Uranium(IV) adsorption by natural organic matter in anoxic sediments

DOE PAGES

Bone, Sharon E.; Dynes, James J.; Cliff, John; ...

2017-01-09

Uranium is an important carbon-free fuel source and environmental contaminant that accumulates in the tetravalent state, U(IV), in anoxic sediments, such as ore deposits, marine basins, and contaminated aquifers. However, little is known about the speciation of U(IV) in low-temperature geochemical environments, inhibiting the development of a conceptual model of U behavior. Until recently, U(IV) was assumed to exist predominantly as the sparingly soluble mineral uraninite (UO 2+x) in anoxic sediments; however, studies now show that this is not often the case. Yet a model of U(IV) speciation in the absence of mineral formation under field-relevant conditions has not yetmore » been developed. Uranium(IV) speciation controls its reactivity, particularly its susceptibility to oxidative mobilization, impacting its distribution and toxicity. Here we show adsorption to organic carbon and organic carbon-coated clays dominate U(IV) speciation in an organic-rich natural substrate under field-relevant conditions. Whereas previous research assumed that U(IV) speciation is dictated by the mode of reduction (i.e., whether reduction is mediated by microbes or by inorganic reductants), our results demonstrate that mineral formation can be diminished in favor of adsorption, regardless of reduction pathway. Projections of U transport and bioavailability, and thus its threat to human and ecosystem health, must consider U(IV) adsorption to organic matter within the sediment environment.« less

Environmental proteomics reveals early microbial community responses to biostimulation at a uranium- and nitrate-contaminated site.

PubMed

Chourey, Karuna; Nissen, Silke; Vishnivetskaya, Tatiana; Shah, Manesh; Pfiffner, Susan; Hettich, Robert L; Löffler, Frank E

2013-10-01

High-performance MS instrumentation coupled with improved protein extraction techniques enables metaproteomics to identify active members of soil and groundwater microbial communities. Metaproteomics workflows were applied to study the initial responses (i.e. 4 days post treatment) of the indigenous aquifer microbiota to biostimulation with emulsified vegetable oil (EVO) at a uranium-contaminated site. Members of the Betaproteobacteria (i.e. Dechloromonas, Ralstonia, Rhodoferax, Polaromonas, Delftia, Chromobacterium) and the Firmicutes dominated the biostimulated aquifer community. Proteome characterization revealed distinct differences between the microbial biomass collected from groundwater influenced by biostimulation and groundwater collected upgradient of the EVO injection points. In particular, proteins involved in ammonium assimilation, EVO degradation, and polyhydroxybutyrate granule formation were prominent following biostimulation. Interestingly, the atypical NosZ of Dechloromonas spp. was highly abundant, suggesting active nitrous oxide (N2 O) respiration. c-Type cytochromes were barely detected, as was citrate synthase, a biomarker for hexavalent uranium reduction activity, suggesting that uranium reduction has not commenced 4 days post EVO amendment. Environmental metaproteomics identified microbial community responses to biostimulation and elucidated active pathways demonstrating the value of this technique as a monitoring tool and for complementing nucleic acid-based approaches. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-resolution mineralogical characterization and biogeochemical modeling of uranium reaction pathways at the FRC

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen Zhu

2006-06-15

High-Resolution Mineralogical Characterization and Biogeochemical Modeling of Uranium Reduction Pathways at the Oak Ridge Field-Research Center (FRC) Chen Zhu, Indiana University, David R. Veblen, Johns Hopkins University We have successfully completed a proof-of-concept, one-year grant on a three-year proposal from the former NABIR program, and here we seek additional two-year funding to complete and publish the research. Using a state-of-the-art 300-kV, atomic resolution, Field Emission Gun Transmission Electron Microscope (TEM), we have successfully identified three categories of mineral hosts for uranium in contaminated soils: (1) iron oxides; (2) mixed manganese-iron oxides; and (3) uranium phosphates. Method development using parallel electronmore » energy loss spectroscopy (EELS) associated with the TEM shows great promise for characterizing the valence states of immobilized U during bioremediation. We have also collected 27 groundwater samples from two push-pull field biostimulation tests, which form two time series from zero to approximately 600 hours. The temporal evolution in major cations, anions, trace elements, and the stable isotopes 34S, 18O in sulfate, 15N in nitrate, and 13C in dissolved inorganic carbon (DIC) clearly show that biostimulation resulted in reduction of nitrate, Mn(IV), Fe(III), U(VI), sulfate, and Tc(VII), and these reduction reactions were intimately coupled with a complex network of inorganic reactions evident from alkalinity, pH, Na, K, Mg, and Ca concentrations. From these temporal trends, apparent zero order rates were regressed. However, our extensive suite of chemical and isotopic data sets, perhaps the first and only comprehensive data set available at the FRC, show that the derived rates from these field biostimulation experiments are composite and lump-sum rates. There were several reactions that were occurring at the same time but were masked by these pseudo-zero order rates. A reaction-path model comprising a total of nine redox couples (NO3–/NH4+, MnO2(s)/Mn2+, Fe(OH)3(s) /Fe2+, TcO4–/TcO2(s), UO22+/UO2(s), SO42–/HS–, CO2/CH4, ethanol/acetate, and H+/H2.) is used to simulate the temporal biogeochemical evolution observed in the field tests. Preliminary results show that the models based on thermodynamics and more complex rate laws can generate the apparent zero order rates when several concurrent or competing reactions occur. Professor Alex Halliday of Oxford University, UK, and his postdoctoral associates are measuring the uranium isotopes in our groundwater samples. Newly developed state-of-the-art analytical techniques in measuring variability in 235U/238U offer the potential to distinguish biotic and abiotic uranium reductive mechanisms.« less

Subsurface Conditions Controlling Uranium Incorporation in Iron Oxides: A Redox Stable Sink

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fendorf, Scott

2016-04-05

Toxic metals and radionuclides throughout the U.S. Department of Energy Complex pose a serious threat to ecosystems and to human health. Of particular concern is the redox-sensitive radionuclide uranium, which is classified as a priority pollutant in soils and groundwaters at most DOE sites owing to its large inventory, its health risks, and its mobility with respect to primary waste sources. The goal of this research was to contribute to the long-term mission of the Subsurface Biogeochemistry Program by determining reactions of uranium with iron (hydr)oxides that lead to long-term stabilization of this pervasive contaminant. The research objectives of thismore » project were thus to (1) identify the (bio)geochemical conditions, including those of the solid-phase, promoting uranium incorporation in Fe (hydr)oxides, (2) determine the magnitude of uranium incorporation under a variety of relevant subsurface conditions in order to quantify the importance of this pathway when in competition with reduction or adsorption; (3) identify the mechanism(s) of U(VI/V) incorporation in Fe (hydr)oxides; and (4) determine the stability of these phases under different biogeochemical (inclusive of redox) conditions. Our research demonstrates that redox transformations are capable of achieving U incorporation into goethite at ambient temperatures, and that this transformation occurs within days at U and Fe(II) concentrations that are common in subsurface geochemical environments with natural ferrihydrites—inclusive of those with natural impurities. Increasing Fe(II) or U concentration, or initial pH, made U(VI) reduction to U(IV) a more competitive sequestration pathway in this system, presumably by increasing the relative rate of U reduction. Uranium concentrations commonly found in contaminated subsurface environments are often on the order of 1-10 μM, and groundwater Fe(II) concentrations can reach exceed 1 mM in reduced zones of the subsurface. The redox-driven U(V) incorporation mechanism may help to explain U retention in some geologic materials, improving our understanding of U-based geochronology and the redox status of ancient geochemical environments. Additionally, U(VI) may be incorporated within silicate minerals though encapsulation of U-bearing iron oxides, leading to a redox stable solid. Our research detailing previously unrecognized mechanism of U incorporation within sediment minerals may even lead to new approaches for in situ contamination remediation techniques, and will help refine models of U fate and transport in reduced subsurface zones.« less

Mechanisms and Rates of U(VI) Reduction by Fe(II) in Homogeneous Aqueous Solution and the Role of U(V) Disproportionation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Collins, Richard N.; Rosso, Kevin M.

Molecular-level pathways in the aqueous redox transformation of uranium by iron remain unclear, despite the importance of this knowledge for predicting uranium transport and distribution in natural and engineered environments. As the relative importance of homogeneous versus heterogeneous pathways is difficult to probe experimentally, here we apply computational molecular simulation to isolate rates of key one electron transfer reactions in the homogeneous pathway. By comparison to experimental observations the role of the heterogeneous pathway also becomes clear. Density functional theory (DFT) and Marcus theory calculations for all primary monomeric species at pH values ≤7 show for UO22+ and its hydrolysismore » species UO2OH+ and UO2(OH)20 that reduction by Fe2+ is thermodynamically favorable, though kinetically limited for UO22+. An inner-sphere encounter complex between UO2OH+ and Fe2+ was the most stable for the first hydrolysis species and displayed an electron transfer rate constant ket = 4.3 × 103 s-1. Three stable inner- and outer-sphere encounter complexes between UO2(OH)20 and Fe2+ were found, with electron transfer rate constants ranging from ket = 7.6 × 102 to 7.2 × 104 s-1. Homogeneous reduction of these U(VI) hydrolysis species to U(V) is, therefore, predicted to be facile. In contrast, homogeneous reduction of UO2+ by Fe2+ was found to be thermodynamically unfavorable, suggesting the possible importance of U(V)-U(V) disproportionation as a route to U(IV). Calculations on homogeneous disproportionation, however, while yielding a stable outer-sphere U(V)-U(V) encounter complex, indicate that this electron transfer reaction is not feasible at circumneutral pH. Protonation of both axial O atoms of acceptor U(V) (i.e., by H3O+) was found to be a prerequisite to stabilize U(IV), consistent with the experimental observation that the rate of this reaction is inversely correlated with pH. Thus, despite prevailing notions that U(V) is rapidly eliminated by homogeneous disproportionation, this pathway is irrelevant at environmental conditions.« less

Environmental proteomics reveals early microbial community responses to biostimulation at a uranium- and nitrate-contaminated site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chourey, Karuna; Nissen, Silke; Vishnivetskaya, T.

2013-01-01

High performance mass spectrometry instrumentation coupled with improved protein extraction techniques enable metaproteomics to identify active members of soil and groundwater microbial communities. Metaproteomics workflows were applied to study the initial responses (i.e., 4 days post treatment) of the indigenous aquifer microbiota to biostimulation with emulsified vegetable oil (EVO) at a uranium-contaminated site. Members of the Betaproteobacteria (i.e., Dechloromonas, Ralstonia, Rhodoferax, Polaromonas, Delftia, Chromobacterium) and Firmicutes dominated the biostimulated aquifer community. Proteome characterization revealed distinct differences in protein expression between the microbial biomass collected from groundwater influenced by biostimulation and groundwater collected up-gradient of the EVO injection points. In particular,more » proteins involved in ammonium assimilation, EVO degradation, and polyhydroxybutyrate (PHB) granule formation were prominent following biostimulation. Interestingly, the atypical NosZ of a Dechloromonas sp. was highly expressed suggesting active nitrous oxide (N2O) respiration. c-type cytochromes were barely detected, as was citrate synthase, a biomarker for hexavalent uranium reduction activity, suggesting that metal reduction has not commenced 4 days post EVO delivery. Environmental metaproteomics identified microbial community responses to biostimulation and elucidated active pathways demonstrating the value of this technique for complementing nucleic acid-based approaches.« less

Global Modeling of Uranium Molecular Species Formation Using Laser-Ablated Plasmas

NASA Astrophysics Data System (ADS)

Curreli, Davide; Finko, Mikhail; Azer, Magdi; Armstrong, Mike; Crowhurst, Jonathan; Radousky, Harry; Rose, Timothy; Stavrou, Elissaios; Weisz, David; Zaug, Joseph

2016-10-01

Uranium is chemically fractionated from other refractory elements in post-detonation nuclear debris but the mechanism is poorly understood. Fractionation alters the chemistry of the nuclear debris so that it no longer reflects the chemistry of the source weapon. The conditions of a condensing fireball can be simulated by a low-temperature plasma formed by vaporizing a uranium sample via laser heating. We have developed a global plasma kinetic model in order to model the chemical evolution of U/UOx species within an ablated plasma plume. The model allows to track the time evolution of the density and energy of an uranium plasma plume moving through an oxygen atmosphere of given fugacity, as well as other relevant quantities such as average electron and gas temperature. Comparison of model predictions with absorption spectroscopy of uranium-ablated plasmas provide preliminary insights on the key chemical species and evolution pathways involved during the fractionation process. This project was sponsored by the DoD, Defense Threat Reduction Agency, Grant HDTRA1-16-1-0020. This work was performed in part under the auspices of the U.S. DoE by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Electron transfer at the cell-uranium interface in Geobacter spp.

PubMed

Reguera, Gemma

2012-12-01

The in situ stimulation of Fe(III) oxide reduction in the subsurface stimulates the growth of Geobacter spp. and the precipitation of U(VI) from groundwater. As with Fe(III) oxide reduction, the reduction of uranium by Geobacter spp. requires the expression of their conductive pili. The pili bind the soluble uranium and catalyse its extracellular reductive precipitation along the pili filaments as a mononuclear U(IV) complexed by carbon-containing ligands. Although most of the uranium is immobilized by the pili, some uranium deposits are also observed in discreet regions of the outer membrane, consistent with the participation of redox-active foci, presumably c-type cytochromes, in the extracellular reduction of uranium. It is unlikely that cytochromes released from the outer membrane could associate with the pili and contribute to the catalysis, because scanning tunnelling microscopy spectroscopy did not reveal any haem-specific electronic features in the pili, but, rather, showed topographic and electronic features intrinsic to the pilus shaft. Pili not only enhance the rate and extent of uranium reduction per cell, but also prevent the uranium from traversing the outer membrane and mineralizing the cell envelope. As a result, pili expression preserves the essential respiratory activities of the cell envelope and the cell's viability. Hence the results support a model in which the conductive pili function as the primary mechanism for the reduction of uranium and cellular protection in Geobacter spp.

PRODUCTION OF URANIUM METAL BY CARBON REDUCTION

DOEpatents

Holden, R.B.; Powers, R.M.; Blaber, O.J.

1959-09-22

The preparation of uranium metal by the carbon reduction of an oxide of uranium is described. In a preferred embodiment of the invention a charge composed of carbon and uranium oxide is heated to a solid mass after which it is further heated under vacuum to a temperature of about 2000 deg C to produce a fused uranium metal. Slowly ccoling the fused mass produces a dendritic structure of uranium carbide in uranium metal. Reacting the solidified charge with deionized water hydrolyzes the uranium carbide to finely divide uranium dioxide which can be separated from the coarser uranium metal by ordinary filtration methods.

Microbial reduction of uranium

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.; Gorby, Y.A.; Landa, E.R.

1991-01-01

REDUCTION of the soluble, oxidized form of uranium, U(VI), to insoluble U(IV) is an important mechanism for the immobilization of uranium in aquatic sediments and for the formation of some uranium ores1-10. U(VI) reduction has generally been regarded as an abiological reaction in which sulphide, molecular hydrogen or organic compounds function as the reductant1,2,5,11. Microbial involvement in U(VI) reduction has been considered to be limited to indirect effects, such as microbial metabolism providing the reduced compounds for abiological U(VI) reduction and microbial cell walls providing a surface to stimulate abiological U(VI) reduction1,12,13. We report here, however, that dissimilatory Fe(III)-reducing microorganisms can obtain energy for growth by electron transport to U(VI). This novel form of microbial metabolism can be much faster than commonly cited abiological mechanisms for U(VI) reduction. Not only do these findings expand the known potential terminal electron acceptors for microbial energy transduction, they offer a likely explanation for the deposition of uranium in aquatic sediments and aquifers, and suggest a method for biological remediation of environments contaminated with uranium.

Extracellular reduction of uranium via Geobacter conductive pili as a protective cellular mechanism.

PubMed

Cologgi, Dena L; Lampa-Pastirk, Sanela; Speers, Allison M; Kelly, Shelly D; Reguera, Gemma

2011-09-13

The in situ stimulation of Fe(III) oxide reduction by Geobacter bacteria leads to the concomitant precipitation of hexavalent uranium [U(VI)] from groundwater. Despite its promise for the bioremediation of uranium contaminants, the biological mechanism behind this reaction remains elusive. Because Fe(III) oxide reduction requires the expression of Geobacter's conductive pili, we evaluated their contribution to uranium reduction in Geobacter sulfurreducens grown under pili-inducing or noninducing conditions. A pilin-deficient mutant and a genetically complemented strain with reduced outer membrane c-cytochrome content were used as controls. Pili expression significantly enhanced the rate and extent of uranium immobilization per cell and prevented periplasmic mineralization. As a result, pili expression also preserved the vital respiratory activities of the cell envelope and the cell's viability. Uranium preferentially precipitated along the pili and, to a lesser extent, on outer membrane redox-active foci. In contrast, the pilus-defective strains had different degrees of periplasmic mineralization matching well with their outer membrane c-cytochrome content. X-ray absorption spectroscopy analyses demonstrated the extracellular reduction of U(VI) by the pili to mononuclear tetravalent uranium U(IV) complexed by carbon-containing ligands, consistent with a biological reduction. In contrast, the U(IV) in the pilin-deficient mutant cells also required an additional phosphorous ligand, in agreement with the predominantly periplasmic mineralization of uranium observed in this strain. These findings demonstrate a previously unrecognized role for Geobacter conductive pili in the extracellular reduction of uranium, and highlight its essential function as a catalytic and protective cellular mechanism that is of interest for the bioremediation of uranium-contaminated groundwater.

Uranium Sequestration During Biostimulated Reduction and In Response to the Return of Oxic Conditions In Shallow Aquifers

USGS Publications Warehouse

Fuller, Christopher C.; Johnson, Kelly J.; Akstin, Katherine; Singer, David M.; Yabusaki, Steven B.; Fang, Yilin; Fuhrmann, M.

2015-01-01

A proposed approach for groundwater remediation of uranium contamination is to generate reducing conditions by stimulating the growth of microbial populations through injection of electron donor compounds into the subsurface. Sufficiently reducing conditions will result in reduction of soluble hexavalent uranium, U(VI), and precipitation of the less soluble +4 oxidation state uranium, U(IV). This process is termed biostimulated reduction. A key issue in the remediation of uranium (U) contamination in aquifers by biostimulated reduction is the long term stability of the sequestered uranium. Three flow-through column experiments using aquifer sediment were used to evaluate the remobilization of bioreduced U sequestered under conditions in which biostimulation extended well into sulfate reduction to enhance precipitation of reduced sulfur phases such as iron sulfides. One column received added ferrous iron, Fe(II), increasing production of iron sulfides, to test their effect on remobilization of the sequestered uranium, either by serving as a redox buffer by competing for dissolved oxygen, or by armoring the reduced uranium. During biostimulation of the ambient microbial population with acetate, dissolved uranium was lowered by a factor of 2.5 or more with continued removal for over 110 days of biostimulation, well after the onset of sulfate reduction at ~30 days. Sequestered uranium was essentially all U(IV) resulting from the formation of nano-particulate uraninite that coated sediment grains to a thickness of a few 10’s of microns, sometimes in association with S and Fe. A multicomponent biogeochemical reactive transport model simulation of column effluents during biostimulation was generally able to describe the acetate oxidation, iron, sulfate, and uranium reduction for all three columns using parameters derived from simulations of field scale biostimulation experiments. Columns were eluted with artificial groundwater at equilibrium with atmospheric oxygen to simulate the upper limit of dissolved oxygen in recharge water. Overall about 9% of total uranium removed from solution during biostimulation was remobilized. Release of U during oxic elution was a continuous process over 140 days with dissolved uranium concentrations about 0.2 and 0.8 aM for columns with and without ferrous iron addition, respectively. Uranium remaining on the sediment was in the reduced form. The prolonged period of biostimulation and concomitant sulfate reduction appears to limit the rate of U(IV) oxidative remobilization in contrast to a large release observed for columns in previous studies that did not undergo sulfate reduction. Although continued sulfate reduction may cause decreased permeability from precipitation of iron sulfide, the greater apparent stability of the sequestered U(IV) provided by the sustained biostimulation should be considered in design of field scale remediation efforts. Remobilization of uranium following biostimulated reduction should be tested further at the field scale.

Reductive stripping process for the recovery of uranium from wet-process phosphoric acid

DOEpatents

Hurst, Fred J.; Crouse, David J.

1984-01-01

A reductive stripping flow sheet for recovery of uranium from wet-process phosphoric acid is described. Uranium is stripped from a uranium-loaded organic phase by a redox reaction converting the uranyl to uranous ion. The uranous ion is reoxidized to the uranyl oxidation state to form an aqueous feed solution highly concentrated in uranium. Processing of this feed through a second solvent extraction cycle requires far less stripping reagent as compared to a flow sheet which does not include the reductive stripping reaction.

Erythrocytes of uranium miners: the activity of the pentose phosphate pathway

PubMed Central

Vích, Z.; Novosad, F.; Brychtová, V.

1970-01-01

Vích, Z., Novosad, F., and Brychtová, V. (1970).Brit. J. industr. Med.,27, 287-290. Erythrocytes of uranium miners: the activity of the pentose phosphate pathway. The functioning of erythrocytes was studied by determination of the activity of the pentose phosphate pathway in 431 individuals - 221 uranium miners, 42 employees of a uranium ore trimming station (30 of whom were exposed), 36 former uranium miners, 32 coal miners, and 100 persons not working in mines and with no previous exposure. In the groups exposed to long-term occupational radiation, the activity of the pentose phosphate cycle was found to be enhanced. This finding was interpreted as evidence for a change in the functional state of the erythrocytes in exposed persons due to the effects of radiation on the genesis of red cells in the bone marrow. PMID:5448126

The roles of organic matter in the formation of uranium deposits in sedimentary rocks

USGS Publications Warehouse

Spirakis, C.S.

1996-01-01

Because reduced uranium species have a much smaller solubility than oxidized uranium species and because of the strong association of organic matter (a powerful reductant) with many uranium ores, reduction has long been considered to be the precipitation mechanism for many types of uranium deposits. Organic matter may also be involved in the alterations in and around tabular uranium deposits, including dolomite precipitation, formation of silicified layers, iron-titanium oxide destruction, dissolution of quartz grains, and precipitation of clay minerals. The diagenetic processes that produced these alterations also consumed organic matter. Consequently, those tabular deposits that underwent the more advanced stages of diagenesis, including methanogenesis and organic acid generation, display the greatest range of alterations and contain the smallest amount of organic matter. Because of certain similarities between tabular uranium deposits and Precambrian unconformity-related deposits, some of the same processes might have been involved in the genesis of Precambrian unconformity-related deposits. Hydrologic studies place important constraints on genetic models of various types of uranium deposits. In roll-front deposits, oxidized waters carried uranium to reductants (organic matter and pyrite derived from sulfate reduction by organic matter). After these reductants were oxidized at any point in the host sandstone, uranium minerals were reoxidized and transported further down the flow path to react with additional reductants. In this manner, the uranium ore migrated through the sandstone at a rate slower than the mineralizing ground water. In the case of tabular uranium deposits, the recharge of surface water into the ground water during flooding of lakes carried soluble humic material to the water table or to an interface where humate precipitated in tabular layers. These humate layers then established the chemical conditions for mineralization and related alterations. In the case of Precambrian unconformity-related deposits, free thermal convection in the thick sandstones overlying the basement rocks carried uranium to concentrations of organic matter in the basement rocks.

Enhanced uranium immobilization and reduction by Geobacter sulfurreducens biofilms.

PubMed

Cologgi, Dena L; Speers, Allison M; Bullard, Blair A; Kelly, Shelly D; Reguera, Gemma

2014-11-01

Biofilms formed by dissimilatory metal reducers are of interest to develop permeable biobarriers for the immobilization of soluble contaminants such as uranium. Here we show that biofilms of the model uranium-reducing bacterium Geobacter sulfurreducens immobilized substantially more U(VI) than planktonic cells and did so for longer periods of time, reductively precipitating it to a mononuclear U(IV) phase involving carbon ligands. The biofilms also tolerated high and otherwise toxic concentrations (up to 5 mM) of uranium, consistent with a respiratory strategy that also protected the cells from uranium toxicity. The enhanced ability of the biofilms to immobilize uranium correlated only partially with the biofilm biomass and thickness and depended greatly on the area of the biofilm exposed to the soluble contaminant. In contrast, uranium reduction depended on the expression of Geobacter conductive pili and, to a lesser extent, on the presence of the c cytochrome OmcZ in the biofilm matrix. The results support a model in which the electroactive biofilm matrix immobilizes and reduces the uranium in the top stratum. This mechanism prevents the permeation and mineralization of uranium in the cell envelope, thereby preserving essential cellular functions and enhancing the catalytic capacity of Geobacter cells to reduce uranium. Hence, the biofilms provide cells with a physically and chemically protected environment for the sustained immobilization and reduction of uranium that is of interest for the development of improved strategies for the in situ bioremediation of environments impacted by uranium contamination. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

Enhanced Uranium Immobilization and Reduction by Geobacter sulfurreducens Biofilms

PubMed Central

Cologgi, Dena L.; Speers, Allison M.; Bullard, Blair A.; Kelly, Shelly D.

2014-01-01

Biofilms formed by dissimilatory metal reducers are of interest to develop permeable biobarriers for the immobilization of soluble contaminants such as uranium. Here we show that biofilms of the model uranium-reducing bacterium Geobacter sulfurreducens immobilized substantially more U(VI) than planktonic cells and did so for longer periods of time, reductively precipitating it to a mononuclear U(IV) phase involving carbon ligands. The biofilms also tolerated high and otherwise toxic concentrations (up to 5 mM) of uranium, consistent with a respiratory strategy that also protected the cells from uranium toxicity. The enhanced ability of the biofilms to immobilize uranium correlated only partially with the biofilm biomass and thickness and depended greatly on the area of the biofilm exposed to the soluble contaminant. In contrast, uranium reduction depended on the expression of Geobacter conductive pili and, to a lesser extent, on the presence of the c cytochrome OmcZ in the biofilm matrix. The results support a model in which the electroactive biofilm matrix immobilizes and reduces the uranium in the top stratum. This mechanism prevents the permeation and mineralization of uranium in the cell envelope, thereby preserving essential cellular functions and enhancing the catalytic capacity of Geobacter cells to reduce uranium. Hence, the biofilms provide cells with a physically and chemically protected environment for the sustained immobilization and reduction of uranium that is of interest for the development of improved strategies for the in situ bioremediation of environments impacted by uranium contamination. PMID:25128347

Process for continuous production of metallic uranium and uranium alloys

DOEpatents

Hayden, H.W. Jr.; Horton, J.A.; Elliott, G.R.B.

1995-06-06

A method is described for forming metallic uranium, or a uranium alloy, from uranium oxide in a manner which substantially eliminates the formation of uranium-containing wastes. A source of uranium dioxide is first provided, for example, by reducing uranium trioxide (UO{sub 3}), or any other substantially stable uranium oxide, to form the uranium dioxide (UO{sub 2}). This uranium dioxide is then chlorinated to form uranium tetrachloride (UCl{sub 4}), and the uranium tetrachloride is then reduced to metallic uranium by reacting the uranium chloride with a metal which will form the chloride of the metal. This last step may be carried out in the presence of another metal capable of forming one or more alloys with metallic uranium to thereby lower the melting point of the reduced uranium product. The metal chloride formed during the uranium tetrachloride reduction step may then be reduced in an electrolysis cell to recover and recycle the metal back to the uranium tetrachloride reduction operation and the chlorine gas back to the uranium dioxide chlorination operation. 4 figs.

Process for continuous production of metallic uranium and uranium alloys

DOEpatents

Hayden, Jr., Howard W.; Horton, James A.; Elliott, Guy R. B.

1995-01-01

A method is described for forming metallic uranium, or a uranium alloy, from uranium oxide in a manner which substantially eliminates the formation of uranium-containing wastes. A source of uranium dioxide is first provided, for example, by reducing uranium trioxide (UO.sub.3), or any other substantially stable uranium oxide, to form the uranium dioxide (UO.sub.2). This uranium dioxide is then chlorinated to form uranium tetrachloride (UCl.sub.4), and the uranium tetrachloride is then reduced to metallic uranium by reacting the uranium chloride with a metal which will form the chloride of the metal. This last step may be carried out in the presence of another metal capable of forming one or more alloys with metallic uranium to thereby lower the melting point of the reduced uranium product. The metal chloride formed during the uranium tetrachloride reduction step may then be reduced in an electrolysis cell to recover and recycle the metal back to the uranium tetrachloride reduction operation and the chlorine gas back to the uranium dioxide chlorination operation.

Remediation of uranium contaminated soils with bicarbonate extraction and microbial U(VI) reduction

USGS Publications Warehouse

Philips , Elizabeth J.P.; Landa, Edward R.; Lovely, Derek R.

1995-01-01

A process for concentrating uranium from contaminated soils in which the uranium is first extracted with bicarbonate and then the extracted uranium is precipitated with U(VI)-reducing microorganisms was evaluated for a variety of uranuum-contaminated soils. Bicarbonate (100 mM) extracted 20–94% of the uranium that was extracted with nitric acid. The U(VI)-reducing microorganism,Desulfovibrio desulfuricans reduced the U(VI) to U(IV) in the bicarbonate extracts. In some instances unidentified dissolved extracted components, presumably organics, gave the extract a yellow color and inhibited U(VI) reduction and/or the precipitation of U(IV). Removal of the dissolved yellow material with the addition of hydrogen peroxide alleviated this inhibition. These results demonstrate that bicarbonate extraction of uranium from soil followed by microbial U(VI) reduction might be an effective mechanism for concentrating uranium from some contaminated soils.

METHOD FOR THE REDUCTION OF URANIUM COMPOUNDS

DOEpatents

Cooke, W.H.; Crawford, J.W.C.

1959-05-12

An improved technique of preparing massive metallic uranium by the reaction at elevated temperature between an excess of alkali in alkaline earth metal and a uranium halide, such ss uranium tetrafluoride is presented. The improvement comprises employing a reducing atmosphere of hydrogen or the like, such as coal gas, in the vessel during the reduction stage and then replacing the reducing atmosphere with argon gas prior to cooling to ambient temperature.

Analysis of radon reduction and ventilation systems in uranium mines in China.

PubMed

Hu, Peng-hua; Li, Xian-jie

2012-09-01

Mine ventilation is the most important way of reducing radon in uranium mines. At present, the radon and radon progeny levels in Chinese uranium mines where the cut and fill stoping method is used are 3-5 times higher than those in foreign uranium mines, as there is not much difference in the investments for ventilation protection between Chinese uranium mines and international advanced uranium mines with compaction methodology. In this paper, through the analysis of radon reduction and ventilation systems in Chinese uranium mines and the comparison of advantages and disadvantages between a variety of ventilation systems in terms of radon control, the authors try to illustrate the reasons for the higher radon and radon progeny levels in Chinese uranium mines and put forward some problems in three areas, namely the theory of radon control and ventilation systems, radon reduction ventilation measures and ventilation management. For these problems, this paper puts forward some proposals regarding some aspects, such as strengthening scrutiny, verifying and monitoring the practical situation, making clear ventilation plans, strictly following the mining sequence, promoting training of ventilation staff, enhancing ventilation system management, developing radon reduction ventilation technology, purchasing ventilation equipment as soon as possible in the future, and so on.

METHOD OF ROLLING URANIUM

DOEpatents

Smith, C.S.

1959-08-01

A method is described for rolling uranium metal at relatively low temperatures and under non-oxidizing conditions. The method involves the steps of heating the uranium to 200 deg C in an oil bath, withdrawing the uranium and permitting the oil to drain so that only a thin protective coating remains and rolling the oil coated uranium at a temperature of 200 deg C to give about a 15% reduction in thickness at each pass. The operation may be repeated to accomplish about a 90% reduction without edge cracking, checking or any appreciable increase in brittleness.

Volumetric determination of uranium titanous sulfate as reductant before oxidimetric titration

USGS Publications Warehouse

Wahlberg, J.S.; Skinner, D.L.; Rader, L.F.

1957-01-01

Need for a more rapid volumetric method for the routine determination of uranium in uranium-rich materials has led to the development of a method that uses titanous sulfate as a reductant before oxidimetric titration. Separation of the hydrogen sulfide group is not necessary. Interfering elements precipitated by cupferron are removed by automatic filtrations made simultaneously rather than by the longer chloroform extraction method. Uranium is reduced from VI to IV by addition of an excess of titanous sulfate solution, cupric ion serving as an indicator by forming red metallic copper when reduction is complete. The copper is reoxidized by addition of mercuric perchlorate. The reduced uranium is then determined by addition of excess ferric sulfate and titration with ceric sulfate. The method has proved to be rapid, accurate, and economical.

Method of precipitating uranium from an aqueous solution and/or sediment

DOEpatents

Tokunaga, Tetsu K; Kim, Yongman; Wan, Jiamin

2013-08-20

A method for precipitating uranium from an aqueous solution and/or sediment comprising uranium and/or vanadium is presented. The method includes precipitating uranium as a uranyl vanadate through mixing an aqueous solution and/or sediment comprising uranium and/or vanadium and a solution comprising a monovalent or divalent cation to form the corresponding cation uranyl vanadate precipitate. The method also provides a pathway for extraction of uranium and vanadium from an aqueous solution and/or sediment.

Effect of Reaction Pathway on the Extent and Mechanism of Uranium(VI) Immobilization with Calcium and Phosphate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mehta, Vrajesh S.; Maillot, Fabien; Wang, Zheming

Phosphate addition to subsurface environments contaminated with uranium can be used as an in situ remediation approach. Batch experiments were conducted to evaluate the dependence of the extent and mechanism of uranium uptake on the pathway for reaction with calcium phosphates. At pH 4.0 and 6.0 uranium uptake occurred via autunite (Ca(UO2)(PO4)3) precipitation irrespective of the starting forms of calcium and phosphate. At pH 7.5, the uptake mechanism depended on the nature of the calcium and phosphate. When dissolved uranium, calcium, and phosphate were added simultaneously, uranium was structurally incorporated into a newly formed amorphous calcium phosphate solid. Adsorption wasmore » the dominant removal mechanism for uranium contacted with pre-formed amorphous calcium phosphate solids,. When U(VI) was added to a suspension containing amorphous calcium phosphate solids as well as dissolved calcium and phosphate, then removal occurred through precipitation (57±4 %) of autunite and adsorption (43±4 %) onto calcium phosphate. The solid phase speciation of the uranium was determined using X-ray absorption spectroscopy and laser induced fluorescence spectroscopy. Dissolved uranium, calcium, and phosphate concentrations with saturation index calculations helped identify removal mechanisms and determine thermodynamically favorable solid phases.« less

Kinetic study of the carbothermic synthesis of uranium monocarbide microspheres

NASA Astrophysics Data System (ADS)

Mukerjee, S. K.; Dehadraya, J. V.; Vaidya, V. N.; Sood, D. D.

1990-06-01

Uranium monocarbide microspheres were synthesized by carbothermic reduction of porous uranium oxide microspheres with uniformly dispersed carbon black. Kinetics of the reduction was studied under vacuum and flowing inert gas from 1250 to 1550° C. The carbon monoxide gas concentration in the effluent stream during reduction was used to determine the rate of carbide formation. Under vacuum, reduction was found to be controlled by reaction at the reactant-product interface whereas under flowing gas conditions, the diffusion of carbon monoxide gas through the carbide layer was the rate controlling process. The activation energy was 335.1 ± 8.6 and 363.7 ± 7.6 kJ/mol for reduction under vacuum and flowing gas, respectively.

Uranium-mediated electrocatalytic dihydrogen production from water.

PubMed

Halter, Dominik P; Heinemann, Frank W; Bachmann, Julien; Meyer, Karsten

2016-02-18

Depleted uranium is a mildly radioactive waste product that is stockpiled worldwide. The chemical reactivity of uranium complexes is well documented, including the stoichiometric activation of small molecules of biological and industrial interest such as H2O, CO2, CO, or N2 (refs 1 - 11), but catalytic transformations with actinides remain underexplored in comparison to transition-metal catalysis. For reduction of water to H2, complexes of low-valent uranium show the highest potential, but are known to react violently and uncontrollably forming stable bridging oxo or uranyl species. As a result, only a few oxidations of uranium with water have been reported so far; all stoichiometric. Catalytic H2 production, however, requires the reductive recovery of the catalyst via a challenging cleavage of the uranium-bound oxygen-containing ligand. Here we report the electrocatalytic water reduction observed with a trisaryloxide U(III) complex [(((Ad,Me)ArO)3mes)U] (refs 18 and 19)--the first homogeneous uranium catalyst for H2 production from H2O. The catalytic cycle involves rare terminal U(IV)-OH and U(V)=O complexes, which have been isolated, characterized, and proven to be integral parts of the catalytic mechanism. The recognition of uranium compounds as potentially useful catalysts suggests new applications for such light actinides. The development of uranium-based catalysts provides new perspectives on nuclear waste management strategies, by suggesting that mildly radioactive depleted uranium--an abundant waste product of the nuclear power industry--could be a valuable resource.

In-situ evidence for uranium immobilization and remobilization

USGS Publications Warehouse

Senko, John M.; Istok, Jonathan D.; Suflita, Joseph M.; Krumholz, Lee R.

2002-01-01

The in-situ microbial reduction and immobilization of uranium was assessed as a means of preventing the migration of this element in the terrestrial subsurface. Uranium immobilization (putatively identified as reduction) and microbial respiratory activities were evaluated in the presence of exogenous electron donors and acceptors with field push−pull tests using wells installed in an anoxic aquifer contaminated with landfill leachate. Uranium(VI) amended at 1.5 μM was reduced to less than 1 nM in groundwater in less than 8 d during all field experiments. Amendments of 0.5 mM sulfate or 5 mM nitrate slowed U(VI) immobilization and allowed for the recovery of 10% and 54% of the injected element, respectively, as compared to 4% in the unamended treatment. Laboratory incubations confirmed the field tests and showed that the majority of the U(VI) immobilized was due to microbial reduction. In these tests, nitrate treatment (7.5 mM) inhibited U(VI) reduction, and nitrite was transiently produced. Further push−pull tests were performed in which either 1 or 5 mM nitrate was added with 1.0 μM U(VI) to sediments that already contained immobilized uranium. After an initial loss of the amendments, the concentration of soluble U(VI) increased and eventually exceeded the injected concentration, indicating that previously immobilized uranium was remobilized as nitrate was reduced. Laboratory experiments using heat-inactivated sediment slurries suggested that the intermediates of dissimilatory nitrate reduction (denitrification or dissimilatory nitrate reduction to ammonia), nitrite, nitrous oxide, and nitric oxide were all capable of oxidizing and mobilizing U(IV). These findings indicate that in-situ subsurface U(VI) immobilization can be expected to take place under anaerobic conditions, but the permanence of the approach can be impaired by disimilatory nitrate reduction intermediates that can mobilize previously reduced uranium.

