Aquasols: on the role of secondary minima.

Experiments are presented that test the hypothesis of deposition into and reentrainment from secondary minima during flow through porous media. The release of deposited particles following a decrease in ionic strength is inconsistent with deposition in the primary minimum of either simple DLVO interaction energy curves (which suggest that deposition is irreversible) or Born-DLVO interaction energy curves (which create a finite primary minimum that deepens with decreasing ionic strength). The observed release of particles is, on the other hand, consistent with deposition in the secondary minimum because this energy minimum decreases and can disappear with decreasing ionic strength. The implications for colloid transport of a reversible deposition process in the secondary minimum are very different from those of a process involving irreversible deposition in the primary minimum. First, particles that are continually captured and released will travel much farther in the subsurface than might be expected if the classic irreversible filtration model is applied. Second, and perhaps more significantly, deposition in the secondary well can increase with increasing particle size. Although particle transport by convective diffusion increases as particle size decreases, particle "attachment" in secondary minima decreases with decreasing particle size. Thus, smaller particles (those with diameters in the order of a few tens of nanometers) would be more effective in the facilitated transport of highly sorbing contaminants such as hydrophobic organic molecules, metals, and radionuclides. Other contaminants are themselves particles, such as viruses (tens of nanometers in diameter) and bacteria (near 1 microm in diameter). Due to this difference in size, viruses could be transported over much larger distances than bacteria. Third, the transport of colloids and, hence, the transport of contaminants associated with them, depends on the Hamaker constant of the particle-water-aquifer media system. Colloids of lower Hamaker constant are likely to be transported farther than colloids of higher Hamaker constant. The extent of adsorption of specific contaminants and the Hamaker constant for the particle-aquifer system are both characteristics of the particles and contribute to the effectiveness of colloid-facilitated transport. Finally, the solution chemistry of the pore waters (through pH, ionic strength, types of solutes, and the valence of the ions) ultimately controls the deposition and release of colloidal particles in porous media. The pH determines the charge density and surface potential of the surfaces. When the surfaces are similarly charged, their interaction can be unfavorable, with an energy barrier and secondary minimum. The ionic strength and valence of the ions determines the shape of the interaction energy curve, including the presence and height of the energy barrier and the presence and depth of the secondary well. Since the subsequent release of a particle depends on the mode in which the particle is deposited (primary or secondary), these factors are particularly important in determining the extent of colloid transport in the subsurface.