Moving air-water interfaces can detach colloidal particles from stationary surfaces. The objective of this study was to quantify the effects of advancing and receding air-water interfaces on colloid detachment as a function of interface velocity. We deposited fluorescent, negatively charged, carboxylate-modified polystyrene colloids (diameter of 1 μm) into a cylindrical glass channel. The colloids were hydrophilic with an advancing air-water contact angle of 60° and a receding contact angle of 40°. After colloid deposition, two air bubbles were sequentially introduced into the glass channel and passed through the channel at different velocities (0.5, 7.7, 72, 982, and 10,800 cm/h). The passage of the bubbles represented a sequence of receding and advancing air-water interfaces. Colloids remaining in the glass channel after each interface passage were visualized with confocal microscopy and quantified by image analysis. The advancing air-water interface was significantly more effective in detaching colloids from the glass surface than the receding interface. Most of the colloids were detached during the first passage of the advancing air-water interface, while the subsequent interface passages did not remove significant amounts of colloids. Forces acting on the colloids calculated from theory corroborate our experimental results, and confirm that the detachment forces (surface tension forces) during the advancing air-water interface movement were stronger than during the receding movement. Theory indicates that, for hydrophilic colloids, the advancing interface movement generally exerts a stronger detachment force than the receding, except when the hysteresis of the colloid-air-water contact angle is small and that of the channel-air-water contact angle is large.

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.

Air-water interfaces interact strongly with colloidal particles by capillary forces. The magnitude of the interaction force depends on, among other things, the particle shape. Here, we investigate the effects of particle shape on colloid detachment by a moving air-water interface. We used hydrophilic polystyrene colloids with four different shapes (spheres, barrels, rods, and oblong disks), but otherwise identical surface properties. The nonspherical shapes were created by stretching spherical microspheres on a film of polyvinyl alcohol (PVA). The colloids were then deposited onto the inner surface of a glass channel. An air bubble was introduced into the channel and passed through, thereby generating a receding followed by an advancing air-water interface. The detachment of colloids by the air-water interfaces was visualized with a confocal microscope, quantified by image analysis, and analyzed statistically to determine significant differences. For all colloid shapes, the advancing air-water interface caused pronounced colloid detachment (>63%), whereas the receding interface was ineffective in colloid detachment (<1.5%). Among the different colloid shapes, the barrels were most readily removed (94%) by the advancing interface, followed by the spheres and oblong disks (80%) and the rods (63%). Colloid detachment was significantly affected by colloid shape. The presence of an edge, as it occurs in a barrel-shaped colloid, promoted colloid detachment because the air-water interface is being pinned at the edge of the colloid. This suggests that the magnitude of colloid mobilization and transport in porous media is underestimated for edged particles and overestimated for rodlike particles when a sphere is used as a model colloid.

Capillary fringe fluctuations due to changing water tables lead to displacement of air-water interfaces in soils and sediments. These moving air-water interfaces can mobilize colloids. We visualized colloids interacting with moving air-water interfaces during capillary fringe fluctuations by confocal microscopy. We simulated capillary fringe fluctuations in a glass-bead-filled column. We studied four specific conditions: (1) colloids suspended in the aqueous phase, (2) colloids attached to the glass beads in an initially wet porous medium, (3) colloids attached to the glass beads in an initially dry porous medium, and (4) colloids suspended in the aqueous phase with the presence of a static air bubble. Confocal images confirmed that the capillary fringe fluctuations affect colloid transport behavior. Hydrophilic negatively charged colloids initially suspended in the aqueous phase were deposited at the solid-water interface after a drainage passage, but then were removed by subsequent capillary fringe fluctuations. The colloids that were initially attached to the wet or dry glass bead surface were detached by moving air-water interfaces in the capillary fringe. Hydrophilic negatively charged colloids did not attach to static air-bubbles, but hydrophobic negatively charged and hydrophilic positively charged colloids did. Our results demonstrate that capillary fringe fluctuations are an effective means for colloid mobilization.

Model colloids are usually spherical, but natural colloids have irregular geometries. Transport experiments of spherical colloids may not reflect the transport characteristics of natural colloids in porous media. We investigated saturated and unsaturated transport of colloids with spherical and angular shapes under steady-state, flow conditions. A pulse of negatively-charged colloids was introduced into a silica sand column at three different effective water saturations (Se = 0.31, 0.45, and 1.0). Colloids were introduced under high ionic strength of [106]mM to cause attachment to the secondary energy minimum and later released by changing the pore water to low ionic strength. After the experiment, sand was sampled from different depths (0, -4, and -11 cm) for scanning electron microscopy (SEM) analysis and colloid extraction. Water saturation affected colloid transport with more retention under low than under high saturation. Colloids were retained and released from a secondary energy minimum with more angular-shaped colloids being retained and released. Colloids extracted from the sand revealed highest colloid deposition in the top layer and decreasing deposition with depth. Pore straining and grain-grain wedging dominated colloid retention.