Developing uranium dicarbide-graphite porous materials for the SPES project

NASA Astrophysics Data System (ADS)

Biasetto, L.; Zanonato, P.; Carturan, S.; Di Bernardo, P.; Colombo, P.; Andrighetto, A.; Prete, G.

2010-09-01

Uranium carbide dispersed in graphite was produced under vacuum by means of carbothermic reduction of different uranium oxides (UO 2, U 3O 8 and UO 3), using graphite as the source of carbon. The thermal process was monitored by mass spectrometry and the gas evolution confirmed the reduction of the U 3O 8 and UO 3 oxides to UO 2 before the carbothermic reaction, that started to occur at T > 1000 °C. XRD analysis confirmed the formation of α-UC 2 and of a minor amount of UC. The morphology of the produced uranium carbide was not affected by the oxides employed as the source of uranium.

URANIUM RECOVERY FROM COMPOSITE UF$sub 4$ REDUCTION BOMB WASTES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, E R; Doyle, R L; Coleman, J R

1954-01-28

A number of techniques have been investigated on a laboratory-scale for separating uranium from fluorides during the recovery of uranium from UF4 reduction bomb wastes (C-oxide) by an HCl leach - NH4OH precipitation process. Among these are included adsorption of fluorides from filtered leach liquors, fractional precipitation of fluorides and uranium, complexing of fluorides into forms soluble in slightly acid solutions, and fluoride volatilization from the uranium concentrate. Solubility studies of CaF2 and MgF2 in aqueous hydrochloric acid at various acidities and temperatures were also conducted. A description of the production-scale processing of C-oxide in the FMPC scrap plant hasmore » been included.« less

Uranium mineralization and unconformities: how do they correlate? - A look beyond the classic unconformity-type deposit model?

NASA Astrophysics Data System (ADS)

Markwitz, Vanessa; Porwal, Alok; Campbell McCuaig, T.; Kreuzer, Oliver P.

2010-05-01

Uranium deposits are usually classified based on the characteristics of their host rocks and geological environments (Dahlkamp, 1993; OECD/NEA Red Book and IAEA, 2000; Cuney, 2009). The traditional unconformity-related deposit types are the most economical deposits in the world, with the highest grades amongst all uranium deposit types. In order to predict undiscovered uranium deposits, there is a need to understand the spatial association of uranium mineralization with structures and unconformities. Hydrothermal uranium deposits develop by uranium enriched fluids from source rocks, transported along permeable pathways to their depositional environment. Unconformities are not only separating competent from incompetent sequences, but provide the physico-chemical gradient in the depositional environment. They acted as important fluid flow pathways for uranium to migrate not only for surface-derived oxygenated fluids, but also for high oxidized metamorphic and magmatic fluids, dominated by their geological environment in which the unconformities occur. We have carried out comprehensive empirical spatial analyses of various types of uranium deposits in Australia, and first results indicate that there is a strong spatial correlation between unconformities and uranium deposits, not only for traditional unconformity-related deposits but also for other styles. As a start we analysed uranium deposits in Queensland and in particular Proterozoic metasomatic-related deposits in the Mount Isa Inlier and Late Carboniferous to Early Permian volcanic-hosted uranium occurrences in Georgetown and Charters Towers Regions show strong spatial associations with contemporary and older unconformities. The Georgetown Inlier in northern Queensland consists of a diverse range of rocks, including Proterozoic and early Palaeozoic metamorphic rocks and granites and late Palaeozoic volcanic rocks and related granites. Uranium-molybdenum (+/- fluorine) mineralization in the Georgetown inlier varies from strata- to structure-bound and occurs above regional unconformities. The Proterozoic basins in the Mount Isa Inlier rest unconformably on Palaeoproterozoic basement accompanied by volcanic and igneous rocks, which were deformed and metamorphosed in the Mesoproterozoic. Uranium occurrences in the Western Succession of Mount Isa are either hosted in clastic metasediments or mafic volcanics that belong to the Palaeoproterozoic Eastern Creek Volcanics. Uranium and vanadium mineralization occur in metasomatised and hematite-magnetite-carbonate alteration zones, bounded by major faults and regional unconformities. The results of this study highlight the importance of unconformities in uranium minerals systems as possible fluid pathways and/or surfaces of physico-chemical contrast that could have facilitated the precipitation of uranium, not only in classical unconformity style uranium deposits but in several other styles of uranium mineralization as well. References Cuney, M., 2009. The extreme diversity of uranium deposits. Mineralium Deposita, 44, 3-9. Dahlkamp, F. J., 1993. Uranium ore deposits. Springer, Berlin, p 460. OECD / NEA Red Book & IAEA, 2000. Uranium 1999: Resources, Production and Demand. OECD Nuclear Energy Agency and International Atomic Energy Agency, Paris.

Sensitivity of geological, geochemical and hydrologic parameters in complex reactive transport systems for in-situ uranium bioremediation

NASA Astrophysics Data System (ADS)

Yang, G.; Maher, K.; Caers, J.

2015-12-01

Groundwater contamination associated with remediated uranium mill tailings is a challenging environmental problem, particularly within the Colorado River Basin. To examine the effectiveness of in-situ bioremediation of U(VI), acetate injection has been proposed and tested at the Rifle pilot site. There have been several geologic modeling and simulated contaminant transport investigations, to evaluate the potential outcomes of the process and identify crucial factors for successful uranium reduction. Ultimately, findings from these studies would contribute to accurate predictions of the efficacy of uranium reduction. However, all these previous studies have considered limited model complexities, either because of the concern that data is too sparse to resolve such complex systems or because some parameters are assumed to be less important. Such simplified initial modeling, however, limits the predictive power of the model. Moreover, previous studies have not yet focused on spatial heterogeneity of various modeling components and its impact on the spatial distribution of the immobilized uranium (U(IV)). In this study, we study the impact of uncertainty on 21 parameters on model responses by means of recently developed distance-based global sensitivity analysis (DGSA), to study the main effects and interactions of parameters of various types. The 21 parameters include, for example, spatial variability of initial uranium concentration, mean hydraulic conductivity, and variogram structures of hydraulic conductivity. DGSA allows for studying multi-variate model responses based on spatial and non-spatial model parameters. When calculating the distances between model responses, in addition to the overall uranium reduction efficacy, we also considered the spatial profiles of the immobilized uranium concentration as target response. Results show that the mean hydraulic conductivity and the mineral reaction rate are the two most sensitive parameters with regard to the overall uranium reduction. But in terms of spatial distribution of immobilized uranium, initial conditions of uranium concentration and spatial uncertainty in hydraulic conductivity also become important. These analyses serve as the first step of further prediction practices of the complex uranium transport and reaction systems.

Release of 226Ra from uranium mill tailings by microbial Fe(III) reduction

USGS Publications Warehouse

Landa, E.R.; Phillips, E.J.P.; Lovley, D.R.

1991-01-01

Uranium mill tailings were anaerobically incubated in the presence of H2 with Alteromonas putrefaciens, a bacterium known to couple the oxidation of H2 and organic compounds to the reduction of Fe(III) oxides. There was a direct correlation between the extent of Fe(III) reduction and the accumulation of dissolved 226Ra. In sterile tailings in which Fe(III) was not reduced, there was negligible leaching of 226Ra. The behavior of Ba was similar to that of Ra in inoculated and sterile systems. These results demonstrate that under anaerobic conditions, microbial reduction of Fe(III) may result in the release of dissolved 226Ra from uranium mill tailings. ?? 1991.

Reductive stripping process for uranium recovery from organic extracts

DOEpatents

Hurst, F.J. Jr.

1983-06-16

In the reductive stripping of uranium from an organic extractant in a uranium recovery process, the use of phosphoric acid having a molarity in the range of 8 to 10 increases the efficiency of the reductive stripping and allows the strip step to operate with lower aqueous to organic recycle ratios and shorter retention time in the mixer stages. Under these operating conditions, less solvent is required in the process, and smaller, less expensive process equipment can be utilized. The high strength H/sub 3/PO/sub 4/ is available from the evaporator stage of the process.

Reductive stripping process for uranium recovery from organic extracts

DOEpatents

Hurst, Jr., Fred J.

1985-01-01

In the reductive stripping of uranium from an organic extractant in a uranium recovery process, the use of phosphoric acid having a molarity in the range of 8 to 10 increases the efficiency of the reductive stripping and allows the strip step to operate with lower aqueous to organic recycle ratios and shorter retention time in the mixer stages. Under these operating conditions, less solvent is required in the process, and smaller, less expensive process equipment can be utilized. The high strength H.sub.3 PO.sub.4 is available from the evaporator stage of the process.

Reduction of uranium by cytochrome c3 of Desulfovibrio vulgaris

USGS Publications Warehouse

Lovley, D.R.; Widman, P.K.; Woodward, J.C.; Phillips, E.J.P.

1993-01-01

The mechanism for U(VI) reduction by Desulfovibrio vulgaris (Hildenborough) was investigated. The H2-dependent U(VI) reductase activity in the soluble fraction of the cells was lost when the soluble fraction was passed over a cationic exchange column which extracted cytochrome c3. Addition of cytochrome c3 back to the soluble fraction that had been passed over the cationic exchange column restored the U(VI)-reducing capacity. Reduced cytochrome c3 was oxidized by U(VI), as was a c-type cytochrome(s) in whole-cell suspensions. When cytochrome c3 was combined with hydrogenase, its physiological electron donor, U(VI) was reduced in the presence of H2. Hydrogenase alone could not reduce U(VI). Rapid U(VI) reduction was followed by a subsequent slow precipitation of the U(IV) mineral uraninite. Cytochrome c3 reduced U(VI) in a uranium-contaminated surface water and groundwater. Cytochrome c3 provides the first enzyme model for the reduction and biomineralization of uranium in sedimentary environments. Furthermore, the finding that cytochrome c3 can catalyze the reductive precipitation of uranium may aid in the development of fixed-enzyme reactors and/or organisms with enhanced U(VI)-reducing capacity for the bioremediation of uranium- contaminated waters and waste streams.

Use of Sodium Dithionite as Part of a More Efficient Groundwater Restoration Method Following In-situ Recovery of Uranium at the Smith-Ranch Highland Site in Wyoming

NASA Astrophysics Data System (ADS)

Harris, R.; Reimus, P. W.; Ware, D.; Williams, K.; Chu, D.; Perkins, G.; Migdissov, A. A.; Bonwell, C.

2017-12-01

Uranium is primarily mined for nuclear power production using an aqueous extraction technique called in-situ recovery (ISR). ISR can pollute groundwater with residual uranium and other heavy metals. Reverse osmosis and groundwater sweep are currently used to restore groundwater after ISR mining, but are not permanent solutions. Sodium dithionite is being tested as part of a method to more permanently restore groundwater after ISR mining at the Smith-Ranch Highland site in Wyoming. Sodium dithionite is a chemical reductant that can reduce sediments that were oxidized during ISR. The reduced sediments can reduce soluble uranium (VI) in the groundwater to insoluble uranium (IV). Laboratory studies that use sodium dithionite to treat sediments and waters from the site may help predict how it will behave during a field deployment. An aqueous batch experiment showed that sodium dithionite reduced uranium in post-mined untreated groundwater from 38 ppm to less than 1 ppm after 1 day. A sediment reduction batch experiment showed that sodium dithionite-treated sediments were capable of reducing uranium in post-mined untreated groundwater from 38 ppm to 2 ppm after 7 days. One column experiment is showing post-mined sodium dithionite-treated sediments are capable of reducing uranium in post-mined groundwater for over 30 pore volumes past the initial injection. While these results are promising for field deployments of sodium dithionite, another column experiment with sodium dithionite-treated sediments containing uranium rich organic matter is showing net production of uranium instead of uranium uptake. Sodium dithionite appears to liberate uranium from the organic matter. Another sediment reduction experiment is being conducted to further investigate this hypothesis. These experiments are helping guide plans for field deployments of sodium dithionite at uranium ISR mining sites.

Bioreduction and immobilization of uranium in situ: a case study at a USA Department of Energy radioactive waste site, Oak Ridge, Tennessee

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Weimin; Carley, Jack M; Watson, David B

Bioremediation of uranium contaminated groundwater was tested by delivery of ethanol as an electron donor source to stimulate indigenous microbial bioactivity for reduction and immobilization of uranium in situ, followed by tests of stability of uranium sequestration in the bioreduced area via delivery of dissolved oxygen or nitrate at the US Department of energy's Integrated Field Research Challenge site located at Oak Ridge, Tennessee, USA. After long term treatment that spanned years, uranium in groundwater was reduced from 40-60 mg {center_dot} L{sup -1} to <0.03 mg {center_dot} L{sup -1}, below the USA EPA standard for drinking water. The bioreduced uraniummore » was stable under anaerobic or anoxic conditions, but addition of DO and nitrate to the bioreduced zone caused U remobilization. The change in the microbial community and functional microorganisms related to uranium reduction and oxidation were characterized. The delivery of ethanol as electron donor stimulated the activities of indigenous microorganisms for reduction of U(VI) to U(IV). Results indicated that the immobilized U could be partially remobilized by D0 and nitrate via microbial activity. An anoxic environmental condition without nitrate is essential to maintain the stability of bioreduced uranium.« less

Method for converting uranium oxides to uranium metal

DOEpatents

Duerksen, Walter K.

1988-01-01

A process is described for converting scrap and waste uranium oxide to uranium metal. The uranium oxide is sequentially reduced with a suitable reducing agent to a mixture of uranium metal and oxide products. The uranium metal is then converted to uranium hydride and the uranium hydride-containing mixture is then cooled to a temperature less than -100.degree. C. in an inert liquid which renders the uranium hydride ferromagnetic. The uranium hydride is then magnetically separated from the cooled mixture. The separated uranium hydride is readily converted to uranium metal by heating in an inert atmosphere. This process is environmentally acceptable and eliminates the use of hydrogen fluoride as well as the explosive conditions encountered in the previously employed bomb-reduction processes utilized for converting uranium oxides to uranium metal.

Alternative Anodes for the Electrolytic Reduction of Uranium Dioxide

NASA Astrophysics Data System (ADS)

Merwin, Augustus

Reprocessing of spent nuclear fuel is an essential step in closing the nuclear fuel cycle. In order to consume current stockpiles, ceramic uranium dioxide spent nuclear fuel will be subjected to an electrolytic reduction process. The current reduction process employs a platinum anode and a stainless steel alloy 316 cathode in a molten salt bath consisting of LiCl-2wt% Li 2O and occurs at 700°C. A major shortcoming of the existing process is the degradation of the platinum anode under the severely oxidizing conditions encountered during electrolytic reduction. This work investigates alternative anode materials for the electrolytic reduction of uranium oxide. The high temperature and extreme oxidizing conditions encountered in these studies necessitated a unique set of design constraints on the system. Thus, a customized experimental apparatus was designed and constructed. The electrochemical experiments were performed in an electrochemical reactor placed inside a furnace. This entire setup was housed inside a glove box, in order to maintain an inert atmosphere. This study investigates alternative anode materials through accelerated corrosion testing. Surface morphology was studied using scanning electron microscopy. Surface chemistry was characterized using energy dispersive spectroscopy and Raman spectroscopy. Electrochemical behavior of candidate materials was evaluated using potentiodynamic polarization characteristics. After narrowing the number of candidate electrode materials, ferrous stainless steel alloy 316, nickel based Inconel 718 and elemental tungsten were chosen for further investigation. Of these materials only tungsten was found to be sufficiently stable at the anodic potential required for electrolysis of uranium dioxide in molten salt. The tungsten anode and stainless steel alloy 316 cathode electrode system was studied at the required reduction potential for UO2 with varying lithium oxide concentrations. Electrochemical impedance spectroscopy showed mixed (kinetic and diffusion) control and an overall low impedance due to extreme corrosion. It was observed that tungsten is sufficiently stable in LiCl - 2wt% Li 2O at 700°C at the required anodic potential for the reduction of uranium oxide. This study identifies tungsten to be a superior anode material to platinum for the electrolytic reduction of uranium oxide, both in terms of superior corrosion behavior and reduced cost, and thus recommends that tungsten be further investigated as an alternative anode for the electrolytic reduction of uranium dioxide.

Chemical aspects of uranium behavior in soils: A review

NASA Astrophysics Data System (ADS)

Vodyanitskii, Yu. N.

2011-08-01

Uranium has varying degrees of oxidation (+4 and +6) and is responsive to changes in the redox potential of the environment. It is deposited at the reduction barrier with the participation of biota and at the sorption barrier under oxidative conditions. Iron (hydr)oxides are the strongest sorbents of uranium. Uranium, being an element of medium biological absorption, can accumulate (relative to thorium) in the humus horizons of some soils. The high content of uranium in uncontaminated soils is most frequently inherited from the parent rocks in the regions of positive U anomalies: in the soils developed on oil shales and in the marginal zone of bogs at the reduction barrier. The development of nuclear and coal-fired power engineering resulted in the environmental contamination with uranium. The immobilization of anthropogenic uranium at artificial geochemical barriers is based on two preconditions: the stimulation of on-site metal-reducing bacteria or the introduction of strong mineral reducers, e.g., Fe at low degrees of oxidation.

Evidence for single metal two electron oxidative addition and reductive elimination at uranium.

PubMed

Gardner, Benedict M; Kefalidis, Christos E; Lu, Erli; Patel, Dipti; McInnes, Eric J L; Tuna, Floriana; Wooles, Ashley J; Maron, Laurent; Liddle, Stephen T

2017-12-01

Reversible single-metal two-electron oxidative addition and reductive elimination are common fundamental reactions for transition metals that underpin major catalytic transformations. However, these reactions have never been observed together in the f-block because these metals exhibit irreversible one- or multi-electron oxidation or reduction reactions. Here we report that azobenzene oxidises sterically and electronically unsaturated uranium(III) complexes to afford a uranium(V)-imido complex in a reaction that satisfies all criteria of a single-metal two-electron oxidative addition. Thermolysis of this complex promotes extrusion of azobenzene, where H-/D-isotopic labelling finds no isotopomer cross-over and the non-reactivity of a nitrene-trap suggests that nitrenes are not generated and thus a reductive elimination has occurred. Though not optimally balanced in this case, this work presents evidence that classical d-block redox chemistry can be performed reversibly by f-block metals, and that uranium can thus mimic elementary transition metal reactivity, which may lead to the discovery of new f-block catalysis.

Uranium-mediated electrocatalytic dihydrogen production from water

NASA Astrophysics Data System (ADS)

Halter, Dominik P.; Heinemann, Frank W.; Bachmann, Julien; Meyer, Karsten

2016-02-01

Depleted uranium is a mildly radioactive waste product that is stockpiled worldwide. The chemical reactivity of uranium complexes is well documented, including the stoichiometric activation of small molecules of biological and industrial interest such as H2O, CO2, CO, or N2 (refs 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11), but catalytic transformations with actinides remain underexplored in comparison to transition-metal catalysis. For reduction of water to H2, complexes of low-valent uranium show the highest potential, but are known to react violently and uncontrollably forming stable bridging oxo or uranyl species. As a result, only a few oxidations of uranium with water have been reported so far; all stoichiometric. Catalytic H2 production, however, requires the reductive recovery of the catalyst via a challenging cleavage of the uranium-bound oxygen-containing ligand. Here we report the electrocatalytic water reduction observed with a trisaryloxide U(III) complex [((Ad,MeArO)3mes)U] (refs 18 and 19)—the first homogeneous uranium catalyst for H2 production from H2O. The catalytic cycle involves rare terminal U(IV)-OH and U(V)=O complexes, which have been isolated, characterized, and proven to be integral parts of the catalytic mechanism. The recognition of uranium compounds as potentially useful catalysts suggests new applications for such light actinides. The development of uranium-based catalysts provides new perspectives on nuclear waste management strategies, by suggesting that mildly radioactive depleted uranium—an abundant waste product of the nuclear power industry—could be a valuable resource.

PRODUCTION OF URANIUM

DOEpatents

Spedding, F.H.; Wilhelm, H.A.; Keller, W.H.

1958-04-15

The production of uranium metal by the reduction of uranium tetrafluoride is described. Massive uranium metal of high purily is produced by reacting uranium tetrafluoride with 2 to 20% stoichiometric excess of magnesium at a temperature sufficient to promote the reaction and then mantaining the reaction mass in a sealed vessel at temperature in the range of 1150 to 2000 d C, under a superatomospheric pressure of magnesium for a period of time sufficient 10 allow separation of liquid uranium and liquid magnesium fluoride into separate layers.

Using a probabilistic approach in an ecological risk assessment simulation tool: test case for depleted uranium (DU).

PubMed

Fan, Ming; Thongsri, Tepwitoon; Axe, Lisa; Tyson, Trevor A

2005-06-01

A probabilistic approach was applied in an ecological risk assessment (ERA) to characterize risk and address uncertainty employing Monte Carlo simulations for assessing parameter and risk probabilistic distributions. This simulation tool (ERA) includes a Window's based interface, an interactive and modifiable database management system (DBMS) that addresses a food web at trophic levels, and a comprehensive evaluation of exposure pathways. To illustrate this model, ecological risks from depleted uranium (DU) exposure at the US Army Yuma Proving Ground (YPG) and Aberdeen Proving Ground (APG) were assessed and characterized. Probabilistic distributions showed that at YPG, a reduction in plant root weight is considered likely to occur (98% likelihood) from exposure to DU; for most terrestrial animals, likelihood for adverse reproduction effects ranges from 0.1% to 44%. However, for the lesser long-nosed bat, the effects are expected to occur (>99% likelihood) through the reduction in size and weight of offspring. Based on available DU data for the firing range at APG, DU uptake will not likely affect survival of aquatic plants and animals (<0.1% likelihood). Based on field and laboratory studies conducted at APG and YPG on pocket mice, kangaroo rat, white-throated woodrat, deer, and milfoil, body burden concentrations observed fall into the distributions simulated at both sites.

Uranium(IV) adsorption by natural organic matter in anoxic sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bone, Sharon E.; Dynes, James J.; Cliff, John

2017-01-09

Uranium is an important fuel source and a global environmental contaminant. It accumulates in the tetravalent state, U(IV), in anoxic sediments, including ore deposits, marine basins, and contaminated aquifers. However, very little is known about the speciation of U(IV) in low temperature geochemical environments, inhibiting the development of a conceptual model of U behavior. Until recently, U(IV) was assumed to exist predominantly as the sparingly soluble mineral uraninite (UO 2) in anoxic sediments; yet studies now show that UO 2 is not often dominant in these environments. However, a model of U(IV) speciation under environmentally relevant conditions has not yetmore » been developed. Here we show that complexes of U(IV) adsorb on organic carbon and organic carbon-coated clays in an organic-rich natural substrate under field-relevant conditions. Whereas previous research assumed that the U(IV) product depended on the reduction pathway, our results demonstrate that UO 2 formation can be inhibited simply by decreasing the U:solid ratio. Thus, it is the number and type of surface ligands that controls U(IV) speciation subsequent to U(VI) reduction. Projections of U transport and bioavailability, and thus its threat to human and ecosystem health, must consider retention of U(IV) ions within the local sediment environment.« less

Biogenic non-crystalline U(IV) revealed as major component in uranium ore deposits

NASA Astrophysics Data System (ADS)

Bhattacharyya, Amrita; Campbell, Kate M.; Kelly, Shelly D.; Roebbert, Yvonne; Weyer, Stefan; Bernier-Latmani, Rizlan; Borch, Thomas

2017-06-01

Historically, it is believed that crystalline uraninite, produced via the abiotic reduction of hexavalent uranium (U(VI)) is the dominant reduced U species formed in low-temperature uranium roll-front ore deposits. Here we show that non-crystalline U(IV) generated through biologically mediated U(VI) reduction is the predominant U(IV) species in an undisturbed U roll-front ore deposit in Wyoming, USA. Characterization of U species revealed that the majority (~58-89%) of U is bound as U(IV) to C-containing organic functional groups or inorganic carbonate, while uraninite and U(VI) represent only minor components. The uranium deposit exhibited mostly 238U-enriched isotope signatures, consistent with largely biotic reduction of U(VI) to U(IV). This finding implies that biogenic processes are more important to uranium ore genesis than previously understood. The predominance of a relatively labile form of U(IV) also provides an opportunity for a more economical and environmentally benign mining process, as well as the design of more effective post-mining restoration strategies and human health-risk assessment.

Biogenic non-crystalline U(IV) revealed as major component in uranium ore deposits

PubMed Central

Bhattacharyya, Amrita; Campbell, Kate M.; Kelly, Shelly D.; Roebbert, Yvonne; Weyer, Stefan; Bernier-Latmani, Rizlan; Borch, Thomas

2017-01-01

Historically, it is believed that crystalline uraninite, produced via the abiotic reduction of hexavalent uranium (U(VI)) is the dominant reduced U species formed in low-temperature uranium roll-front ore deposits. Here we show that non-crystalline U(IV) generated through biologically mediated U(VI) reduction is the predominant U(IV) species in an undisturbed U roll-front ore deposit in Wyoming, USA. Characterization of U species revealed that the majority (∼58-89%) of U is bound as U(IV) to C-containing organic functional groups or inorganic carbonate, while uraninite and U(VI) represent only minor components. The uranium deposit exhibited mostly 238U-enriched isotope signatures, consistent with largely biotic reduction of U(VI) to U(IV). This finding implies that biogenic processes are more important to uranium ore genesis than previously understood. The predominance of a relatively labile form of U(IV) also provides an opportunity for a more economical and environmentally benign mining process, as well as the design of more effective post-mining restoration strategies and human health-risk assessment. PMID:28569759

Biogenic non-crystalline U (IV) revealed as major component in uranium ore deposits

DOE PAGES

Bhattacharyya, Amrita; Campbell, Kate M.; Kelly, Shelly D.; ...

2017-06-01

Historically, it is believed that crystalline uraninite, produced via the abiotic reduction of hexavalent uranium (U (VI)) is the dominant reduced U species formed in low-temperature uranium roll-front ore deposits. Here we show that non-crystalline U (IV) generated through biologically mediated U (VI) reduction is the predominant U (IV) species in an undisturbed U roll-front ore deposit in Wyoming, USA. Characterization of U species revealed that the majority (~58-89%) of U is bound as U (IV) to C-containing organic functional groups or inorganic carbonate, while uraninite and U (VI) represent only minor components. The uranium deposit exhibited mostly 238U-enriched isotopemore » signatures, consistent with largely biotic reduction of U (VI) to U (IV). This finding implies that biogenic processes are more important to uranium ore genesis than previously understood. The predominance of a relatively labile form of U (IV) also provides an opportunity for a more economical and environmentally benign mining process, as well as the design of more effective post-mining restoration strategies and human health-risk assessment.« less

Biogenic non-crystalline U(IV) revealed as major component in uranium ore deposits.

PubMed

Bhattacharyya, Amrita; Campbell, Kate M; Kelly, Shelly D; Roebbert, Yvonne; Weyer, Stefan; Bernier-Latmani, Rizlan; Borch, Thomas

2017-06-01

Historically, it is believed that crystalline uraninite, produced via the abiotic reduction of hexavalent uranium (U (VI) ) is the dominant reduced U species formed in low-temperature uranium roll-front ore deposits. Here we show that non-crystalline U (IV)  generated through biologically mediated U (VI)  reduction is the predominant U (IV)  species in an undisturbed U roll-front ore deposit in Wyoming, USA. Characterization of U species revealed that the majority (∼58-89%) of U is bound as U (IV) to C-containing organic functional groups or inorganic carbonate, while uraninite and U (VI) represent only minor components. The uranium deposit exhibited mostly 238 U-enriched isotope signatures, consistent with largely biotic reduction of U (VI) to U (IV) . This finding implies that biogenic processes are more important to uranium ore genesis than previously understood. The predominance of a relatively labile form of U (IV) also provides an opportunity for a more economical and environmentally benign mining process, as well as the design of more effective post-mining restoration strategies and human health-risk assessment.

Biogenic non-crystalline U (IV) revealed as major component in uranium ore deposits

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhattacharyya, Amrita; Campbell, Kate M.; Kelly, Shelly D.

Historically, it is believed that crystalline uraninite, produced via the abiotic reduction of hexavalent uranium (U (VI)) is the dominant reduced U species formed in low-temperature uranium roll-front ore deposits. Here we show that non-crystalline U (IV) generated through biologically mediated U (VI) reduction is the predominant U (IV) species in an undisturbed U roll-front ore deposit in Wyoming, USA. Characterization of U species revealed that the majority (~58-89%) of U is bound as U (IV) to C-containing organic functional groups or inorganic carbonate, while uraninite and U (VI) represent only minor components. The uranium deposit exhibited mostly 238U-enriched isotopemore » signatures, consistent with largely biotic reduction of U (VI) to U (IV). This finding implies that biogenic processes are more important to uranium ore genesis than previously understood. The predominance of a relatively labile form of U (IV) also provides an opportunity for a more economical and environmentally benign mining process, as well as the design of more effective post-mining restoration strategies and human health-risk assessment.« less

Biogenic non-crystalline U(IV) revealed as major component in uranium ore deposits

USGS Publications Warehouse

Bhattacharyya, Amrita; Campbell, Kate M.; Kelly, Shelly; Roebbert, Yvonne; Weyer, Stefan; Bernier-Latmani, Rizlan; Borch, Thomas

2017-01-01

Historically, it is believed that crystalline uraninite, produced via the abiotic reduction of hexavalent uranium (U(VI)) is the dominant reduced U species formed in low-temperature uranium roll-front ore deposits. Here we show that non-crystalline U(IV) generated through biologically mediated U(VI) reduction is the predominant U(IV) species in an undisturbed U roll-front ore deposit in Wyoming, USA. Characterization of U species revealed that the majority (∼58-89%) of U is bound as U(IV)to C-containing organic functional groups or inorganic carbonate, while uraninite and U(VI) represent only minor components. The uranium deposit exhibited mostly 238U-enriched isotope signatures, consistent with largely biotic reduction of U(VI) to U(IV). This finding implies that biogenic processes are more important to uranium ore genesis than previously understood. The predominance of a relatively labile form of U(IV) also provides an opportunity for a more economical and environmentally benign mining process, as well as the design of more effective post-mining restoration strategies and human health-risk assessment.

Non-enzymatic U(VI) interactions with biogenic mackinawite

NASA Astrophysics Data System (ADS)

Veeramani, H.; Qafoku, N. P.; Kukkadapu, R. K.; Murayama, M.; Hochella, M. F.

2011-12-01

Reductive immobilization of hexavalent uranium [U(VI)] by stimulation of dissimilatory metal and/or sulfate reducing bacteria (DMRB or DSRB) has been extensively researched as a remediation strategy for subsurface U(VI) contamination. These bacteria derive energy by reducing oxidized metals as terminal electron acceptors, often utilizing organic substrates as electron donors. Thus, when evaluating the potential for in-situ uranium remediation in heterogeneous subsurface media, it is important to understand how the presence of alternative electron acceptors such as Fe(III) and sulfate affect U(VI) remediation and the long term behavior and reactivity of reduced uranium. Iron, an abundant subsurface element, represents a substantial sink for electrons from DMRB, and the reduction of Fe(III) leads to the formation of dissolved Fe(II) or to reactive biogenic Fe(II)- and mixed Fe(II)/Fe(III)- mineral phases. Consequently, abiotic U(VI) reduction by reactive forms of biogenic Fe(II) minerals could be a potentially important process for uranium immobilization. In our study, the DMRB Shewanella putrefaciens CN32 was used to synthesize a biogenic Fe(II)-bearing sulfide mineral: mackinawite, that has been characterized by XRD, SEM, HRTEM and Mössbauer spectroscopy. Batch experiments involving treated biogenic mackinawite and uranium (50:1 molar ratio) were carried out at room temperature under strict anoxic conditions. Following complete removal of uranium from solution, the biogenic mackinawite was analyzed by a suite of analytical techniques including XAS, HRTEM and Mössbauer spectroscopy to determine the speciation of uranium and investigate concomitant Fe(II)-phase transformation. Determining the speciation of uranium is critical to success of a remediation strategy. The present work elucidates non-enzymatic/abiotic molecular scale redox interactions between biogenic mackinawite and uranium.

Microbial links between sulfate reduction and metal retention in uranium- and heavy metal-contaminated soil.

PubMed

Sitte, Jana; Akob, Denise M; Kaufmann, Christian; Finster, Kai; Banerjee, Dipanjan; Burkhardt, Eva-Maria; Kostka, Joel E; Scheinost, Andreas C; Büchel, Georg; Küsel, Kirsten

2010-05-01

Sulfate-reducing bacteria (SRB) can affect metal mobility either directly by reductive transformation of metal ions, e.g., uranium, into their insoluble forms or indirectly by formation of metal sulfides. This study evaluated in situ and biostimulated activity of SRB in groundwater-influenced soils from a creek bank contaminated with heavy metals and radionuclides within the former uranium mining district of Ronneburg, Germany. In situ activity of SRB, measured by the (35)SO(4)(2-) radiotracer method, was restricted to reduced soil horizons with rates of < or =142 +/- 20 nmol cm(-3) day(-1). Concentrations of heavy metals were enriched in the solid phase of the reduced horizons, whereas pore water concentrations were low. X-ray absorption near-edge structure (XANES) measurements demonstrated that approximately 80% of uranium was present as reduced uranium but appeared to occur as a sorbed complex. Soil-based dsrAB clone libraries were dominated by sequences affiliated with members of the Desulfobacterales but also the Desulfovibrionales, Syntrophobacteraceae, and Clostridiales. [(13)C]acetate- and [(13)C]lactate-biostimulated soil microcosms were dominated by sulfate and Fe(III) reduction. These processes were associated with enrichment of SRB and Geobacteraceae; enriched SRB were closely related to organisms detected in soils by using the dsrAB marker. Concentrations of soluble nickel, cobalt, and occasionally zinc declined < or =100% during anoxic soil incubations. In contrast to results in other studies, soluble uranium increased in carbon-amended treatments, reaching < or =1,407 nM in solution. Our results suggest that (i) ongoing sulfate reduction in contaminated soil resulted in in situ metal attenuation and (ii) the fate of uranium mobility is not predictable and may lead to downstream contamination of adjacent ecosystems.

Microbial Links between Sulfate Reduction and Metal Retention in Uranium- and Heavy Metal-Contaminated Soil▿

PubMed Central

Sitte, Jana; Akob, Denise M.; Kaufmann, Christian; Finster, Kai; Banerjee, Dipanjan; Burkhardt, Eva-Maria; Kostka, Joel E.; Scheinost, Andreas C.; Büchel, Georg; Küsel, Kirsten

2010-01-01

Sulfate-reducing bacteria (SRB) can affect metal mobility either directly by reductive transformation of metal ions, e.g., uranium, into their insoluble forms or indirectly by formation of metal sulfides. This study evaluated in situ and biostimulated activity of SRB in groundwater-influenced soils from a creek bank contaminated with heavy metals and radionuclides within the former uranium mining district of Ronneburg, Germany. In situ activity of SRB, measured by the 35SO42− radiotracer method, was restricted to reduced soil horizons with rates of ≤142 ± 20 nmol cm−3 day−1. Concentrations of heavy metals were enriched in the solid phase of the reduced horizons, whereas pore water concentrations were low. X-ray absorption near-edge structure (XANES) measurements demonstrated that ∼80% of uranium was present as reduced uranium but appeared to occur as a sorbed complex. Soil-based dsrAB clone libraries were dominated by sequences affiliated with members of the Desulfobacterales but also the Desulfovibrionales, Syntrophobacteraceae, and Clostridiales. [13C]acetate- and [13C]lactate-biostimulated soil microcosms were dominated by sulfate and Fe(III) reduction. These processes were associated with enrichment of SRB and Geobacteraceae; enriched SRB were closely related to organisms detected in soils by using the dsrAB marker. Concentrations of soluble nickel, cobalt, and occasionally zinc declined ≤100% during anoxic soil incubations. In contrast to results in other studies, soluble uranium increased in carbon-amended treatments, reaching ≤1,407 nM in solution. Our results suggest that (i) ongoing sulfate reduction in contaminated soil resulted in in situ metal attenuation and (ii) the fate of uranium mobility is not predictable and may lead to downstream contamination of adjacent ecosystems. PMID:20363796

FLAME DENITRATION AND REDUCTION OF URANIUM NITRATE TO URANIUM DIOXIDE

DOEpatents

Hedley, W.H.; Roehrs, R.J.; Henderson, C.M.

1962-06-26

A process is given for converting uranyl nitrate solution to uranium dioxide. The process comprises spraying fine droplets of aqueous uranyl nitrate solution into a hightemperature hydrocarbon flame, said flame being deficient in oxygen approximately 30%, retaining the feed in the flame for a sufficient length of time to reduce the nitrate to the dioxide, and recovering uranium dioxide. (AEC)

URANIUM RECOVERY PROCESS

DOEpatents

Bailes, R.H.; Long, R.S.; Olson, R.S.; Kerlinger, H.O.

1959-02-10

A method is described for recovering uranium values from uranium bearing phosphate solutions such as are encountered in the manufacture of phosphate fertilizers. The solution is first treated with a reducing agent to obtain all the uranium in the tetravalent state. Following this reduction, the solution is treated to co-precipitate the rcduced uranium as a fluoride, together with other insoluble fluorides, thereby accomplishing a substantially complete recovery of even trace amounts of uranium from the phosphate solution. This precipitate usually takes the form of a complex fluoride precipitate, and after appropriate pre-treatment, the uranium fluorides are leached from this precipitate and rccovered from the leach solution.

