[en] In cultures of Desulfovibrio desulfuricansG20 the effects of iron(III) (hydr)oxides (hematite, goethite, and ferrihydrite) on microbial reduction and reoxidation of uranium (U) were evaluated under lactate-limited sulfate-reducing conditions. With lactate present, G20 reduced U(VI) in both 1,4-piperazinediethanesulfonate (PIPES) and bicarbonate buffer. Once lactate was depleted, however, microbially reduced U served as an electron donor to reduce Fe(III) present in iron(III) (hydr)oxides. With the same initial amount of Fe(III) (10 mmol/L) for each iron(III) (hydr)oxide,reoxidation of U(IV) was greater with hematite than with goethite or ferrihydrite. As the initial mass loading of hematite increased from 0 to 20 mmol of Fe(III)/L, the rate and extent of U(IV) reoxidation increased. Subsequent addition of hematite [15 mmol of Fe(III)/L] to stationary-phase cultures containing microbially reduced U(IV) also resulted in rapid reoxidation to U(VI). Analysis by U L3-edge X-ray absorption near-edge spectroscopy (XANES) of microbially reduced U particles yielded spectra similar to that of natural uraninite. Observations by high-resolution transmission electron microscopy, selected area electron diffraction, and energy-dispersive X-ray spectroscopic analysis confirmed that precipitated U associated with cells was uraninite with particle diameters of 3-5 nm. By the same techniques, iron sulfide precipitates were found to have a variable Fe and S stoichiometry and were not associated with cells

[en] U(VI) dissolved in a modified lactate-C medium (either sulfate- or lactate-limited) was reacted with a mixture of an Fe(III)-(hydr)oxide mineral (hematite, goethite, or ferrihydrite) and quartz under anoxic conditions and equivalent mineral surface areas. After sorption equilibration, the suspensions were inoculated with a sulfate-reducing bacterium (SRB, Desulfovibrio desulfuricans G20). Inoculation of the suspensions containing sulfate-limited medium yielded significant SRB growth, along with concomitant reduction of sulfate and removal of U(VI) from solution. Inoculation of the suspensions containing lactate-limited medium yielded similar results while lactate was still present. Once the lactate was depleted, however, some of the U that had been removed from solution was re-solubilized in the hematite treatment and, to a lesser extent, in the goethite treatment. No re-solubilization was observed in the lactate-limited ferrihydrite treatment even after a prolonged incubation of four months. Analysis by U L3-edge XANES spectroscopy of mineral specimens sampled without inoculation yielded a typical U(VI) spectrum. Mineral specimens sampled at the end of the experiment yielded spectra similar to that of uraninite, thus providing strong evidence for SRB-promoted removal of U(VI) from solution by reductive precipitation of uraninite. Consequently, U re-solubilization was attributed to re-oxidation of the uraninite by Fe(III) present in the (hydr)oxide phases. Our results thus suggest that inoculation with SRB mediates reduction of soluble U(VI) to an insoluble U(IV) oxide so long as a suitable electron donor is available. Depletion of the electron donor may result in partial re-oxidation of the U(IV) to soluble U(VI) species when the surfaces of crystalline Fe(III) (hydr)oxides are incompletely reduced by reaction with SRB-generated sulfide

