Capillary suction under unsaturated condition drives strong specific affinity of ions at the surface of clay mineral

Mineral-solution interface is of great importance in many soil and geochemical processes as well as industrial applications. Most relevant studies were based on saturated condition and given the corresponding theory, model, and mechanism. However, soils are usually in the non-saturation with different capillary suction. Our study presents substantially different scenery for ions interacting with mineral surface under unsaturated condition using molecular dynamics method. Under partially hydrated state, both cations (Ca²⁺) and anions (Cl^-) can be adsorbed as outer-sphere complexes at the montmorillonite surface, and the number significantly increased with the increase of unsaturated degree. Ions preferred to interact with clay mineral instead of water molecules under unsaturated state, and the mobility of both cations and anions substantially decreased with the increase of capillary suction as reflected by the diffusion coefficient analysis. Potential of mean force calculations further clearly revealed that the adsorption strength of both Ca²⁺ and Cl^- increased with capillary suction. Such an increase was more obvious for Cl^- compared to Ca²⁺, despite the adsorption strength of Cl^- was much weaker than Ca²⁺ at a certain capillary suction. Therefore, it is the capillary suction under unsaturated condition that drives the strong specific affinity of ions at the surface of clay mineral, which was tightly related to the steric effect of confined water film, the destruction of EDL structure, and the cation-anion pair interaction. This suggests that our common understanding of mineral-solution interaction should be largely improved.