Characterization of Uranium Contamination, Transport, and Remediation at Rocky Flats - Across Remediation into Post-Closure

NASA Astrophysics Data System (ADS)

Janecky, D. R.; Boylan, J.; Murrell, M. T.

2009-12-01

The Rocky Flats Site is a former nuclear weapons production facility approximately 16 miles northwest of Denver, Colorado. Built in 1952 and operated by the Atomic Energy Commission and then Department of Energy, the Site was remediated and closed in 2005, and is currently undergoing long-term surveillance and monitoring by the DOE Office of Legacy Management. Areas of contamination resulted from roughly fifty years of operation. Of greatest interest, surface soils were contaminated with plutonium, americium, and uranium; groundwater was contaminated with chlorinated solvents, uranium, and nitrates; and surface waters, as recipients of runoff and shallow groundwater discharge, have been contaminated by transport from both regimes. A region of economic mineralization that has been referred to as the Colorado Mineral Belt is nearby, and the Schwartzwalder uranium mine is approximately five miles upgradient of the Site. Background uranium concentrations are therefore elevated in many areas. Weapons-related activities included work with enriched and depleted uranium, contributing anthropogenic content to the environment. Using high-resolution isotopic analyses, Site-related contamination can be distinguished from natural uranium in water samples. This has been instrumental in defining remedy components, and long-term monitoring and surveillance strategies. Rocky Flats hydrology interlinks surface waters and shallow groundwater (which is very limited in volume and vertical and horizontal extent). Surface water transport pathways include several streams, constructed ponds, and facility surfaces. Shallow groundwater has no demonstrated connection to deep aquifers, and includes natural preferential pathways resulting primarily from porosity in the Rocky Flats alluvium, weathered bedrock, and discontinuous sandstones. In addition, building footings, drains, trenches, and remedial systems provide pathways for transport at the site. Removal of impermeable surfaces (buildings, roads, and so on) during the Site closure efforts resulted in major changes to surface and shallow groundwater flow. Consistent with previous documentation of uranium operations and contamination, only very small amounts of highly enriched uranium are found in a small number of water samples, generally from the former Solar Ponds complex and central Industrial Area. Depleted uranium is more widely distributed at the site, and water samples exhibit the full range of depleted plus natural uranium mixtures. However, one third of the samples are found to contain only natural uranium, and three quarters of the samples are found to contain more than 90% natural uranium - substantial fractions given that the focus of these analyses was on evaluating potentially contaminated waters. Following site closure, uranium concentrations have increased at some locations, particularly for surface water samples. Overall, isotopic ratios at individual locations have been relatively consistent, indicating that the increases in concentrations are due to decreases in dilution flow following removal of impermeable surfaces and buildings.

Role of U(VI) Adsorption in U(VI) Reduction by Geobacter Species.

DOE Office of Scientific and Technical Information (OSTI.GOV)

None, None

2009-03-09

Previous work had suggested that Acholeplasma palmae has a higher capacity for uranium sorption than other bacteria studied. Sorption studies were performed with cells in suspension in various solutions containing uranium and results were used to generate uranium-biosorption isotherms.

Biological pathways of exposure and ecotoxicity values for uranium and associated radionuclides: Chapter D in Hydrological, geological, and biological site characterization of breccia pipe uranium deposits in Northern Arizona

USGS Publications Warehouse

Hinck, Jo E.; Linder, Greg L.; Finger, Susan E.; Little, Edward E.; Tillitt, Donald E.; Kuhne, Wendy

2010-01-01

This chapter compiles available chemical and radiation toxicity information for plants and animals from the scientific literature on naturally occurring uranium and associated radionuclides. Specifically, chemical and radiation hazards associated with radionuclides in the uranium decay series including uranium, thallium, thorium, bismuth, radium, radon, protactinium, polonium, actinium, and francium were the focus of the literature compilation. In addition, exposure pathways and a food web specific to the segregation areas were developed. Major biological exposure pathways considered were ingestion, inhalation, absorption, and bioaccumulation, and biota categories included microbes, invertebrates, plants, fishes, amphibians, reptiles, birds, and mammals. These data were developed for incorporation into a risk assessment to be conducted as part of an environmental impact statement for the Bureau of Land Management, which would identify representative plants and animals and their relative sensitivities to exposure of uranium and associated radionuclides. This chapter provides pertinent information to aid in the development of such an ecological risk assessment but does not estimate or derive guidance thresholds for radionuclides associated with uranium. Previous studies have not attempted to quantify the risks to biota caused directly by the chemical or radiation releases at uranium mining sites, although some information is available for uranium mill tailings and uranium mine closure activities. Research into the biological impacts of uranium exposure is strongly biased towards human health and exposure related to enriched or depleted uranium associated with the nuclear energy industry rather than naturally occurring uranium associated with uranium mining. Nevertheless, studies have reported that uranium and other radionuclides can affect the survival, growth, and reproduction of plants and animals. Exposure to chemical and radiation hazards is influenced by a plant’s or an animal’s life history and surrounding environment. Various species of plants, invertebrates, fishes, amphibians, reptiles, birds, and mammals found in the segregation areas that are considered species of concern by State and Federal agencies were included in the development of the site-specific food web. The utilization of subterranean habitats (burrows in uranium-rich areas, burrows in waste rock piles or reclaimed mining areas, mine tunnels) in the seasonally variable but consistently hot, arid environment is of particular concern in the segregation areas. Certain species of reptiles, amphibians, birds, and mammals in the segregation areas spend significant amounts of time in burrows where they can inhale or ingest uranium and other radionuclides through digging, eating, preening, and hibernating. Herbivores may also be exposed though the ingestion of radionuclides that have been aerially deposited on vegetation. Measured tissues concentrations of uranium and other radionuclides are not available for any species of concern in the segregation areas. The sensitivity of these animals to uranium exposure is unknown based on the existing scientific literature, and species-specific uranium presumptive effects levels were only available for two endangered fish species known to inhabit the segregation areas. Overall, the chemical toxicity data available for biological receptors of concern were limited, although chemical and radiation toxicity guidance values are available from several sources. However, caution should be used when directly applying these values to northern Arizona given the unique habitat and life history strategies of biological receptors in the segregation areas and the fact that some guidance values are based on models rather than empirical (laboratory or field) data. No chemical toxicity information based on empirical data is available for reptiles, birds, or wild mammals; therefore, the risks associated with uranium and other radionuclides are unknown for these biota.

Absorption, accumulation and biological effects of depleted uranium in Peyer's patches of rats.

PubMed

Dublineau, I; Grison, S; Grandcolas, L; Baudelin, C; Tessier, C; Suhard, D; Frelon, S; Cossonnet, C; Claraz, M; Ritt, J; Paquet, P; Voisin, P; Gourmelon, P

2006-10-29

The digestive tract is the entry route for radionuclides following the ingestion of contaminated food and/or water wells. It was recently characterized that the small intestine was the main area of uranium absorption throughout the gastrointestinal tract. This study was designed to determine the role played by the Peyer's patches in the intestinal absorption of uranium, as well as the possible accumulation of this radionuclide in lymphoid follicles and the toxicological or pathological consequences on the Peyer's patch function subsequent to the passage and/or accumulation of uranium. Results of experiments performed in Ussing chambers indicate that the apparent permeability to uranium in the intestine was higher (10-fold) in the mucosa than in Peyer's patches ((6.21+/-1.21 to 0.55+/-0.35)x10(-6)cm/s, respectively), demonstrating that the small intestinal epithelium was the preferential pathway for the transmucosal passage of uranium. A quantitative analysis of uranium by ICP-MS following chronic contamination with depleted uranium during 3 or 9 months showed a preferential accumulation of uranium in Peyer's patches (1355% and 1266%, respectively, at 3 and 9 months) as compared with epithelium (890% and 747%, respectively, at 3 and 9 months). Uranium was also detected in the mesenteric lymph nodes ( approximately 5-fold after contamination with DU). The biological effects of this accumulation of depleted uranium after chronic contamination were investigated in Peyer's patches. There was no induction of the apoptosis pathway after chronic DU contamination in Peyer's patches. The results indicate no change in the cytokine expression (Il-10, TGF-beta, IFN-gamma, TNF-alpha, MCP-1) in Peyer's patches and in mesenteric lymph nodes, and no modification in the uptake of yeast cells by Peyer's patches. In conclusion, this study shows that the Peyer's patches were a site of retention for uranium following the chronic ingestion of this radionuclide, without any biological consequences of such accumulation on Peyer's patch functions.

Understanding Uranium Behavior in a Reduced Aquifer

NASA Astrophysics Data System (ADS)

Janot, N.; Lezama-Pacheco, J. S.; Williams, K. H.; Bernier-Latmani, R.; Long, P. E.; Davis, J. A.; Fox, P. M.; Yang, L.; Giammar, D.; Cerrato, J. M.; Bargar, J.

2012-12-01

Uranium contamination of groundwater is a concern at several US Department of Energy sites, such Old Rifle, CO. Uranium transport in the environment is mainly controlled by its oxidation state, since oxidized U(VI) is relatively mobile, whereas U(IV) is relatively insoluble. Bio-remediation of contaminated aquifers aims at immobilizing uranium in a reduced form. Previous laboratory and field studies have shown that adding electron donor (lactate, acetate, ethanol) to groundwater stimulates the activity of metal- and sulfate-reducing bacteria, which promotes U(VI) reduction in contaminated aquifers. However, obtaining information on chemical and physical forms of U, Fe and S species for sediments biostimulated in the field, as well as kinetic parameters such as U(VI) reduction rate, is challenging due to the low concentration of uranium in the aquifers (typically < 10 ppm) and the expense of collecting large number of cores. An in-situ technique has been developed for studying uranium, iron and sulfur reduction dynamics during such bioremediation episodes. This technique uses in-well columns to obtain direct access to chemical and physical forms of U(IV) produced in the aquifer, evolving microbial communities, and trace and major ion groundwater constituents. While several studies have explored bioreduction of uranium under sulfate-reducing conditions, less attention has been paid to the initial iron-reducing phase, noted as being of particular importance to uranium removal. The aim of this work was to assess the formation of U(IV) during the early stages of a bio-remediation experiment at the Old Rifle site, CO, from early iron-reducing conditions to the transition to sulfate-reducing conditions. Several in-well chromatographic columns packed with sediment were deployed and were sampled at different days after the start of bio-reduction. X-ray absorption spectroscopy and X-ray microscopy were used to obtain information on Fe, S and U speciation and distribution. Chemical extractions of the reduced sediments have also been performed, to determine the rate of Fe(II) and U(IV) accumulation.

Surface reactions kinetics between nanocrystalline magnetite and uranyl.

PubMed

Missana, Tiziana; Maffiotte, César; García-Gutiérrez, Miguel

2003-05-01

Magnetite is the most important end member of iron corrosion products under reducing environment, which is the condition expected in a deep geological high level radioactive waste disposal. Nanocrystalline magnetite was synthesized in the laboratory and its physicochemical properties were analyzed in detail. The kinetics of the adsorption of U(VI) and the kinetics of the actinide reduction to a lower oxidation state, in presence of the oxide, were studied by means of batch sorption techniques and X-ray photoelectron spectroscopy (XPS) analysis. The results showed that the uranium sorption and reduction processes on the magnetite surface have very fast kinetics (hours), the reduction process being triggered by sorption. XPS measurements showed that the speciation of uranium at the surface does not show significant changes with time (from 1 day to 3 months), as well as the quantity of uranium detected at the surface. The surface speciation depended on the initial pH of the contact solution. Considering that the Eh of equilibrium between magnetite and the solution, under our experimental conditions, is slightly positive (50-100 mV), the uranium reduction would also be thermodynamically possible within the liquid phase. However, the kinetics of reduction in the liquid occur at a much slower rate which, in turn, has to depend on the attainment of the magnetite/solution equilibrium. The decrease of uranium in solution, observed after the uranyl adsorption stage, and particularly at acidic pH, is most probably due to the precipitation of U(IV) formed in the solution.

Industrial Production of Uranium; PRODUCCION INDUSTRIAL DE URANIO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pedregal, J.D.

1956-01-01

The purity requirements of uranium and the necessity of purifying the uranium compounds previous to its metallurgical treatment are briefly discussed as an introduction to the different methods reduction to the metal. The methods which are used by the Junta de Energia Nuclear are indicated. (tr-auth)

Efficacy of Biostimulation for Uranium Sequestration: Coupled Effects Sediment/Groundwater Geochemistry and Microbiology

NASA Astrophysics Data System (ADS)

Xu, J.; Veeramani, H.; Qafoku, N. P.; Singh, G.; Pruden, A.; Kukkadapu, R. K.; Hochella, M. F., Jr.

2015-12-01

A systematic flow-through column study was conducted using sediments and groundwater from the subsurface at the U.S. Department of Energy's Integrated Field Research Challenge (IFRC) site in Rifle, Colorado, to better understand the efficacy of uranium removal from the groundwater with and without biostimulation in the form of acetate amendments. The interactive effects of acetate amendment, groundwater/sediment geochemistry, and intrinsic bacterial community composition were evaluated using four types of sediments, collected from different uranium-contaminated (D08, LQ107, CD) or non-contaminated (RABS) aquifers. Subtle variations in the sediments' geochemistry in terms of mineral compositions, particle sizes, redox conditions, and metal(loid) co-contaminants had a marked effect on the uranium removal efficiency, following a descending trend of D08 (~ 90 to 95%) >> RABS (~ 20 to 25) ≥ LQ107 (~ 15 to 20%) > CD (~ -10 to 0%). Overall, biostimulation of the sediments with acetate drove deeper anoxic conditions and observable shifts in bacterial population structures. The abundance of dissimilatory sulfate-reduction genes (i.e., drsA), markers of sulfate-reducing bacteria, were highest in the sediments that performed best in terms of uranium removal. By comparison, no obvious associations were found between the uranium removal efficiency and the abundance of typical iron-reducing microorganisms, e.g., Geobacter spp. In the sediments where bacterial biomass was relatively low and sulfate-reduction was not detected (i.e., CD), abiotic adsorption onto fine mineral surfaces such as phyllosilates likely played a dominant role in the attenuation of aqueous uranium. In these scenarios, however, acetate amendment induced significant remobilization of the sequestered uranium and other heavy metals (e.g., strontium), leading to zero or negative uranium removal efficiencies (i.e., CD). The results of this study suggest that reductive immobilization of uranium can be effectively achieved under predominantly sulfate-reducing conditions in sediment microenvironments when bioavailable iron (III) (oxyhydr)oxides are mostly depleted, and provide insight into the integrated roles of sediment geochemistry, mineralogy, and bacterial population dynamics.

Uranium speciation and stability after reductive immobilization in aquifer sediments

NASA Astrophysics Data System (ADS)

Sharp, Jonathan O.; Lezama-Pacheco, Juan S.; Schofield, Eleanor J.; Junier, Pilar; Ulrich, Kai-Uwe; Chinni, Satya; Veeramani, Harish; Margot-Roquier, Camille; Webb, Samuel M.; Tebo, Bradley M.; Giammar, Daniel E.; Bargar, John R.; Bernier-Latmani, Rizlan

2011-11-01

It has generally been assumed that the bioreduction of hexavalent uranium in groundwater systems will result in the precipitation of immobile uraninite (UO 2). In order to explore the form and stability of uranium immobilized under these conditions, we introduced lactate (15 mM for 3 months) into flow-through columns containing sediments derived from a former uranium-processing site at Old Rifle, CO. This resulted in metal-reducing conditions as evidenced by concurrent uranium uptake and iron release. Despite initial augmentation with Shewanella oneidensis, bacteria belonging to the phylum Firmicutes dominated the biostimulated columns. The immobilization of uranium (˜1 mmol U per kg sediment) enabled analysis by X-ray absorption spectroscopy (XAS). Tetravalent uranium associated with these sediments did not have spectroscopic signatures representative of U-U shells or crystalline UO 2. Analysis by microfocused XAS revealed concentrated micrometer regions of solid U(IV) that had spectroscopic signatures consistent with bulk analyses and a poor proximal correlation (μm scale resolution) between U and Fe. A plausible explanation, supported by biogeochemical conditions and spectral interpretations, is uranium association with phosphoryl moieties found in biomass; hence implicating direct enzymatic uranium reduction. After the immobilization phase, two months of in situ exposure to oxic influent did not result in substantial uranium remobilization. Ex situ flow-through experiments demonstrated more rapid uranium mobilization than observed in column oxidation studies and indicated that sediment-associated U(IV) is more mobile than biogenic UO 2. This work suggests that in situ uranium bioimmobilization studies and subsurface modeling parameters should be expanded to account for non-uraninite U(IV) species associated with biomass.

Comparison of the Environment, Health, And Safety Characteristics of Advanced Thorium- Uranium and Uranium-Plutonium Fuel Cycles

NASA Astrophysics Data System (ADS)

Ault, Timothy M.

The environment, health, and safety properties of thorium-uranium-based (''thorium'') fuel cycles are estimated and compared to those of analogous uranium-plutonium-based (''uranium'') fuel cycle options. A structured assessment methodology for assessing and comparing fuel cycle is refined and applied to several reference fuel cycle options. Resource recovery as a measure of environmental sustainability for thorium is explored in depth in terms of resource availability, chemical processing requirements, and radiological impacts. A review of available experience and recent practices indicates that near-term thorium recovery will occur as a by-product of mining for other commodities, particularly titanium. The characterization of actively-mined global titanium, uranium, rare earth element, and iron deposits reveals that by-product thorium recovery would be sufficient to satisfy even the most intensive nuclear demand for thorium at least six times over. Chemical flowsheet analysis indicates that the consumption of strong acids and bases associated with thorium resource recovery is 3-4 times larger than for uranium recovery, with the comparison of other chemical types being less distinct. Radiologically, thorium recovery imparts about one order of magnitude larger of a collective occupational dose than uranium recovery. Moving to the entire fuel cycle, four fuel cycle options are compared: a limited-recycle (''modified-open'') uranium fuel cycle, a modified-open thorium fuel cycle, a full-recycle (''closed'') uranium fuel cycle, and a closed thorium fuel cycle. A combination of existing data and calculations using SCALE are used to develop material balances for the four fuel cycle options. The fuel cycle options are compared on the bases of resource sustainability, waste management (both low- and high-level waste, including used nuclear fuel), and occupational radiological impacts. At steady-state, occupational doses somewhat favor the closed thorium option while low-level waste volumes slightly favor the closed uranium option, although uncertainties are significant in both cases. The high-level waste properties (radioactivity, decay heat, and ingestion radiotoxicity) all significantly favor the closed fuel cycle options (especially the closed thorium option), but an alternative measure of key fission product inventories that drive risk in a repository slightly favors the uranium fuel cycles due to lower production of iodine-129. Resource requirements are much lower for the closed fuel cycle options and are relatively similar between thorium and uranium. In additional to the steady-state results, a variety of potential transition pathways are considered for both uranium and thorium fuel cycle end-states. For dose, low-level waste, and fission products contributing to repository risk, the differences among transition impacts largely reflected the steady-state differences. However, the HLW properties arrived at a distinctly opposite result in transition (strongly favoring uranium, whereas thorium was strongly favored at steady-state), because used present-day fuel is disposed without being recycled given that uranium-233, rather than plutonium, is the primarily fissile nuclide at the closed thorium fuel cycle's steady-state. Resource consumption was the only metric was strongly influenced by the specific transition pathway selected, favoring those pathways that more quickly arrived at steady-state through higher breeding ratio assumptions regardless of whether thorium or uranium was used.

Uraniferous opal, Virgin Valley, Nevada: conditions of formation and implications for uranium exploration

USGS Publications Warehouse

Zielinski, R.A.

1982-01-01

Uraniferous, fluorescent opal, which occurs in tuffaceous sedimentary rocks at Virgin Valley, Nevada, records the temperature and composition of uranium-rich solutions as well as the time of uranium-silica coprecipitation. Results are integrated with previous geologic and geochronologic data for the area to produce a model for uranium mobility that may be used to explore for uranium deposits in similar geologic settings. Uraniferous opal occurs as replacements of diatomite, or silicic air-fall ash layers in tuffaceous lakebeds of the Virgin Valley Formation (Miocene) of Merriam (1907). Fission-track radiography shows uranium to be homogeneously dispersed throughout the opal structure, suggesting coprecipitation of dissolved uranium and silica gel. Fluid inclusions preserved within opal replacements of diatomite have homogenization temperatures in the epithermal range and are of low salinity. Four samples of opal from one locality all have U-Pb apparent ages which suggest uraniferous opal precipitation in late Pliocene time. These ages correspond to a period of local, normal faulting, and highangle faults may have served as vertical conduits for transport of deep, thermalized ground water to shallower levels. Lateral migration of rising solutions occurred at intersections of faults with permeable strata. Silica and some uranium were dissolved from silica-rich host strata of 5-20 ppm original uranium content and reprecipitated as the solutions cooled. The model predicts that in similar geologic settings, ore-grade concentrations of uranium will occur in permeable strata that intersect high-angle faults and that contain uranium source rocks as well as efficient reductant traps for uranium. In the absence of sufficient quantities of reductant materials, uranium will be flushed from the system or will accumulate in low-grade disseminated hosts such as uraniferous opal. ?? 1982.

Microbial reduction of uranium (VI) by Bacillus sp. dwc-2: A macroscopic and spectroscopic study.

PubMed

Li, Xiaolong; Ding, Congcong; Liao, Jiali; Du, Liang; Sun, Qun; Yang, Jijun; Yang, Yuanyou; Zhang, Dong; Tang, Jun; Liu, Ning

2017-03-01

The microbial reduction of U(VI) by Bacillus sp. dwc-2, isolated from soil in Southwest China, was explored using transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge spectroscopy (XANES). Our studies indicated that approximately 16.0% of U(VI) at an initial concentration of 100mg/L uranium nitrate could be reduced by Bacillus sp. dwc-2 at pH8.2 under anaerobic conditions at room temperature. Additionally, natural organic matter (NOM) played an important role in enhancing the bioreduction of U(VI) by Bacillus sp. dwc-2. XPS results demonstrated that the uranium presented mixed valence states (U(VI) and U(IV)) after bioreduction, which was subsequently confirmed by XANES. Furthermore, the TEM and high resolution transmission electron microscopy (HRTEM) analysis suggested that the reduced uranium was bioaccumulated mainly within the cell and as a crystalline structure on the cell wall. These observations implied that the reduction of uranium may have a significant effect on its fate in the soil environment in which these bacterial strains occur. Copyright © 2016. Published by Elsevier B.V.

Redox behavior of uranium at the nanoporous aluminum oxide-water interface: implications for uranium remediation.

PubMed

Jung, Hun Bok; Boyanov, Maxim I; Konishi, Hiromi; Sun, Yubing; Mishra, Bhoopesh; Kemner, Kenneth M; Roden, Eric E; Xu, Huifang

2012-07-03

Sorption-desorption experiments show that the majority (ca. 80-90%) of U(VI) presorbed to mesoporous and nanoporous alumina could not be released by extended (2 week) extraction with 50 mM NaHCO(3) in contrast with non-nanoporous α alumina. The extent of reduction of U(VI) presorbed to aluminum oxides was semiquantitatively estimated by comparing the percentages of uranium desorbed by anoxic sodium bicarbonate between AH(2)DS-reacted and unreacted control samples. X-ray absorption spectroscopy confirmed that U(VI) presorbed to non-nanoporous alumina was rapidly and completely reduced to nanoparticulate uraninite by AH(2)DS, whereas reduction of U(VI) presorbed to nanoporous alumina was slow and incomplete (<5% reduction after 1 week). The observed nanopore size-dependent redox behavior of U has important implications in developing efficient remediation techniques for the subsurface uranium contamination because the efficiency of in situ bioremediation depends on how effectively and rapidly U(VI) bound to sediment or soil can be converted to an immobile phase.

Magnesium fluoride reduction-vessel liners. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Latham-Brown, C.E.

1986-03-26

The work described in this report details a program that demonstrated a method by which magnesium fluoride, the by-product of the reduction reaction of uranium tetrafluoride to uranium metal could be used to replace the present graphite used to line the reduction vessel. Utilization of magnesium fluoride (MgF2) as a reduction-vessel liner has the potential to decrease carbon contamination and thereby reduce DU derby rejects due to chemistry. Additionally, there would be the elimination of the cost of the graphite crucible liner and the associated disposal costs by replacement with the by-product of the reduction reaction, which is magnesium fluoride.more » The process would ultimately result in reduced manufacturing costs for derby metal and higher yield of finished penetrators. This was to be accomplished in such a manner as to produce uranium metal derbies which would be accommodated into the present Nuclear Metals-Carolina Metals penetrator production process with minimal changes in equipment and procedures.« less

Réduction des nitrates et de l'uranium par les bactéries indigènes

NASA Astrophysics Data System (ADS)

Abdelouas, Abdesselam; Lutze, Werner; Nuttall, Eric

1998-07-01

A bioremediation concept has been developed to clean up ground water contaminated with nitrate (1200 mg·L -1) and uranium (0.25 mg·L -1). We studied the Tuba City mill tailings site, Arizona, USA. Indigenous bacteria capable of catalyzing the reduction of NO 3- and U(VI) were identified in the ground water and in the host rock, the Navajo sandstone. After complete reduction of O 2 and NO 3- within one week, U(VI) was reduced and precipitated as uraninite. Final uranium concentrations < 15 μg·L -1 were reached after a few weeks at 24 °C. Iron sulfide also precipitated as a result of reduction of Fe(III) on the sand surface and sulfate in the ground water. U(VI) was not reduced by sulfide. It was found that enzymatic reduction of U(VI) is faster than abiotic reduction under the conditions given by the composition of the ground water.

PROCESS FOR PRODUCTION OF URANIUM

DOEpatents

Crawford, J.W.C.

1959-09-29

A process is described for the production of uranium by the autothermic reduction of an anhydrous uranium halide with an alkaline earth metal, preferably magnesium One feature is the initial reduction step which is brought about by locally bringing to reaction temperature a portion of a mixture of the reactants in an open reaction vessel having in contact with the mixture a lining of substantial thickness composed of calcium fluoride. The lining is prepared by coating the interior surface with a plastic mixture of calcium fluoride and water and subsequently heating the coating in situ until at last the exposed surface is substantially anhydrous.

40 CFR 421.323 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2013 CFR

2013-07-01

... Uranium Subcategory § 421.323 Effluent limitations guidelines representing the degree of effluent... Limitations for the Secondary Uranium Subcategory Pollutant or pollutant property Maximum for any 1 day Maximum for monthly average mg/kg (pounds per million pounds) of uranium processed in the refinery...

40 CFR 421.323 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2012 CFR

2012-07-01

... Uranium Subcategory § 421.323 Effluent limitations guidelines representing the degree of effluent... Limitations for the Secondary Uranium Subcategory Pollutant or pollutant property Maximum for any 1 day Maximum for monthly average mg/kg (pounds per million pounds) of uranium processed in the refinery...

40 CFR 421.323 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2014 CFR

2014-07-01

... Uranium Subcategory § 421.323 Effluent limitations guidelines representing the degree of effluent... Limitations for the Secondary Uranium Subcategory Pollutant or pollutant property Maximum for any 1 day Maximum for monthly average mg/kg (pounds per million pounds) of uranium processed in the refinery...

40 CFR 421.322 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2014 CFR

2014-07-01

... CATEGORY Secondary Uranium Subcategory § 421.322 Effluent limitations guidelines representing the degree of... filtrate. BPT Limitations for the Secondary Uranium Subcategory Pollutant or pollutant property Maximum for any 1 day Maximum for monthly average mg/kg (pounds per million pounds) of uranium processed in the...

40 CFR 421.322 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2012 CFR

2012-07-01

... CATEGORY Secondary Uranium Subcategory § 421.322 Effluent limitations guidelines representing the degree of... filtrate. BPT Limitations for the Secondary Uranium Subcategory Pollutant or pollutant property Maximum for any 1 day Maximum for monthly average mg/kg (pounds per million pounds) of uranium processed in the...

40 CFR 421.322 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2013 CFR

2013-07-01

... CATEGORY Secondary Uranium Subcategory § 421.322 Effluent limitations guidelines representing the degree of... filtrate. BPT Limitations for the Secondary Uranium Subcategory Pollutant or pollutant property Maximum for any 1 day Maximum for monthly average mg/kg (pounds per million pounds) of uranium processed in the...

Electrochemical separation of uranium in the molten system LiF-NaF-KF-UF4

NASA Astrophysics Data System (ADS)

Korenko, M.; Straka, M.; Szatmáry, L.; Ambrová, M.; Uhlíř, J.

2013-09-01

This article is focused on the electrochemical investigation (cyclic voltammetry and related studies) of possible reduction of U4+ ions to metal uranium in the molten system LiF-NaF-KF(eut.)-UF4 that can provide basis for the electrochemical extraction of uranium from molten salts. Two-step reduction mechanism for U4+ ions involving one electron exchange in soluble/soluble U4+/U3+ system and three electrons exchange in the second step were found on the nickel working electrode. Both steps were found to be reversible and diffusion controlled. Based on cyclic voltammetry, the diffusion coefficients of uranium ions at 530 °C were found to be D(U4+) = 1.64 × 10-5 cm2 s-1 and D(U3+) 1.76 × 10-5 cm2 s-1. Usage of the nickel spiral electrode for electrorefining of uranium showed fairly good feasibility of its extraction. However some oxidant present during the process of electrorefining caused that the solid deposits contained different uranium species such as UF3, UO2 and K3UO2F5.

PROCESS OF PREPARING A FLUORIDE OF TETRAVLENT URANIUM

DOEpatents

Wheelwright, E.J.

1959-02-17

A method is described for producing a fluoride salt pf tetravalent uranium suitable for bomb reduction to metallic uranium. An aqueous solution of uranyl nitrate is treated with acetic acid and a nitrite-suppressor and then contacted with metallic lead whereby uranium is reduced from the hexavalent to the tetravalent state and soluble lead acetate is formed. Sulfate ions are then added to the solution to precipitate and remove the lead values. Hydrofluoric acid and alkali metal ions are then added causing the formation of an alkali metal uranium double-fluoride in which the uranium is in the tetravalent state. After recovery, this precipitate is suitable for using in the limited production of metallic uranium.

Effect of bicarbonate on aging and reactivity of nanoscale zerovalent iron (nZVI) toward uranium removal.

PubMed

Hua, Yilong; Wang, Wei; Huang, Xiaoyue; Gu, Tianhang; Ding, Dexin; Ling, Lan; Zhang, Wei-Xian

2018-06-01

Bicarbonate, ubiquitous in natural and waste waters is an important factor regulating the rate and efficiency of pollutant separation and transformation. For example, it can form complexes with U(VI) in the aqueous phase and at the solid-water interface. In this work, we investigated the effect of bicarbonate on the aging of nanoscale zero-valent (nZVI) in the context of U(VI) reduction and removal from wastewater. For fresh nZVI, over 99% aqueous uranium was separated in less than 10 min, of which 83% was reduced from U(VI) to U(IV). When nZVI was aged in water, its activity for U(VI) sequestration and reduction was significantly reduced. Batch experiments showed that for nZVI aged in the presence of 10 mM bicarbonate, only 20.3% uranium was reduced to U(IV) after 6 h reactions. Characterizations of the iron nanoparticles with spherical aberration corrected scanning transmission electron microscopy (Cs-STEM) suggest that in fresh nZVI, uranium was concentrated at the nanoparticle center; whereas in nZVI aged in bicarbonate, uranium was largely deposited on the outer surface of the nanoparticles. Furthermore, aged nZVI without bicarbonate contained more lepidocrocite (γ-FeOOH) while aged nZVI in the presence of bicarbonate had more magnetite/maghemite (Fe 3 O 4 /γ-Fe 2 O 3 ). This could be attributed to the formation of carbonate green rust and pH buffer effect of . Primary mechanisms for U(VI) removal with nZVI include reduction, sorption and/or precipitation. Results demonstrate that bicarbonate alter the aging products of nZVI, and reduces the separation efficiency and reduction capability for uranium removal. Copyright © 2018. Published by Elsevier Ltd.

Uranium Bio-accumulation and Cycling as revealed by Uranium Isotopes in Naturally Reduced Sediments from the Upper Colorado River Basin

NASA Astrophysics Data System (ADS)

Lefebvre, Pierre; Noël, Vincent; Jemison, Noah; Weaver, Karrie; Bargar, John; Maher, Kate

2016-04-01

Uranium (U) groundwater contamination following oxidized U(VI) releases from weathering of mine tailings is a major concern at numerous sites across the Upper Colorado River Basin (CRB), USA. Uranium(IV)-bearing solids accumulated within naturally reduced zones (NRZs) characterized by elevated organic carbon and iron sulfide compounds. Subsequent re-oxidation of U(IV)solid to U(VI)aqueous then controls the release to groundwater and surface water, resulting in plume persistence and raising public health concerns. Thus, understanding the extent of uranium oxidation and reduction within NRZs is critical for assessing the persistence of the groundwater contamination. In this study, we measured solid-phase uranium isotope fractionation (δ238/235U) of sedimentary core samples from four study sites (Shiprock, NM, Grand Junction, Rifle and Naturita, CO) using a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS). We observe a strong correlation between U accumulation and the extent of isotopic fractionation, with Δ238U up to +1.8 ‰ between uranium-enriched and low concentration zones. The enrichment in the heavy isotopes within the NRZs appears to be especially important in the vadose zone, which is subject to variations in water table depth. According to previous studies, this isotopic signature is consistent with biotic reduction processes associated with metal-reducing bacteria. Positive correlations between the amount of iron sulfides and the accumulation of reduced uranium underline the importance of sulfate-reducing conditions for U(IV) retention. Furthermore, the positive fractionation associated with U reduction observed across all sites despite some variations in magnitude due to site characteristics, shows a regional trend across the Colorado River Basin. The maximum extent of 238U enrichment observed in the NRZ proximal to the water table further suggests that the redox cycling of uranium, with net release of U(VI) to the groundwater by non-fractionating oxidation, is occurring within this zone. Thus, release of uranium from the NRZs may play a critical role in the persistence of groundwater contamination at these sites.

Study of the Dry Processing of Uranium Ores; ETUDE DES TRAITEMENTS DE MINERAIS D'URANIUM PAR VOIE SECHE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guillet, H.

1959-02-01

A description is given of direct fluorination of preconcentrated uranium ores in order to obtain the hexafluoride. After normal sulfuric acid treatment of the ore to eliminate silica, the uranium is precipitated by lime to obtain either impure calcium uranate of medium grade, or containing around 10% of uranium. This concentrate is dried in an inert atmosphere and then treated with a current of elementary fluorine. The uranium hexafluoride formed is condensed at the outlet of the reaction vessel and may be used either for reduction to tetrafluoride and the subsequent manufacture of uranium metal or as the initial productmore » in a diffusion plant. (auth)« less

Depleted uranium: properties, military use and health risks.

PubMed

Fairlie, Ian

2009-01-01

This article describes uranium and depleted uranium (DU), their similar isotopic compositions, how DU arises, its use in munitions and armour-proofing, and its pathways for human exposures. Particular attention is paid to the evidence of DU's health effects from cell and animal experiments and from epidemiology studies. It is concluded that a precautionary approach should be adopted to DU and that there should be a moratorium on its use by military forces. International efforts to this end are described.

Reoxidation of uranium metal immersed in a Li2O-LiCl molten salt after electrolytic reduction of uranium oxide

NASA Astrophysics Data System (ADS)

Choi, Eun-Young; Jeon, Min Ku; Lee, Jeong; Kim, Sung-Wook; Lee, Sang Kwon; Lee, Sung-Jai; Heo, Dong Hyun; Kang, Hyun Woo; Jeon, Sang-Chae; Hur, Jin-Mok

2017-03-01

We present our findings that uranium (U) metal prepared by using the electrolytic reduction process for U oxide (UO2) in a Li2O-LiCl salt can be reoxidized into UO2 through the reaction between the U metal and Li2O in LiCl. Two salt types were used for immersion of the U metal: one was the salt used for electrolytic reduction, and the other was applied to the unused LiCl salts with various concentrations of Li2O and Li metal. Our results revealed that the degree of reoxidation increases with the increasing Li2O concentration in LiCl and that the presence of the Li metal in LiCl suppresses the reoxidation of the U metal.

PRODUCTION OF URANIUM

DOEpatents

Ruehle, A.E.; Stevenson, J.W.

1957-11-12

An improved process is described for the magnesium reduction of UF/sub 4/ to produce uranium metal. In the past, there have been undesirable premature reactions between the Mg and the bomb liner or the UF/sub 4/ before the actual ignition of the bomb reaction. Since these premature reactions impair the yield of uranium metal, they have been inhibited by forming a protective film upon the particles of Mg by reacting it with hydrated uranium tetrafluoride, sodium bifluoride, uranyl fluoride, or uranium trioxide. This may be accomplished by adding about 0.5 to 2% of the additive to the bomb charge.

Direct electrochemical reduction of solid uranium oxide in molten fluoride salts

NASA Astrophysics Data System (ADS)

Gibilaro, Mathieu; Cassayre, Laurent; Lemoine, Olivier; Massot, Laurent; Dugne, Olivier; Malmbeck, Rikard; Chamelot, Pierre

2011-07-01

The direct electrochemical reduction of UO 2 solid pellets was carried out in LiF-CaF 2 (+2 mass.% Li 2O) at 850 °C. An inert gold anode was used instead of the usual reactive sacrificial carbon anode. In this case, oxidation of oxide ions present in the melt yields O 2 gas evolution on the anode. Electrochemical characterisations of UO 2 pellets were performed by linear sweep voltammetry at 10 mV/s and reduction waves associated to oxide direct reduction were observed at a potential 150 mV more positive in comparison to the solvent reduction. Subsequent, galvanostatic electrolyses runs were carried out and products were characterised by SEM-EDX, EPMA/WDS, XRD and microhardness measurements. In one of the runs, uranium oxide was partially reduced and three phases were observed: nonreduced UO 2 in the centre, pure metallic uranium on the external layer and an intermediate phase representing the initial stage of reduction taking place at the grain boundaries. In another run, the UO 2 sample was fully reduced. Due to oxygen removal, the U matrix had a typical coral-like structure which is characteristic of the pattern observed after the electroreduction of solid oxides.

