Publications

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.

A number of Hanford tanks have leaked high level radioactive wastes (HLW) into the surrounding unconsolidated sediments. The disequilibrium between atmospheric C0{sub 2} or silica-rich soils and the highly caustic (pH > 13) fluids is a driving force for numerous reactions. Hazardous dissolved components such as {sup 133}Cs, {sup 79}Se, {sup 99}Tc may be adsorbed or sequestered by alteration phases, or released in the vadose zone for further transport by surface water. Additionally, it is likely that precipitation and alteration reactions will change the soil permeability and consequently the fluid flow path in the sediments. In order to ascertain the location and mobility/immobility of the radionuclides from leaked solutions within the vadose zone, the authors are currently studying the chemical reactions between: (1) tank simulant solutions and Hanford soil fill minerals; and (2) tank simulant solutions and C0{sub 2}. The authors are investigating soil-solution reactions at: (1) elevated temperatures (60--200 C) to simulate reactions which occur immediately adjacent a radiogenically heated tank; and (2) ambient temperature (25 C) to simulate reactions which take place further from the tanks. The authors studies show that reactions at elevated temperature result in dissolution of silicate minerals and precipitation of zeolitic phases. At 25 C, silicate dissolution is not significant except where smectite clays are involved. However, at this temperature CO{sub 2} uptake by the solution results in precipitation of Al(OH){sub 3} (bayerite). In these studies, radionuclide analogues (Cs, Se and Re--for Tc) were partially removed from the test solutions both during high-temperature fluid-soil interactions and during room temperature bayerite precipitation. Altered soils would permanently retain a fraction of the Cs but essentially all of the Se and Re would be released once the plume was past and normal groundwater came in contact with the contaminated soil. Bayerite, however, will retain significant amounts of all three radionuclides.

Abstract not provided.

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.