[en] Biostimulation field experiments with acetate amendment are being performed at a former uranium mill tailings site in Rifle, Colorado, to investigate subsurface processes controlling in situ bioremediation of uranium-contaminated groundwater. An important part of the research is identifying and quantifying field-scale models of the principal terminal electron-accepting processes (TEAPs) during biostimulation and the consequent biogeochemical impacts to the subsurface receiving environment. Integrating abiotic chemistry with the microbially mediated TEAPs in the reaction network brings into play geochemical observations (e.g., pH, alkalinity, redox potential, major ions, and secondary minerals) that the reactive transport model must recognize. These additional constraints provide for a more systematic and mechanistic interpretation of the field behaviors during biostimulation. The reaction network specification developed for the 2002 biostimulation field experiment was successfully applied without additional calibration to the 2003 and 2007 field experiments. The robustness of the model specification is significant in that (1) the 2003 biostimulation field experiment was performed with 3 times higher acetate concentrations than the previous biostimulation in the same field plot (i.e., the 2002 experiment), and (2) the 2007 field experiment was performed in a new unperturbed plot on the same site. The biogeochemical reactive transport simulations accounted for four TEAPs, two distinct functional microbial populations, two pools of bioavailable Fe(III) minerals (iron oxides and phyllosilicate iron), uranium aqueous and surface complexation, mineral precipitation, and dissolution. The conceptual model for bioavailable iron reflects recent laboratory studies with sediments from the Old Rifle Uranium Mill Tailings Remedial Action (UMTRA) site that demonstrated that the bulk (∼90%) of Fe(III) bioreduction is associated with the phyllosilicates rather than the iron oxides. The uranium reaction network includes a U(VI) surface complexation model based on laboratory studies with Old Rifle UMTRA sediments and aqueous complexation reactions that include ternary complexes (e.g., calcium-uranyl-carbonate). The bioreduced U(IV), Fe(II), and sulfide components produced during the experiments are strongly associated with the solid phases and may play an important role in long-term uranium immobilization

[en] Biofilms of sulfate-reducing bacteria Desulfovibrio desulfuricans G20 were used to reduce dissolved U(VI)and subsequently immobilize U(IV) in the presence of uranium-complexing carbonates. The biofilms were grown in three identically operated fixed bed reactors, filled with three types of minerals: one noncarbonate-bearing mineral(hematite) and two carbonate-bearing minerals (calcite and dolomite). The source of carbonates in the reactors filled with calcite and dolomite were the minerals, while in the reactor filled with hematite it was a 10 mM carbonate buffer, pH 7.2, which we added to the growth medium. Our five-month study demonstrated that the sulfate-reducing biofilms grown in all reactors were able to immobilize/reduce uranium efficiently, despite the presence of uranium-complexing carbonates

[en] Hexavalent uranium [U(VI)] was immobilized using biofilms of the sulfate-reducing bacterium (SRB) Desulfovibrio desulfuricans G20. The biofilms were grown in flat-plate continuous-flow reactors using lactate as the electron donor and sulfate as the electron acceptor. U(VI) was continuously fed into the reactor for 32 weeks at a concentration of 126 ?M. During this time, the soluble U(VI) was removed (between 88 and 96% of feed) from solution and immobilized in the biofilms. The dynamics of U immobilization in the sulfate-reducing biofilms were quantified by estimating: (1) microbial activity in the SRB biofilm, defined as the hydrogen sulfide (H2S) production rate and estimated from the H2S concentration profiles measured using microelectrodes across the biofilms; (2) concentration of dissolved U in the solution; and (3) the mass of U precipitated in the biofilm. Results suggest that U was immobilized in the biofilms as a result of two processes: (1) enzymatically and (2) chemically, by reacting with microbially generated H2S. Visual inspection showed that the dissolved sulfide species reacted with U(VI) to produce a black precipitate. Synchrotron-based U L3-edge X-ray absorption near edge structure (XANES) spectroscopy analysis of U precipitated abiotically by sodium sulfide indicated that U(VI) had been reduced to U(IV). Selected-area electron diffraction pattern and crystallographic analysis of transmission electron microscope lattice-fringe images confirmed the structure of precipitated U as being that of uraninite