Radiological Modeling for Determination of Derived Concentration Levels of an Area with Uranium Residual Material - 13533

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perez-Sanchez, Danyl

As a result of a pilot project developed at the old Spanish 'Junta de Energia Nuclear' to extract uranium from ores, tailings materials were generated. Most of these residual materials were sent back to different uranium mines, but a small amount of it was mixed with conventional building materials and deposited near the old plant until the surrounding ground was flattened. The affected land is included in an area under institutional control and used as recreational area. At the time of processing, uranium isotopes were separated but other radionuclides of the uranium decay series as Th-230, Ra-226 and daughters remainmore » in the residue. Recently, the analyses of samples taken at different ground's depths confirmed their presence. This paper presents the methodology used to calculate the derived concentration level to ensure that the reference dose level of 0.1 mSv y-1 used as radiological criteria. In this study, a radiological impact assessment was performed modeling the area as recreational scenario. The modelization study was carried out with the code RESRAD considering as exposure pathways, external irradiation, inadvertent ingestion of soil, inhalation of resuspended particles, and inhalation of radon (Rn-222). As result was concluded that, if the concentration of Ra-226 in the first 15 cm of soil is lower than, 0.34 Bq g{sup -1}, the dose would not exceed the reference dose. Applying this value as a derived concentration level and comparing with the results of measurements on the ground, some areas with a concentration of activity slightly higher than latter were found. In these zones the remediation proposal has been to cover with a layer of 15 cm of clean material. This action represents a reduction of 85% of the dose and ensures compliance with the reference dose. (authors)« less

Efficacy of acetate-amended biostimulation for uranium sequestration: Combined analysis of sediment/groundwater geochemistry and bacterial community structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Jie; Veeramani, Harish; Qafoku, Nikolla P.

Systematic flow-through column experiments were conducted using sediments and ground water collected from different subsurface localities at the U.S. Department of Energy's Integrated Field Research Challenge site in Rifle, Colorado. The principal purpose of this study is to gain a better understanding of the interactive effects of groundwater geochemistry, sediment mineralogy, and indigenous bacterial community structures on the efficacy of uranium removal from the groundwater with/without acetate amendment. Overall, we find that the subtle variations in the sediments' mineralogy, particle size, redox conditions, as well as contents of metal(loid) co-contaminants showed a pronounced effect on the associated bacterial population andmore » composition, which mainly determines the system's performance with respect to uranium removal. Positive relationship was identified between the abundance of dissimilatory sulfate-reduction genes (i.e., drsA), markers of sulfatereducing bacteria, and the sediments' propensity to sequester aqueous uranium. In contrast, no obvious connections were observed between the abundance of common iron-reducing bacteria, e.g., Geobacter spp., and the sediments' ability to sequester uranium. In the sediments with low bacterial biomass and the absence of sulfate-reducing conditions, abiotic adsorption onto mineral surfaces such as phyllosilicates likely played a relatively major role in the attenuation of aqueous uranium; however, in these scenarios, acetate amendment induced detectable rebounds in the effluent uranium concentrations. The results of this study suggest that reductive immobilization of uranium can be achieved under predominantly sulfate-reducing conditions, and provide insight into the integrated roles of various biogeochemical components in long-term uranium sequestration.« less

Electrochemical method of producing eutectic uranium alloy and apparatus

DOEpatents

Horton, James A.; Hayden, H. Wayne

1995-01-01

An apparatus and method for continuous production of liquid uranium alloys through the electrolytic reduction of uranium chlorides. The apparatus includes an electrochemical cell formed from an anode shaped to form an electrolyte reservoir, a cathode comprising a metal, such as iron, capable of forming a eutectic uranium alloy having a melting point less than the melting point of pure uranium, and molten electrolyte in the reservoir comprising a chlorine or fluorine containing salt and uranium chloride. The method of the invention produces an eutectic uranium alloy by creating an electrolyte reservoir defined by a container comprising an anode, placing an electrolyte in the reservoir, the electrolyte comprising a chlorine or fluorine containing salt and uranium chloride in molten form, positioning a cathode in the reservoir where the cathode comprises a metal capable of forming an uranium alloy having a melting point less than the melting point of pure uranium, and applying a current between the cathode and the anode.

Electrochemical method of producing eutectic uranium alloy and apparatus

DOEpatents

Horton, J.A.; Hayden, H.W.

1995-01-10

An apparatus and method are disclosed for continuous production of liquid uranium alloys through the electrolytic reduction of uranium chlorides. The apparatus includes an electrochemical cell formed from an anode shaped to form an electrolyte reservoir, a cathode comprising a metal, such as iron, capable of forming a eutectic uranium alloy having a melting point less than the melting point of pure uranium, and molten electrolyte in the reservoir comprising a chlorine or fluorine containing salt and uranium chloride. The method of the invention produces an eutectic uranium alloy by creating an electrolyte reservoir defined by a container comprising an anode, placing an electrolyte in the reservoir, the electrolyte comprising a chlorine or fluorine containing salt and uranium chloride in molten form, positioning a cathode in the reservoir where the cathode comprises a metal capable of forming an uranium alloy having a melting point less than the melting point of pure uranium, and applying a current between the cathode and the anode. 2 figures.

40 CFR 471.72 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2014 CFR

2014-07-01

... CATEGORY Uranium Forming Subcategory § 471.72 Effluent limitations representing the degree of effluent... Maximum for monthly average mg/off-kg (pounds per million off-pounds) of uranium extruded Cadmium 0.007 0... extruded or forged uranium heat treated Cadmium 0.006 0.003 Chromium 0.012 0.005 Copper 0.040 0.019 Lead 0...

40 CFR 471.72 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2012 CFR

2012-07-01

... CATEGORY Uranium Forming Subcategory § 471.72 Effluent limitations representing the degree of effluent... Maximum for monthly average mg/off-kg (pounds per million off-pounds) of uranium extruded Cadmium 0.007 0... extruded or forged uranium heat treated Cadmium 0.006 0.003 Chromium 0.012 0.005 Copper 0.040 0.019 Lead 0...

METHOD OF DEHYDRATING URANIUM TETRAFLUORIDE

DOEpatents

Davis, J.O.; Fogel, C.C.; Palmer, W.E.

1962-12-18

Drying and dehydration of aqueous-precipitated uranium tetrafluoride are described. The UF/sub 4/ which normally contains 3 to 4% water, is dispersed into the reaction zone of an operating reactor wherein uranium hexafluoride is being reduced to UF/sub 4/ with hydrogen. The water-containing UF/sub 4/ is dried and blended with the UF/sub 4/ produced in the reactor without interfering with the reduction reaction. (AEC)

URANIUM RECOVERY PROCESS

DOEpatents

Stevenson, J.W.; Werkema, R.G.

1959-07-28

The recovery of uranium from magnesium fluoride slag obtained as a by- product in the production of uranium metal by the bomb reduction prccess is presented. Generally the recovery is accomplished by finely grinding the slag, roasting ihe ground slag air, and leaching the roasted slag with a hot, aqueous solution containing an excess of the sodium bicarbonate stoichiometrically required to form soluble uranium carbonate complex. The roasting is preferably carried out at between 425 and 485 deg C for about three hours. The leaching is preferably done at 70 to 90 deg C and under pressure. After leaching and filtration the uranium may be recovered from the clear leach liquor by any desired method.

Impact of homogeneous strain on uranium vacancy diffusion in uranium dioxide

DOE PAGES

Goyal, Anuj; Phillpot, Simon R.; Subramanian, Gopinath; ...

2015-03-03

We present a detailed mechanism of, and the effect of homogeneous strains on, the migration of uranium vacancies in UO 2. Vacancy migration pathways and barriers are identified using density functional theory and the effect of uniform strain fields are accounted for using the dipole tensor approach. We report complex migration pathways and noncubic symmetry associated with the uranium vacancy in UO 2 and show that these complexities need to be carefully accounted for to predict the correct diffusion behavior of uranium vacancies. We show that under homogeneous strain fields, only the dipole tensor of the saddle with respect tomore » the minimum is required to correctly predict the change in the energy barrier between the strained and the unstrained case. Diffusivities are computed using kinetic Monte Carlo simulations for both neutral and fully charged state of uranium single and divacancies. We calculate the effect of strain on migration barriers in the temperature range 800–1800 K for both vacancy types. Homogeneous strains as small as 2% have a considerable effect on diffusivity of both single and divacancies of uranium, with the effect of strain being more pronounced for single vacancies than divacancies. In contrast, the response of a given defect to strain is less sensitive to changes in the charge state of the defect. Further, strain leads to anisotropies in the mobility of the vacancy and the degree of anisotropy is very sensitive to the nature of the applied strain field for strain of equal magnitude. Our results indicate that the influence of strain on vacancy diffusivity will be significantly greater when single vacancies dominate the defect structure, such as sintering, while the effects will be much less substantial under irradiation conditions where divacancies dominate.« less

Exogenous contamination of uranium in human scalp hair.

PubMed

Muikku, Maarit; Heikkinen, Tarja

2012-06-01

The use of human scalp hair as a bioindicator of occupational or environmental exposure has been the subject of some debate over the years. One problem is how to distinguish internal contamination from external contamination. In this study, possibility that elevated levels of natural uranium in human hair are partly due to the exogenously bound uranium from uranium-rich household water was tested. Hair samples from six adult volunteers were cut and then exposed externally to uranium by using washing water with highly elevated levels of natural uranium. After that, and before making the analysis using inductively coupled plasma mass spectrometry (ICP-MS), the samples were washed using two commonly used washing procedures in order to remove external contamination. No quantitative information was gained in the tests, but it was shown that the use of uranium-rich water when washing hair affects the uranium concentration in hair. Although the samples were cleaned according to widely used washing procedures before the analysis, the uranium concentrations in hair were about three orders of magnitude higher after the tests. The possibility of external contamination should be kept in mind, especially when considering hair as an excretion pathway for estimating internal dose.

Reduction of uranium by Desulfovibrio desulfuricans

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.

1992-01-01

The possibility that sulfate-reducing microorganisms contribute to U(VI) reduction in sedimentary environments was investigated. U(VI) was reduced to U(IV) when washed cells of sulfate-grown Desulfovibrio desulfuricans were suspended in a bicarbonate buffer with lactate or H2 as the electron donor. There was no U(VI) reduction in the absence of an electron donor or when the cells were killed by heat prior to the incubation. The rates of U(VI) reduction were comparable to those in respiratory Fe(III)-reducing microorganisms. Azide or prior exposure of the cells to air did not affect the ability of D. desulfuricans to reduce U(VI). Attempts to grow D. desulfuricans with U(VI) as the electron acceptor were unsuccessful. U(VI) reduction resulted in the extracellular precipitation of the U(IV) mineral uraninite. The presence of sulfate had no effect on the rate of U(VI) reduction. Sulfate and U(VI) were reduced simultaneously. Enzymatic reduction of U(VI) by D. desulfuricans was much faster than nonenzymatic reduction of U(VI) by sulfide, even when cells of D. desulfuricans were added to provide a potential catalytic surface for the nonenzymatic reaction. The results indicate that enzymatic U(VI) reduction by sulfate-reducing microorganisms may be responsible for the accumulation of U(IV) in sulfidogenic environments. Furthermore, since the reduction of U(VI) to U(IV) precipitates uranium from solution, D. desulfuricans might be a useful organisms for recovering uranium from contaminated waters and waste streams.

PROCESS FOR SEPARATING PLUTONIUM FROM IMPURITIES

DOEpatents

Wahl, A.C.

1957-11-12

A method is described for separating plutonium from aqueous solutions containing uranium. It has been found that if the plutonium is reduced to its 3+ valence state, and the uranium present is left in its higher valence state, then the differences in solubility between certain salts (e.g., oxalates) of the trivalent plutonium and the hexavalent uranium can be used to separate the metals. This selective reduction of plutonium is accomplished by adding iodide ion to the solution, since iodide possesses an oxidation potential sufficient to reduce plutonium but not sufficient to reduce uranium.

In situ Bioreduction of Uranium (VI) in Groundwater and Sediments with Edible Oil as the Electron Donor

NASA Astrophysics Data System (ADS)

Wu, W.; Watson, D. B.; Mehlhorn, T.; Zhang, G.; Earles, J.; Lowe, K.; Phillips, J.; Boyanov, M.; Kemner, K. M.; Schadt, C. W.; Brooks, S. C.; Criddle, C.; Jardine, P.

2009-12-01

In situ bioremediation of a uranium-contaminated aquifer was conducted at the US DOE Environmental Remediation Sciences Program (ERSP) Integrated Field Research Challenge (IFRC) site, in Oak Ridge, TN. Edible oil was tested as a slow-release electron donor for microbially mediated U (VI) reduction. Uranium contaminated sediments from the site were used in laboratory microcosm tests to study the feasibility of using this electron donor under anaerobic, ambient temperature conditions. Parallel microcosms were established using ethanol as electron donor for comparison. The tests also examined the impact of sulfate concentrations on U (VI) reduction. The oil was degraded by indigenous microorganisms with acetate as a major product but at a much slower rate than ethanol. The rapid removal of U (VI) from the aqueous phase occurred concurrently with acetate production and sulfate reduction. Initial U(VI) concentration in the aqueous phase increased with increased sulfate concentration (1 vs. 5 mM), likely due to U(VI) desorption from the solid phase, but more U(VI) was reduced with higher initial sulfate level. Finally, the bioreaction in microcosms progressed to methanogenesis. Subsequently, a field test with the edible oil was conducted in a highly permeable gravelly layer (hydraulic conductivity 0.076 cm/sec). Groundwater at the site contained 5-6 μM U; 1.0-1.2 mM sulfate; 3-4 mM Ca; pH 6.8. Diluted emulsified oil (20% solution) was injected into three injection wells within 2 hrs. Geochemical analysis of site groundwater demonstrated the sequential reduction of nitrate, Mn, Fe(III) and sulfate. Transient accumulation of acetate was observed as an intermediate in the oil degradation. Reduction and removal of uranium from groundwater was observed in all wells connected to the injection wells after 2-4 weeks. Uranium concentrations in groundwater were reduced to below 0.126 μM (EPA drinking water standard), at some well locations. Rebound of U in groundwater was observed together with the rebound of sulfate concentrations as the oil was consumed. Uranium (VI) reduction to U (IV) in the microcosm and in situ field tests was confirmed by X-ray near-edge absorption spectroscopy analysis. Bacterial populations in microcosms and field samples were analyzed using 16S rRNA gene libraries and Geochip analysis.

Constraining the role of iron in environmental nitrogen transformations. Dual stable isotope systematics of abiotic NO 2- reduction by Fe(II) and its production of N 2O

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnston, David; Wankel, Scott David; Buchwald, Carolyn

Redox reactions involving nitrogen and iron have been shown to have important implications for mobilization of priority contaminants. Thus, an understanding of the linkages between their biogeochemical cycling is critical for predicting subsurface mobilization of radionuclides such as uranium. Despite mounting evidence for biogeochemical interactions between iron and nitrogen, our understanding of their environmental importance remains limited. Here we present an investigation of abiotic nitrite (NO 2 -) reduction by Fe(II) or ‘chemodenitrification,’ and its relevance to the production of nitrous oxide (N 2O), specifically focusing on dual (N and O) isotope systematics under a variety of environmentally relevant conditions.more » We observe a range of kinetic isotope effects that are regulated by reaction rates, with faster rates at higher pH (~8), higher concentrations of Fe(II) and in the presence of mineral surfaces. A clear non-linear relationship between rate constant and kinetic isotope effects of NO 2 - reduction was evident (with larger isotope effects at slower rates) and is interpreted as reflecting the dynamics of Fe(II)-N reaction intermediates. N and O isotopic composition of product N 2O also suggests a complex network of parallel and/or competing pathways. Our findings suggest that NO 2 - reduction by Fe(II) may represent an important abiotic source of environmental N 2O, especially in iron-rich environments experiencing dynamic redox variations. This study provides a multi-compound, multi-isotope framework for evaluating the environmental occurrence of abiotic NO 2 - reduction and N 2O formation, helping future studies constrain the relative roles of abiotic and biological N 2O production pathways.« less

In situ mobility of uranium in the presence of nitrate following sulfate-reducing conditions.

PubMed

Paradis, Charles J; Jagadamma, Sindhu; Watson, David B; McKay, Larry D; Hazen, Terry C; Park, Melora; Istok, Jonathan D

2016-04-01

Reoxidation and mobilization of previously reduced and immobilized uranium by dissolved-phase oxidants poses a significant challenge for remediating uranium-contaminated groundwater. Preferential oxidation of reduced sulfur-bearing species, as opposed to reduced uranium-bearing species, has been demonstrated to limit the mobility of uranium at the laboratory scale yet field-scale investigations are lacking. In this study, the mobility of uranium in the presence of nitrate oxidant was investigated in a shallow groundwater system after establishing conditions conducive to uranium reduction and the formation of reduced sulfur-bearing species. A series of three injections of groundwater (200 L) containing U(VI) (5 μM) and amended with ethanol (40 mM) and sulfate (20 mM) were conducted in ten test wells in order to stimulate microbial-mediated reduction of uranium and the formation of reduced sulfur-bearing species. Simultaneous push-pull tests were then conducted in triplicate well clusters to investigate the mobility of U(VI) under three conditions: 1) high nitrate (120 mM), 2) high nitrate (120 mM) with ethanol (30 mM), and 3) low nitrate (2 mM) with ethanol (30 mM). Dilution-adjusted breakthrough curves of ethanol, nitrate, nitrite, sulfate, and U(VI) suggested that nitrate reduction was predominantly coupled to the oxidation of reduced-sulfur bearing species, as opposed to the reoxidation of U(IV), under all three conditions for the duration of the 36-day tests. The amount of sulfate, but not U(VI), recovered during the push-pull tests was substantially more than injected, relative to bromide tracer, under all three conditions and further suggested that reduced sulfur-bearing species were preferentially oxidized under nitrate-reducing conditions. However, some reoxidation of U(IV) was observed under nitrate-reducing conditions and in the absence of detectable nitrate and/or nitrite. This suggested that reduced sulfur-bearing species may not be fully effective at limiting the mobility of uranium in the presence of dissolved and/or solid-phase oxidants. The results of this field study confirmed those of previous laboratory studies which suggested that reoxidation of uranium under nitrate-reducing conditions can be substantially limited by preferential oxidation of reduced sulfur-bearing species. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

In situ mobility of uranium in the presence of nitrate following sulfate-reducing conditions

DOE PAGES

Paradis, Charles J.; Jagadamma, Sindhu; Watson, David B.; ...

2016-02-11

Reoxidation and mobilization of previously reduced and immobilized uranium by dissolved phase oxidants poses a significant challenge for remediating uranium-contaminated groundwater. Preferential oxidation of reduced sulfur-bearing species, as opposed to reduced uranium bearing species, has been demonstrated to limit the mobility of uranium at the laboratory scale yet field-scale investigations are lacking. Here in this study, the mobility of uranium in the presence of nitrate oxidant was investigated in a shallow groundwater system after establishing conditions conducive to uranium reduction and the formation of reduced sulfur-bearing species. A series of three injections of groundwater (200 L) containing U(VI) (5 μM)more » and amended with ethanol (40 mM) and sulfate (20 mM) were conducted in ten test wells in order to stimulate microbial mediated reduction of uranium and the formation of reduced sulfur-bearing species. Simultaneous push-pull tests were then conducted in triplicate well clusters to investigate the mobility of U(VI) under three conditions: 1) high nitrate (120 mM), 2) high nitrate (120 mM) with ethanol (30 mM), and 3) low nitrate (2 mM) with ethanol (30 mM). Dilution-adjusted breakthrough curves of ethanol, nitrate, nitrite, sulfate, and U(VI) suggested that nitrate reduction was predominantly coupled to the oxidation of reduced-sulfur bearing species, as opposed to the reoxidation of U(IV), under all three conditions for the duration of the 36-day tests. The amount of sulfate, but not U(VI), recovered during the push-pull tests was substantially more than injected, relative to bromide tracer, under all three conditions and further suggested that reduced sulfur-bearing species were preferentially oxidized under nitrate-reducing conditions. However, some reoxidation of U(IV) was observed under nitrate-reducing conditions and in the absence of detectable nitrate and/or nitrite. This suggested that reduced sulfur-bearing species may not be fully effective at limiting the mobility of uranium in the presence of dissolved and/or solid-phase oxidants. Lastly, the results of this field study confirmed those of previous laboratory studies which suggested that reoxidation of uranium under nitrate-reducing conditions can be substantially limited by preferential oxidation of reduced sulfur-bearing species.« less

XANES and EXAFS investigation of uranium incorporation on nZVI in the presence of phosphate.

PubMed

Qiu, Muqing; Wang, Min; Zhao, Qingzhou; Hu, Baowei; Zhu, Yuling

2018-06-01

Effect of phosphate on the reduction of U(VI) on nZVI was determined by batch, XPS, XANES and EXAFS techniques. The batch experiments showed that nZVI was quite effective for the removal of uranium under the anaerobic conditions, whereas the addition of phosphate enhanced uranium removal over wide pH range. At low pH, the reduction of U(VI) to U(IV) significantly decreased with increasing phosphate concentration by XPS and XANES analysis. According to EXAFS analysis, the occurrence of UU shell at 10 mg/L phosphate and pH 4.0 was similar to that of U (IV) O 2 (s), whereas the UP and UFe shells were observed at 50 mg/L phosphate, revealing that reductive co-precipitate (U (IV) O 2 (s)) and precipitation of uranyl-phosphate were observed at low and high phosphate, respectively. The findings are crucial for the prediction of the effect of phosphate on the speciation and binding of uranium by nZVI at low pH, which is significant in controlling the mobility of U(VI) in contaminated environments. Copyright © 2018 Elsevier Ltd. All rights reserved.

Linking Specific Heterotrophic Bacterial Populations to Bioreduction of Uranium and Nitrate in Contaminated Subsurface Sediments by Using Stable Isotope Probing▿†

PubMed Central

Akob, Denise M.; Kerkhof, Lee; Küsel, Kirsten; Watson, David B.; Palumbo, Anthony V.; Kostka, Joel E.

2011-01-01

Shifts in terminal electron-accepting processes during biostimulation of uranium-contaminated sediments were linked to the composition of stimulated microbial populations using DNA-based stable isotope probing. Nitrate reduction preceded U(VI) and Fe(III) reduction in [13C]ethanol-amended microcosms. The predominant, active denitrifying microbial groups were identified as members of the Betaproteobacteria, whereas Actinobacteria dominated under metal-reducing conditions. PMID:21948831

Spatial Distribution of an Uranium-Respiring Betaproteobacterium at the Rifle, CO Field Research Site

PubMed Central

Koribanics, Nicole M.; Tuorto, Steven J.; Lopez-Chiaffarelli, Nora; McGuinness, Lora R.; Häggblom, Max M.; Williams, Kenneth H.; Long, Philip E.; Kerkhof, Lee J.

2015-01-01

The Department of Energy’s Integrated Field-Scale Subsurface Research Challenge Site (IFRC) at Rifle, Colorado was created to address the gaps in knowledge on the mechanisms and rates of U(VI) bioreduction in alluvial sediments. Previous studies at the Rifle IFRC have linked microbial processes to uranium immobilization during acetate amendment. Several key bacteria believed to be involved in radionuclide containment have been described; however, most of the evidence implicating uranium reduction with specific microbiota has been indirect. Here, we report on the cultivation of a microorganism from the Rifle IFRC that reduces uranium and appears to utilize it as a terminal electron acceptor for respiration with acetate as electron donor. Furthermore, this bacterium constitutes a significant proportion of the subsurface sediment community prior to biostimulation based on TRFLP profiling of 16S rRNA genes. 16S rRNA gene sequence analysis indicates that the microorganism is a betaproteobacterium with a high similarity to Burkholderia fungorum. This is, to our knowledge, the first report of a betaproteobacterium capable of uranium respiration. Our results indicate that this microorganism occurs commonly in alluvial sediments located between 3-6 m below ground surface at Rifle and may play a role in the initial reduction of uranium at the site. PMID:25874721

Spatial distribution of an uranium-respiring betaproteobacterium at the Rifle, CO field research site

DOE PAGES

Koribanics, Nicole M.; Tuorto, Steven J.; Lopez-Chiaffarelli, Nora; ...

2015-04-13

The Department of Energy’s Integrated Field-Scale Subsurface Research Challenge Site (IFRC) at Rifle, Colorado was created to address the gaps in knowledge on the mechanisms and rates of U(VI) bioreduction in alluvial sediments. Previous studies at the Rifle IFRC have linked microbial processes to uranium immobilization during acetate amendment. Several key bacteria believed to be involved in radionuclide containment have been described; however, most of the evidence implicating uranium reduction with specific microbiota has been indirect. Here, we report on the cultivation of a microorganism from the Rifle IFRC that reduces uranium and appears to utilize it as a terminalmore » electron acceptor for respiration with acetate as electron donor. Furthermore, this bacterium constitutes a significant proportion of the subsurface sediment community prior to biostimulation based on TRFLP profiling of 16S rRNA genes. 16S rRNA gene sequence analysis indicates that the microorganism is a betaproteobacterium with a high similarity to Burkholderia fungorum. This is, to our knowledge, the first report of a betaproteobacterium capable of uranium respiration. Our results indicate that this microorganism occurs commonly in alluvial sediments located between 3-6 m below ground surface at Rifle and may play a role in the initial reduction of uranium at the site.« less

Efficacy of acetate-amended biostimulation for uranium sequestration: Combined analysis of sediment/groundwater geochemistry and bacterial community structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Jie; Veeramani, Harish; Qafoku, Nikolla P.

Systematic flow-through column experiments were conducted using sediments and ground water collected from different subsurface localities at the U.S. Department of Energy’s Integrated Field Research Challenge site in Rifle, Colorado. The principal purpose of this study is to gain a better understanding of the interactive effects of groundwater geochemistry, sediment mineralogy, and indigenous bacterial community structures on the efficacy of uranium removal from the groundwater with/without acetate amendment. Overall, we find that the subtle variations in the sediments’ mineralogy, particle size, redox conditions, as well as contents of metal(loid) co-contaminants showed a pronounced effect on the associated bacterial population andmore » composition, which mainly determines the system’s performance with respect to uranium removal. Positive relationship was identified between the abundance of dissimilatory sulfate-reduction genes (i.e., drsA), markers of sulfate-reducing bacteria, and the sediments’ propensity to sequester aqueous uranium. In contrast, no obvious connections were observed between the abundance of common iron-reducing bacteria, e.g., Geobacter spp., and the sediments’ ability to sequester uranium. In the sediments with low bacterial biomass and the absence of sulfate-reducing conditions, abiotic adsorption onto mineral surfaces such as phyllosilicates likely played a relatively major role in the attenuation of aqueous uranium; however, in these scenarios, acetate amendment induced detectable rebounds in the effluent uranium concentrations. The results of this study suggest that reductive immobilization of uranium can be achieved under predominantly sulfate-reducing conditions, and provide insight into the integrated roles of various biogeochemical components in long-term uranium sequestration.« less

Simultaneous reduction of arsenic(V) and uranium(VI) by mackinawite: role of uranyl arsenate precipitate formation.

PubMed

Troyer, Lyndsay D; Tang, Yuanzhi; Borch, Thomas

2014-12-16

Uranium (U) and arsenic (As) often occur together naturally and, as a result, can be co-contaminants at sites of uranium mining and processing, yet few studies have examined the simultaneous redox dynamics of U and As. This study examines the influence of arsenate (As(V)) on the reduction of uranyl (U(VI)) by the redox-active mineral mackinawite (FeS). As(V) was added to systems containing 47 or 470 μM U(VI) at concentrations ranging from 0 to 640 μM. In the absence of As(V), U was completely removed from solution and fully reduced to nano-uraninite (nano-UO2). While the addition of As(V) did not reduce U uptake, at As(V) concentrations above 320 μM, the reduction of U(VI) was limited due to the formation of a trögerite-like uranyl arsenate precipitate. The presence of U also significantly inhibited As(V) reduction. While less U(VI) reduction to nano-UO2 may take place in systems with high As(V) concentrations, formation of trögerite-like mineral phases may be an acceptable reclamation end point due to their high stability under oxic conditions.

Sandstone type uranium deposits in the Ordos Basin, Northwest China: A case study and an overview

NASA Astrophysics Data System (ADS)

Akhtar, Shamim; Yang, Xiaoyong; Pirajno, Franco

2017-09-01

This paper provides a comprehensive review on studies of sandstone type uranium deposits in the Ordos Basin, Northwest China. As the second largest sedimentary basin, the Ordos Basin has great potential for targeting sandstone type U mineralization. The newly found and explored Dongsheng and Diantou sandstone type uranium deposits are hosted in the Middle Jurassic Zhilou Formation. A large number of investigations have been conducted to trace the source rock compositions and relationship between lithic subarkose sandstone host rock and uranium mineralization. An optical microscopy study reveals two types of alteration associated with the U mineralization: chloritization and sericitization. Some unusual mineral structures, with compositional similarity to coffinite, have been identified in a secondary pyrite by SEM These mineral phases are proposed to be of bacterial origin, following high resolution mapping of uranium minerals and trace element determinations in situ. Moreover, geochemical studies of REE and trace elements constrained the mechanism of uranium enrichment, displaying LREE enrichment relative to HREE. Trace elements such as Pb, Mo and Ba have a direct relationship with uranium enrichment and can be used as index for mineralization. The source of uranium ore forming fluids and related geological processes have been studied using H, O and C isotope systematics of fluid inclusions in quartz veins and the calcite cement of sandstone rocks hosting U mineralization. Both H and O isotopic compositions of fluid inclusions reveal that ore forming fluids are a mixture of meteoric water and magmatic water. The C and S isotopes of the cementing material of sandstone suggest organic origin and bacterial sulfate reduction (BSR), providing an important clue for U mineralization. Discussion of the ore genesis shows that the greenish gray sandstone plays a crucial role during processes leading to uranium mineralization. Consequently, an oxidation-reduction model for sandstone-type uranium deposit is proposed, which can elucidate the source of uranium in the deposits of the Ordos Basin, based on the role of organic materials and sulfate reducing bacteria. We discuss the mechanism of uranium deposition responsible for the genesis of these large sandstone type uranium deposits in this unique sedimentary basin.

Evaluation of depleted uranium in the environment at Aberdeen Proving Grounds, Maryland and Yuma Proving Grounds, Arizona. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kennedy, P.L.; Clements, W.H.; Myers, O.B.

1995-01-01

This report represents an evaluation of depleted uranium (DU) introduced into the environment at the Aberdeen Proving Grounds (APG), Maryland and Yuma Proving Grounds (YPG) Arizona. This was a cooperative project between the Environmental Sciences and Statistical Analyses Groups at LANL and with the Department of Fishery and Wildlife Biology at Colorado State University. The project represents a unique approach to assessing the environmental impact of DU in two dissimilar ecosystems. Ecological exposure models were created for each ecosystem and sensitivity/uncertainty analyses were conducted to identify exposure pathways which were most influential in the fate and transport of DU inmore » the environment. Research included field sampling, field exposure experiment, and laboratory experiments. The first section addresses DU at the APG site. Chapter topics include bioenergetics-based food web model; field exposure experiments; bioconcentration by phytoplankton and the toxicity of U to zooplankton; physical processes governing the desorption of uranium from sediment to water; transfer of uranium from sediment to benthic invertebrates; spead of adsorpion by benthic invertebrates; uptake of uranium by fish. The final section of the report addresses DU at the YPG site. Chapters include the following information: Du transport processes and pathway model; field studies of performance of exposure model; uptake and elimination rates for kangaroo rates; chemical toxicity in kangaroo rat kidneys.« less

The role of uranium-arene bonding in H2O reduction catalysis

NASA Astrophysics Data System (ADS)

Halter, Dominik P.; Heinemann, Frank W.; Maron, Laurent; Meyer, Karsten

2018-03-01

The reactivity of uranium compounds towards small molecules typically occurs through stoichiometric rather than catalytic processes. Examples of uranium catalysts reacting with water are particularly scarce, because stable uranyl groups form that preclude the recovery of the uranium compound. Recently, however, an arene-anchored, electron-rich uranium complex has been shown to facilitate the electrocatalytic formation of H2 from H2O. Here, we present the precise role of uranium-arene δ bonding in intermediates of the catalytic cycle, as well as details of the atypical two-electron oxidative addition of H2O to the trivalent uranium catalyst. Both aspects were explored by synthesizing mid- and high-valent uranium-oxo intermediates and by performing comparative studies with a structurally related complex that cannot engage in δ bonding. The redox activity of the arene anchor and a covalent δ-bonding interaction with the uranium ion during H2 formation were supported by density functional theory analysis. Detailed insight into this catalytic system may inspire the design of ligands for new uranium catalysts.

Modeling Reduction of Uranium U(VI) under Variable Sulfate Concentrations by Sulfate-Reducing Bacteria

PubMed Central

Spear, John R.; Figueroa, Linda A.; Honeyman, Bruce D.

2000-01-01

The kinetics for the reduction of sulfate alone and for concurrent uranium [U(VI)] and sulfate reduction, by mixed and pure cultures of sulfate-reducing bacteria (SRB) at 21 ± 3°C were studied. The mixed culture contained the SRB Desulfovibrio vulgaris along with a Clostridium sp. determined via 16S ribosomal DNA analysis. The pure culture was Desulfovibrio desulfuricans (ATCC 7757). A zero-order model best fit the data for the reduction of sulfate from 0.1 to 10 mM. A lag time occurred below cell concentrations of 0.1 mg (dry weight) of cells/ml. For the mixed culture, average values for the maximum specific reaction rate, Vmax, ranged from 2.4 ± 0.2 μmol of sulfate/mg (dry weight) of SRB · h−1) at 0.25 mM sulfate to 5.0 ± 1.1 μmol of sulfate/mg (dry weight) of SRB · h−1 at 10 mM sulfate (average cell concentration, 0.52 mg [dry weight]/ml). For the pure culture, Vmax was 1.6 ± 0.2 μmol of sulfate/mg (dry weight) of SRB · h−1 at 1 mM sulfate (0.29 mg [dry weight] of cells/ml). When both electron acceptors were present, sulfate reduction remained zero order for both cultures, while uranium reduction was first order, with rate constants of 0.071 ± 0.003 mg (dry weight) of cells/ml · min−1 for the mixed culture and 0.137 ± 0.016 mg (dry weight) of cells/ml · min−1 (U0 = 1 mM) for the D. desulfuricans culture. Both cultures exhibited a faster rate of uranium reduction in the presence of sulfate and no lag time until the onset of U reduction in contrast to U alone. This kinetics information can be used to design an SRB-dominated biotreatment scheme for the removal of U(VI) from an aqueous source. PMID:10966381

CONTINUOUS PRECIPITATION METHOD FOR CONVERSION OF URANYL NITRATE TO URANIUM HEXAFLUORIDE

DOEpatents

Reinhart, G.M.; Collopy, T.J.

1962-11-13

A continuous precipitation process is given for converting a uranyl nitrate solution to uranium tetrafluoride. A stream of the uranyl nitrate solution and a stream of an aqueous ammonium hydroxide solution are continuously introduced into an agitated reaction zone maintained at a pH of 5.0 to 6.5. Flow rates are adjusted to provide a mean residence time of the resulting slurry in the reaction zone of at least 30 minutes. After a startup period of two hours the precipitate is recovered from the effluent stream by filtration and is converted to uranium tetrafluoride by reduction to uranium dioxide with hydrogen and reaction of the uranium dioxide with anhydrous hydrogen fluoride. (AEC)

Effects of aqueous uranyl speciation on the kinetics of microbial uranium reduction

DOE PAGES

Belli, Keaton M.; DiChristina, Thomas J.; Van Cappellen, Philippe; ...

2015-02-16

The ability to predict the success of the microbial reduction of soluble U(VI) to highly insoluble U(IV) as an in situ bioremediation strategy is complicated by the wide range of geochemical conditions at contaminated sites and the strong influence of aqueous uranyl speciation on the bioavailability and toxicity of U(VI) to metal-reducing bacteria. In order to determine the effects of aqueous uranyl speciation on uranium bioreduction kinetics, incubations and viability assays with Shewanella putrefaciens strain 200 were conducted over a range of pH and dissolved inorganic carbon (DIC), Ca 2+, and Mg 2+ concentrations. A speciation-dependent kinetic model was developedmore » to reproduce the observed time series of total dissolved uranium concentration over the range of geochemical conditions tested. The kinetic model yielded the highest rate constant for the reduction of uranyl non-carbonate species (i.e., the ‘free’ hydrated uranyl ion, uranyl hydroxides, and other minor uranyl complexes), indicating that they represent the most readily reducible fraction of U(VI) despite being the least abundant uranyl species in solution. In the presence of DIC, Ca 2+, and Mg 2+ is suppressed during the formation of more bioavailable uranyl non-carbonate species and resulted in slower bioreduction rates. At high concentrations of bioavailable U(VI), however, uranium toxicity to S. putrefaciens inhibited bioreduction, and viability assays confirmed that the concentration of non-carbonate uranyl species best predicts the degree of toxicity. The effect of uranium toxicity was accounted for by incorporating the free ion activity model of metal toxicity into the bioreduction rate law. These results demonstrate that, in the absence of competing terminal electron acceptors, uranium bioreduction kinetics can be predicted over a wide range of geochemical conditions based on the bioavailability and toxicity imparted on U(VI) by solution composition. Finally, these findings also imply that the concentration of uranyl non-carbonate species, despite being extremely low, is a determining factor controlling uranium bioreduction at contaminated sites.« less

Uranium removal from a contaminated effluent using a combined microbial and nanoparticle system.

