated silica sand. We also performed adsorption experiments to evaluate whether adsorption plays a relevant role on the effect of saturating solution conductivity and pH. Given their environmental relevance and different electrochemical characteristics, we focused on exploring the influence of Cu²⁺ and Na⁺ adsorption on the SIP signature. The adsorption results confirm the expected and modeled pH influence on the adsorption of both Cu²⁺ and Na⁺. The measured quadrature conductivity spectra indicate that pH and solution conductivity control the electrical double layer electrochemical state and its capacitive behavior. On the contrary, no appreciable SIP signal changes are associated with ion substitution. The adsorption experiments highlight low values of site occupancy for Na and Cu, which suggests that the effects of pH and fluid conductivity are unrelated to their control on the ion adsorption. We interpret the solution conductivity as a proxy for ionic strength. The relative importance of pH and solution conductivity over ion type helps to further constrain the interpretation of SIP results in field geochemical and biogeochemical characterization and monitoring.