[en] This is a letter report summarizing work performed in FY2008 to determine the rates of carbon tetrachloride hydrolysis at temperatures close to actual groundwater temperatures. The report describes the project, the methodology, and the results obtained since the project's inception in FY2006. Measurements of hydrolysis rates in homogeneous solution have been completed for temperaturs of 70 C through 40 C, with additional data available at 30 C and 20 C. These results show no difference between the rates in deionized H2O and in filter-sterilized Hanford-Site groundwater. Moreover, the rates measured are 2-3 times slower than predicted from the open literature. Measurements of rates involving sterile suspensions of Hanford-Site sediment in Hanford-Site groundwater, however, show faster hydrolysis at temperatures below 40 C. Extrapolation of the current data available suggests a six-fold increase in rate would be expected at groundwater temperature of 16 C due to the presence of the sediment. This result translates into a 78-year half-life, rather than the 470-680 year half-life that would be predicted from rate determinations in homogeneous solution. The hydrolysis rate data at 20 C, in contrast to those at higher temperatures, are preliminary and have low statistical power. While significant (p < 0.05) differences between the heterogeneous and homogeneous systems are seen at 30 C, the results at 20 C are not statistically significant at this level due to limited data and the very slow nature of the reaction. More time is needed to collect data at these low temperatures to improve the statistical power of our observation. Given the critical need for hydrolysis rate data at temperatures relevant to groundwater systems, we have three recommendations for future work. First, we recommend a continuation of the sampling and analysis of the remaining long-term sealed-ampule experiments described in this report. These are primarily 20 C and 30 C experiments. The data at 20 C, which are most germane to the groundwater environment, will likely take two more years before they are complete. Second, due to the importance of heterogeneous effects, we recommend the continuation of sampling and analysis for a similar set of experiments looking at hydrolysis rates of CT and CF in contact with individual minerals (montmorillonite, kaolinite, albite, and muscovite) or Hanford-Site sediment, and, for CF, in homogeneous solutions. These experiments were set up under a separate project funded by a congressional earmark (EM-22) for which funding expired at the end of FY08. Third, we strongly recommend development of a 13C/12C isotope ratio mass spectrometry (IRMS) approach for determination of hydrolysis rates at groundwater temperatures and relevant CT and CF concentrations. The technique is sensitive enough that we expect to be able to shorten the time required for a rate-constant determination by 20-fold. Thus, a 5-year experiment conducted by the sealed-ampule approach could be shortened to 3 months by the IRMS approach. This sensitivity also would allow the IRMS technique to be used to follow hydrolysis rates at concentrations found in groundwater plumes at Hanford.

[en] There are many circumstances in science where the process of measuring the properties of a system alters the system. An imaging process can exert an inadvertent effect on the object being observed. Consequently, what we observe does not necessarily represent what had been present before the observation. Normally this effect can be ignored if the consequence of such a change is believed not to be significant. The expansion of nanostructured materials has made high resolution transmission electron microscopy one of the indispensable tools for probing the characteristics of nano-materials. Modification of nanoparticles by the electron beam during their imaging has been widely noticed and this is generally believed to be due to electron beam induced heating effect, defect formation in the particles, charging of the particle, or excitation of surrounding gases. However, an explicit experimental identification of which process dominates is often very hard to establish. We report the thickening of native oxide layer on iron nanoparticle under electron beam irradiation. Based on atomic level imaging, electron diffraction, and computer simulation, we have direct evidence that the protecting oxide layer formed on Fe nanoparticle at room temperature in air continues to grow during an electron beam bombardment in the vacuum system typical of most TEM systems. Partial illumination of a nanoparticle and observation of the shell thickening conclusively demonstrates that many of the mechanisms postulated to explain such processes are not occurring to a significant extent. The observed growth is not related to the electron beam induced heating of the nanoparticle, or residual oxygen ionization, or establishment of an electrical field, rather it is related to electron beam facilitated mass transport across the oxide layer (a defect related process)