PubMed

Baiget, Mar; Constantí, Magda; López, M Teresa; Medina, Francesc

2013-09-25

Reduction of soluble uranium(VI) to insoluble uranium(IV) for remediating a uranium-contaminated effluent (EF-03) was examined using a biotic and abiotic integrated system. Shewanella putrefaciens was first used and reduced U(VI) in a synthetic medium but not in the EF-03 effluent sample. Subsequently the growth of autochthonous microorganisms was stimulated with lactate. When lactate was supported on active carbon 77% U(VI) was removed in 4 days. Separately, iron nanoparticles that were 50 nm in diameter reduced U(VI) by 60% in 4 hours. The efficiency of uranium(VI) removal was improved to 96% in 30 min by using a system consisting of lactate and iron nanoparticles immobilized on active carbon. Lactate also stimulated the growth of potential uranium-reducing microorganisms in the EF-03 sample. This system can be efficiently used for the bioremediation of uranium-contaminated effluents. Copyright © 2013 Elsevier B.V. All rights reserved.

Enriched but not depleted uranium affects central nervous system in long-term exposed rat.

PubMed

Houpert, Pascale; Lestaevel, Philippe; Bussy, Cyrill; Paquet, François; Gourmelon, Patrick

2005-12-01

Uranium is well known to induce chemical toxicity in kidneys, but several other target organs, such as central nervous system, could be also affected. Thus in the present study, the effects on sleep-wake cycle and behavior were studied after chronic oral exposure to enriched or depleted uranium. Rats exposed to 4% enriched uranium for 1.5 months through drinking water, accumulated twice as much uranium in some key areas such as the hippocampus, hypothalamus and adrenals than did control rats. This accumulation was correlated with an increase of about 38% of the amount of paradoxical sleep, a reduction of their spatial working memory capacities and an increase in their anxiety. Exposure to depleted uranium for 1.5 months did not induce these effects, suggesting that the radiological activity induces the primary events of these effects of uranium.

Universal fuel basket for use with an improved oxide reduction vessel and electrorefiner vessel

DOEpatents

Herrmann, Steven D.; Mariani, Robert D.

2002-01-01

A basket, for use in the reduction of UO.sub.2 to uranium metal and in the electrorefining of uranium metal, having a continuous annulus between inner and outer perforated cylindrical walls, with a screen adjacent to each wall. A substantially solid bottom and top plate enclose the continuous annulus defining a fuel bed. A plurality of scrapers are mounted adjacent to the outer wall extending longitudinally thereof, and there is a mechanism enabling the basket to be transported remotely.

DOUBLE-BAKED, SELF-CHANNELLING ELECTRODE

DOEpatents

Piper, R.D.; Leifield, R.F.

1963-03-12

A method is given for making an electrode for use in the electrolytic reduction of uranium oxides to uranium metal in a fused salt electrolyte. Uranlum oxide such as UO/sub 2/ is mixed with somewhat less than the stoichiometric amount of carbon needed for the reduction, and the mixture is baked and crushed to make a nonspherical material. The latter is then mixed with a carbon binder sufficient to satisfy stoichiometry, pressed into a shape such as a cylinder, and baked. (AEC)

Exposure pathways and biological receptors: baseline data for the canyon uranium mine, Coconino County, Arizona

USGS Publications Warehouse

Hinck, Jo E.; Linder, Greg L.; Darrah, Abigail J.; Drost, Charles A.; Duniway, Michael C.; Johnson, Matthew J.; Méndez-Harclerode, Francisca M.; Nowak, Erika M.; Valdez, Ernest W.; van Riper, Charles; Wolff, S.W.

2014-01-01

Recent restrictions on uranium mining within the Grand Canyon watershed have drawn attention to scientific data gaps in evaluating the possible effects of ore extraction to human populations as well as wildlife communities in the area. Tissue contaminant concentrations, one of the most basic data requirements to determine exposure, are not available for biota from any historical or active uranium mines in the region. The Canyon Uranium Mine is under development, providing a unique opportunity to characterize concentrations of uranium and other trace elements, as well as radiation levels in biota, found in the vicinity of the mine before ore extraction begins. Our study objectives were to identify contaminants of potential concern and critical contaminant exposure pathways for ecological receptors; conduct biological surveys to understand the local food web and refine the list of target species (ecological receptors) for contaminant analysis; and collect target species for contaminant analysis prior to the initiation of active mining. Contaminants of potential concern were identified as arsenic, cadmium, chromium, copper, lead, mercury, nickel, selenium, thallium, uranium, and zinc for chemical toxicity and uranium and associated radionuclides for radiation. The conceptual exposure model identified ingestion, inhalation, absorption, and dietary transfer (bioaccumulation or bioconcentration) as critical contaminant exposure pathways. The biological survey of plants, invertebrates, amphibians, reptiles, birds, and small mammals is the first to document and provide ecological information on .200 species in and around the mine site; this study also provides critical baseline information about the local food web. Most of the species documented at the mine are common to ponderosa pine Pinus ponderosa and pinyon–juniper Pinus–Juniperus spp. forests in northern Arizona and are not considered to have special conservation status by state or federal agencies; exceptions are the locally endemic Tusayan flameflower Phemeranthus validulus, the long-legged bat Myotis volans, and the Arizona bat Myotis occultus. The most common vertebrate species identified at the mine site included the Mexican spadefoot toad Spea multiplicata, plateau fence lizard Sceloporus tristichus, violetgreen swallow Tachycineta thalassina, pygmy nuthatch Sitta pygmaea, purple martin Progne subis, western bluebird Sialia mexicana, deermouse Peromyscus maniculatus, valley pocket gopher Thomomys bottae, cliff chipmunk Tamias dorsalis, black-tailed jackrabbit Lepus californicus, mule deer Odocoileus hemionus, and elk Cervus canadensis. A limited number of the most common species were collected for contaminant analysis to establish baseline contaminant and radiological concentrations prior to ore extraction. These empirical baseline data will help validate contaminant exposure pathways and potential threats from contaminant exposures to ecological receptors. Resource managers will also be able to use these data to determine the extent to which local species are exposed to chemical and radiation contamination once the mine is operational and producing ore. More broadly, these data could inform resource management decisions on mitigating chemical and radiation exposure of biota at high-grade uranium breccia pipes throughout the Grand Canyon watershed.

PROCESS OF TREATING URANIUM HEXAFLUORIDE AND PLUTONIUM HEXAFLUORIDE MIXTURES WITH SULFUR TETRAFLUORIDE TO SEPARATE SAME

DOEpatents

Steindler, M.J.

1962-07-24

A process was developed for separating uranium hexafluoride from plutonium hexafluoride by the selective reduction of the plutonium hexafluoride to the tetrafluoride with sulfur tetrafluoride at 50 to 120 deg C, cooling the mixture to --60 to -100 deg C, and volatilizing nonreacted sulfur tetrafluoride and sulfur hexafluoride formed at that temperature. The uranium hexafluoride is volatilized at room temperature away from the solid plutonium tetrafluoride. (AEC)

Assessment of age-dependent uranium intake due to drinking water in Hyderabad, India.

PubMed

Balbudhe, A Y; Srivastava, S K; Vishwaprasad, K; Srivastava, G K; Tripathi, R M; Puranik, V D

2012-03-01

A study has been done to assess the uranium intake through drinking water. The area of study is twin cities of Hyderabad and Secunderabad, India. Uranium concentration in water samples was analysed by laser-induced fluorimetry. The associated age-dependent uranium intake was estimated by taking the prescribed water intake values. The concentration of uranium varies from below detectable level (minimum detectable level = 0.20 ± 0.02 μg l(-1)) to 2.50 ± 0.18 μg l(-1), with the geometric mean (GM) of 0.67 μg l(-1) in tap water, whereas in ground water, the range is 0.60 ± 0.05 to 82 ± 7.1 µg l(-1) with GM of 10.07 µg l(-1). The daily intake of uranium by drinking water pathway through tap water for various age groups is found to vary from 0.14 to 9.50 µg d(-1) with mean of 1.55 µg d(-1).

SINGLE-STEP CONVERSION OF UO$sub 3$ TO UF$sub 4$

DOEpatents

Moore, J.E.

1960-07-12

A description is given of the preparation of uranium tetrafluoride by reacting a hexavalent uranium compound with a pclysaccharide and gaseous hydrogen fluoride at an elevated temperature. Uranium trioxide and starch are combined with water to form a doughy mixture. which is extruded into pellets and dried. The pellets are then contacted with HF at a temperature from 500 to 700 deg C in a moving bed reactor to prcduce UF/sub 4/. Reduction of the hexavalent uranium to UO/sub 2/ and conversion of the UO/sub 2/ to UF/sub 4/ are accomplished simultaneously in this process.

FUSED SALT PROCESS FOR RECOVERY OF VALUES FROM USED NUCLEAR REACTOR FUELS

DOEpatents

Moore, R.H.

1960-08-01

A process is given for recovering plutonium from a neutron-irradiated uranium mass (oxide or alloy) by dissolving the mass in an about equimolar alkali metalaluminum double chloride, adding aluminum metal to the mixture obtained at a temperature of between 260 and 860 deg C, and separating a uranium-containing metal phase and a plutonium-chloride- and fission-product chloridecontaining salt phase. Dissolution can be expedited by passing carbon tetrachloride vapors through the double salt. Separation without reduction of plutonium from neutron- bombarded uranium and that of cerium from uranium are also discussed.

Chronic Exposure to Uranium from Gestation: Effects on Behavior and Neurogenesis in Adulthood

PubMed Central

Dinocourt, Céline; Culeux, Cécile; Legrand, Marie; Elie, Christelle; Lestaevel, Philippe

2017-01-01

Uranium exposure leads to cerebral dysfunction involving for instance biochemical, neurochemical and neurobehavioral effects. Most studies have focused on mechanisms in uranium-exposed adult animals. However, recent data on developing animals have shown that the developing brain is also sensitive to uranium. Models of uranium exposure during brain development highlight the need to improve our understanding of the effects of uranium. In a model in which uranium exposure began from the first day of gestation, we studied the neurobehavioral consequences as well as the progression of hippocampal neurogenesis in animals from dams exposed to uranium. Our results show that 2-month-old rats exposed to uranium from gestational day 1 displayed deficits in special memory and a prominent depressive-like phenotype. Cell proliferation was not disturbed in these animals, as shown by 5-bromo-2′deoxyuridine (BrdU)/neuronal specific nuclear protein (NeuN) immunostaining in the dentate gyrus. However, in some animals, the pyramidal cell layer was dispersed in the CA3 region. From our previous results with the same model, the hypothesis of alterations of neurogenesis at prior stages of development is worth considering, but is probably not the only one. Therefore, further investigations are needed to correlate cerebral dysfunction and its underlying mechanistic pathways. PMID:28513543

Chronic Exposure to Uranium from Gestation: Effects on Behavior and Neurogenesis in Adulthood.

PubMed

Dinocourt, Céline; Culeux, Cécile; Legrand, Marie; Elie, Christelle; Lestaevel, Philippe

2017-05-17

Uranium exposure leads to cerebral dysfunction involving for instance biochemical, neurochemical and neurobehavioral effects. Most studies have focused on mechanisms in uranium-exposed adult animals. However, recent data on developing animals have shown that the developing brain is also sensitive to uranium. Models of uranium exposure during brain development highlight the need to improve our understanding of the effects of uranium. In a model in which uranium exposure began from the first day of gestation, we studied the neurobehavioral consequences as well as the progression of hippocampal neurogenesis in animals from dams exposed to uranium. Our results show that 2-month-old rats exposed to uranium from gestational day 1 displayed deficits in special memory and a prominent depressive-like phenotype. Cell proliferation was not disturbed in these animals, as shown by 5-bromo-2'deoxyuridine (BrdU)/neuronal specific nuclear protein (NeuN) immunostaining in the dentate gyrus. However, in some animals, the pyramidal cell layer was dispersed in the CA3 region. From our previous results with the same model, the hypothesis of alterations of neurogenesis at prior stages of development is worth considering, but is probably not the only one. Therefore, further investigations are needed to correlate cerebral dysfunction and its underlying mechanistic pathways.

High Useful Yield and Isotopic Analysis of Uranium by Resonance Ionization Mass Spectrometry

DOE PAGES

Savina, Michael R.; Isselhardt, Brett H.; Kucher, Andrew; ...

2017-05-09

Useful yields from resonance ionization mass spectrometry can be extremely high compared to other mass spectrometry techniques, but uranium analysis shows strong matrix effects arising from the tendency of uranium to form strongly bound oxide molecules that do not dissociate appreciably on energetic ion bombardment. Here, we demonstrate a useful yield of 24% for metallic uranium. Modeling the laser ionization and ion transmission processes shows that the high useful yield is attributable to a high ion fraction achieved by resonance ionization. We quantify the reduction of uranium oxide surface layers by Ar + and Ga + sputtering. The useful yieldmore » for uranium atoms from a uranium dioxide matrix is 0.4% and rises to 2% when the surface is in sputter equilibrium with the ion beam. The lower useful yield from the oxide is almost entirely due to uranium oxide molecules reducing the neutral atom content of the sputtered flux. We also demonstrate rapid isotopic analysis of solid uranium oxide at a precision of <0.5% relative standard deviation using relatively broadband lasers to mitigate spectroscopic fractionation.« less

High Useful Yield and Isotopic Analysis of Uranium by Resonance Ionization Mass Spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Savina, Michael R.; Isselhardt, Brett H.; Kucher, Andrew

Useful yields from resonance ionization mass spectrometry can be extremely high compared to other mass spectrometry techniques, but uranium analysis shows strong matrix effects arising from the tendency of uranium to form strongly bound oxide molecules that do not dissociate appreciably on energetic ion bombardment. Here, we demonstrate a useful yield of 24% for metallic uranium. Modeling the laser ionization and ion transmission processes shows that the high useful yield is attributable to a high ion fraction achieved by resonance ionization. We quantify the reduction of uranium oxide surface layers by Ar + and Ga + sputtering. The useful yieldmore » for uranium atoms from a uranium dioxide matrix is 0.4% and rises to 2% when the surface is in sputter equilibrium with the ion beam. The lower useful yield from the oxide is almost entirely due to uranium oxide molecules reducing the neutral atom content of the sputtered flux. We also demonstrate rapid isotopic analysis of solid uranium oxide at a precision of <0.5% relative standard deviation using relatively broadband lasers to mitigate spectroscopic fractionation.« less

Role of U(VI) Reduction by Geobacter species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lovely, Derrick

2008-12-23

Previous work had suggested that Acholeplasma palmae has a higher capacity for uranium sorption than other bacteria studied. Sorption studies were performed with cells in suspension in various solutions containing uranium, and results were used to generate uranium-biosorption isotherms. Results from this study showed that the U(VI) sorption capacity of G. uraniireducens was relatively similar in simple solutions, such as sodium chloride or bicarbonate. However, this ability to sorb uranium significantly decreased in groundwater. This suggested that certain chemicals present in the groundwater were inhibiting the ability of cell components of Geobacter to adsorb uranium. It was hypothesized that uraniummore » removal would also be diminished in the bicarbonate solution. However, this did not seem to be the case, as uranium was as easily removed in the bicarbonate solution as in the sodium chloride solution.« less

Characterization of uranium redox state in organic-rich Eocene sediments.

PubMed

Cumberland, Susan A; Etschmann, Barbara; Brugger, Joël; Douglas, Grant; Evans, Katy; Fisher, Louise; Kappen, Peter; Moreau, John W

2018-03-01

The presence of organic matter (OM) has a profound impact on uranium (U) redox cycling, either limiting or promoting the mobility of U via binding, reduction, or complexation. To understand the interactions between OM and U, we characterised U oxidation state and speciation in nine OM-rich sediment cores (18 samples), plus a lignite sample from the Mulga Rock polymetallic deposit in Western Australia. Uranium was unevenly dispersed within the analysed samples with 84% of the total U occurring in samples containing >21 wt % OM. Analyses of U speciation, including x-ray absorption spectroscopy and bicarbonate extractions, revealed that U existed predominately (∼71%) as U(VI), despite the low pH (4.5) and nominally reducing conditions within the sediments. Furthermore, low extractability by water, but high extractability by a bi-carbonate solution, indicated a strong association of U with particulate OM. The unexpectedly high proportion of U(VI) relative to U(IV) within the OM-rich sediments implies that OM itself does not readily reduce U, and the reduction of U is not a requirement for immobilizing uranium in OM-rich deposits. The fact that OM can play a significant role in limiting the mobility and reduction of U(VI) in sediments is important for both U-mining and remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Uranium reduction and microbial community development in response to stimulation with different electron donors.

PubMed

Barlett, Melissa; Moon, Hee Sun; Peacock, Aaron A; Hedrick, David B; Williams, Kenneth H; Long, Philip E; Lovley, Derek; Jaffe, Peter R

2012-07-01

Stimulating microbial reduction of soluble U(VI) to less soluble U(IV) shows promise as an in situ bioremediation strategy for uranium contaminated groundwater, but the optimal electron donors for promoting this process have yet to be identified. The purpose of this study was to better understand how the addition of various electron donors to uranium-contaminated subsurface sediments affected U(VI) reduction and the composition of the microbial community. The simple electron donors, acetate or lactate, or the more complex donors, hydrogen-release compound (HRC) or vegetable oil, were added to the sediments incubated in flow-through columns. The composition of the microbial communities was evaluated with quantitative PCR probing specific 16S rRNA genes and functional genes, phospholipid fatty acid analysis, and clone libraries. All the electron donors promoted U(VI) removal, even though the composition of the microbial communities was different with each donor. In general, the overall biomass, rather than the specific bacterial species, was the factor most related to U(VI) removal. Vegetable oil and HRC were more effective in stimulating U(VI) removal than acetate. These results suggest that the addition of more complex organic electron donors could be an excellent option for in situ bioremediation of uranium-contaminated groundwater.

From Nanowires to Biofilms: An Exploration of Novel Mechanisms of Uranium Transformation Mediated by Geobacter Bacteria

DOE Office of Scientific and Technical Information (OSTI.GOV)

REGUERA, GEMMA

2014-01-16

One promising strategy for the in situ bioremediation of radioactive groundwater contaminants that has been identified by the SBR Program is to stimulate the activity of dissimilatory metal-reducing microorganisms to reductively precipitate uranium and other soluble toxic metals. The reduction of U(VI) and other soluble contaminants by Geobacteraceae is directly dependent on the reduction of Fe(III) oxides, their natural electron acceptor, a process that requires the expression of Geobacter’s conductive pili (pilus nanowires). Expression of conductive pili by Geobacter cells leads to biofilm development on surfaces and to the formation of suspended biogranules, which may be physiological closer to biofilmsmore » than to planktonic cells. Biofilm development is often assumed in the subsurface, particularly at the matrix-well screen interface, but evidence of biofilms in the bulk aquifer matrix is scarce. Our preliminary results suggest, however, that biofilms develop in the subsurface and contribute to uranium transformations via sorption and reductive mechanisms. In this project we elucidated the mechanism(s) for uranium immobilization mediated by Geobacter biofilms and identified molecular markers to investigate if biofilm development is happening in the contaminated subsurface. The results provided novel insights needed in order to understand the metabolic potential and physiology of microorganisms with a known role in contaminant transformation in situ, thus having a significant positive impact in the SBR Program and providing novel concept to monitor, model, and predict biological behavior during in situ treatments.« less

40 CFR 471.72 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2011 CFR

2011-07-01

... average mg/off-kg (pounds per million off-pounds) of uranium extruded Cadmium 0.007 0.003 Chromium 0.013 0... uranium heat treated Cadmium 0.006 0.003 Chromium 0.012 0.005 Copper 0.040 0.019 Lead 0.009 0.004 Nickel 0... million off-pounds) of uranium surface treated Cadmium 0.006 0.002 Chromium 0.010 0.004 Copper 0.035 0.017...

40 CFR 471.72 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2010 CFR

2010-07-01

... average mg/off-kg (pounds per million off-pounds) of uranium extruded Cadmium 0.007 0.003 Chromium 0.013 0... uranium heat treated Cadmium 0.006 0.003 Chromium 0.012 0.005 Copper 0.040 0.019 Lead 0.009 0.004 Nickel 0... million off-pounds) of uranium surface treated Cadmium 0.006 0.002 Chromium 0.010 0.004 Copper 0.035 0.017...

Anaerobic bioremediation of hexavalent uranium in groundwater by reductive precipitation with methanogenic granular sludge.

PubMed

Tapia-Rodriguez, Aida; Luna-Velasco, Antonia; Field, Jim A; Sierra-Alvarez, Reyes

2010-04-01

Uranium has been responsible for extensive contamination of groundwater due to releases from mill tailings and other uranium processing waste. Past evidence has confirmed that certain bacteria can enzymatically reduce soluble hexavalent uranium (U(VI)) to insoluble tetravalent uranium (U(IV)) under anaerobic conditions in the presence of appropriate electron donors. This paper focuses on the evaluation of anaerobic granular sludge as a source of inoculum for the bioremediation of uranium in water. Batch experiments were performed with several methanogenic anaerobic granular sludge samples and different electron donors. Abiotic controls consisting of heat-killed inoculum and non-inoculated treatments confirmed the biological removal process. In this study, unadapted anaerobic granular sludge immediately reduced U(VI), suggesting an intrinsic capacity of the sludge to support this process. The high biodiversity of anaerobic granular sludge most likely accounts for the presence of specific microorganisms capable of reducing U(VI). Oxidation by O(2) was shown to resolubilize the uranium. This observation combined with X-ray diffraction evidence of uraninite confirmed that the removal during anaerobic treatment was due to reductive precipitation. The anaerobic removal activity could be sustained after several respikes of U(VI). The U(VI) removal was feasible without addition of electron donors, indicating that the decay of endogenous biomass substrates was contributing electron equivalents to the process. Addition of electron donors, such as H(2) stimulated the removal of U(VI) to varying degrees. The stimulation was greater in sludge samples with lower endogenous substrate levels. The present work reveals the potential application of anaerobic granular sludge for continuous bioremediation schemes to treat uranium-contaminated water. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

Model-Based Analysis of the Role of Biological, Hydrological and Geochemical Factors Affecting Uranium Bioremediation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Jiao; Scheibe, Timothy D.; Mahadevan, Radhakrishnan

2011-01-24

Uranium contamination is a serious concern at several sites motivating the development of novel treatment strategies such as the Geobacter-mediated reductive immobilization of uranium. However, this bioremediation strategy has not yet been optimized for the sustained uranium removal. While several reactive-transport models have been developed to represent Geobacter-mediated bioremediation of uranium, these models often lack the detailed quantitative description of the microbial process (e.g., biomass build-up in both groundwater and sediments, electron transport system, etc.) and the interaction between biogeochemical and hydrological process. In this study, a novel multi-scale model was developed by integrating our recent model on electron capacitancemore » of Geobacter (Zhao et al., 2010) with a comprehensive simulator of coupled fluid flow, hydrologic transport, heat transfer, and biogeochemical reactions. This mechanistic reactive-transport model accurately reproduces the experimental data for the bioremediation of uranium with acetate amendment. We subsequently performed global sensitivity analysis with the reactive-transport model in order to identify the main sources of prediction uncertainty caused by synergistic effects of biological, geochemical, and hydrological processes. The proposed approach successfully captured significant contributing factors across time and space, thereby improving the structure and parameterization of the comprehensive reactive-transport model. The global sensitivity analysis also provides a potentially useful tool to evaluate uranium bioremediation strategy. The simulations suggest that under difficult environments (e.g., highly contaminated with U(VI) at a high migration rate of solutes), the efficiency of uranium removal can be improved by adding Geobacter species to the contaminated site (bioaugmentation) in conjunction with the addition of electron donor (biostimulation). The simulations also highlight the interactive effect of initial cell concentration and flow rate on U(VI) reduction.« less

In situ spectroscopy and spectroelectrochemistry of uranium in high-temperature alkali chloride molten salts.

PubMed

Polovov, Ilya B; Volkovich, Vladimir A; Charnock, John M; Kralj, Brett; Lewin, Robert G; Kinoshita, Hajime; May, Iain; Sharrad, Clint A

2008-09-01

Soluble uranium chloride species, in the oxidation states of III+, IV+, V+, and VI+, have been chemically generated in high-temperature alkali chloride melts. These reactions were monitored by in situ electronic absorption spectroscopy. In situ X-ray absorption spectroscopy of uranium(VI) in a molten LiCl-KCl eutectic was used to determine the immediate coordination environment about the uranium. The dominant species in the melt was [UO 2Cl 4] (2-). Further analysis of the extended X-ray absorption fine structure data and Raman spectroscopy of the melts quenched back to room temperature indicated the possibility of ordering beyond the first coordination sphere of [UO 2Cl 4] (2-). The electrolytic generation of uranium(III) in a molten LiCl-KCl eutectic was also investigated. Anodic dissolution of uranium metal was found to be more efficient at producing uranium(III) in high-temperature melts than the cathodic reduction of uranium(IV). These high-temperature electrolytic processes were studied by in situ electronic absorption spectroelectrochemistry, and we have also developed in situ X-ray absorption spectroelectrochemistry techniques to probe both the uranium oxidation state and the uranium coordination environment in these melts.

Electrochemical and spectroscopic evidence on the one-electron reduction of U(VI) to U(V) on magnetite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Ke; Ilton, Eugene S.; Antonio, Mark R.

2015-05-19

Reduction of U(VI) to U(IV) on mineral surfaces has been considered as a one-step two electron process. However, stabilized U(V), with no evidence of U(IV), found in recent studies indicates U(VI) can undergo a one electron reduction to U(V) without further progression to U(IV). We investigated the mechanisms of uranium reduction by reducing U(VI) electrochemically on a magnetite electrode at pH 3.4 . The one electron reduction of U(VI) was first confirmed using the cyclic voltammetry method. Formation of nano-size uranium precipitates on the surface of magnetite at reducing potentials and dissolution of the solids at oxidizing potentials were observedmore » by in situ electrochemical AFM. XPS analysis of the magnetite electrodes polarized in uranium solutions at voltages from 0.1 ~ 0.9 V (vs. Ag/AgCl) showed the presence of only U(V) and U(VI). The highest amount of U(V) relative to U(VI) was prepared at 0.7 V, where the longest average U–Oaxial distance of 2.05 ± 0.01 Å was evident in the same sample revealed by EXAFS analysis. The results demonstrate that the electrochemical reduction of U(VI) on magnetite only yields U(V), even at a potential of 0.9 V, which favors the one-electron reduction mechanism. U(V) did not disproportionate but stabilized on magnetite through precipitation of mixed-valence state U(VI)/U(V) solids.« less

Microbial Community Changes in Response to Ethanol or Methanol Amendments for U(VI) Reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vishnivetskaya, Tatiana A; Brandt, Craig C; Madden, Andrew

2010-01-01

Microbial community responses to ethanol, methanol and methanol + humics amendments in relationship to uranium bioremediation were studied in laboratory microcosm experiments using sediments and ground water from a uranium-contaminated site in Oak Ridge, Tennessee. Ethanol addition always resulted in uranium reduction at rate of 0.8-1.0 mol l-1 d-1 while methanol addition did so occasionally at rate 0.95 mol l-1 d-1. The type of carbon source added, the duration of incubation, and the sampling site influenced the bacterial community structure upon incubation. Analysis of 16S rRNA gene clone libraries indicated (1) bacterial communities found in ethanol- and methanol-amended samples withmore » U(VI) reduction were similar due to presence of -Proteobacteria, and -Proteobacteria (members of the families Burkholderiaceae, Comamonadaceae, Oxalobacteraceae, and Rhodocyclaceae); (2) methanol-amended samples without U(VI) reduction exhibited the lowest diversity and the bacterial community contained 69.2-92.8% of the family Methylophilaceae; and (3) the addition of humics resulted in an increase of phylogenetic diversity of -Proteobacteria (Rodoferax, Polaromonas, Janthinobacterium, Methylophilales, unclassified) and Firmicutes (Desulfosporosinus, Clostridium).« less

Final Scientific/Technical Report – DE-FG02-06ER64172 – Reaction-Based Reactive Transport Modeling of Iron Reduction and Uranium Immobilization at Area 2 of the NABIR Field Research Center – Subproject to Co-PI Eric E. Roden

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eric E. Roden

2009-03-17

This report summarizes research conducted in conjunction with a project entitled “Reaction-Based Reactive Transport Modeling of Iron Reduction and Uranium Immobilization at Area 2 of the NABIR Field Research Center”, which was funded through the Integrative Studies Element of the former NABIR Program (now the Environmental Remediation Sciences Program) within the Office of Biological and Environmental Research. Dr. William Burgos (The Pennsylvania State University) was the overall PI/PD for the project, which included Brian Dempsey (Penn State), Gour-Tsyh (George) Yeh (Central Florida University), and Eric Roden (formerly at The University of Alabama, now at the University of Wisconsin) as separately-fundedmore » co-PIs. The project focused on development of a mechanistic understanding and quantitative models of coupled Fe(III)/U(VI) reduction in FRC Area 2 sediments. The work builds on our previous studies of microbial Fe(III) and U(VI) reduction, and was directly aligned with the Scheibe et al. ORNL FRC Field Project at Area 2. Area 2 is a shallow pathway for migration of contaminated groundwater to seeps in the upper reach of Bear Creek at ORNL, mainly through a ca. 1 m thick layer of gravel located 4-5 m below the ground surface. The gravel layer is sandwiched between an overlying layer of disturbed fill material, and 2-3 m of undisturbed shale saprolite derived from the underlying Nolichucky Shale bedrock. The fill was put in place when contaminated soils were excavated and replaced by native saprolite from an uncontaminated area within Bear Creek Valley; the gravel layer was presumably installed prior to addition of the fill in order to provide a stable surface for the operation of heavy machinery. The undisturbed saprolite is highly weathered bedrock that has unconsolidated character but retains much of the bedding and fracture structure of the parent rock (shale with interbedded limestone). Hydrological tracer studies conducted during the Scheibe et al. field project indicate that the gravel layer receives input of uranium from both upstream sources and from diffusive mass transfer out of highly contaminated fill and saprolite materials above and below the gravel layer. This research sought to examine biogeochemical processes likely to take place in the less conductive materials above and below the gravel during the in situ ethanol biostimulation experiment conducted at Area 2 during 2005-2006. The in situ experiment in turn examined the hypothesis that injection of electron donor into this layer would induce formation of a redox barrier in the less conductive materials, resulting in decreased mass transfer of uranium out these materials and attendant declines in groundwater U(VI) concentration. Our research was directed toward the following three major objectives relevant to formation of this redox barrier: (1) elucidate the kinetics and mechanisms of reduction of solid-phase Fe(III) and U(VI) in Area 2 sediments; (2) evaluate the potential for long-term sustained U(IV) reductive immobilization in Area 2 sediments; (3) numerically simulate the suite of hydrobiogeochemical processes occurring in experimental systems so as to facilitate modeling of in situ U(IV) immobilization at the field-scale.« less

Evidence of isotopic fractionation of natural uranium in cultured human cells

NASA Astrophysics Data System (ADS)

Paredes, Eduardo; Avazeri, Emilie; Malard, Véronique; Vidaud, Claude; Reiller, Pascal E.; Ortega, Richard; Nonell, Anthony; Isnard, Hélène; Chartier, Frédéric; Bresson, Carole

2016-12-01

The study of the isotopic fractionation of endogen elements and toxic heavy metals in living organisms for biomedical applications, and for metabolic and toxicological studies, is a cutting-edge research topic. This paper shows that human neuroblastoma cells incorporated small amounts of uranium (U) after exposure to 10 µM natural U, with preferential uptake of the 235U isotope with regard to 238U. Efforts were made to develop and then validate a procedure for highly accurate n(238U)/n(235U) determinations in microsamples of cells. We found that intracellular U is enriched in 235U by 0.38 ± 0.13‰ (2σ, n = 7) relative to the exposure solutions. These in vitro experiments provide clues for the identification of biological processes responsible for uranium isotopic fractionation and link them to potential U incorporation pathways into neuronal cells. Suggested incorporation processes are a kinetically controlled process, such as facilitated transmembrane diffusion, and the uptake through a high-affinity uranium transport protein involving the modification of the uranyl (UO22+) coordination sphere. These findings open perspectives on the use of isotopic fractionation of metals in cellular models, offering a probe to track uptake/transport pathways and to help decipher associated cellular metabolic processes.

Evidence of isotopic fractionation of natural uranium in cultured human cells

PubMed Central

Paredes, Eduardo; Avazeri, Emilie; Malard, Véronique; Vidaud, Claude; Reiller, Pascal E.; Ortega, Richard; Nonell, Anthony; Isnard, Hélène; Chartier, Frédéric; Bresson, Carole

2016-01-01

The study of the isotopic fractionation of endogen elements and toxic heavy metals in living organisms for biomedical applications, and for metabolic and toxicological studies, is a cutting-edge research topic. This paper shows that human neuroblastoma cells incorporated small amounts of uranium (U) after exposure to 10 µM natural U, with preferential uptake of the 235U isotope with regard to 238U. Efforts were made to develop and then validate a procedure for highly accurate n(238U)/n(235U) determinations in microsamples of cells. We found that intracellular U is enriched in 235U by 0.38 ± 0.13‰ (2σ, n = 7) relative to the exposure solutions. These in vitro experiments provide clues for the identification of biological processes responsible for uranium isotopic fractionation and link them to potential U incorporation pathways into neuronal cells. Suggested incorporation processes are a kinetically controlled process, such as facilitated transmembrane diffusion, and the uptake through a high-affinity uranium transport protein involving the modification of the uranyl (UO22+) coordination sphere. These findings open perspectives on the use of isotopic fractionation of metals in cellular models, offering a probe to track uptake/transport pathways and to help decipher associated cellular metabolic processes. PMID:27872304

Evidence of isotopic fractionation of natural uranium in cultured human cells.

PubMed

Paredes, Eduardo; Avazeri, Emilie; Malard, Véronique; Vidaud, Claude; Reiller, Pascal E; Ortega, Richard; Nonell, Anthony; Isnard, Hélène; Chartier, Frédéric; Bresson, Carole

2016-12-06

The study of the isotopic fractionation of endogen elements and toxic heavy metals in living organisms for biomedical applications, and for metabolic and toxicological studies, is a cutting-edge research topic. This paper shows that human neuroblastoma cells incorporated small amounts of uranium (U) after exposure to 10 µM natural U, with preferential uptake of the 235 U isotope with regard to 238 U. Efforts were made to develop and then validate a procedure for highly accurate n( 238 U)/n( 235 U) determinations in microsamples of cells. We found that intracellular U is enriched in 235 U by 0.38 ± 0.13‰ (2σ, n = 7) relative to the exposure solutions. These in vitro experiments provide clues for the identification of biological processes responsible for uranium isotopic fractionation and link them to potential U incorporation pathways into neuronal cells. Suggested incorporation processes are a kinetically controlled process, such as facilitated transmembrane diffusion, and the uptake through a high-affinity uranium transport protein involving the modification of the uranyl (UO 2 2+ ) coordination sphere. These findings open perspectives on the use of isotopic fractionation of metals in cellular models, offering a probe to track uptake/transport pathways and to help decipher associated cellular metabolic processes.

Target and method for the production of fission product molybdenum-99

DOEpatents

Vandegrift, George F.; Vissers, Donald R.; Marshall, Simon L.; Varma, Ravi

1989-01-01

A target for the reduction of fission product Mo-99 is prepared from uranium of low U-235 enrichment by coating a structural support member with a preparatory coating of a substantially oxide-free substrate metal. Uranium metal is electrodeposited from a molten halide electrolytic bath onto a substrate metal. The electrodeposition is performed at a predetermined direct current rate or by using pulsed plating techniques which permit relaxation of accumulated uranium ion concentrations within the melt. Layers of as much as to 600 mg/cm.sup.2 of uranium can be prepared to provide a sufficient density to produce acceptable concentrations of fission product Mo-99.

Reduction of uranium hexafluoride to tetrafluoride by using the hydrogen atoms

NASA Astrophysics Data System (ADS)

Aleksandrov, B. P.; Gordon, E. B.; Ivanov, A. V.; Kotov, A. A.; Smirnov, V. E.

2016-09-01

We consider the reduction of UF6 to UF4 by chemical reaction with hydrogen atoms originated in the powerful chemical generator. The principal design of such a chemical convertor is described. The results of the mathematical modeling of the thermodynamics and kinetics of the UF6 to UF4 reduction process are analyzed. The few options for the hydrogen atom generator design are proposed. A layout of the experimental setup with the chemical reactor is presented. The high efficiency together with the ability of the process scaling without loss of its efficiency makes this approach to the uranium hexafluoride depletion into tetrafluoride promising for its application in the industry.

Variations in the uranium isotopic compositions of uranium ores from different types of uranium deposits

NASA Astrophysics Data System (ADS)

Uvarova, Yulia A.; Kyser, T. Kurt; Geagea, Majdi Lahd; Chipley, Don

2014-12-01

Variations in 238U/235U and 234U/238U ratios were measured in uranium minerals from a spectrum of uranium deposit types, as well as diagenetic phosphates in uranium-rich basins and peraluminous rhyolites and associated autunite mineralisation from Macusani Meseta, Peru. Mean δ238U values of uranium minerals relative to NBL CRM 112-A are 0.02‰ for metasomatic deposits, 0.16‰ for intrusive, 0.18‰ for calcrete, 0.18‰ for volcanic, 0.29‰ for quartz-pebble conglomerate, 0.29‰ for sandstone-hosted, 0.44‰ for unconformity-type, and 0.56‰ for vein, with a total range in δ238U values from -0.30‰ to 1.52‰. Uranium mineralisation associated with igneous systems, including low-temperature calcretes that are sourced from U-rich minerals in igneous systems, have low δ238U values of ca. 0.1‰, near those of their igneous sources, whereas uranium minerals in basin-hosted deposits have higher and more variable values. High-grade unconformity-related deposits have δ238U values around 0.2‰, whereas lower grade unconformity-type deposits in the Athabasca, Kombolgie and Otish basins have higher δ238U values. The δ234U values for most samples are around 0‰, in secular equilibrium, but some samples have δ234U values much lower or higher than 0‰ associated with addition or removal of 234U during the past 2.5 Ma. These δ238U and δ234U values suggest that there are at least two different mechanisms responsible for 238U/235U and 234U/238U variations. The 234U/238U disequilibria ratios indicate recent fluid interaction with the uranium minerals and preferential migration of 234U. Fractionation between 235U and 238U is a result of nuclear-field effects with enrichment of 238U in the reduced insoluble species (mostly UO2) and 235U in oxidised mobile species as uranyl ion, UO22+, and its complexes. Therefore, isotopic fractionation effects should be reflected in 238U/235U ratios in uranium ore minerals formed either by reduction of uranium to UO2 or chemical precipitation in the form of U6+ minerals. The δ238U values of uranium ore minerals from a variety of deposits are controlled by the isotopic signature of the uranium source, the efficiency of uranium reduction in the case of UO2 systems, and the degree to which uranium was previously removed from the fluid, with less influence from temperature of ore formation and later alteration of the ore. Uranium isotopes are potentially superb tracers of redox in natural systems.

