Publications

Abstract not provided.

To confirm conversion of soil Pb to pyromorphite [Pb{sub 5}(PO{sub 4}){sub 3}Cl], a Pb contaminated soil collected adjacent to a historical smelter was reacted with hydroxyapatite in slurries of soil and hydroxyapatite separated by a dialysis membrane and incubated. A crystalline precipitate formed on the dialysis membrane in the slurry systems was identified as chloropyromorphite. Soluble species measured in the soil slurry indicated that dissolution of solid-phase soil Pb was the rate-limiting step for pyromorphite formation. Additionally samples reacted with hydroxyapatite were incubated at field-capacity moisture content. The sequential chemical extraction used to identify species in the field-moist soil incubation experiment showed that hydroxyapatite treatment reduced the first four fractions of extractable Pb and correspondingly increased the recalcitrant extraction residue fraction by 35% of total Pb at 0 d incubation and by 45% after 240 d incubation. the increase in the extraction residue fraction in the 240 d incubation as compared to the 0 d incubation implies that the reaction occurs in the soil but the increase in the hydroxyapatite amended 0 d incubated soil as compared to the control soil illustrates the chemical extraction procedure caused changes in the extractability. Thus, the chemical extraction procedure cannot easily be utilized to confirm changes occurring in the soil as a result of incubation. Extended x-ray absorption fine structure (EXAFS) spectroscopy indicated that the 240 d incubated hydroxyapatite treatment caused a change in the average, local molecular bonding environment of soil Pb. Low-temperature EXAFS spectra (chi data and radial structure functions - RSFs) showed a high degree of similarity between the chemical extraction residue and synthetic pyromorphite. Thus, confirming that the change of soil Pb to pyromorphite is possible by simple amendments of hydroxyapatite to soil.

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.

The US Department of Energy (DOE) has millions of gallons of high level nuclear waste stored in underground tanks at Hanford, Washington and Savannah River, South Carolina. These tanks will eventually be emptied and decommissioned. This will leave a residue of sludge adhering to the interior tank surfaces that may contaminate groundwaters with radionuclides and RCRA metals. Experimentation on such sludges is both dangerous and prohibitively expensive so there is a great advantage to developing artificial sludges. The US DOE Environmental Management Science Program (EMSP) has funded a program to investigate the feasibility of developing such materials. The following text reports on the success of this program, and suggests that much of the radioisotope inventory left in a tank will not move out into the surrounding environment. Ultimately, such studies may play a significant role in developing safe and cost effective tank closure strategies.

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.

Abstract not provided.

Uranium and its fission product Tc in aerobic environment will be in the forms of UO{sub 2}{sup 2+} and TcO{sub 4}{sup {minus}}. Reduced forms of tetravalent U and Tc are sparingly soluble. As determined by transmission electron microscopy, the reduction of uranyl acetate by immobilized cells of Desulfovibrio desulfuricans results in the production of black uraninite nanocrystals precipitated outside the cell. Some nanocrystals are associated with outer membranes of the cell as revealed from cross sections of these metabolic active sulfate-reducing bacteria. The nanocrystals have an average diameter of 5 nm and have anhedral shape. The reduction of Re{sup 7+} by cells of Desulfovibrio desulfuricans is fast in media containing H{sub 2} an electron donor, and slow in media containing lactic acid. It is proposed that the cytochrome in these cells has an important role in the reduction of uranyl and Re{sup 7+} is (a chemical analogue for Tc{sup 7+}) through transferring an electron from molecular hydrogen or lactic acid to the oxyions of UO{sub 2}{sup 2+} and TcO{sub 4}{sup {minus}}.

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.

Junction field effect transistors (JFET) are fabricated on a GaN epitaxial structure grown by metal organic chemical vapor deposition (MOCVD). The DC and microwave characteristics of the device are presented. A junction breakdown voltage of 56 V is obtained corresponding to the theoretical limit of the breakdown field in GaN for the doping levels used. A maximum extrinsic transconductance (g_m) of 48 mS/mm and a maximum source-drain current of 270 mA/mm are achieved on a 0.8 µ m gate JFET device at V_GS= 1 V and V_DS=15 V. The intrinsic transconductance, calculated from the measured g_m and the source series resistance, is 81 mS/mm. The f_T and f_max for these devices are 6 GHz and 12 GHz, respectively. These JFETs exhibit a significant current reduction after a high drain bias is applied, which is attributed to a partially depleted channel caused by trapped hot-electrons in the semi-insulating GaN buffer layer. A theoretical model describing the current collapse is described, and an estimate for the length of the trapped electron region is given.

Transformation of unstable lead [Pb(ll)] forms into insoluble pyromorphite, [Pb5(P04)3(OH, Cl, F...)], by addition of phosphate to Pb contaminated soil has been proposed as a remediation technology which reduces the mobility and bioavailability of Pb. Under aerobic condition, oxidation of dissolved sulfide increases dissolution of galena (PbS), causing it to become a source of liable Pb forms in soils, sediments and wastes. Thus, a galena ore was reacted with synthetic hydroxyapatite [Ca5(P04)30H] under various pH condition to determine the formation rate of pyromorphite and the volubility of galena under the ambient conditions. In a 6 day reaction period the dissolution rate of galena increased with pH due to the oxidation of dissolved sulfide. Correspondingly, formation of chloropyrornorphite became apparent in the galena- apatite suspensions with increasing pH. The insignificant effect of mineral P/Pb molar ratio on the formation of chloropyromorphite implied that dissolution of galena was the rate limiting step.

Cerrusite (PbC03) is soluble under acidic conditions and considered to be a highly bioavailable soil Pb species. In this study, synthetic cerrusite and hydroxyapatite [Ca5(P04)30H] were reacted under constant and dynamic pH conditions with various P/Pb molar ratios in an attempt to evaluate the effect of reaction kinetics on the formation of chloropyromorphite (Pb5(P04)3Cl) and solubilization of Pb. Under constant pH conditions, dissolution rates of both cerrusite and apatite were rapid when pH was low. Complete conversion of Pb from cerrusite to chloropyromorphite occurred within 60 tin at pH 4 and below when the amount of phosphate in the added apatite was stoichoimetrically equal to that needed to transform all added Pb into chloropyromorphite. The concentration of soluble Pb depended upon the volubility of chloropyromorphite. The dissolution rates of apatite and cerrusite decreased with increasing pH, and the transformation was incomplete at pH 5 and above in the 60 rnin reaction period. The soluble Pb level, therefore, was determined by the volubility of cerrusite. In the dynamic pH system which simulated the gastrointestinal tract (GI tract) system, a complete transformation of Pb from cerrusite to chloropyromorphite was achieved due to the complete dissolution of apatite and cerrusite at the initial low pHs. Chloropyromorphite was the exclusive reaction product in both constant and dynamic pH systems as indicated by XRD analysis. The differences in transformation rate and the control of Pb volubility between the reactions occurring in constant and dynamic pH systems indicate the significance of kinetics in controlling the bioavailability of Pb and the potential for the reaction to occur during ingestion.