Colloids having the same surface charge sign as the bulk of the geologic media in a groundwater system may be able to travel through the system faster than soluble species because they will follow fluid streamlines more closely and they should have less tendency to diffuse into pores or dead spaces in the media than soluble species. Synthetic colloids with uniform, controlled properties may be ideal for serving as {open_quotes}worst-case{close_quotes} tracers that provide lower-bound estimates of contaminant travel times in hydrologic systems. This report discusses a review of the literature pertaining to colloid transport in single saturated natural fractures. After a brief background discussion to put the literature review in perspective, the phenomenon of colloid transport in saturated fractures is divided into three major topics, each of which is reviewed in detail: (1) saturated fluid flow through fractures; (2) colloid transport by convection, diffusion, and force fields; and (3) colloid interactions with surfaces. It is suggested that these phenomena be accounted for in colloid transport models by using (1) lubrication theory to describe water flow through fractures, (2) particle tracking methods to describe colloid transport in fractures, and (3) a kinetic boundary layer approximation to describe colloid interactions with fracture walls. These methods offer better computational efficiency and better experimental accessibility to model parameters than rigorously solving the complete governing equations.

Many contaminants in groundwater strongly interact with the immobile porous matrix, which retards their movement relative to groundwater flow. Colloidal particles, which are often present in groundwater, have a relatively small size and large specific surface area which makes it possible for them to also adsorb pollutants. The sorption of tracers to colloids may enhance their mobility in groundwater, relative to the case where colloids are not present. A class of pollutants for which colloid-facilitated transport may be of particular significance are radioactive isotopes. A major reason for why geologic repositories are considered suitable for the disposal of spent nuclear fuel is the strong affinity of many radionuclides to adsorb onto the porous matrix. Therefore, radionuclides accidentally released, would be contained in the geological media by adsorption or filtration until sufficient decay takes place. However, the presence of colloids may enhance radionuclide mobility in the groundwater, and reduce the efficiency of geologic media to act as a natural barrier.

The goal of this project was to identify the chemical and physical factors that control the transport of colloids in fractured materials, and develop a generalized capability to predict colloid attachment and detachment based on hydraulic factors (head, flow rate), physical processes and structure (fracture aperture, matrix porosity), and chemical properties (surface properties of colloids, solution chemistry, and mineralogy of fracture surfaces). Both aqueous chemistry and physical structure of geologic formations influenced transport. Results of studies at all spatial scales reached consensus on the importance of several key controlling variables: (1) colloid retention is dominated by chemical conditions favoring colloid-wall interactions; (2) even in the presence of conditions favorable to colloid collection, deposited colloids are remobilized over long times and this process contributes substantially to the overall extent of transport; (3) diffusive exchange between water-conducting fractures and finer fractures and pores acts to ''buffer'' the effects of the major fracture network structure, and reduces predictive uncertainties. Predictive tools were developed that account for fundamental mechanisms of colloid dynamics in fracture geometry, and linked to larger-scale processes in networks of fractures. The results of our study highlight the key role of physical and hydrologic factors, and processes of colloid remobilization that are potentially of even greater importance to colloid transport in the vadose zone than in saturated conditions. We propose that this work be extended to focus on understanding vadose zone transport processes so that they can eventually be linked to the understanding and tools developed in our previous project on transport in saturated groundwater systems.

Rainfall experiments were conducted using intact soil cores and an instrumented soil pedon to examine the effect of physical heterogeneity and rainfall characteristics on the mobilization of colloids, organic matter, cesium, and strontium in a fractured soil. To measure the spatial variability of infiltration of colloids and contaminants, samples were collected through a 19-port grid placed below the soil core in laboratory study and in 27 samplers at multiple depths in the soil pedon in the field study. Cesium and strontium were applied to the soil cores and the soil pedon prior to mobilization experiments. Rainwater solutions of multiple ionic strengths and organic matter concentrations were applied to the soil cores and soil pedon to mobilize in situ colloids, cesium, and strontium. The mobilization of colloids and metal cations occurred through preferential flow paths in the soil cores. Compared to steady rainfall, greater amounts of colloids were mobilized during rainfall interrupted by pauses, which indicates that the supply of colloids to be mobilized was replenished during the pauses. A maximum in the amount of mobilized colloids were mobilized during a rainfall following a pause of 2.5 d. Pauses of shorter or longer duration resulted in less colloid mobilization. Freeze-thaw cycles, a transient condition in winter, enhanced colloid mobilization and colloid-facilitated transport of cesium and strontium in the soil cores. The exchange of solutes between the soil matrix and macropores caused a hysteretic mobilization of colloids, cesium, and strontium during changes in ionic strength. Colloid-facilitated mobilization of cesium and strontium was important at low ionic strength in fractures where slow flow allowed greater exchange of flow between the fractures and the surrounding matrix. The release of cesium and strontium by cation exchange occurred at high ionic strength in fractures where there is a little exchange of pore water with the surrounding matrix. The results of the field experiment suggested that ion exchange, and not organic matter- or colloid-facilitated transport, was the dominant mechanism for mobilization of cesium and strontium through the macropores of the fractured soil.