Uranium oxide catalysts: environmental applications for treatment of chlorinated organic waste from nuclear industry.

PubMed

Lazareva, Svetlana; Ismagilov, Zinfer; Kuznetsov, Vadim; Shikina, Nadezhda; Kerzhentsev, Mikhail

2018-02-05

Huge amounts of nuclear waste, including depleted uranium, significantly contribute to the adverse environmental situation throughout the world. An approach to the effective use of uranium oxides in catalysts for the deep oxidation of chlorine-containing hydrocarbons is suggested. Investigation of the catalytic activity of the synthesized supported uranium oxide catalysts doped with Cr, Mn and Co transition metals in the chlorobenzene oxidation showed that these catalysts are comparable with conventional commercial ones. Physicochemical properties of the catalysts were studied by X-ray diffraction, temperature-programmed reduction with hydrogen (H 2 -TPR), and Fourier transform infrared spectroscopy. The higher activity of Mn- and Co-containing uranium oxide catalysts in the H 2 -TPR and oxidation of chlorobenzene in comparison with non-uranium catalysts may be related to the formation of a new disperse phase represented by uranates. The study of chlorobenzene adsorption revealed that the surface oxygen is involved in the catalytic process.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fincke, J.R.; Swank, W.D.; Haggard, D.C.

This paper describes the experimental demonstration of a process for the direct plasma reduction of depleted uranium hexafluoride to uranium metal. The process exploits the large departures from equilibrium that can be achieved in the rapid supersonic expansion of a totally dissociated and partially ionized mixture of UF{sub 6}, Ar, He, and H{sub 2}. The process is based on the rapid condensation of subcooled uranium vapor and the relatively slow rate of back reaction between metallic uranium and HF to F{sub 2} to reform stable fluorides. The high translational velocities and rapid cooling result in an overpopulation of atomic hydrogenmore » which persists throughout the expansion process. Atomic hydrogen shifts the equilibrium composition by inhibiting the reformation of uranium-fluorine compounds. This process has the potential to reduce the cost of reducing UF{sub 6} to uranium metal with the added benefit of being a virtually waste free process. The dry HF produced is a commodity which has industrial value.« less

URANIUM PRECIPITATION PROCESS

DOEpatents

Thunaes, A.; Brown, E.A.; Smith, H.W.; Simard, R.

1957-12-01

A method for the recovery of uranium from sulfuric acid solutions is described. In the present process, sulfuric acid is added to the uranium bearing solution to bring the pH to between 1 and 1.8, preferably to about 1.4, and aluminum metal is then used as a reducing agent to convert hexavalent uranium to the tetravalent state. As the reaction proceeds, the pH rises amd a selective precipitation of uranium occurs resulting in a high grade precipitate. This process is an improvement over the process using metallic iron, in that metallic aluminum reacts less readily than metallic iron with sulfuric acid, thus avoiding consumption of the reducing agent and a raising of the pH without accomplishing the desired reduction of the hexavalent uranium in the solution. Another disadvantage to the use of iron is that positive ferric ions will precipitate with negative phosphate and arsenate ions at the pH range employed.

A new formulation containing calixarene molecules as an emergency treatment of uranium skin contamination.

PubMed

Spagnul, Aurélie; Bouvier-Capely, Céline; Phan, Guillaume; Rebière, François; Fattal, Elias

2010-09-01

Cutaneous contamination represents the second highest contamination pathway in the nuclear industry. Despite that the entry of actinides such as uranium into the body through intact or wounded skin can induce a high internal exposure, no specific emergency treatment for cutaneous contamination exists. In the present work, an innovative formulation dedicated to uranium skin decontamination was developed. The galenic form consists in an oil-in-water nanoemulsion, which contains a tricarboxylic calixarene known for its high uranium affinity and selectivity. The physicochemical characterization of this topical form revealed that calixarene molecules are located at the surface of the dispersed oil droplets of the nanoemulsion, being thus potentially available for uranium chelation. It was demonstrated in preliminary in vitro experiments by using an adapted ultrafiltration method that the calixarene nanoemulsion was able to extract and retain more than 80% of uranium from an aqueous uranyl nitrate contamination solution. First ex vivo experiments carried out in Franz diffusion cells on pig ear skin explants during 24 h showed that the immediate application of the calixarene nanoemulsion on a skin contaminated by a uranyl nitrate solution allowed a uranium transcutaneous diffusion decrease of about 98% through intact and excoriated skins. The calixarene nanoemulsion developed in this study thus seems to be an efficient emergency system for uranium skin decontamination.

Microbial Communities in Contaminated Sediments, Associated with Bioremediation of Uranium to Submicromolar Levels▿

PubMed Central

Cardenas, Erick; Wu, Wei-Min; Leigh, Mary Beth; Carley, Jack; Carroll, Sue; Gentry, Terry; Luo, Jian; Watson, David; Gu, Baohua; Ginder-Vogel, Matthew; Kitanidis, Peter K.; Jardine, Philip M.; Zhou, Jizhong; Criddle, Craig S.; Marsh, Terence L.; Tiedje, James M.

2008-01-01

Microbial enumeration, 16S rRNA gene clone libraries, and chemical analysis were used to evaluate the in situ biological reduction and immobilization of uranium(VI) in a long-term experiment (more than 2 years) conducted at a highly uranium-contaminated site (up to 60 mg/liter and 800 mg/kg solids) of the U.S. Department of Energy in Oak Ridge, TN. Bioreduction was achieved by conditioning groundwater above ground and then stimulating growth of denitrifying, Fe(III)-reducing, and sulfate-reducing bacteria in situ through weekly injection of ethanol into the subsurface. After nearly 2 years of intermittent injection of ethanol, aqueous U levels fell below the U.S. Environmental Protection Agency maximum contaminant level for drinking water and groundwater (<30 μg/liter or 0.126 μM). Sediment microbial communities from the treatment zone were compared with those from a control well without biostimulation. Most-probable-number estimations indicated that microorganisms implicated in bioremediation accumulated in the sediments of the treatment zone but were either absent or in very low numbers in an untreated control area. Organisms belonging to genera known to include U(VI) reducers were detected, including Desulfovibrio, Geobacter, Anaeromyxobacter, Desulfosporosinus, and Acidovorax spp. The predominant sulfate-reducing bacterial species were Desulfovibrio spp., while the iron reducers were represented by Ferribacterium spp. and Geothrix spp. Diversity-based clustering revealed differences between treated and untreated zones and also within samples of the treated area. Spatial differences in community structure within the treatment zone were likely related to the hydraulic pathway and to electron donor metabolism during biostimulation. PMID:18456853

Identifying and overcoming the constraints that prevent the full implementation of decommissioning and remediation programs in uranium mining sites.

PubMed

Franklin, Mariza Ramalho; Fernandes, Horst Monken

2013-05-01

Environmental remediation of radioactive contamination is about achieving appropriate reduction of exposures to ionizing radiation. This goal can be achieved by means of isolation or removal of the contamination source(s) or by breaking the exposure pathways. Ideally, environmental remediation is part of the planning phase of any industrial operation with the potential to cause environmental contamination. This concept is even more important in mining operations due to the significant impacts produced. This approach has not been considered in several operations developed in the past. Therefore many legacy sites face the challenge to implement appropriate remediation plans. One of the first barriers to remediation works is the lack of financial resources as environmental issues used to be taken in the past as marginal costs and were not included in the overall budget of the company. This paper analyses the situation of the former uranium production site of Poços de Caldas in Brazil. It is demonstrated that in addition to the lack of resources, other barriers such as the lack of information on site characteristics, appropriate regulatory framework, funding mechanisms, stakeholder involvement, policy and strategy, technical experience and mechanism for the appropriation of adequate technical expertise will play key roles in preventing the implementation of remediation programs. All these barriers are discussed and some solutions are suggested. It is expected that lessons learned from the Poços de Caldas legacy site may stimulate advancement of more sustainable options in the development of future uranium production centers. Copyright © 2011 Elsevier Ltd. All rights reserved.

Characterization of the Environmentally Induced Chemical Transformations of Uranium Tetrafluoride

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wellons, M.

A key challenge with nuclear safeguards environmental sampling is identification of the materials post release due to subsequent chemical reactions with ambient water and oxygen. Uranium Tetrafluoride (UF4) is of interest as an intermediate in both the upstream and downstream portions of uranium feedstock and metal production processes used in nuclear fuel production; however minimal published research exists relating to UF4 hydrolysis. FY16 efforts were dedicated to in-situ Raman spectroscopy and X-ray diffraction characterization of UF4 during exposure to various relative humidity conditions. This effort mapped several hydrolysis reaction pathways and identified both intermediate, and terminal progeny species.

Injection of Emulsified Vegetable Oil for Long-Term Bioreduction of Uranium

NASA Astrophysics Data System (ADS)

Brooks, S. C.; Watson, D. B.; Schadt, C. W.; Jardine, P. M.; Gihring, T. M.; Zhang, G.; Mehlhorn, T.; Lowe, K.; Phillips, J.; Earles, J.; Wu, W.; Criddle, C. S.; Kemner, K. M.; Boyanov, M.

2011-12-01

In situ bioremediation of a uranium and nitrate-contaminated aquifer with the slow-release electron donor, emulsified vegetable oil (EVO), was tested at the US DOE Subsurface Biogeochemical Research Program (SBR) Integrated Field Research Challenge (IFRC) site, in Oak Ridge, TN. The EVO injection took place in Area 2 of the IFRC located about 300 m downgradient of the former S-3 disposal ponds. Liquid wastes, disposed in the ponds from 1951 to 1983, were primarily composed of nitric acid, plating wastes containing various metals (Cr, Ni) radionuclides (U, Tc), inorganics (nitrate, sulfate) and organic contaminants (tetrachloroethylene, acetone). Prior pond closure in 1987, large volumes of waste fluids migrated into the subsurface, down Bear Creek Valley and into Bear Creek. Contaminants detected at Area 2 were transported through a high permeability gravelly fill that is considered a preferred transport pathway for U to Bear Creek. Groundwater in the gravelly fill is contaminated with U (1-3 mg/L), sulfate (95-130 mg/L), and nitrate (20-40 mg/L) and 500 mg/kg or higher U has been detected on the solid phase of the fill material. The objective of this study is to investigate the feasibility and long-term sustainability of U(VI) reduction and immobilization, and nitrate degradation in the high permeability, high flow gravel fill using EVO as the electron donor. A one-time EVO injection was conducted over a 2 hour period in the highly permeable gravel (hydraulic conductivity 0.08 cm/sec) in the well instrumented IFRC Area 2 field plot. Extensive monitoring of geochemical parameters, dissolved gases and microbial populations were conducted during the test. A bromide tracer test was conducted prior to the injection of the EVO to assess transport pathways and rates. Geochemical analysis of site groundwater demonstrated the sequential bioreduction of oxygen, nitrate, Mn(IV), Fe(III) and sulfate. Transient accumulation of acetate was observed as an intermediate in the oil degradation. Reduction and removal of U and nitrate from groundwater was observed in all wells in hydraulic connection to the injection wells after 2-4 weeks. U concentrations in groundwater were reduced to below 30 ppb (US EPA drinking water standard) at some well locations and nitrate was reduced to below detectable levels. Rebound of U in groundwater was observed together with the rebound of sulfate concentrations as the EVO was consumed. The flux of U and nitrate contamination from groundwater to the surface water receptor (Bear Creek) was significantly reduced by the EVO injection over a one year period. Uranium (VI) reduction to U(IV) in the field tests was confirmed by X-ray absorption near-edge spectroscopy (XANES) analysis. The reduced U(IV) was determined by X-ray absorption fine structure (XAFS) to be in an Fe-U complex, not uraninite. The activities of major Fe(III)- and sulfate-reducing bacteria with U(VI)-reducing capability as well as methanogens was stimulated after injection of the oil.

Cellular localization of uranium in the renal proximal tubules during acute renal uranium toxicity.

PubMed

Homma-Takeda, Shino; Kitahara, Keisuke; Suzuki, Kyoko; Blyth, Benjamin J; Suya, Noriyoshi; Konishi, Teruaki; Terada, Yasuko; Shimada, Yoshiya

2015-12-01

Renal toxicity is a hallmark of uranium exposure, with uranium accumulating specifically in the S3 segment of the proximal tubules causing tubular damage. As the distribution, concentration and dynamics of accumulated uranium at the cellular level is not well understood, here, we report on high-resolution quantitative in situ measurements by high-energy synchrotron radiation X-ray fluorescence analysis in renal sections from a rat model of uranium-induced acute renal toxicity. One day after subcutaneous administration of uranium acetate to male Wistar rats at a dose of 0.5 mg uranium kg(-1) body weight, uranium concentration in the S3 segment of the proximal tubules was 64.9 ± 18.2 µg g(-1) , sevenfold higher than the mean renal uranium concentration (9.7 ± 2.4 µg g(-1) ). Uranium distributed into the epithelium of the S3 segment of the proximal tubules and highly concentrated uranium (50-fold above mean renal concentration) in micro-regions was found near the nuclei. These uranium levels were maintained up to 8 days post-administration, despite more rapid reductions in mean renal concentration. Two weeks after uranium administration, damaged areas were filled with regenerating tubules and morphological signs of tissue recovery, but areas of high uranium concentration (100-fold above mean renal concentration) were still found in the epithelium of regenerating tubules. These data indicate that site-specific accumulation of uranium in micro-regions of the S3 segment of the proximal tubules and retention of uranium in concentrated areas during recovery are characteristics of uranium behavior in the kidney. Copyright © 2015 John Wiley & Sons, Ltd.

Uranium(VI) interactions with mackinawite in the presence and absence of bicarbonate and oxygen.

PubMed

Gallegos, Tanya J; Fuller, Christopher C; Webb, Samuel M; Betterton, William

2013-07-02

Mackinawite, Fe(II)S, samples loaded with uranium (10(-5), 10(-4), and 10(-3) mol U/g FeS) at pH 5, 7, and 9, were characterized using X-ray absorption spectroscopy and X-ray diffraction to determine the effects of pH, bicarbonate, and oxidation on uptake. Under anoxic conditions, a 5 g/L suspension of mackinawite lowered 5 × 10(-5) M uranium(VI) to below 30 ppb (1.26 × 10(-7) M) U. Between 82 and 88% of the uranium removed from solution by mackinawite was U(IV) and was nearly completely reduced to U(IV) when 0.012 M bicarbonate was added. Near-neighbor coordination consisting of uranium-oxygen and uranium-uranium distances indicates the formation of uraninite in the presence and absence of bicarbonate, suggesting reductive precipitation as the dominant removal mechanism. Following equilibration in air, mackinawite was oxidized to mainly goethite and sulfur and about 76% of U(IV) was reoxidized to U(VI) with coordination of uranium to axial and equatorial oxygen, similar to uranyl. Additionally, uranium-iron distances, typical of coprecipitation of uranium with iron oxides, and uranium-sulfur distances indicating bidentate coordination of U(VI) to sulfate were evident. The affinity of mackinawite and its oxidation products for U(VI) provides impetus for further study of mackinawite as a potential reactive medium for remediation of uranium-contaminated water.

10 CFR Appendix E to Part 110 - Illustrative List of Chemical Exchange or Ion Exchange Enrichment Plant Equipment and Components...

Code of Federal Regulations, 2010 CFR

2010-01-01

... designed or prepared electrochemical reduction cells to reduce uranium from one valence state to another for uranium enrichment using the chemical exchange process. The cell materials in contact with process solutions must be corrosion resistant to concentrated hydrochloric acid solutions. The cell cathodic...

Reactive transport of uranium in a groundwater bioreduction study: Insights from high-temporal resolution 238U/235U data

NASA Astrophysics Data System (ADS)

Shiel, A. E.; Johnson, T. M.; Lundstrom, C. C.; Laubach, P. G.; Long, P. E.; Williams, K. H.

2016-08-01

We conducted a detailed investigation of U isotopes in conjunction with a broad geochemical investigation during field-scale biostimulation and desorption experiments. This investigation was carried out in the uranium-contaminated alluvial aquifer of the Rifle field research site. In this well-characterized setting, a more comprehensive understanding of U isotope geochemistry is possible. Our results indicate that U isotope fractionation is consistently observed across multiple experiments at the Rifle site. Microbially-mediated reduction is suggested to account for most or all of the observed fractionation as abiotic reduction has been demonstrated to impart much smaller, often near-zero, isotopic fractionation or isotopic fractionation in the opposite direction. Data from some time intervals are consistent with a simple model for transport and U(VI) reduction, where the fractionation factor (ε = +0.65‰ to +0.85‰) is consistent with experimental studies. However, during other time intervals the observed patterns in our data indicate the importance of other processes in governing U concentrations and 238U/235U ratios. For instance, we demonstrate that departures from Rayleigh behavior in groundwater systems arise from the presence of adsorbed species. We also show that isotope data are sensitive to the onset of oxidation after biostimulation ends, even in the case where reduction continues to remove contaminant uranium downstream. Our study and the described conceptual model support the use of 238U/235U ratios as a tool for evaluating the efficacy of biostimulation and potentially other remedial strategies employed at Rifle and other uranium-contaminated sites.

Volumetric determination of uranium using titanous sulfate as reductant before oxidimetric titration

USGS Publications Warehouse

Wahlberg, James S.; Skinner, Dwight L.; Rader, Lewis F.

1956-01-01

A new method for determining uranium in samples containing 0.05 percent or more U3O8, using titanous sulfate as reducing agent, is much shorter, faster, and has fewer interferences than conventional methods using reductor columns. The sample is dissolved with sulfuric, nitric, perchloric, and hydrofluoric acids. Elements that would otherwise form insoluble fluorides are kept in solution by complexing the fluoride ion with boric acid. A precipitation is made with cupferron to remove interfering elements. The solution is filtered to remove the precipitated cupferrates instead of extracting them with chloroform as is usually done. Filtration is preferred to extraction because any niobium that may be in solution forms an insoluble cupferrate that may be removed by filtering but is very difficult to extract with chloroform. Excess cupferron is destroyed by oxidizing with nitric and perchloric acids, and evaporating to dense fumes of sulfuric acid. The uranium is reduced to U(IV) by the addition of titanous sulfate, with cupric sulfate used as an indicator of the completeness of the reduction. Metallic copper is formed when all the uranium is reduced. The reduced copper is then reoxidized by the addition of mercuric perchlorate, an excess of ferric sulfate added, and the solution titrated immediately with standard ceric sulfate with ferroin as an indicator. Precision of the method compared favorable with methods in common use, both for uranium ores and for most types of uranium-rich materials.

Nuclear energy in Europe: uranium flow modeling and fuel cycle scenario trade-offs from a sustainability perspective.

PubMed

Tendall, Danielle M; Binder, Claudia R

2011-03-15

The European nuclear fuel cycle (covering the EU-27, Switzerland and Ukraine) was modeled using material flow analysis (MFA).The analysis was based on publicly available data from nuclear energy agencies and industries, national trade offices, and nongovernmental organizations. Military uranium was not considered due to lack of accessible data. Nuclear fuel cycle scenarios varying spent fuel reprocessing, depleted uranium re-enrichment, enrichment assays, and use of fast neutron reactors, were established. They were then assessed according to environmental, economic and social criteria such as resource depletion, waste production, chemical and radiation emissions, costs, and proliferation risks. The most preferable scenario in the short term is a combination of reduced tails assay and enrichment grade, allowing a 17.9% reduction of uranium demand without significantly increasing environmental, economic, or social risks. In the long term, fast reactors could theoretically achieve a 99.4% decrease in uranium demand and nuclear waste production. However, this involves important costs and proliferation risks. Increasing material efficiency is not systematically correlated with the reduction of other risks. This suggests that an overall optimization of the nuclear fuel cycle is difficult to obtain. Therefore, criteria must be weighted according to stakeholder interests in order to determine the most sustainable solution. This paper models the flows of uranium and associated materials in Europe, and provides a decision support tool for identifying the trade-offs of the alternative nuclear fuel cycles considered.

Nitrogen reduction and functionalization by a multimetallic uranium nitride complex

NASA Astrophysics Data System (ADS)

Falcone, Marta; Chatelain, Lucile; Scopelliti, Rosario; Živković, Ivica; Mazzanti, Marinella

2017-07-01

Molecular nitrogen (N2) is cheap and widely available, but its unreactive nature is a challenge when attempting to functionalize it under mild conditions with other widely available substrates (such as carbon monoxide, CO) to produce value-added compounds. Biological N2 fixation can do this, but the industrial Haber-Bosch process for ammonia production operates under harsh conditions (450 degrees Celsius and 300 bar), even though both processes are thought to involve multimetallic catalytic sites. And although molecular complexes capable of binding and even reducing N2 under mild conditions are known, with co-operativity between metal centres considered crucial for the N2 reduction step, the multimetallic species involved are usually not well defined, and further transformation of N2-binding complexes to achieve N-H or N-C bond formation is rare. Haber noted, before an iron-based catalyst was adopted for the industrial Haber-Bosch process, that uranium and uranium nitride materials are very effective heterogeneous catalysts for ammonia production from N2. However, few examples of uranium complexes binding N2 are known, and soluble uranium complexes capable of transforming N2 into ammonia or organonitrogen compounds have not yet been identified. Here we report the four-electron reduction of N2 under ambient conditions by a fully characterized complex with two UIII ions and three K+ centres held together by a nitride group and a flexible metalloligand framework. The addition of H2 and/or protons, or CO to the resulting complex results in the complete cleavage of N2 with concomitant N2 functionalization through N-H or N-C bond-forming reactions. These observations establish that a molecular uranium complex can promote the stoichiometric transformation of N2 into NH3 or cyanate, and that a flexible, electron-rich, multimetallic, nitride-bridged core unit is a promising starting point for the design of molecular complexes capable of cleaving and functionalizing N2 under mild conditions.

Bacterial population dynamics during uranium reduction andre-oxidation: Application of a novel high density oligonucleotidemicroarray approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brodie, Eoin L.; DeSantis, Todd Z.; Joyner, Dominique C.

2006-01-30

Reduction of soluble uranium U(VI) to less-soluble uraniumU(IV) is a promising approach to minimize migration from contaminatedaquifers. It is generally assumed that, under constant reducingconditions, U(IV) is stable and immobile; however, in a previous study,we documented reoxidation of U(IV) under continuous reducing conditions(Wan et al., Environ. Sci. Technol. 2005, 39:6162 6169). To determine ifchanges in microbial community composition were a factor in U(IV)reoxidation, we employed a high-density phylogenetic DNA microarray (16Smicroarray) containing 500,000 probes to monitor changes in bacterialpopulations during this remediation process. Comparison of the 16Smicroarray with clone libraries demonstrated successful detection andclassification of most clone groups. Analysis ofmore » the most dynamic groupsof 16S rRNA gene amplicons detected by the 16S microarray identified fiveclusters of bacterial subfamilies responding in a similar manner. Thisapproach demonstrated that amplicons of known metal-reducing bacteriasuch as Geothrix fermentans (confirmed by quantitative PCR) and thosewithin the Geobacteraceae were abundant during U(VI) reduction and didnot decline during the U(IV) reoxidation phase. Significantly, it appearsthat the observed reoxidation of uranium under reducing conditionsoccurred despite elevated microbial activity and the consistent presenceof metal-reducing bacteria. High-density phylogenetic microarraysconstitute a powerful tool, enabling the detection and monitoring of asubstantial portion of the microbial population in a routine, accurate,and reproducible manner.« less

Breccia-pipe uranium mining in northern Arizona; estimate of resources and assessment of historical effects

USGS Publications Warehouse

Bills, Donald J.; Brown, Kristin M.; Alpine, Andrea E.; Otton, James K.; Van Gosen, Bradley S.; Hinck, Jo Ellen; Tillman, Fred D.

2011-01-01

About 1 million acres of Federal land in the Grand Canyon region of Arizona were temporarily withdrawn from new mining claims in July 2009 by the Secretary of the Interior because of concern that increased uranium mining could have negative impacts on the land, water, people, and wildlife. During a 2-year interval, a Federal team led by the Bureau of Land Management is evaluating the effects of withdrawing these lands for extended periods. As part of this team, the U.S. Geological Survey (USGS) conducted a series of short-term studies to examine the historical effects of breccia-pipe uranium mining in the region. The USGS studies provide estimates of uranium resources affected by the possible land withdrawal, examine the effects of previous breccia-pipe mining, summarize water-chemistry data for streams and springs, and investigate potential biological pathways of exposure to uranium and associated contaminants. This fact sheet summarizes results through December 2009 and outlines further research needs.

Uranium azide photolysis results in C-H bond activation and provides evidence for a terminal uranium nitride

NASA Astrophysics Data System (ADS)

Thomson, Robert K.; Cantat, Thibault; Scott, Brian L.; Morris, David E.; Batista, Enrique R.; Kiplinger, Jaqueline L.

2010-09-01

Uranium nitride [U≡N]x is an alternative nuclear fuel that has great potential in the expanding future of nuclear power; however, very little is known about the U≡N functionality. We show, for the first time, that a terminal uranium nitride complex can be generated by photolysis of an azide (U-N=N=N) precursor. The transient U≡N fragment is reactive and undergoes insertion into a ligand C-H bond to generate new N-H and N-C bonds. The mechanism of this unprecedented reaction has been evaluated through computational and spectroscopic studies, which reveal that the photochemical azide activation pathway can be shut down through coordination of the terminal azide ligand to the Lewis acid B(C6F5)3. These studies demonstrate that photochemistry can be a powerful tool for inducing redox transformations for organometallic actinide complexes, and that the terminal uranium nitride fragment is reactive, cleaving strong C-H bonds.

Facile Reductive Silylation of UO22+ to Uranium(IV) Chloride.

PubMed

Kiernicki, John J; Zeller, Matthias; Bart, Suzanne C

2017-01-19

General reductive silylation of the UO 2 2+ cation occurs readily in a one-pot, two-step stoichiometric reaction at room temperature to form uranium(IV) siloxides. Addition of two equivalents of an alkylating reagent to UO 2 X 2 (L) 2 (X=Cl, Br, I, OTf; L=triphenylphosphine oxide, 2,2'-bipyridyl) followed by two equivalents of a silyl (pseudo)halide, R 3 Si-X (R=aryl, alkyl, H; X=Cl, Br, I, OTf, SPh), cleanly affords (R 3 SiO) 2 UX 2 (L) 2 in high yields. Support is included for the key step in the process, reduction of U VI to U V . This procedure is applicable to a wide range of commercially available uranyl salts, silyl halides, and alkylating reagents. Under this protocol, one equivalent of SiCl 4 or two equivalents of Me 2 SiCl 2 results in direct conversion of the uranyl to uranium(IV) tetrachloride. Full spectroscopic and structural characterization of the siloxide products is reported. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pfiffner, Susan M.; Brandt, Craig C.; Kostka, Joel E.

Our current research represents a joint effort between Oak Ridge National Laboratory (ORNL), Florida State University (FSU), and the University of Tennessee. ORNL will serve as the lead institution with Dr. A.V. Palumbo responsible for project coordination, integration, and deliverables. This project was initiated in November, 2004, in the Integrative Studies Element of the NABIR program. The overall goal of our project is to provide an improved understanding of the relationships between microbial community structure, geochemistry, and metal reduction rates. The research seeks to address the following questions: Is the metabolic diversity of the in situ microbial community sufficiently largemore » and redundant that bioimmobilization of uranium will occur regardless of the type of electron donor added to the system? Are their donor specific effects that lead to enrichment of specific community members that then impose limits on the functional capabilities of the system? Will addition of humics change rates of uranium reduction without changing community structure? Can resource-ratio theory be used to understand changes in uranium reduction rates and community structure with respect to changing C:P ratios?« less

Teratogenicity of depleted uranium aerosols: A review from an epidemiological perspective

PubMed Central

Hindin, Rita; Brugge, Doug; Panikkar, Bindu

2005-01-01

Background Depleted uranium is being used increasingly often as a component of munitions in military conflicts. Military personnel, civilians and the DU munitions producers are being exposed to the DU aerosols that are generated. Methods We reviewed toxicological data on both natural and depleted uranium. We included peer reviewed studies and gray literature on birth malformations due to natural and depleted uranium. Our approach was to assess the "weight of evidence" with respect to teratogenicity of depleted uranium. Results Animal studies firmly support the possibility that DU is a teratogen. While the detailed pathways by which environmental DU can be internalized and reach reproductive cells are not yet fully elucidated, again, the evidence supports plausibility. To date, human epidemiological data include case examples, disease registry records, a case-control study and prospective longitudinal studies. Discussion The two most significant challenges to establishing a causal pathway between (human) parental DU exposure and the birth of offspring with defects are: i) distinguishing the role of DU from that of exposure to other potential teratogens; ii) documentation on the individual level of extent of parental DU exposure. Studies that use biomarkers, none yet reported, can help address the latter challenge. Thoughtful triangulation of the results of multiple studies (epidemiological and other) of DU teratogenicity contributes to disentangling the roles of various potentially teratogenic parental exposures. This paper is just such an endeavor. Conclusion In aggregate the human epidemiological evidence is consistent with increased risk of birth defects in offspring of persons exposed to DU. PMID:16124873

Target and method for the production of fission product molybdenum-99

DOEpatents

Vandegrift, G.F.; Vissers, D.R.; Marshall, S.L.; Varma, R.

1987-10-26

A target for the reduction of fission product Mo-99 is prepared from uranium of low U-235 enrichment by coating a structural support member with a preparatory coating of a substantially oxide-free substrate metal. Uranium metal is electrodeposited from a molten halide electrolytic bath onto a substrate metal. The electrodeposition is performed at a predetermined direct current rate or by using pulsed plating techniques which permit relaxation of accumulated uranium ion concentrations within the melt. Layers of as much as to 600 mg/cm/sup 2/ of uranium can be prepared to provide a sufficient density to produce acceptable concentrations of fission product Mo-99. 2 figs.

Uranium(VI) interactions with mackinawite in the presence and absence of bicarbonate and oxygen

USGS Publications Warehouse

Gallegos, Tanya J.; Fuller, Christopher C.; Webb, Samuel M.; Betterton, William J.

2013-01-01

Mackinawite, Fe(II)S, samples loaded with uranium (10-5, 10-4, and 10-3 mol U/g FeS) at pH 5, 7, and 9, were characterized using X-ray absorption spectroscopy and X-ray diffraction to determine the effects of pH, bicarbonate, and oxidation on uptake. Under anoxic conditions, a 5 g/L suspension of mackinawite lowered 5 × 10-5 M uranium(VI) to below 30 ppb (1.26 × 10-7 M) U. Between 82 and 88% of the uranium removed from solution by mackinawite was U(IV) and was nearly completely reduced to U(IV) when 0.012 M bicarbonate was added. Near-neighbor coordination consisting of uranium–oxygen and uranium-uranium distances indicates the formation of uraninite in the presence and absence of bicarbonate, suggesting reductive precipitation as the dominant removal mechanism. Following equilibration in air, mackinawite was oxidized to mainly goethite and sulfur and about 76% of U(IV) was reoxidized to U(VI) with coordination of uranium to axial and equatorial oxygen, similar to uranyl. Additionally, uranium-iron distances, typical of coprecipitation of uranium with iron oxides, and uranium-sulfur distances indicating bidentate coordination of U(VI) to sulfate were evident. The affinity of mackinawite and its oxidation products for U(VI) provides impetus for further study of mackinawite as a potential reactive medium for remediation of uranium-contaminated water.

Manufacturing Process Development to Produce Depleted Uranium Wire for EBAM Feedstock

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alexander, David John; Clarke, Kester Diederik; Coughlin, Daniel Robert

2015-06-30

Wire produced from depleted uranium (DU) is needed as feedstock for the Electron-Beam Additive Manufacturing (EBAM) process. The goal is to produce long lengths of DU wire with round or rectangular cross section, nominally 1.5 mm (0.060 inches). It was found that rolling methods, rather than swaging or drawing, are preferable for production of intermediate quantities of DU wire. Trials with grooveless rolling have shown that it is suitable for initial reductions of large stock. Initial trials with grooved rolling have been successful, for certain materials. Modified square grooves (square round-bottom vee grooves) with 12.5 % reduction of area permore » pass have been selected for the reduction process.« less

Mechanism of uranium (VI) removal by two anaerobic bacterial communities.

PubMed

Martins, Mónica; Faleiro, Maria Leonor; da Costa, Ana M Rosa; Chaves, Sandra; Tenreiro, Rogério; Matos, António Pedro; Costa, Maria Clara

2010-12-15

The mechanism of uranium (VI) removal by two anaerobic bacterial consortia, recovered from an uncontaminated site (consortium A) and other from an uranium mine (consortium U), was investigated. The highest efficiency of U (VI) removal by both consortia (97%) occurred at room temperature and at pH 7.2. Furthermore, it was found that U (VI) removal by consortium A occurred by enzymatic reduction and bioaccumulation, while the enzymatic process was the only mechanism involved in metal removal by consortium U. FTIR analysis suggested that after U (VI) reduction, U (IV) could be bound to carboxyl, phosphate and amide groups of bacterial cells. Phylogenetic analysis of 16S rRNA showed that community A was mainly composed by bacteria closely related to Sporotalea genus and Rhodocyclaceae family, while community U was mainly composed by bacteria related to Clostridium genus and Rhodocyclaceae family. Copyright © 2010 Elsevier B.V. All rights reserved.

The role of chemical reactions in the Chernobyl accident

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grishanin, E. I., E-mail: egrishanin@orexovo.net

2010-12-15

It is shown that chemical reactions played an essential role in the Chernobyl accident at all of its stages. It is important that the reactor before the explosion was at maximal xenon poisoning, and its reactivity, apparently, was not destroyed by the explosion. The reactivity release due to decay of Xe-235 on the second day after the explosion led to a reactor power of 80-110 MW. Owing to this power, the chemical reactions of reduction of uranium, plutonium, and other metals at a temperature of about 2000 Degree-Sign C occurred in the core. The yield of fission products thus sharplymore » increased. Uranium and other metals flew down in the bottom water communications and rooms. After reduction of the uranium and its separation from the graphite, the chain reaction stopped, the temperature of the core decreased, and the activity yield stopped.« less

Bioremediation of uranium-contaminated groundwater: a systems approach to subsurface biogeochemistry.

PubMed

Williams, Kenneth H; Bargar, John R; Lloyd, Jonathan R; Lovley, Derek R

2013-06-01

Adding organic electron donors to stimulate microbial reduction of highly soluble U(VI) to less soluble U(IV) is a promising strategy for immobilizing uranium in contaminated subsurface environments. Studies suggest that diagnosing the in situ physiological status of the subsurface community during uranium bioremediation with environmental transcriptomic and proteomic techniques can identify factors potentially limiting U(VI) reduction activity. Models which couple genome-scale in silico representations of the metabolism of key microbial populations with geochemical and hydrological models may be able to predict the outcome of bioremediation strategies and aid in the development of new approaches. Concerns remain about the long-term stability of sequestered U(IV) minerals and the release of co-contaminants associated with Fe(III) oxides, which might be overcome through targeted delivery of electrons to select microorganisms using in situ electrodes. Copyright © 2012 Elsevier Ltd. All rights reserved.

Identification of bacteria synthesizing ribosomal RNA in response to uranium addition during biostimulation at the Rifle, CO Integrated Field Research site

DOE PAGES

McGuinness, Lora R.; Wilkins, Michael J.; Williams, Kenneth H.; ...

2015-09-18

Understanding which organisms are capable of reducing uranium at historically contaminated sites provides crucial information needed to evaluate treatment options and outcomes. One approach is determination of the bacteria which directly respond to uranium addition. In this research, uranium amendments were made to groundwater samples from a site of ongoing biostimulation with acetate. The active microbes in the planktonic phase were deduced by monitoring ribosomes production via RT-PCR. The results indicated several microorganisms were synthesizing ribosomes in proportion with uranium amendment up to 2 μM. Concentrations of U (VI) >2 μM were generally found to inhibit ribosome synthesis. Two activemore » bacteria responding to uranium addition in the field were close relatives of Desulfobacter postgateii and Geobacter bemidjiensis. Since RNA content often increases with growth rate, our findings suggest it is possible to rapidly elucidate active bacteria responding to the addition of uranium in field samples and provides a more targeted approach to stimulate specific populations to enhance radionuclide reduction in contaminated sites.« less

Identification of Bacteria Synthesizing Ribosomal RNA in Response to Uranium Addition During Biostimulation at the Rifle, CO Integrated Field Research Site

PubMed Central

McGuinness, Lora R.; Wilkins, Michael J.; Williams, Kenneth H.; Long, Philip E.; Kerkhof, Lee J.

2015-01-01

Understanding which organisms are capable of reducing uranium at historically contaminated sites provides crucial information needed to evaluate treatment options and outcomes. One approach is determination of the bacteria which directly respond to uranium addition. In this study, uranium amendments were made to groundwater samples from a site of ongoing biostimulation with acetate. The active microbes in the planktonic phase were deduced by monitoring ribosomes production via RT-PCR. The results indicated several microorganisms were synthesizing ribosomes in proportion with uranium amendment up to 2 μM. Concentrations of U (VI) >2 μM were generally found to inhibit ribosome synthesis. Two active bacteria responding to uranium addition in the field were close relatives of Desulfobacter postgateii and Geobacter bemidjiensis. Since RNA content often increases with growth rate, our findings suggest it is possible to rapidly elucidate active bacteria responding to the addition of uranium in field samples and provides a more targeted approach to stimulate specific populations to enhance radionuclide reduction in contaminated sites. PMID:26382047

Proteomic analysis reveals contrasting stress response to uranium in two nitrogen-fixing Anabaena strains, differentially tolerant to uranium.

