Mixing Controlled Adsorption at the Liquid-Solid Interfaces in Unsaturated Porous Media

The unsaturated zone, located between the soil surface and the phreatic level, plays an important role in defining the fate of any substance entering the subsoil. In addition to the processes of flow and transport taking place in the liquid phase, surface reactions such as adsorption to the solid phase may occur and increase the residence time of the substance entering the system. In this study, we aim to understand the pore-scale mechanisms that control adsorption in unsaturated systems. We combine 2D pore-scale experimental images with numerical simulations to analyze flow, transport, and adsorption under different liquid saturation degrees. We demonstrate the role of mixing on adsorption at the liquid-solid interfaces by analyzing the deformation in time of a pulse-injected surfactant. We also analyze the impact of the isotherm functional shape and the inclusion of the liquid-gas interfaces as adsorption sites on this surface reaction. The enhancement of mixing as saturation decreases is accompanied by a reduction in the amount of adsorbed mass, located mainly along preferential flow paths, where the solute is primarily transported. For the same isotherm, a nonlinear behavior of adsorption as a function of liquid saturation has been observed. This is explained by the nonlinear variation of the volume fraction of liquid behaving as preferential path or stagnation zone as liquid saturation decreases, despite the linear decrease in the surface area of solids accessible for adsorption.