Role of air‐water interfaces in colloid transport in porous media: A review

Abstract Air‐water interfaces play an important role in unsaturated porous media, giving rise to phenomena like capillarity. Less recognized and understood are interactions of colloids with the air‐water interface in porous media and the implications of these interactions for fate and transport of colloids. In this review, we discuss how colloids, both suspended in the aqueous phase and attached at pore walls, interact with air‐water interfaces in porous media. We discuss the theory of colloid/air‐water interface interactions, based on the different forces acting between colloids and the air‐water interface (DLVO, hydrophobic, capillary forces) and based on thermodynamic considerations (Gibbs free energy). Subsurface colloids are usually electrostatically repelled from the air‐water interface because most subsurface colloids and the air‐water are negatively charged. However, hydrophobic interactions can lead to attraction to the air‐water interface. When colloids are at the air‐water interface, capillary forces are usually dominant over other forces. Moving air‐water interfaces are effective in mobilizing and transporting colloids from surfaces. Thermodynamic considerations show that, for a colloid, the air‐water interface is the favored state as compared with the suspension phase, except for hydrophilic colloids in the nanometer size range. Experimental evidence indicates that colloid mobilization in soils often occurs through macropores, although matrix transport is also prevalent in absence of macropores. Moving air‐water interfaces, e.g., occurring during infiltration, imbibition, or drainage, have been shown to scour colloids from surfaces and translocate colloids. Colloids can also be pinned to surfaces by thin water films and capillary menisci at the air‐water‐solid interface line, causing colloid retention and immobilization. Air‐water interfaces thus can both mobilize or immobilize colloids in porous media, depending on hydrodynamics and colloid and surface chemistry.