PubMed

Panda, Bandita; Basu, Bhakti; Acharya, Celin; Rajaram, Hema; Apte, Shree Kumar

2017-01-01

Two strains of the nitrogen-fixing cyanobacterium Anabaena, native to Indian paddy fields, displayed differential sensitivity to exposure to uranyl carbonate at neutral pH. Anabaena sp. strain PCC 7120 and Anabaena sp. strain L-31 displayed 50% reduction in survival (LD 50 dose), following 3h exposure to 75μM and 200μM uranyl carbonate, respectively. Uranium responsive proteome alterations were visualized by 2D gel electrophoresis, followed by protein identification by MALDI-ToF mass spectrometry. The two strains displayed significant differences in levels of proteins associated with photosynthesis, carbon metabolism, and oxidative stress alleviation, commensurate with their uranium tolerance. Higher uranium tolerance of Anabaena sp. strain L-31 could be attributed to sustained photosynthesis and carbon metabolism and superior oxidative stress defense, as compared to the uranium sensitive Anabaena sp. strain PCC 7120. Uranium responsive proteome modulations in two nitrogen-fixing strains of Anabaena, native to Indian paddy fields, revealed that rapid adaptation to better oxidative stress management, and maintenance of metabolic and energy homeostasis underlies superior uranium tolerance of Anabaena sp. strain L-31 compared to Anabaena sp. strain PCC 7120. Copyright © 2016 Elsevier B.V. All rights reserved.

Harnessing redox activity for the formation of uranium tris(imido) compounds

NASA Astrophysics Data System (ADS)

Anderson, Nickolas H.; Odoh, Samuel O.; Yao, Yiyi; Williams, Ursula J.; Schaefer, Brian A.; Kiernicki, John J.; Lewis, Andrew J.; Goshert, Mitchell D.; Fanwick, Phillip E.; Schelter, Eric J.; Walensky, Justin R.; Gagliardi, Laura; Bart, Suzanne C.

2014-10-01

Classically, late transition-metal organometallic compounds promote multielectron processes solely through the change in oxidation state of the metal centre. In contrast, uranium typically undergoes single-electron chemistry. However, using redox-active ligands can engage multielectron reactivity at this metal in analogy to transition metals. Here we show that a redox-flexible pyridine(diimine) ligand can stabilize a series of highly reduced uranium coordination complexes by storing one, two or three electrons in the ligand. These species reduce organoazides easily to form uranium-nitrogen multiple bonds with the release of dinitrogen. The extent of ligand reduction dictates the formation of uranium mono-, bis- and tris(imido) products. Spectroscopic and structural characterization of these compounds supports the idea that electrons are stored in the ligand framework and used in subsequent reactivity. Computational analyses of the uranium imido products probed their molecular and electronic structures, which facilitated a comparison between the bonding in the tris(imido) structure and its tris(oxo) analogue.

Removal of uranium (VI) from aqueous systems by nanoscale zero-valent iron particles suspended in carboxy-methyl cellulose

NASA Astrophysics Data System (ADS)

Popescu (Hoştuc), Ioana-Carmen; Filip, Petru; Humelnicu, Doina; Humelnicu, Ionel; Scott, Thomas Bligh; Crane, Richard Andrew

2013-11-01

Carboxy-methyl-cellulose (CMC), a common "delivery vehicle" for the subsurface deployment of iron nanoparticles (INP) has been tested in the current work for the removal of aqueous uranium from synthetic water samples. A comparison of the removal of aqueous uranium from solutions using carboxy-methyl-cellulose with and without iron nanoparticles (CMC-INP and CMC, respectively) was tested over a 48 h reaction period. Analysis of liquid samples using spectrophotometry determined a maximum sorption capacity of uranium, Qmax, of 185.18 mg/g and 322.58 mg/g for CMC and CMC-INP respectively, providing strong evidence of an independent aqueous uranium removal ability exhibited by CMC. The results point out that CMC provides an additional capacity for aqueous uranium removal. Further tests are required to determine whether similar behaviour will be observed for other aqueous contaminant species and if the presence of CMC within a INP slurry inhibits or aids the reactivity, reductive capacity and affinity of INP for aqueous contaminant removal.

Exposure pathways and health effects associated with chemical and radiological toxicity of natural uranium: a review.

PubMed

Brugge, Doug; de Lemos, Jamie L; Oldmixon, Beth

2005-01-01

Natural uranium exposure derives from the mining, milling, and processing of uranium ore, as well as from ingestion of groundwater that is naturally contaminated with uranium. Ingestion and inhalation are the primary routes of entry into the body. Absorption of uranium from the lungs or digestive track is typically low but can vary depending on compound specific solubility. From the blood, two-thirds of the uranium is excreted in urine over the first 24 hours and up to 80% to 90% of uranium deposited in the bone leaves the body within 1.5 years. The primary health outcomes of concern documented with respect to uranium are renal, developmental, reproductive, diminished bone growth, and DNA damage. The reported health effects derive from experimental animal studies and human epidemiology. The Lowest Observed Adverse Effect Level (LOAEL) derived from animal studies is 50 microg/m3 for inhalation and 60 ug/kg body weight/day for ingestion. The current respiratory standard of the Occupational Safety and Health Administration (OSHA), 50 microg/m3, affords no margin of safety. Considering the safety factors for species and individual variation, the ingestion LOAEL corresponds to the daily consumption set by the World Health Organization Drinking Water Standard at 2 microg/L. Based on economic considerations, the United States Environmental Protection Agency maximum contaminant level is 30 microg/L. Further research is needed, with particular attention on the impact of uranium on indigenous populations, on routes of exposure in communities near uranium sites, on the combined exposures present at many uranium sites, on human developmental defects, and on health effects at or below established exposure standards.

Selective Extraction of Uranium from Liquid or Supercritical Carbon Dioxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Farawila, Anne F.; O'Hara, Matthew J.; Wai, Chien M.

2012-07-31

Current liquid-liquid extraction processes used in recycling irradiated nuclear fuel rely on (1) strong nitric acid to dissolve uranium oxide fuel, and (2) the use of aliphatic hydrocarbons as a diluent in formulating the solvent used to extract uranium. The nitric acid dissolution process is not selective. It dissolves virtually the entire fuel meat which complicates the uranium extraction process. In addition, a solvent washing process is used to remove TBP degradation products, which adds complexity to the recycling plant and increases the overall plant footprint and cost. A liquid or supercritical carbon dioxide (l/sc -CO2) system was designed tomore » mitigate these problems. Indeed, TBP nitric acid complexes are highly soluble in l/sc -CO2 and are capable of extracting uranium directly from UO2, UO3 and U3O8 powders. This eliminates the need for total acid dissolution of the irradiated fuel. Furthermore, since CO2 is easily recycled by evaporation at room temperature and pressure, it eliminates the complex solvent washing process. In this report, we demonstrate: (1) A reprocessing scheme starting with the selective extraction of uranium from solid uranium oxides into a TBP-HNO3 loaded Sc-CO2 phase, (2) Back extraction of uranium into an aqueous phase, and (3) Conversion of recovered purified uranium into uranium oxide. The purified uranium product from step 3 can be disposed of as low level waste, or mixed with enriched uranium for use in a reactor for another fuel cycle. After an introduction on the concept and properties of supercritical fluids, we first report the characterization of the different oxides used for this project. Our extraction system and our online monitoring capability using UV-Vis absorbance spectroscopy directly in sc-CO2 is then presented. Next, the uranium extraction efficiencies and kinetics is demonstrated for different oxides and under different physical and chemical conditions: l/sc -CO2 pressure and temperature, TBP/HNO3 complex used, reductant or complexant used for selectivity, and ionic liquids used as supportive media. To complete the extraction and recovery cycle, we then demonstrate uranium back extraction from the TBP loaded sc-CO2 phase into an aqueous phase and the characterization of the uranium complex formed at the end of this process. Another aspect of this project was to limit proliferation risks by either co-extracting uranium and plutonium, or by leaving plutonium behind by selectively extracting uranium. We report that the former is easily achieved, since plutonium is in the tetravalent or hexavalent oxidation state in the oxidizing environment created by the TBP-nitric acid complex, and is therefore co-extracted. The latter is more challenging, as a reductant or complexant to plutonium has to be used to selectively extract uranium. After undertaking experiments on different reducing or complexing systems (e.g., AcetoHydroxamic Acid (AHA), Fe(II), ascorbic acid), oxalic acid was chosen as it can complex tetravalent actinides (Pu, Np, Th) in the aqueous phase while allowing the extraction of hexavalent uranium in the sc-CO2 phase. Finally, we show results using an alternative media to commonly used aqueous phases: ionic liquids. We show the dissolution of uranium in ionic liquids and its extraction using sc-CO2 with and without the presence of AHA. The possible separation of trivalent actinides from uranium is also demonstrated in ionic liquids using neodymium as a surrogate and diglycolamides as the extractant.« less

Investigation of residual anode material after electrorefining uranium in molten chloride salt

NASA Astrophysics Data System (ADS)

Rose, M. A.; Williamson, M. A.; Willit, J.

2015-12-01

A buildup of material at uranium anodes during uranium electrorefining in molten chloride salts has been observed. Potentiodynamic testing has been conducted using a three electrode cell, with a uranium working electrode in both LiCl/KCl eutectic and LiCl each containing ∼5 mol% UCl3. The anodic current response was observed at 50° intervals between 450 °C and 650 °C in the eutectic salt. These tests revealed a buildup of material at the anode in LiCl/KCl salt, which was sampled at room temperature, and analyzed using ICP-MS, XRD and SEM techniques. Examination of the analytical data, current response curves and published phase diagrams has established that as the uranium anode dissolves, the U3+ ion concentration in the diffusion layer surrounding the electrode rises precipitously to levels, which may at low temperatures exceed the solubility limit for UCl3 or in the case of the eutectic salt for K2UCl5. The reduction in current response observed at low temperature in eutectic salt is eliminated at 650 °C, where K2UCl5 is absent due to its congruent melting and only simple concentration polarization effects are seen. In LiCl similar concentration effects are seen though significantly longer time at applied potential is required to effect a reduction in the current response as compared to the eutectic salt.

Sustained removal of uranium from contaminated groundwater following stimulation of dissimilatory metal reduction.

PubMed

N'Guessan, A Lucie; Vrionis, Helen A; Resch, Charles T; Long, Philip E; Lovley, Derek R

2008-04-15

Previous field studies on in situ bioremediation of uranium-contaminated groundwater in an aquifer in Rifle, Colorado identified two distinct phases following the addition of acetate to stimulate microbial respiration. In phase I, Geobacter species are the predominant organisms, Fe(III) is reduced, and microbial reduction of soluble U(VI) to insoluble U(IV) removes uranium from the groundwater. In phase II, Fe(III) is depleted, sulfate is reduced, and sulfate-reducing bacteria predominate. Long-term monitoring revealed an unexpected third phase during which U(VI) removal continues even after acetate additions are stopped. All three of these phases were successfully reproduced in flow-through sediment columns. When sediments from the third phase were heat sterilized, the capacity for U(VI) removal was lost. In the live sediments U(VI) removed from the groundwater was recovered as U(VI) in the sediments. This contrasts to the recovery of U(IV) in sediments resulting from the reduction of U(VI) to U(IV) during the Fe(III) reduction phase in acetate-amended sediments. Analysis of 16S rRNA gene sequences in the sediments in which U(VI) was being adsorbed indicated that members of the Firmicutes were the predominant organisms whereas no Firmicutes sequences were detected in background sediments which did not have the capacity to sorb U(VI), suggesting that the U(VI) adsorption might be due to the presence of these living organisms or at least their intact cell components. This unexpected enhanced adsorption of U(VI) onto sediments following the stimulation of microbial growth in the subsurface may potentially enhance the cost effectiveness of in situ uranium bioremediation.

Geology of uranium in the Chadron area, Nebraska and South Dakota

USGS Publications Warehouse

Dunham, Robert Jacob

1961-01-01

The Chadron area covers 375 square miles about 25 miles southeast of the Black Hills. Recurrent mild tectonic activity and erosion on the Chadron arch, a compound anticlinal uplift of regional extent, exposed 1900 feet of Upper Cretaceous rocks, mostly marine shale containing pyrite and organic matter, and 600 feet of Oligocene and Miocene rocks, mostly terrestrial fine-grained sediment containing volcanic ash. Each Cretaceous formation truncated by the sub-Oligocene unconformity is stained yellow and red, leached, kaolinized, and otherwise altered to depths as great as 55 feet. The composition and profile of the altered material indicate lateritic soil; indirect evidence indicates Eocene(?) age. In a belt through the central part of the area, the Brule formation of Oligocene age is a sequence of bedded gypsum, clay, dolomite, and limestone more than 300 feet thick. Uranium in Cretaceous shale in 58 samples averages 0.002 percent, ten times the average for the earths crust. Association with pyrite and organic matter indicates low valency. The uranium probably is syngenetic or nearly so. Uranium in Eocene(?) soil in 43 samples averages 0.054 percent, ranging up to 1.12 percent. The upper part of the soil is depleted in uranium; enriched masses in the basal part of the soil consist of remnants of bedrock shale and are restricted to the highest reaches of the ancient oxidation-reduction interface. The uranium is probably in the from of a low-valent mineral, perhaps uraninite. Modern weathering of Cretaceous shale is capable of releasing as much as 0.780 ppm uranium to water. Eocene(?) weathering probably caused enrichment of the ancient soil through 1) leaching of Cretaceous shale, 2) downward migration of uranyl complex ions, and 3) reduction of hydrogen sulfide at the water table. Uranium minerals occur in the basal 25 feet of the gypsum facies of the Brule formation at the two localities where the gypsum is carbonaceous; 16 samples average 0.066 percent uranium and range up to 0.43 percent. Elsewhere uranium in dolomite and limestone in the basal 25 feet of the gypsum facies in 10 samples averages 0.007 percent, ranging up to 0.12 percent. Localization of the uranium at the base of the gypsum facies suggests downward moving waters; indirect evidence that the water from which the gypsum was deposited was highly alkaline suggests that the uranium was leached from volcanic ash in Oligocene time.

Investigations for the Recycle of Pyroprocessed Uranium

NASA Astrophysics Data System (ADS)

Westphal, B. R.; Price, J. C.; Chambers, E. E.; Patterson, M. N.

Given the renewed interest in uranium from the pyroprocessing of used nuclear fuel in a molten salt system, the two biggest hurdles for marketing the uranium are radiation levels and transuranic content. A radiation level as low as possible is desired so that handling operations can be performed directly with the uranium. The transuranic content of the uranium will affect the subsequent waste streams generated and, thus also should be minimized. Although the pyroprocessing technology was originally developed without regard to radiation and transuranic levels, adaptations to the process have been considered. Process conditions have been varied during the distillation and casting cycles of the process with increasing temperature showing the largest effect on the reduction of radiation levels. Transuranic levels can be reduced significantly by incorporating a pre-step in the salt distillation operation to remove a majority of the salt prior to distillation.

Geologic report on the Sand Wash Drilling Project, Moffat and Routt Counties, Colorado

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carter, T.E.; Wayland, T.E.

1981-09-01

The Sand Wash Basin Drilling Project comprises twenty-seven (27) drill holes located in Moffat and Routt Counties, northwest Colorado, having an aggregate depth of 26,107.5 feet (7957.6 m). The holes penetrate the Browns Park Formation of Miocene age, which is a tuffaceous continental sandstone deposited in fluvial, eolian, and lacustrine environments. Partly based on project drilling results, uranium potential resource estimates for this formation in the $50/lb U/sub 3/O/sub 8/ forward-cost category have been increased by 34,476 tons U/sub 3/O/sub 8/ (35,036 metric tons). Three areas between Maybell and Craig, Colorado, considered favorable for uranium occurrences were verified as favorablemore » by project drilling, and a fourth favorable area northwest of Maybell has been expanded. In addition, project drilling results indicate two new favorable areas, one north and northwest and one south of Steamboat Springs, Colorado. Anomalous radioactivity was detected in drill holes in all six study areas of the project. The most important factor in concentrating significant amounts of uranium in the target formation appears to be the availability of gaseous or liquid hydrocarbons and/or hydrogen sulfide gas as reductants. Where subjacent formations supply these reductants to the Browns Park Formation, project drilling encountered 0.05 percent to 0.01 percent uranium concentrations. Potential, though unproven, sources of these reductants are believed to underlie parts of all six project study areas.« less

Influence of microorganisms on the oxidation state distribution of multivalent actinides under anoxic conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reed, Donald Timothy; Borkowski, Marian; Lucchini, Jean - Francois

2010-12-10

The fate and potential mobility of multivalent actinides in the subsurface is receiving increased attention as the DOE looks to cleanup the many legacy nuclear waste sites and associated subsurface contamination. Plutonium, uranium and neptunium are the near-surface multivalent contaminants of concern and are also key contaminants for the deep geologic disposal of nuclear waste. Their mobility is highly dependent on their redox distribution at their contamination source as well as along their potential migration pathways. This redox distribution is often controlled, especially in the near-surface where organic/inorganic contaminants often coexist, by the direct and indirect effects of microbial activity.more » Under anoxic conditions, indirect and direct bioreduction mechanisms exist that promote the prevalence of lower-valent species for multivalent actinides. Oxidation-state-specific biosorption is also an important consideration for long-term migration and can influence oxidation state distribution. Results of ongoing studies to explore and establish the oxidation-state specific interactions of soil bacteria (metal reducers and sulfate reducers) as well as halo-tolerant bacteria and Archaea for uranium, neptunium and plutonium will be presented. Enzymatic reduction is a key process in the bioreduction of plutonium and uranium, but co-enzymatic processes predominate in neptunium systems. Strong sorptive interactions can occur for most actinide oxidation states but are likely a factor in the stabilization of lower-valent species when more than one oxidation state can persist under anaerobic microbiologically-active conditions. These results for microbiologically active systems are interpreted in the context of their overall importance in defining the potential migration of multivalent actinides in the subsurface.« less

Proliferation dangers associated with nuclear medicine: getting weapons-grade uranium out of radiopharmaceutical production.

PubMed

Williams, Bill; Ruff, Tilman A

2007-01-01

Abolishing the threat of nuclear war requires the outlawing of nuclear weapons and dismantling current nuclear weapon stockpiles, but also depends on eliminating access to fissile material (nuclear weapon fuel). The near-universal use of weapons-grade, highly enriched uranium (HEU) to produce radiopharmaceuticals is a significant proliferation hazard. Health professionals have a strategic opportunity and obligation to progress the elimination of medically-related commerce in HEU, closing one of the most vulnerable pathways to the much-feared 'terrorist bomb'.

Influence of Bicarbonate, Sulfate, and Electron Donors on Biological reduction of Uranium and Microbial Community Composition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Wensui; Zhou, Jizhong; Wu, Weimin

2007-01-01

A microcosm study was performed to investigate the effect of ethanol and acetate on uranium(VI) biological reduction and microbial community changes under various geochemical conditions. Each microcosm contained an uranium-contaminated sediment (up to 2.8 g U/kg) suspended in buffer with bicarbonate at concentrations of either 1 mM or 40 mM and sulfate at either 1.1 or 3.2 mM. Ethanol or acetate was used as an electron donor. Results indicate that ethanol yielded in significantly higher U(VI) reduction rates than acetate. A low bicarbonate concentration (1 mM) was favored for U(VI) bioreduction to occur in sediments, but high concentrations of bicarbonatemore » (40 mM) and sulfate (3.2 mM) decreased the reduction rates of U(VI). Microbial communities were dominated by species from the Geothrix genus and Proteobacteria phylum in all microcosms. However, species in the Geobacteraceae family capable of reducing U(VI) were significantly enriched by ethanol and acetate in low bicarbonate buffer. Ethanol increased the population of unclassified Desulfuromonales, while acetate increased the population of Desulfovibrio. Additionally, species in the Geobacteraceae family were not enriched in high bicarbonate buffer, but the Geothrix and the unclassified Betaproteobacteria species were enriched. This study concludes that ethanol could be a better electron donor than acetate for reducing U(VI) under given experimental conditions, and electron donor and geoundwater geochemistry alter microbial communities responsible for U(VI) reduction.« less

Drinking Water with Uranium below the U.S. EPA Water Standard Causes Estrogen Receptor–Dependent Responses in Female Mice

PubMed Central

Raymond-Whish, Stefanie; Mayer, Loretta P.; O’Neal, Tamara; Martinez, Alisyn; Sellers, Marilee A.; Christian, Patricia J.; Marion, Samuel L.; Begay, Carlyle; Propper, Catherine R.; Hoyer, Patricia B.; Dyer, Cheryl A.

2007-01-01

Background The deleterious impact of uranium on human health has been linked to its radioactive and heavy metal–chemical properties. Decades of research has defined the causal relationship between uranium mining/milling and onset of kidney and respiratory diseases 25 years later. Objective We investigated the hypothesis that uranium, similar to other heavy metals such as cadmium, acts like estrogen. Methods In several experiments, we exposed intact, ovariectomized, or pregnant mice to depleted uranium in drinking water [ranging from 0.5 μg/L (0.001 μM) to 28 mg/L (120 μM). Results Mice that drank uranium-containing water exhibited estrogenic responses including selective reduction of primary follicles, increased uterine weight, greater uterine luminal epithelial cell height, accelerated vaginal opening, and persistent presence of cornified vaginal cells. Coincident treatment with the antiestrogen ICI 182,780 blocked these responses to uranium or the synthetic estrogen diethylstilbestrol. In addition, mouse dams that drank uranium-containing water delivered grossly normal pups, but they had significantly fewer primordial follicles than pups whose dams drank control tap water. Conclusions Because of the decades of uranium mining/milling in the Colorado plateau in the Four Corners region of the American Southwest, the uranium concentration and the route of exposure used in these studies are environmentally relevant. Our data support the conclusion that uranium is an endocrine-disrupting chemical and populations exposed to environmental uranium should be followed for increased risk of fertility problems and reproductive cancers. PMID:18087588

Method for cleaning bomb-reduced uranium derbies

DOEpatents

Banker, John G.; Wigginton, Hubert L.; Beck, David E.; Holcombe, Cressie E.

1981-01-01

The concentration of carbon in uranium metal ingots induction cast from derbies prepared by the bomb-reduction of uranium tetrafluoride in the presence of magnesium is effectively reduced to less than 100 ppm by removing residual magnesium fluoride from the surface of the derbies prior to casting. This magnesium fluoride is removed from the derbies by immersing them in an alkali metal salt bath which reacts with and decomposes the magnesium fluoride. A water quenching operation followed by a warm nitric acid bath and a water rinse removes the residual salt and reaction products from the derbies.

Method for cleaning bomb-reduced uranium derbies

DOEpatents

Banker, J.G.; Wigginton, H.L.; Beck, D.E.; Holcombe, C.E.

The concentration of carbon in uranium metal ingots induction cast from derbies prepared by the bomb-reduction of uranium tetrafluoride in the presence of magnesium is effectively reduced to less than 100 ppM by removing residual magnesium fluoride from the surface of the derbies prior to casting. This magnesium fluoride is removed from the derbies by immersing them in an alkali metal salt bath which reacts with and decomposes the magnesium fluoride. A water quenching operation followed by a warm nitric acid bath and a water rinse removes the residual salt and reaction products from the derbies.

Method for oxygen reduction in a uranium-recovery process. [US DOE patent application

DOEpatents

Hurst, F.J.; Brown, G.M.; Posey, F.A.

1981-11-04

An improvement in effecting uranium recovery from phosphoric acid solutions is provided by sparging dissolved oxygen contained in solutions and solvents used in a reductive stripping stage with an effective volume of a nonoxidizing gas before the introduction of the solutions and solvents into the stage. Effective volumes of nonoxidizing gases, selected from the group consisting of argon, carbon dioxide, carbon monoxide, helium, hydrogen, nitrogen, sulfur dioxide, and mixtures thereof, displace oxygen from the solutions and solvents thereby reduce deleterious effects of oxygen such as excessive consumption of elemental or ferrous iron and accumulation of complex iron phosphates or cruds.

Pilot Study to Evaluate Hydrogen Injection for Stimulating Reduction and Immobilization of Uranium in Groundwater at an ISR Mining Site

NASA Astrophysics Data System (ADS)

Clapp, L. W.; Cabezas, J.; Gamboa, Y.; Fernandez, W.

2011-12-01

State and federal regulations require that groundwater at in-situ recovery (ISR) uranium mining operations be restored to pre-mining conditions. Reverse osmosis (RO) filtration of several pore volumes of the post-leached groundwater and reinjection of the clean permeate is the most common technology currently used for restoring groundwater at uranium ISR sites. However, this approach does not revert the formation back to its initial reducing conditions, which can potentially impede timely groundwater restoration. In-situ biostimulation of indigenous iron- and sulfate reducing bacteria by injection of organic electron donors (e.g., ethanol, acetate, and lactate) to promote soluble uranium reduction and immobilization has been the subject of previous studies. However, injection of organic substrates has been observed to cause aquifer clogging near the injection point. In addition, U(VI) solubility may be enhanced through complexation with carbonate generated by organic carbon oxidation. An alternative approach that may overcome these problems involves the use of hydrogen as a reductant to promote microbial reduction and immobilization of U(VI) in situ. To test this approach, approximately 100,000 scf of compressed hydrogen gas was injected into a leached unconsolidated sand zone over two months at an ISR mining site. During this time groundwater was recirculated between injection and extraction wells (separated by 130 ft) at a rate of about 40 gpm and bromide was coinjected as a conservative tracer. A well monitoring program has been executed since June 2009 to evaluate the performance of the hydrogen injection. Current results show that U(VI) has been reduced from 4.2 to 0.05 ppm in the area surrounding the injection well and to 2.0 ± 0.3 ppm in the area surrounding the extraction well and two intermediate monitoring wells. Other water quality changes near the injection well include significant decreases in concentrations of Mo, sulfate, Fe, Mn, bicarbonate, Ca, and Eh, and increases in pH, methane, and sulfide. No significant rebound of soluble uranium concentrations was observed, but significant rebounds in molybdenum and sulfate have been observed. Ongoing studies are evaluating the effective zone of influence of the hydrogen injection.

A compartmental model of uranium in human hair for protracted ingestion of natural uranium in drinking water.

PubMed

Li, W B; Karpas, Z; Salonen, L; Kurttio, P; Muikku, M; Wahl, W; Höllriegl, V; Hoeschen, C; Oeh, U

2009-06-01

To predict uranium in human hair due to chronic exposure through drinking water, a compartment representing human hair was added into the uranium biokinetic model developed by the International Commission on Radiological Protection (ICRP). The hair compartmental model was used to predict uranium excretion in human hair as a bioassay indicator due to elevated uranium intakes. Two excretion pathways, one starting from the compartment of plasma and the other from the compartment of intermediate turnover soft tissue, are assumed to transfer uranium to the compartment of hair. The transfer rate was determined from reported uranium contents in urine and in hair, taking into account the hair growth rate of 0.1 g d(-1). The fractional absorption in the gastrointestinal tract of 0.6% was found to fit best to describe the measured uranium levels among the users of drilled wells in Finland. The ingestion dose coefficient for (238)U, which includes its progeny of (234)Th, (234m)Pa, and (234)Pa, was calculated equal to 1.3 x 10(-8) Sv Bq(-1) according to the hair compartmental model. This estimate is smaller than the value of 4.5 x 10(-8) Sv Bq(-1) published by ICRP for the members of the public. In this new model, excretion of uranium through urine is better represented when excretion to the hair compartment is accounted for and hair analysis can provide a means for assessing the internal body burden of uranium. The model is applicable for chronic exposure as well as for an acute exposure incident. In the latter case, the hair sample can be collected and analyzed even several days after the incident, whereas urinalysis requires sample collection shortly after the exposure. The model developed in this study applies to ingestion intakes of uranium.

Crucible cast from beryllium oxide and refractory cement is impervious to flux and molten metal

NASA Technical Reports Server (NTRS)

Jastrzebski, Z. D.

1966-01-01

Crucible from a mixture of a beryllium oxide aggregate and hydraulic refractory cement, and coated with an impervious refractory oxide will not deteriorate in the presence of fused salt- molten metal mixtures such as uranium- magnesium-zinc-halide salt systems. Vessels cast by this process are used in the flux reduction of oxides of thorium and uranium.

Monitoring Physical and Biogeochemical Dynamics of Uranium Bioremediation at the Intermediate Scale

NASA Astrophysics Data System (ADS)

Tarrell, A. N.; Figueroa, L. A.; Rodriguez, D.; Haas, A.; Revil, A.

2011-12-01

Subsurface uranium above desired levels for aquifer use categories exists naturally and from historic mining and milling practices. In situ bioimmobilization offers a cost effective alternative to conventional pump and treat methods by stimulating growth of microorganisms that lead to the reduction and precipitation of uranium. Vital to the long-term success of in situ bioimmobilization is the ability to successfully predict and demonstrate treatment effectiveness to assure that regulatory goals are met. However, successfully monitoring the progress over time is difficult and requires long-term stewardship to ensure effective treatment due to complex physical and biogeochemical heterogeneity. In order to better understand these complexities and the resultant effect on uranium immobilization, innovative systematic monitoring approaches with multiple performance indicators must be investigated. A key issue for uranium bioremediation is the long term stability of solid-phase reduction products. It has been shown that a combination of data from electrode-based monitoring, self-potential monitoring, oxidation reduction potential (ORP), and water level sensors provides insight for identifying and localizing bioremediation activity and can provide better predictions of deleterious biogeochemical change such as pore clogging. In order to test the proof-of-concept of these sensing techniques and to deconvolve redox activity from other electric potential changing events, an intermediate scale 3D tank experiment has been developed. Well-characterized materials will be packed into the tank and an artificial groundwater will flow across the tank through a constant-head boundary. The experiment will utilize these sensing methods to image the electrical current produced by bacteria as well as indications of when and where electrical activity is occurring, such as with the reduction of radionuclides. This work will expand upon current knowledge by exploring the behavior of uranium bioremediation at an intermediate scale, as well as examining the effects from introducing a flow field in a laboratory setting. Data collected from this experiment will help further characterize which factors are contributing to current increases. Additional information concerning the effect of geochemical changes in porosity may also be observed. The results of this work will allow the creation of a new data set collected from a more comprehensive laboratory monitoring network and will allow stakeholders to develop effective decision-making tools on the long-term remediation management at uranium contaminated sites. The data will also aid in the long-term prediction abilities of a reactive transport models. As in situ bioremediation offers a low cost alternative to ex situ treatment methods, the results of this work will help to both reduce cost at existing sites and enable treatment of sites that otherwise have no clear solution.

Bioreduction of U(VI)-Phthalate to a Polymeric U(IV)-Phthalate Colloid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vazquez, G.; Dodge, C; Francis, A

2009-01-01

Phthalic acid, a ubiquitous organic ligand, formed soluble mono- and biligand complexes with a uranyl ion that was then reduced to a U(IV)-phthalate by a Clostridium species under anaerobic conditions. We confirmed the reduction of the hexavalent uranium to the tetravalent oxidation state by UV-vis absorption and X-ray absorption near edge structure spectroscopy. Sequential micro- and ultrafiltration of the solution revealed that the bioreduced uranium was present as a colloid with particles between 0.03 and 0.45 {mu}m. Analysis with extended X-ray absorption fine structure revealed the association of the reduced uranium with the phthalic acid as a repeating biligand 1:2more » U(IV):phthalic acid polymer. This is the first report of the formation of a U(IV) complexed to two phthalic acid molecules in the form of a polymeric colloid. Although it was proposed that the bioreduction and the precipitation of uranium might be an invaluable strategy to immobilize uranium in contaminated environments, our results suggest that the organic ligands present there might hinder the precipitation of the bioreduced uranium under anaerobic conditions and, thereby, enhance its environmental mobility as uranium organic complexes or colloids.« less

Biogenic formation and growth of uraninite (UO₂).

PubMed

Lee, Seung Yeop; Baik, Min Hoon; Choi, Jong Won

2010-11-15

Biogenic UO₂ (uraninite) nanocrystals may be formed as a product of a microbial reduction process in uranium-enriched environments near the Earth's surface. We investigated the size, nanometer-scale structure, and aggregation state of UO₂ formed by iron-reducing bacterium, Shewanella putrefaciens CN32, from a uranium-rich solution. Characterization of biogenic UO₂ precipitates by high-resolution transmission electron microscopy (HRTEM) revealed that the UO₂ nanoparticles formed were highly aggregated by organic polymers. Nearly all of the nanocrystals were networked in more or less 100 nm diameter spherical aggregates that displayed some concentric UO₂ accumulation with heterogeneity. Interestingly, pure UO₂ nanocrystals were piled on one another at several positions via UO₂-UO₂ interactions, which seem to be intimately related to a specific step in the process of growing large single crystals. In the process, calcium that was easily complexed with aqueous uranium(VI) appeared not to be combined with bioreduced uranium(IV), probably due to its lower binding energy. However, when phosphate was added to the system, calcium was found to be easily associated with uranium(IV), forming a new uranium phase, ningyoite. These results will extend the limited knowledge of microbial uraniferous mineralization and may provide new insights into the fate of aqueous uranium complexes.

Establishing Radiological Screening Levels for Defense-related Uranium Mine (DRUM) Sites on BLM Land Using a Recreational Future-use Scenario.

PubMed

Brown, Steven H; Edge, Russel; Elmer, John; McDonald, Michael

2018-06-01

Thousands of former uranium mining sites in the United States, primarily in the southwestern states of Colorado, Arizona, New Mexico, Arizona, and Utah, are being identified and evaluated to assess their potential for causing public and environmental impacts. The common radiological contaminant of concern that characterizes these sites is naturally occurring uranium ore and associated wastes that may have been left behind postmining. The majority of these sites were abandoned and in general, are referred to as abandoned uranium mines, regardless of the government authority currently managing the land or in some cases, assigned responsibility for the oversight of assessment and remediation. The U.S. Department of Energy has identified over 4,000 defense-related uranium mine sites from which uranium ore was purchased by the U.S. government for nuclear defense programs prior to 1970. U.S. Department of Energy has established a program to inventory and perform environmental screening on defense-related uranium mine sites. The focus of this paper is the approximately 2,400 defense-related uranium mine sites located on federal land managed by the Bureau of Land Management and the U.S. Forest Service. This paper presents the results of an analysis to develop radiological screening criteria for U.S. Department of Energy's defense-related uranium mine sites that can be used as input to the overall ranking of these sites for prioritization of additional assessment, reclamation, or remedial actions. For these sites managed by Bureau of Land Management, public access is typically limited to short-term use, primarily for recreational purposes. This is a broad category that can cover a range of possible activities, including camping, hiking, hunting, biking, all-terrain vehicle use, and horseback riding. The radiological screening levels were developed by calculating the radiological dose to future recreational users of defense-related uranium mine sites assuming a future camper spends two weeks per year at the site engaged in recreational activities. Although a number of possible exposure pathways were included in this analysis (inhalation and ingestion of dust and soil, radon and progeny inhalation, and gamma radiation exposure from the soil), it is desirable as a practical matter to determine what gamma exposure rate would ensure that the annual acceptable exposure as determined by the regulatory authority will not be exceeded in the future. Because these sites are generally remote and located in semiarid environments, traditional exposure scenarios often applied in these types of analyses (e.g., subsistent farmers and ranchers), including exposure pathways for the ingestion of locally grown food products and water, were not considered relevant to short-term recreational use.

Sorption behavior of uranium(VI) on a biotite mineral

DOE Office of Scientific and Technical Information (OSTI.GOV)

Idemitsu, K.; Obata, K.; Furuya, H.

1995-12-31

Biotite has the most important role for the sorption of radionuclides in granitic rocks. Experiments on the sorption of uranium(VI) on biotite were conducted to understand the fundamental controls on uranium sorption on biotite mineral, including the effects of pH and uranium concentration in solution. Biotite powder (mesh 32--60) were washed with 1N HCl for a week and were rinsed twice with deionized water for a week. This HCl treatment was necessary to avoid the effects by other minerals. The agreement between surface adsorption coefficient, Ka, of both biotites with and without HCl treatment was within one order of magnitude.more » The peak Ka value was in the range of 0.1 to 0.01 cm{sup 3}/cm{sup 2} around pH 6. A comparison of aqueous uranium speciations and sorption results indicates that neutral uranyl hydroxide could be an important species sorbed on the biotite. Sequential desorption experiments with KCl and HCl solutions were also carried out after sorption experiments to investigate sorption forms of uranium. Approximately 20% of uranium in solution were sorbed on the biotite as an exchangeable ion. The fraction of exchangeable uranium had a little dependence on pH. The other uranium could not be extracted even by 6N HCl solution. It is possible that most of the uranium could be precipitated as U(IV) via Fe(II) reduction on the biotite surface.« less

Microbial biogeochemistry of uranium mill tailings

USGS Publications Warehouse

Landa, Edward R.

2005-01-01

Uranium mill tailings (UMT) are the crushed ore residues from the extraction of uranium (U) from ores. Among the radioactive wastes associated with the nuclear fuel cycle, UMT are unique in terms of their volume and their limited isolation from the surficial environment. For this latter reason, their management and long-term fate has many interfaces with environmental microbial communities and processes. The interactions of microorganisms with UMT have been shown to be diverse and with significant consequences for radionuclide mobility and bioremediation. These radionuclides are associated with the U-decay series. The addition of organic carbon and phosphate is required to initiate the reduction of the U present in the groundwater down gradient of the mills. Investigations on sediment and water from the U-contaminated aquifer, indicates that the addition of a carbon source stimulates the rate of U removal by microbial reduction. Moreover, most attention with respect to passive or engineered removal of U from groundwaters focuses on iron-reducing and sulfate-reducing bacteria.

REACTOR NOZZLE ASSEMBLY

DOEpatents

Capuder, F.C.; Dearwater, J.R.

1959-02-10

An improved nozzle assembly useful in a process for the direct reduction of uranium hexafluoride to uranium tetrafluoride by means of dissociated ammonia in a heated reaction vessel is descrlbed. The nozzle design provides for intimate mixing of the two reactants and at the same time furnishes a layer of dissociated ammonia adjacent to the interior wall of the reaction vessel, thus preventing build-up of the reaction product on the vessel wall.

