Diffusion and retention of Co2+ and Zn2+ in compacted homocationic forms of illite: Role of the electrical double layer
Year: 2025
Type: article
Abstract: Surface diffusion of cationic species has frequently been postulated to explain the results of diffusion studies in compacted clay minerals and clay rocks. However, the underlying mechanism of this process is not well understood, and the factors controlling the diffusive flux are not yet satisfactorily quantified. In this study, the role of ion-specific molecular interactions in the electric double layer formed at the clay mineral-fluid interface is investigated, particularly their effect on the diffusive transport of 57 Co 2+ and 65 Zn 2+ tracers. To this end, in-diffusion experiments were conducted at different background electrolyte concentrations in compacted illite with Li + , Na + , K + and Cs + forms. The alkali cations in this series have decreasing hydration enthalpy ( ) and an increasing effective hydrated ion radius. The diffusion data were interpreted using the “two site protolysis non electrostatic surface complexation/electrical double layer” (2SPNE SC/EDL) model. The diffusion and sorption behaviour of 57 Co 2+ and 65 Zn 2+ in various background electrolyte concentrations and homoionic forms of illite was compared in terms of the effective diffusion coefficient D e and the sorption distribution coefficient R d . The extent of surface diffusion was assessed via surface diffusion ratio ( φ ). The results suggest that of ions is a critical factor controlling surface charge neutralisation, and consequently the distribution of the mobile species between the diffuse layer near the mineral surface and the bulk-like water in macroscopic pores. Although 65 Zn 2+ has higher R d values compared to 57 Co 2+ , the surface diffusion phenomenon is equally relevant for both tracers studied in this work. For the 0.03 M and 0.1 M background electrolytes, φ follows the order , while in 0.5 M electrolyte solution the contribution of surface diffusion is negligible in most of the homocationic forms. • The magnitude of surface diffusion (SD) depends on the homocationic form of illite. • More favourable cation hydration means higher SD (less charge screening) • SD is independent of the cation's sorption properties. • The microstructure of illite is not affected by the type of exchangeable cation.
Source: Applied Geochemistry
Institutions: University of Bern, Paul Scherrer Institute
Language: English
Subfield: Biomaterials
Field: Materials Science
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $3,490
OpenAlex ID: W4407405850