Publications

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Potentially corrosive brines can form during post-closure by deliquescence of salt minerals in dust deposited on the surface of waste packages at Yucca Mountain during operations and the pre-closure ventilation period. Although thermodynamic modeling and experimental studies of brine deliquescence indicates that brines are likely to form, they will be nitrate-rich and non-corrosive. Processes that modify the brines following deliquescence are beneficial with respect to inhibition of corrosion. For example, acid degassing (HCl, HNO3) could dry out brines, but kinetic limitations are likely to limit the effect to increasing their passivity by raising the pH and increasing the NO3/Cl ratio. Predicted dust quantities and maximum brine volumes on the waste package surface are small, and physical isolation of salt minerals in the dust may inhibit formation of eutectic brines and decrease brine volumes. If brines do contact the WP surface, small droplet volumes and layer thicknesses do not support development of diffusive gradients necessary for formation on separate anodic-cathodic zones required for localized corrosion. Finally, should localized corrosion initiate, corrosion product buildup will stifle corrosion, by limiting oxygen access to the metal surface, by capillary retention of brine in corrosion product porosity, or by consumption of brine components (Cl-). © 2006 Materials Research Society.

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This report summarizes the results obtained from a Laboratory Directed Research & Development (LDRD) project entitled 'Investigation of Potential Applications of Self-Assembled Nanostructured Materials in Nuclear Waste Management'. The objectives of this project are to (1) provide a mechanistic understanding of the control of nanometer-scale structures on the ion sorption capability of materials and (2) develop appropriate engineering approaches to improving material properties based on such an understanding.

Acid-base titration and metal sorption experiments were performed on both mesoporous alumina and alumina particles under various ionic strengths. It has been demonstrated that surface chemistry and ion sorption within nanopores can be significantly modified by a nano-scale space confinement. As the pore size is reduced to a few nanometers, the difference between surface acidity constants (ΔpK = pK2 - pK1) decreases, giving rise to a higher surface charge density on a nanopore surface than that on an unconfined solid-solution interface. The change in surface acidity constants results in a shift of ion sorption edges and enhances ion sorption on that nanopore surfaces.

Nanopores are ubiquitous in porous geologic media and may account for >90% of total mineral surface areas. Surface chemistry, ion sorption, and the related geochemical reactions within nanopores can be significantly modified by a nanometer-scale space confinement. As the pore size is reduced to a few nanometers, the difference between surface acidity constants (ΔpK = pK2 - pK1) decreases, giving rise to a higher surface charge density on a nanopore surface than that on an unconfined mineral-water interface. The change in surface acidity constants results in a shift of ion sorption edges and enhances ion sorption on nanopore surfaces. Also, the water activity in a nanopore is greatly reduced, thus increasing the tendency for inner sphere complexation and mineral precipitation. All these effects combine to preferentially enrich trace elements in nanopores, as observed in both field and laboratory studies. The work reported here sheds new light on such fundamental geochemical issues as the irreversibility of ion sorption and desorption, the bioavailability of subsurface contaminants, and the enrichment of trace metals in ore deposits, as well as the kinetics of mineral dissolution and/or precipitation.

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Contaminant release scenarios proposed for the Waste Isolation Pilot Plant (WIPP) repository suggest that the Culebra Dolomite member of the Rustler Formation could be an important radionuclide release path. This thin, vuggy, highly fractured unit is the most transmissive geologic unit overlying the WIPP. Many of the samples obtained from drill cores in the Culebra exhibit fractures that are lined with iron-oxyhydroxide-rich and clay-rich mineral coatings. The coatings are mineralogically distinct from the rock matrix, and may have sorptive characteristics that are different from a clay-poor dolomite matrix. Where locally abundant, such coatings could affect advective/diffusive exchange between matrix blocks and fractures and the accessible mineral surface area available for radionuclide adsorption. Clay minerals are present in the matrix and as fracture coatings in the samples from all the drill core locations examined in this study. Visual examination of rock sample surfaces in the H -19b7 core suggests that at least 7% of the total fracture surface area is coated with iron oxhydroxides or clays. In the samples from H-19b7, the amount of clay disseminated in the matrix varies from <1% to {approx}12 % by weight, and generally increases with stratigraphic height within the unit. In a suite of samples obtained from 12 other locations in the vicinity of the WIPP site, matrix samples from the Culebra contain 0.6--7% clay. These samples were taken from the more transmissive lower two-thirds of the unit (Culebra Units 2-4) which was considered to be the accessible portion of the unit in the WIPP Compliance Certification Application (CCA). Clay minerals also occur as clay-rich laminae and partings with the geometries of primary sedimentary structures and dissolution residues. Such partings are the loci of bedding plane fractures, and have the heaviest clay coatings found in the unit. Crosscutting fractures also commonly exhibit clay mineral coatings, but these are generally discontinuous and much thinner.

Conventional performance assessments assume that radioactive {sup 99}Tc travels as a non-sorbing component with an effective K{sub d} (distribution coefficient) of 0. This is because soil mineral surfaces commonly develop net negative surface charges and pertechnetate (TcO{sub 4}), with large ionic size and low electrical density, is not sorbed onto them. However, a variety of materials have been identified that retain Tc and may eventually lead to promising Tc getters. In assessing Tc getter performance it is important to evaluate the environment in which the getter is to function. In many contaminant plumes Tc will only leach slowly from the source of the contamination and significant dilution is likely. Thus, sub-ppb Tc concentrations are expected and normal groundwater constituents will dominate the aquifer chemistry. In this setting a variety of constituents were found to retard TcO{sub 4}: imogolite, boehmite, hydrotalcite, goethite, copper sulfide and oxide and coal. Near leaking tanks of high level nuclear waste, Tc may be present in mg/L level concentrations and groundwater chemistry will be dominated by constituents from the waste. Both bone char, and to a lesser degree, freshly precipitated Al hydroxides may be effective Tc scavengers in this environment. Thus, the search for Tc getters is far from hopeless, although much remains to be learned about the mechanisms by which these materials retain Tc.