Publications

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This report summarizes progress from the Laboratory Directed Research and Development (LDRD) program during fiscal year 2006. In addition to a programmatic and financial overview, the report includes progress reports from 430 individual R&D projects in 17 categories.

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This report summarizes progress from the Laboratory Directed Research and Development (LDRD) program during fiscal year 2004. In addition to a programmatic and financial overview, the report includes progress reports from 352 individual R and D projects in 15 categories. The 15 categories are: (1) Advanced Concepts; (2) Advanced Manufacturing; (3) Biotechnology; (4) Chemical and Earth Sciences; (5) Computational and Information Sciences; (6) Differentiating Technologies; (7) Electronics and Photonics; (8) Emerging Threats; (9) Energy and Critical Infrastructures; (10) Engineering Sciences; (11) Grand Challenges; (12) Materials Science and Technology; (13) Nonproliferation and Materials Control; (14) Pulsed Power and High Energy Density Sciences; and (15) Corporate Objectives.

We report our conclusions in support of the FY 2003 Science and Technology Milestone ST03-3.5. The goal of the milestone was to develop a research plan for expanding Sandia's capabilities in materials modeling and simulation. From inquiries and discussion with technical staff during FY 2003 we conclude that it is premature to formulate the envisioned coordinated research plan. The more appropriate goal is to develop a set of computational tools for making scale transitions and accumulate experience with applying these tools to real test cases so as to enable us to attack each new problem with higher confidence of success.

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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.

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Radionuclide transport in soils and groundwaters is routinely calculated in performance assessment (PA) codes using simplified conceptual models for radionuclide sorption, such as the K{sub D} approach for linear and reversible sorption. Model inaccuracies are typically addressed by adding layers of conservativeness (e.g., very low K{sub D}'s), and often result in failed transport predictions or substantial increases in site cleanup costs. Realistic assessments of radionuclide transport over a wide range of environmental conditions can proceed only from accurate, mechanistic models of the sorption process. They have focused on the sorption mechanisms and partition coefficients for Cs{sup +}, Sr{sup 2+} and Ba{sup 2+} (analogue for Ra{sup 2+}) onto iron oxides and clay minerals using an integrated approach that includes computer simulations, sorption/desorption measurements, and synchrotron analyses of metal sorbed substrates under geochemically realistic conditions. Sorption of Ba{sup 2+} and Sr{sup 2+} onto smectite is strong, pH-independent, and fully reversible, suggesting that cation exchange at the interlayer basal sites controls the sorption process. Sr{sup 2+} sorbs weakly onto geothite and quartz, and is pH-dependent. Sr{sup 2+} sorption onto a mixture of smectite and goethite, however, is pH- and concentration dependent. The adsorption capacity of montmorillonite is higher than that of goethite, which may be attributed to the high specific surface area and reaction site density of clays. The presence of goethite also appears to control the extent of metal desorption. In-situ, extended X-ray absorption fine structure (EXAFS) spectroscopic measurements for montmorillonite and goethite show that the first shell of adsorbed Ba{sup 2+} is coordinated by 6 oxygens. The second adsorption shell, however, varies with the mineral surface coverage of adsorbed Ba{sup 2+} and the mineral substrate. This suggests that Ba{sup 2+} adsorption on mineral surfaces involves more than one mechanism and that the stability of sorbed complexes will be affected by substrate composition. Molecular modeling of Ba{sup 2+} sorption on goethite and Cs{sup +} sorption on kaolinite surfaces were performed using molecular dynamics techniques with improved Lennard-Jones interatomic potentials under periodic boundary conditions. Ba{sup 2+} was observed to have a preference for inner sphere sorption onto goethite, with the (101) and (110) surfaces representing the controlling sorption surfaces for bulk K{sub D} measurements. Large-scale simulations of Cs{sup +} sorption on kaolinite (1000's of atoms) provide a statistical basis for the theoretical evaluation and prediction of Cs{sup +} K{sub D} values. Results suggest the formation of a strong inner sphere complex for Cs{sup +} on the kaolinite edge surfaces and a weakly bound outer sphere complex on the hydroxyl basal surface.

Technical guidance for performance assessment (PA) of low-level radioactive waste (LLRW) sites is currently dependent upon experimental retardation factors (K{sub D}'s) to predict radionuclide transport. Accurate predictions of waste transport or retardation will require mechanistic models of radionuclide sorption so as to be applicable to a wide range of soil/groundwater environments. To that end, we have investigated Cs{sup +}, Sr{sup +}, and Ba{sup 2+} sorption on several clay and Fe-oxide minerals. Relative metal binding strengths for montmorillonite clay decrease from Ba{sup 2+} to Sr{sup +}, which is similar to that sorption trend noticed for kaolinite. Molecular dynamics simulations for kaolinite suggest that Cs{sup +} is sorbed at aluminol (010) edge sites as an inner-sphere complex and weakly sorbed as an outer-sphere complex on (001) basal surfaces. Sorption is thought to occur on similar sites for smectite clays, however, the basal plane residual charge and its increased basal plane exposure should have a greater influence on metal sorption. On the other hand, phase transformation kinetics (e.g., ferrihydrite to goethite) is a very important control of metal sorption and resorption for Fe-oxides/hydroxides. These results provide a basis for understanding and predicting metal sorption on complex soil minerals.

Technical support for the Hanford Tank Closure Program focused on evaluation of concepts for immobilization of residual contaminants in the Hanford AX tanks and underlying soils, and identification of cost-effective approaches to improve long-term performance of AX tank farm cIosure systems. Project objectives are to develop materials or engineered systems that would significantly reduce the radionuclide transport to the groundwater from AX tanks containing residual waste. We pursued several studies that, if implemented, would help achieve these goals. They include: (1) tank fill design to reduce water inilltration and potential interaction with residual waste; (2) development of in-tank getter materials that would specifically sorb or sequester radionuclides; (3) evaluation of grout emplacement under and around the tanks to prevent waste leakage during waste retrieval or to minimize water infiltration beneath the tanks; (4) development of getters that will chemically fix specific radionuclides in soils under tanks; and (5) geochemical and hydrologic modeling of waste-water-soil-grout interactions. These studies differ in scope from the reducing grout tank fill employed at the Savannah River Site in that our strategy improves upon tank fill design by providing redundancy in the barriers to radionuclide migration and by modification the hydrogeochemistry external to the tanks.

A key issue in performance assessment of low-level radioactive waste sites is predicting the transport and retardation of radionuclides through local soils under a variety of hydrologic and geochemical conditions. Improved transport codes should include a mechanistic model of radionuclide retardation. The authors have been investigating metal sorption (Cs{sup +}, Sr{sup 2+}, and Ba{sup 2+}) on a simple clay mineral (kaolinite) to better understand the geochemical interactions of common soil minerals with contaminated groundwaters. These studies include detailed characterizations of kaolinite surfaces, experimental adsorption measurements, surface complexation modeling, and theoretical simulations of cation sorption. The aluminol edge (010) site has been identified as the most likely site for metal sorption on kaolinite in natural solutions. Relative metal binding strengths decrease from Ba{sup 2+} to Sr{sup 2+} to Cs{sup +}, with some portion sorbed on both kaolinite edges and basal surfaces. Some Cs{sup +} also appears to be irreversibly sorbed on both sites. Molecular dynamics simulations suggest that Cs{sup +} is sorbed at aluminol (010) edge sites as an inner-sphere complex and weakly sorbed as an outer-sphere complex on (001) basal surfaces. These results provide the basis to understand and predict metal sorption onto kaolinite, and a framework to characterize sorption processes on more complex clay minerals.