[en] The combination of zero-valent iron and a clay-type amendment is often observed to have a synergistic effect on the rate of reduction reactions. In this paper, electrochemical techniques are used to determine the mechanism of interaction between the iron and smectite clay minerals. Iron electrodes coated with an evaporated smectite suspension (clay-modified iron electrodes, CMIEs) were prepared using five different smectites: SAz-1, SWa-1, STx-1, SWy-1, and SHCa-1. All the smectites were exchanged with Na+ and one sample of SWy-1 was also exchanged with Mg2+. Potentiodynamic potential scans and cyclic voltammograms were taken using the CMIEs and uncoated but passivated iron electrodes. These electrochemical experiments, along with measurements of the amount of Fe2+ and Fe3+ sorbed in the smectite coating, suggested that the smectite removed the passive layer of the underlying iron electrode during the evaporation process. Cyclic voltammograms taken after the CMIEs were biased at the active-passive transition potential for varying amounts of time suggested that the smectite limited growth of a passive layer, preventing passivation. These results are attributed to the Broensted acidity of the smectite as well as to its ability to sorb iron cations. Oxides that did form on the surface of the iron in the presence of the smectite when it was biased anodically seemed to be different than those that form on the surface of an uncoated iron electrode under otherwise similar conditions; this difference suggested that the smectite reacted with the Fe2+ formed from the oxidation of the underlying iron. No significant correlation could be found between the ability of the smectite to remove the iron passive film and the smectite type. The results have implications for the mixing of sediments and iron particles in permeable reactive barriers, underground storage of radioactive waste in steel canisters, and the use of smectite supports in preventing aggregation of nano-sized zero-valent iron.

[en] Aqueous dissolution of the (1014) surface of calcite was observed at pH near 9 using an atomic force microscope equipped with a fluid cell. The influence of carbonate, Sr, and Mn ion concentrations were observed. Carbonate ions were shown to have a step-specific effect on calcite dissolution. At low levels (5 mu-M) of carbonate, the retreat rate of the more structurally open[441]+steps was than the retreat rate of the structurally confined[441]-steps, leading to anisotropic dissolution. Increasing the carbonate level to 200 mu-M decreased the rate of retreat of both steps, but the[411]+step was slowed to a much greater extent making the dissolution nearly isotropic. At high levels (800 mu-M) of carbonate, the rate of retreat of the[441]+step was slower than that of the[441]-step making dissolution anisotropic in the opposite sense to that observed at low levels of carbonate. This decrease in step velocity at high carbonate levels was attributed to a corresponding increase in the reaction (i.e., precipitation) as the solution approached saturation with respect to calcite, and thus is related to the rate of incorporation of calcium cations into the structure. In addition to changing the rate, this back reaction also altered the shape of etch pits formed by dissolution. Strontium cations were also shown to have a step-specific effect on calcite dissolution similar to that of carbonate, suggesting that strontium is preferentially incorporated into the[441]-step to a greater extent than strontium. When the solution exceeded saturation with respect to rhodochrosite, calcite dissolution was nearly isotropic. These results suggest that the small manganese ion (r= 83 pm), is readily incorporated into both[441]+ and[441]-steps, in contrast to the larger Ca (r= 100 pm) and Sr (r= 131 pm) cations, which are preferentially incorporated into the[441]+step

[en] Thermoluminescence (TL) and Electron Paramagnetic Resonance (EPR) dosimetry were used to measure dose effects in borosilicate glass with time, from 10 minutes to ∼60 days following exposure to a dose of up to 10,000 Rad. TL and EPR results were consistent and performed similarly, with both techniques capable of achieving an estimated limit of detection of between 50-100 Rad. Three peaks were identified in the TL glow curve at roughly 110 C, 205 C, and 225 C. The intensity of the 205 C peak was the dominant peak over the time period of this study. The stability of all of the peaks with time since irradiation increased with their corresponding temperature and little or no variation was observed in the glow curve response to a specified total dose attained at different dose rates. The intensity of the 205 C peak decreased logarithmically with time regardless of total dose. Based upon a conservative limit of detection of 330 Rad, a 10,000 Rad dose would still be detected 2.7E3 years after exposure. This paper introduces the concept of intrinsic dosimetry, the consideration of a measured dose received to container walls in concert with the physical characteristics of the radioactive material contained inside those walls, as a method for gathering rather unique pathway information about the history of that sample. Three hypothetical scenarios are presented to introduce this method and to illustrate how intrinsic dosimetry might benefit the fields of nuclear forensics and waste management.