Rock fractures can serve as water conducting structures for fluid flow and mass transport within the Earth's crust. Large apertures, which enable high flow velocities, and a rock matrix with several orders of magnitude lower permeability, are accountable that those structures serve as preferential conduits for solutes and colloids. The mechanistic understanding of fundamental transport and retention processes is essential to make reliable predictions of the fate of solutes and colloids in the subsurface. This comprehensive topic is of paramount importance in many areas of geo-engineering, for example disposal of nuclear waste in deep geological formations, enhanced geothermal systems, CO2 sequestration, gas and oil industry, and contaminant transport in groundwater systems. This cumulative Ph.D. thesis deals with the investigation of the impact of flow channel geometry on solute and colloid transport through natural rough fractures. The bottom-up approach used in this thesis helped to investigate separately the mechanisms and the processes on mass transport (solute and colloids) in four steps. All experiments in this thesis were conducted under hydraulic and chemical settings establishing laminar flow and overall unfavorable colloid attachment conditions.

To assess the relevance of colloidal influences on radionuclide transport for the long-term safety of a radioactive waste repository, the KOLLORADO-2 project integrates the results of geochemical and hydrogeological studies. The results may serve as a basis for an appraisal of the implications of colloid presence in the vicinity of radioactive waste repositories in different deep geological host-rock formations.

This valuable resource discusses several strategies of manipulating colloids for environmental restoration, identifies advantages and disadvantages of each strategy, and considers obstacles limiting the application of each strategy. Approaches evaluated include the following: Chemical modification of subsurface systems to mobilize or deposit colloids in situ Altering the mobility of microorganisms to improve delivery of microbes for bioremediation Manipulating colloids or biocolloids (bacteria) to change aquifer permeability to either enhance bioremediation or create in situ barriers Introducing modified colloids, surfactants, and emulsions to control colloid mobility or to increase recovery of sorbed contaminants by pump and treat methods Manipulation of Groundwater Colloids for Environmental Restoration also contains short, focused research reports on specific studies relevant to the various approaches under consideration. Subjects covered range from mobility of organic macromolecules by controlled field injection experiments to new techniques that investigate surface chemistry and aggregation of inorganic colloids. Other topics discussed include the depositional behavior and transport of biocolloids in porous media, surfactants as modifiers of surface binding sites on colloids, and genetic engineering of microorganisms to serve as contaminant-scavenging biocolloids. Manipulation of Groundwater Colloids for Environmental Restoration is an excellent resource for research scientists in hydrology, chemistry, and microbiology; environmental consultants; regulators; environmental engineers; bioremediation microbiologists; and engineers.

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.

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.

Colloid-facilitated migration of plutonium in fractured rock has been implicated in both field and laboratory studies. Other reactive radionuclides may also experience enhanced mobility due to groundwater colloids. Model prediction of this process is necessary for assessment of contaminant boundaries in systems for which radionuclides are already in the groundwater and for performance assessment of potential repositories for radioactive waste. Therefore, a reactive transport model is developed and parameterized using results from controlled laboratory fracture column experiments. Silica, montmorillonite and clinoptilolite colloids are used in the experiments along with plutonium and Tritium. The goal of the numerical model is to identify and parameterize the physical and chemical processes that affect the colloid-facilitated transport of plutonium in the fractures. The parameters used in this model are similar in form to those that might be used in a field-scale transport model.