Effect of Co-Contaminants Uranium and Nitrate on Iodine Remediation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szecsody, James E.; Lee, Brady D.; Lawter, Amanda R.

The objective of this study is to evaluate the significance of co-contaminants on the migration and transformation of iodine species in the Hanford subsurface environment. These impacts are relevant because remedies that target individual contaminants like iodine, may not only impact the fate and transport of other contaminants in the subsurface, but also inhibit the effectiveness of a targeted remedy. For example, iodine (as iodate) co-precipitates with calcite, and has been identified as a potential remedy because it immobilizes iodine. Since uranium also co-precipitates with calcite in field sediments, the presence of uranium may also inhibit iodine co-precipitation. Another potentiallymore » significant impact from co-existing contaminants is iodine and nitrate. The presence of nitrate has been shown to promote biogeochemical reduction of iodate to iodide, thereby increasing iodine species subsurface mobility (as iodide exhibits less sorption). Hence, this study reports on both laboratory batch and column experiments that investigated a) the change in iodate uptake mass and rate of uptake into precipitating calcite due to the presence of differing amounts of uranium, b) the amount of change of the iodate bio-reduction rate due to the presence of differing nitrate concentrations, and c) whether nitrite can reduce iodate in the presence of microbes and/or minerals acting as catalysts.« less

Analysis of IAEA Environmental Samples for Plutonium and Uranium by ICP/MS in Support Of International Safeguards

DOE Office of Scientific and Technical Information (OSTI.GOV)

Farmer, Orville T.; Olsen, Khris B.; Thomas, May-Lin P.

2008-05-01

A method for the separation and determination of total and isotopic uranium and plutonium by ICP-MS was developed for IAEA samples on cellulose-based media. Preparation of the IAEA samples involved a series of redox chemistries and separations using TRU® resin (Eichrom). The sample introduction system, an APEX nebulizer (Elemental Scientific, Inc), provided enhanced nebulization for a several-fold increase in sensitivity and reduction in background. Application of mass bias (ALPHA) correction factors greatly improved the precision of the data. By combining the enhancements of chemical separation, instrumentation and data processing, detection levels for uranium and plutonium approached high attogram levels.

Proteome changes in rat serum after a chronic ingestion of enriched uranium: Toward a biological signature of internal contamination and radiological effect.

PubMed

Petitot, F; Frelon, S; Chambon, C; Paquet, F; Guipaud, O

2016-08-22

The civilian and military use of uranium results in an increased risk of human exposure. The toxicity of uranium results from both its chemical and radiological properties that vary with isotopic composition. Validated biomarkers of health effects associated with exposure to uranium are neither sensitive nor specific to uranium radiotoxicity and/or radiological effect. This study aimed at investigating if serum proteins could be useful as biomarkers of both uranium exposure and radiological effect. Male Sprague-Dawley rats were chronically exposed through drinking water to low levels (40mg/L, corresponding to 1mg of uranium per animal per day) of either 4% (235)U-enriched uranium (EU) or 12% EU during 6 weeks. A proteomics approach based on two-dimensional electrophoresis (2D-DIGE) and mass spectrometry (MS) was used to establish protein expression profiles that could be relevant for discriminating between groups, and to identify some differentially expressed proteins following uranium ingestion. It demonstrated that the expressions of 174 protein spots over 1045 quantified spots were altered after uranium exposure (p<0.05). Using both inferential and non-supervised multivariate statistics, we show sets of spots features that lead to a clear discrimination between controls and EU exposed groups on the one hand (21 spots), and between 4% EU and 12% EU on the other hand (7 spots), showing that investigation of the serum proteome may possibly be of relevance to address both uranium contamination and radiological effect. Finally, using bioinformatics tools, pathway analyses of differentially expressed MS-identified proteins find that acute phase, inflammatory and immune responses as well as oxidative stress are likely involved in the response to contamination, suggesting a physiological perturbation, but that does not necessarily lead to a toxic effect. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Fabrication of thorium bearing carbide fuels

DOEpatents

Gutierrez, Rueben L.; Herbst, Richard J.; Johnson, Karl W. R.

1981-01-01

Thorium-uranium carbide and thorium-plutonium carbide fuel pellets have been fabricated by the carbothermic reduction process. Temperatures of 1750.degree. C. and 2000.degree. C. were used during the reduction cycle. Sintering temperatures of 1800.degree. C. and 2000.degree. C. were used to prepare fuel pellet densities of 87% and >94% of theoretical, respectively. The process allows the fabrication of kilogram quantities of fuel with good reproducibility of chemicals and phase composition. Methods employing liquid techniques that form carbide microspheres or alloying-techniques which form alloys of thorium-uranium or thorium-plutonium suffer from limitation on the quantities processed of because of criticality concerns and lack of precise control of process conditions, respectively.

In situ remediation of uranium contaminated groundwater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dwyer, B.P.; Marozas, D.C.

1997-02-01

In an effort to develop cost-efficient techniques for remediating uranium contaminated groundwater at DOE Uranium Mill Tailing Remedial Action (UMTRA) sites nationwide, Sandia National Laboratories (SNL) deployed a pilot scale research project at an UMTRA site in Durango, CO. Implementation included design, construction, and subsequent monitoring of an in situ passive reactive barrier to remove Uranium from the tailings pile effluent. A reactive subsurface barrier is produced by emplacing a reactant material (in this experiment various forms of metallic iron) in the flow path of the contaminated groundwater. Conceptually the iron media reduces and/or adsorbs uranium in situ to acceptablemore » regulatory levels. In addition, other metals such as Se, Mo, and As have been removed by the reductive/adsorptive process. The primary objective of the experiment was to eliminate the need for surface treatment of tailing pile effluent. Experimental design, and laboratory and field results are discussed with regard to other potential contaminated groundwater treatment applications.« less

In situ remediation of uranium contaminated groundwater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dwyer, B.P.; Marozas, D.C.

1997-12-31

In an effort to develop cost-efficient techniques for remediating uranium contaminated groundwater at DOE Uranium Mill Tailing Remedial Action (UMTRA) sites nationwide, Sandia National Laboratories (SNL) deployed a pilot scale research project at an UMTRA site in Durango, CO. Implementation included design, construction, and subsequent monitoring of an in situ passive reactive barrier to remove Uranium from the tailings pile effluent. A reactive subsurface barrier is produced by emplacing a reactant material (in this experiment - various forms of metallic iron) in the flow path of the contaminated groundwater. Conceptually the iron media reduces and/or adsorbs uranium in situ tomore » acceptable regulatory levels. In addition, other metals such as Se, Mo, and As have been removed by the reductive/adsorptive process. The primary objective of the experiment was to eliminate the need for surface treatment of tailing pile effluent. Experimental design, and laboratory and field preliminary results are discussed with regard to other potential contaminated groundwater treatment applications.« less

Illicit Trafficking of Natural Radionuclides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Friedrich, Steinhaeusler; Lyudmila, Zaitseva

2008-08-07

Natural radionuclides have been subject to trafficking worldwide, involving natural uranium ore (U 238), processed uranium (yellow cake), low enriched uranium (<20% U 235) or highly enriched uranium (>20% U 235), radium (Ra 226), polonium (Po 210), and natural thorium ore (Th 232). An important prerequisite to successful illicit trafficking activities is access to a suitable logistical infrastructure enabling an undercover shipment of radioactive materials and, in case of trafficking natural uranium or thorium ore, capable of transporting large volumes of material. Covert en route diversion of an authorised uranium transport, together with covert diversion of uranium concentrate from anmore » operating or closed uranium mines or mills, are subject of case studies. Such cases, involving Israel, Iran, Pakistan and Libya, have been analyzed in terms of international actors involved and methods deployed. Using international incident data contained in the Database on Nuclear Smuggling, Theft and Orphan Radiation Sources (DSTO) and international experience gained from the fight against drug trafficking, a generic Trafficking Pathway Model (TPM) is developed for trafficking of natural radionuclides. The TPM covers the complete trafficking cycle, ranging from material diversion, covert material transport, material concealment, and all associated operational procedures. The model subdivides the trafficking cycle into five phases: (1) Material diversion by insider(s) or initiation by outsider(s); (2) Covert transport; (3) Material brokerage; (4) Material sale; (5) Material delivery. An Action Plan is recommended, addressing the strengthening of the national infrastructure for material protection and accounting, development of higher standards of good governance, and needs for improving the control system deployed by customs, border guards and security forces.« less

Illicit Trafficking of Natural Radionuclides

NASA Astrophysics Data System (ADS)

Friedrich, Steinhäusler; Lyudmila, Zaitseva

2008-08-01

Natural radionuclides have been subject to trafficking worldwide, involving natural uranium ore (U 238), processed uranium (yellow cake), low enriched uranium (<20% U 235) or highly enriched uranium (>20% U 235), radium (Ra 226), polonium (Po 210), and natural thorium ore (Th 232). An important prerequisite to successful illicit trafficking activities is access to a suitable logistical infrastructure enabling an undercover shipment of radioactive materials and, in case of trafficking natural uranium or thorium ore, capable of transporting large volumes of material. Covert en route diversion of an authorised uranium transport, together with covert diversion of uranium concentrate from an operating or closed uranium mines or mills, are subject of case studies. Such cases, involving Israel, Iran, Pakistan and Libya, have been analyzed in terms of international actors involved and methods deployed. Using international incident data contained in the Database on Nuclear Smuggling, Theft and Orphan Radiation Sources (DSTO) and international experience gained from the fight against drug trafficking, a generic Trafficking Pathway Model (TPM) is developed for trafficking of natural radionuclides. The TPM covers the complete trafficking cycle, ranging from material diversion, covert material transport, material concealment, and all associated operational procedures. The model subdivides the trafficking cycle into five phases: (1) Material diversion by insider(s) or initiation by outsider(s); (2) Covert transport; (3) Material brokerage; (4) Material sale; (5) Material delivery. An Action Plan is recommended, addressing the strengthening of the national infrastructure for material protection and accounting, development of higher standards of good governance, and needs for improving the control system deployed by customs, border guards and security forces.

Diffusive parameters of tritiated water and uranium in chalk

DOE Office of Scientific and Technical Information (OSTI.GOV)

Descostes, M.; UMR 8587 CEA, Universite d'Evry, CNRS,; Pili, E.

2012-07-15

The Cretaceous Chalk of North-western Europe exhibits a double porosity (matrix and fracture) providing pathways for both slow and rapid flow of water. The present study aims at understanding and predicting the contaminant transfer properties through a significant section of this formation, with a particular emphasis on diffusion. This requires to study the nature of porosity and to perform diffusion experiments in representative samples using uranium and tritiated water (HTO), respectively taken as a reactive tracer and an inert one. The diffusive parameters, i.e. the accessible porosity and the effective diffusion coefficient were determined. Additional information was obtained with mercurymore » porosimetry, gravimetric water content, textural and mineralogical characterization. The diffusion tests performed with HTO appear to be the best method to measure the total accessible porosity in any type of porous media, especially those having large pore size distributions. Our study demonstrates that classical gravimetric water content measurements are not sensitive to the reduction in pore size as opposed to HTO diffusion tests because capillary water is not extracted by conventional gravimetric method but can still be probed by diffusion experiments. We found effective diffusion coefficients D{sub e}(U(VI)) near 4 x 10{sup -10} m{sup 2}s{sup -1}). The slower migration of U(VI) compared to HTO indicates sorption, with R{sub d}(U(VI)) from 100 to 360 mL g{sup -1}. These values are one order of magnitude larger than other determinations of the U(VI) sorption coefficient because only the matrix porosity is concerned here. The migration of U(VI) in chalk is only limited by sorption on ancillary Fe-Pb-bearing minerals. Transport of HTO and U(VI) is independent of the porosity distribution. Uranium diffusion in the chalk matrix porosity is fast enough to allow the total invasion of the pore space within characteristic time scales of the order of 1000 years. This results in a partitioning of uranium velocities in fracture flow and matrix flow proportionally to the respective fracture and matrix porosities. (authors)« less

SUMMARY TECHNICAL REPORT FOR THE PERIOD JANUARY 1, 1961-MARCH 31, 1961

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burgett, R. ed

1961-05-01

Uranium and TBP Recovery from Waste Solvent. Laboratory and pilot-scale tests were carried out which demonstrated (1) that uranium in waste solvent can be removed by slurrying the solvent with activated charcoal, filtering the slurry, and washing the slurry with water and 3% Na/sub 2/CO/sub 3/ and (2) that TBP can be recovered from the waste solvent by splitting the solvent with HCl and distilling the TBP-rich phase. Improvement of Green Salt Quality. Denitration of ammonium uranyl trinitrate yielded a light, finely divided form of gamma -UO/ sub 3/ with a surface area higher than that of conventional batch potmore » powder; however, its reactivity in reduction and hydrofluorination tests was only moderately higher in comparison. Oxidation-reduction cycles were found to increase the reactivity of UO/sub 2/ toward hydrofluorination. The properties of various UO/sub 2/ samples were determined and correlated with the preparative methods used. Dehydration of Winlo Green Salt. About 27 tons of Winlo green salt was successfully dehydrated to a water content of -0.04% in a hydrofluorination reactor bank in the Green Salt Plant. Recovery of Uranium from MgF/sub 2/ Slag. A process for continuously digesting MgF/sub 2/ slag for uranium recovery was successfully tested on a plant scale. In this process, a water slurry of slag is transferred at a fixed rate and reacted with HCl, and the controlled feed rate reduces the hydrogen concentration. Graphite Liner for Bomb Reduction of Green Salt. An evaluation was made on machined graphite as a replacement for jolt-packed MgF/sub 2/ presently used to line reduction vessels for uranium metal production. Best results were obtained with a onepiece graphite liner fitted inside a steel vessel with an annulus of MgF/sub 2/ between liner and pot. Effects of Feed Material on Ingot Chemical Purity and Yields. The effects of various types of uranium feed stock on the chemical purity and yield of ingots were studied. The following results were obtained: (1) The H content was higher in ingots cast from melts contairing more derby material, (2) the O, N, and C contents of samples from ingot tops were signiicantly lower than those from ingot bottoms, (3) the crude ingot yields were lowest for pigots, briquettes, and heat-shocked grade III derbies, (4) pigots were deleterious to ingot chemical purity, (5) degreased drip crops and dingot extrnsion scrap were deleterious to core-to-good-core yield. Alpha Annealing of Uranium. The effect of a high alpha temperature anneal on the structure and growin index of beta heat treated uranium was evaluated. It was found that longer alpha annealing times gave greater recrystallization and that higher temperatures gave more rapid recrystallization. Delays of up to 6 months between beta heat treatment and alpha anneal did not affect either the recrystallization or the growth index. Billet Drilling. A LeBlond-Carlstedt Rapid Borer was tested as a urarium billet drilling machine and found to give satisfactory results, although some tool breakage occurred. (D.L.C.)« less

Detection of biological uranium reduction using magnetic resonance.

PubMed

Vogt, Sarah J; Stewart, Brandy D; Seymour, Joseph D; Peyton, Brent M; Codd, Sarah L

2012-04-01

The conversion of soluble uranyl ions (UO₂²⁺) by bacterial reduction to sparingly soluble uraninite (UO₂(s)) is being studied as a way of immobilizing subsurface uranium contamination. Under anaerobic conditions, several known types of bacteria including iron and sulfate reducing bacteria have been shown to reduce U (VI) to U (IV). Experiments using a suspension of uraninite (UO₂(s)) particles produced by Shewanella putrefaciens CN32 bacteria show a dependence of both longitudinal (T₁) and transverse (T₂) magnetic resonance (MR) relaxation times on the oxidation state and solubility of the uranium. Gradient echo and spin echo MR images were compared to quantify the effect caused by the magnetic field fluctuations (T*₂) of the uraninite particles and soluble uranyl ions. Since the precipitate studied was suspended in liquid water, the effects of concentration and particle aggregation were explored. A suspension of uraninite particles was injected into a polysaccharide gel, which simulates the precipitation environment of uraninite in the extracellular biofilm matrix. A reduction in the T₂ of the gel surrounding the particles was observed. Tests done in situ using three bioreactors under different mixing conditions, continuously stirred, intermittently stirred, and not stirred, showed a quantifiable T₂ magnetic relaxation effect over the extent of the reaction. Copyright © 2011 Wiley Periodicals, Inc.

Speciation and reactivity of uranium products formed during in situ bioremediation in a shallow alluvial aquifer.

PubMed

Alessi, Daniel S; Lezama-Pacheco, Juan S; Janot, Noémie; Suvorova, Elena I; Cerrato, José M; Giammar, Daniel E; Davis, James A; Fox, Patricia M; Williams, Kenneth H; Long, Philip E; Handley, Kim M; Bernier-Latmani, Rizlan; Bargar, John R

2014-11-04

In this study, we report the results of in situ U(VI) bioreduction experiments at the Integrated Field Research Challenge site in Rifle, Colorado, USA. Columns filled with sediments were deployed into a groundwater well at the site and, after a period of conditioning with groundwater, were amended with a mixture of groundwater, soluble U(VI), and acetate to stimulate the growth of indigenous microorganisms. Individual reactors were collected as various redox regimes in the column sediments were achieved: (i) during iron reduction, (ii) just after the onset of sulfate reduction, and (iii) later into sulfate reduction. The speciation of U retained in the sediments was studied using X-ray absorption spectroscopy, electron microscopy, and chemical extractions. Circa 90% of the total uranium was reduced to U(IV) in each reactor. Noncrystalline U(IV) comprised about two-thirds of the U(IV) pool, across large changes in microbial community structure, redox regime, total uranium accumulation, and reaction time. A significant body of recent research has demonstrated that noncrystalline U(IV) species are more suceptible to remobilization and reoxidation than crystalline U(IV) phases such as uraninite. Our results highlight the importance of considering noncrystalline U(IV) formation across a wide range of aquifer parameters when designing in situ remediation plans.

Speciation and Reactivity of Uranium Products Formed during in Situ Bioremediation in a Shallow Alluvial Aquifer

PubMed Central

2015-01-01

In this study, we report the results of in situ U(VI) bioreduction experiments at the Integrated Field Research Challenge site in Rifle, Colorado, USA. Columns filled with sediments were deployed into a groundwater well at the site and, after a period of conditioning with groundwater, were amended with a mixture of groundwater, soluble U(VI), and acetate to stimulate the growth of indigenous microorganisms. Individual reactors were collected as various redox regimes in the column sediments were achieved: (i) during iron reduction, (ii) just after the onset of sulfate reduction, and (iii) later into sulfate reduction. The speciation of U retained in the sediments was studied using X-ray absorption spectroscopy, electron microscopy, and chemical extractions. Circa 90% of the total uranium was reduced to U(IV) in each reactor. Noncrystalline U(IV) comprised about two-thirds of the U(IV) pool, across large changes in microbial community structure, redox regime, total uranium accumulation, and reaction time. A significant body of recent research has demonstrated that noncrystalline U(IV) species are more suceptible to remobilization and reoxidation than crystalline U(IV) phases such as uraninite. Our results highlight the importance of considering noncrystalline U(IV) formation across a wide range of aquifer parameters when designing in situ remediation plans. PMID:25265543

Estimates of radiological risk from depleted uranium weapons in war scenarios.

PubMed

Durante, Marco; Pugliese, Mariagabriella

2002-01-01

Several weapons used during the recent conflict in Yugoslavia contain depleted uranium, including missiles and armor-piercing incendiary rounds. Health concern is related to the use of these weapons, because of the heavy-metal toxicity and radioactivity of uranium. Although chemical toxicity is considered the more important source of health risk related to uranium, radiation exposure has been allegedly related to cancers among veterans of the Balkan conflict, and uranium munitions are a possible source of contamination in the environment. Actual measurements of radioactive contamination are needed to assess the risk. In this paper, a computer simulation is proposed to estimate radiological risk related to different exposure scenarios. Dose caused by inhalation of radioactive aerosols and ground contamination induced by Tomahawk missile impact are simulated using a Gaussian plume model (HOTSPOT code). Environmental contamination and committed dose to the population resident in contaminated areas are predicted by a food-web model (RESRAD code). Small values of committed effective dose equivalent appear to be associated with missile impacts (50-y CEDE < 5 mSv), or population exposure by water-independent pathways (50-y CEDE < 80 mSv). The greatest hazard is related to the water contamination in conditions of effective leaching of uranium in the groundwater (50-y CEDE < 400 mSv). Even in this worst case scenario, the chemical toxicity largely predominates over radiological risk. These computer simulations suggest that little radiological risk is associated to the use of depleted uranium weapons.

Composition, stability, and measurement of reduced uranium phases for groundwater bioremediation at Old Rifle, CO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Campbell, K. M.; Davis, J. A.; Bargar, J.

2011-10-15

Reductive biostimulation is currently being explored as a possible remediation strategy for uranium (U) contaminated groundwater, and is currently being investigated at a field site in Rifle, CO, USA. The long-term stability of the resulting U(IV) phases is a key component of the overall performance and depends upon a variety of factors, including rate and mechanism of reduction, mineral associations in the subsurface, and propensity for oxidation. To address these factors, several approaches were used to evaluate the redox sensitivity of U: measurement of the rate of oxidative dissolution of biogenic uraninite (UO{sub 2(s)}) deployed in groundwater at Rifle, characterizationmore » of a zone of natural bioreduction exhibiting relevant reduced mineral phases, and laboratory studies of the oxidative capacity of Fe(III) and reductive capacity of Fe(II) with regard to U(IV) and U(VI), respectively.« less

Direct Electrodeposition of UO2 from Uranyl Bis(trifluoromethanesulfonyl)imide Dissolved in 1-Ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide Room Temperature Ionic Liquid System

DOE PAGES

Freiderich, John W.; Wanigasekara, Eranda P.; Sun, Xiao-Guang; ...

2013-11-11

Our study demonstrates a direct electrodeposition of UO 2 at a Pt cathode from a solution of uranyl bis(trifluoromethanesulfonyl)imide [UO 2(NTf 2) 2)] in a bulk room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMIM +NTf 2 –). Cyclic voltammetry (CV) studies revealed two reduction waves corresponding to the conversion of uranium(VI) to uranium(IV), and a mechanism for the overall electroreduction is proposed. A controlled-potential experiment was performed, holding the reduction potential at–1.0 V for 24 h to obtain a brown-black deposit of UO 2 on the Pt cathode. The Faradaic efficiency of the reduction process was determined to be >80%. Themore » UO 2deposit was characterized by powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS).« less

40 CFR 471.71 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2012 CFR

2012-07-01

... SOURCE CATEGORY Uranium Forming Subcategory § 471.71 Effluent limitations representing the degree of... off-pounds) of uranium extruded Cadium 0.117 0.052 Chromium 0.152 0.062 Copper 0.654 0.344 Lead 0.145 0.069 Nickel 0.661 0.437 Fluoride 20.5 9.08 Molybdenum 2.28 1.18 Oil and grease 6.88 4.13 TSS 14.1 6...

40 CFR 471.71 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2014 CFR

2014-07-01

... SOURCE CATEGORY Uranium Forming Subcategory § 471.71 Effluent limitations representing the degree of... off-pounds) of uranium extruded Cadium 0.117 0.052 Chromium 0.152 0.062 Copper 0.654 0.344 Lead 0.145 0.069 Nickel 0.661 0.437 Fluoride 20.5 9.08 Molybdenum 2.28 1.18 Oil and grease 6.88 4.13 TSS 14.1 6...

40 CFR 471.71 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2013 CFR

2013-07-01

... SOURCE CATEGORY Uranium Forming Subcategory § 471.71 Effluent limitations representing the degree of... off-pounds) of uranium extruded Cadium 0.117 0.052 Chromium 0.152 0.062 Copper 0.654 0.344 Lead 0.145 0.069 Nickel 0.661 0.437 Fluoride 20.5 9.08 Molybdenum 2.28 1.18 Oil and grease 6.88 4.13 TSS 14.1 6...

Desferrithiocin Analogue Uranium Decorporation Agents

PubMed Central

Bergeron, Raymond J.; Wiegand, Jan; Singh, Shailendra

2010-01-01

Purpose Previous systematic structure-activity studies of the desferrithiocin (DFT) platform have allowed the design and synthesis of analogues and derivatives of DFT that retain the exceptional iron-clearing activity of the parent, while eliminating its adverse effects. We hypothesized that a similar approach could be adopted to identify DFT-related analogues that could effectively decorporate uranium. Materials and Methods The decorporation properties of nine DFT-related analogues were determined in a bile duct-cannulated rat model. Diethylenetriaminepentaacetic acid (DTPA) served as a positive control. Selected ligands also underwent multiple and delayed dosing regimens. Uranium excretion in urine and bile or stool was determined by inductively coupled plasma mass spectroscopy (ICP-MS); tissue levels of uranium were also assessed. Results The two best clinical candidates are (S)-4,5-dihydro-2-[2-hydroxy-4-(3,6,9-trioxadecyloxy)phenyl]-4-methyl-4-thiazolecarboxylic acid [(S)-4'-(HO)-DADFT-PE (9)], with a 57% reduction in kidney uranium levels on oral (p.o.) administration and (S)-4,5-dihydro-2-[2-hydroxy-3-(3,6,9-trioxadecyloxy)phenyl]-4-methyl-4-thiazolecarboxylic acid [(S)-3'-(HO)-DADFT-PE (10)], with a 62% renal reduction on p.o. administration. The majority of the metal excretion promoted by these analogues is in the bile, thus further reducing kidney actinide exposure. Conclusions While 9 administered p.o. or subcutaneously (s.c.) immediately post-metal is an effective decorporation agent, withholding the dose (s.c.) until 4 h reduced the activity of the compound. Conversion of 9 to its isopropyl ester may circumvent this issue. PMID:19399680

Factors controlling localization of uranium deposits in the Dakota Sandstone, Gallup and Ambrosia Lake mining districts, McKinley County, New Mexico

USGS Publications Warehouse

Pierson, Charles Thomas; Green, Morris W.

1977-01-01

Geologic studies were made at all of the uranium mines and prospects in the Dakota Sandstone of Early(?) and Late Cretaceous age in the Gallup mining district, McKinley County, New Mexico. Dakota mines in the adjacent Ambrosia Lake mining district were visited briefly for comparative purposes. Mines in the eastern part of the Gallup district, and in the Ambrosia Lake district, are on the Chaco slope of the southern San Juan Basin in strata which dip gently northward toward the central part of the basin. Mines in the western part of the Gallup district are along the Gallup hogback (Nutria monocline) in strata which dip steeply westward into the Gallup sag. Geologic factors which controlled formation of the uranium deposits in the Dakota Sandstone are: (1) a source of uranium, believed to be uranium deposits of the underlying Morrison Formation of Late Jurassic age; (2) the accessibility to the Dakota of uranium-bearing solutions from the Morrison; (3) the presence in the Dakota of permeable sandstone beds overlain by impermeable carbonaceous shale beds; and (4) the occurrence within the permeable Dakota sandstone beds of carbonaceous reducing material as bedding-plane laminae, or as pockets of carbonaceous trash. Most of the Dakota uranium deposits are found in the lower part of the formation in marginal-marine distributary-channel sandstones which were deposited in the backshore environment. However, the Hogback no. 4 (Hyde) Mine (Gallup district) occurs in sandy paludal shale of the backshore environment, and another deposit, the Silver Spur (Ambrosia Lake district), is found in what is interpreted to be a massive beach or barrier-bar sandstone of the foreshore environment in the upper part of the Dakota. The sedimentary depositional environment most favorable for the accumulation of uranium is that of backshore areas lateral to main distributary channels, where levee, splay, and some distributary-channel sandstones intertongue with gray carbonaceous shales and siltstones of the well-drained swamp environment. Deposits of black carbonaceous shale which were formed in the poorly drained swamp deposits of the interfluve area are not favorable host rocks for uranium. The depositional energy levels of the various environments in which the sandstone and shale beds of the Dakota were deposited govern the relative favorability of the strata as uranium host rocks. In the report area, uranium usually occurs in carbonaceous sandstone deposited under low- to medium-energy fluvial conditions within distributary channels. A prerequisite, however, is that such sandstone be overlain by impermeable carbonaceous shale beds. Low- to medium-energy fluvial conditions result in the deposition of sandstone beds having detrital carbonaceous material distributed in laminae or in trash pockets on bedding planes. The carbonaceous laminae and trash pockets provide the necessary reductant to cause precipitation of uranium from solution. High-energy fluvial conditions result in the deposition of sandstones having little or no carbonaceous material included to provide a reductant. Very low energy swampy conditions result in carbonaceous shale deposits, which are generally barren of uranium because of their relative impermeability to migrating uranium-bearing solutions.

A model of early formation of uranium molecular oxides in laser-ablated plasmas

NASA Astrophysics Data System (ADS)

Finko, Mikhail; Curreli, Davide; Azer, Magdi; Weisz, David; Crowhurst, Jonathan; Rose, Timothy; Koroglu, Batikan; Radousky, Harry; Zaug, Joseph; Armstrong, Mike

2017-10-01

An important problem within the field of nuclear forensics is fractionation: the formation of post-detonation nuclear debris whose composition does not reflect that of the source weapon. We are investigating uranium fractionation in rapidly cooling plasma using a combined experimental and modeling approach. In particular, we use laser ablation of uranium metal samples to produce a low-temperature plasma with physical conditions similar to a condensing nuclear fireball. Here we present a first plasma-chemistry model of uranium molecular species formation during the early stage of laser ablated plasma evolution in atmospheric oxygen. The system is simulated using a global kinetic model with rate coefficients calculated according to literature data and the application of reaction rate theory. The model allows for a detailed analysis of the evolution of key uranium molecular species and represents the first step in producing a uranium fireball model that is kinetically validated against spatially and temporally resolved spectroscopy measurements. This project was sponsored by the DoD, Defense Threat Reduction Agency, Grant HDTRA1-16- 1-0020. This work was performed in part under the auspices of the U.S. DoE by Lawrence Livermore National Laboratory under Contract DE-AC52- 07NA27344.

Calixarene cleansing formulation for uranium skin contamination.

PubMed

Phan, Guillaume; Semili, Naïma; Bouvier-Capely, Céline; Landon, Géraldine; Mekhloufi, Ghozlene; Huang, Nicolas; Rebière, François; Agarande, Michelle; Fattal, Elias

2013-10-01

An oil-in-water cleansing emulsion containing calixarene molecule, an actinide specific chelating agent, was formulated in order to improve the decontamination of uranium from the skin. Commonly commercialized cosmetic ingredients such as surfactants, mineral oil, or viscosifying agents were used in preparing the calixarene emulsion. The formulation was characterized in terms of size and apparent viscosity measurements and then was tested for its ability to limit uranyl ion permeation through excoriated pig-ear skin explants in 24-h penetration studies. Calixarene emulsion effectiveness was compared with two other reference treatments consisting of DTPA and EHBP solutions. Application of calixarene emulsion induced the highest decontamination effect with an 87% decrease in uranium diffusion flux. By contrast, EHBP and DTPA solutions only allowed a 50% and 55% reduction of uranium permeation, respectively, and had the same effect as a simple dilution of the contamination by pure water. Uranium diffusion decrease was attributed to uranyl ion-specific chelation by calixarene within the formulation, since no significant effect was obtained after application of the same emulsion without calixarene. Thus, calixarene cleansing emulsion could be considered as a promising treatment in case of accidental contamination of the skin by highly diffusible uranium compounds.

Fractionation of 238U/235U by reduction during low temperature uranium mineralisation processes

NASA Astrophysics Data System (ADS)

Murphy, Melissa J.; Stirling, Claudine H.; Kaltenbach, Angela; Turner, Simon P.; Schaefer, Bruce F.

2014-02-01

Investigations of ‘stable’ uranium isotope fractionation during low temperature, redox transformations may provide new insights into the usefulness of the 238U/235U isotope system as a tracer of palaeoredox processes. Sandstone-hosted uranium deposits accumulate at an oxidation/reduction interface within an aquifer from the low temperature reduction of soluble U(VI) complexes in groundwaters, forming insoluble U(IV) minerals. This setting provides an ideal environment in which to investigate the effects of redox transformations on 238U/235U fractionation. Here we present the first coupled measurements of 238U/235U isotopic compositions and U concentrations for groundwaters and mineralised sediment samples from the same redox system in the vicinity of the high-grade Pepegoona sandstone-hosted uranium deposit, Australia. The mineralised sediment samples display extremely variable 238U/235U ratios (herein expressed as δUCRM145238, the per-mil deviation from the international NBL standard CRM145). The majority of mineralised sediment samples have δUCRM145238 values between -1.30±0.05 and 0.55±0.12‰, spanning a ca. 2‰ range. However, one sample has an unusually light isotopic composition of -4.13±0.05‰, which suggests a total range of U isotopic variability of up to ca. 5‰, the largest variation found thus far in a single natural redox system. The 238U/235U isotopic signature of the mineralised sediments becomes progressively heavier (enriched in 238U) along the groundwater flow path. The groundwaters show a greater than 2‰ variation in their 238U/235U ratios, ranging from δUCRM145238 values of -2.39±0.07 to -0.71±0.05‰. The majority of the groundwater data exhibit a clear systematic relationship between 238U/235U isotopic composition and U concentration; samples with the lowest U concentrations have the lowest 238U/235U ratios. The preferential incorporation of 238U during reduction of U(VI) to U(IV) and precipitation of uranium minerals leaves the groundwaters enriched in 235U, resulting in a progressive shift in 238U/235U towards lighter values in the aqueous phase as U is removed. These data can be modelled by a closed system Rayleigh fractionation model, with a fractionation factor (α, representing the 238U/235U composition of the groundwater relative to the solid uranium minerals) ranging from ∼0.9996 to 1.0000, with the majority of datapoints ranging from α values of 0.9998 to 0.9999. The sense and magnitude of the results of this study imply that 238U/235U fractionation is likely to be controlled by volume-dependent nuclear field shift effects during the reduction of U(VI) to U(IV) during mineralisation processes. These findings support the use of the 238U/235U isotopic system as a tracer to constrain the nature and timing of palaeoredox conditions.

Uranium(VI) Reduction by Anaeromyxobacter dehalogenans Strain 2CP-C

PubMed Central

Wu, Qingzhong; Sanford, Robert A.; Löffler, Frank E.

2006-01-01

Previous studies demonstrated growth of Anaeromyxobacter dehalogenans strain 2CP-C with acetate or hydrogen as the electron donor and Fe(III), nitrate, nitrite, fumarate, oxygen, or ortho-substituted halophenols as electron acceptors. In this study, we explored and characterized U(VI) reduction by strain 2CP-C. Cell suspensions of fumarate-grown 2CP-C cells reduced U(VI) to U(IV). More-detailed growth studies demonstrated that hydrogen was the required electron donor for U(VI) reduction and could not be replaced by acetate. The addition of nitrate to U(VI)-reducing cultures resulted in a transitory increase in U(VI) concentration, apparently caused by the reoxidation of reduced U(IV), but U(VI) reduction resumed following the consumption of N-oxyanions. Inhibition of U(VI) reduction occurred in cultures amended with Fe(III) citrate, or citrate. In the presence of amorphous Fe(III) oxide, U(VI) reduction proceeded to completion but the U(VI) reduction rates decreased threefold compared to control cultures. Fumarate and 2-chlorophenol had no inhibitory effects on U(VI) reduction, and both electron acceptors were consumed concomitantly with U(VI). Since cocontaminants (e.g., nitrate, halogenated compounds) and bioavailable ferric iron are often encountered at uranium-impacted sites, the metabolic versatility makes Anaeromyxobacter dehalogenans a promising model organism for studying the complex interaction of multiple electron acceptors in U(VI) reduction and immobilization. PMID:16672509

Preparation of new nano magnetic material Fe3O4@g-C3N4 and good adsorption performance on uranium ion

NASA Astrophysics Data System (ADS)

Long, Wei; Liu, Huijun; Yan, Xueming; Fu, Li

2018-03-01

A new nano magnetic material Fe3O4@g-C3N4 was prepared by deposition reduction method, which performed good adsorption performance to uranium ion. Characterization results showed that the g-C3N4 particles were wrapped around the nano magnetic Fe3O4 particles, and the textural properties of this material was improved, so the adsorption performance to uranium ion was good. Adsorption experiments of this material demonstrated that the optimum pH value was 10, the optimum mass of adsorbent was 6.5 mg and the optimum adsorption time was 150 min in the initial concentration of 140 mg/L uranium ion solution system, and the maximum adsorption capacity was up to 352.1 mg/g and the maximum adsorption rate was more than 90%.

Comparison of Analytical Methods for the Determination of Uranium in Seawater Using Inductively Coupled Plasma Mass Spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wood, Jordana R.; Gill, Gary A.; Kuo, Li-Jung

2016-04-20

Trace element determinations in seawater by inductively coupled plasma mass spectrometry are analytically challenging due to the typically very low concentrations of the trace elements and the potential interference of the salt matrix. In this study, we did a comparison for uranium analysis using inductively coupled plasma mass spectrometry (ICP-MS) of Sequim Bay seawater samples and three seawater certified reference materials (SLEW-3, CASS-5 and NASS-6) using seven different analytical approaches. The methods evaluated include: direct analysis, Fe/Pd reductive precipitation, standard addition calibration, online automated dilution using an external calibration with and without matrix matching, and online automated pre-concentration. The methodmore » which produced the most accurate results was the method of standard addition calibration, recovering uranium from a Sequim Bay seawater sample at 101 ± 1.2%. The on-line preconcentration method and the automated dilution with matrix-matched calibration method also performed well. The two least effective methods were the direct analysis and the Fe/Pd reductive precipitation using sodium borohydride« less

Bicarbonate Impact on U(VI) Bioreduction in a Shallow Alluvial Aquifer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Long, Philip E.; Williams, Kenneth H.; Davis, James A.

Field-scale biostimulation and desorption tracer experiments conducted in a uranium (U) contaminated, shallow alluvial aquifer have provided insight into the coupling of microbiology, biogeochemistry, and hydrogeology that control U mobility in the subsurface. Initial experiments successfully tested the concept that Fe-reducing bacteria such as Geobacter sp. could enzymatically reduce soluble U(VI) to insoluble U(IV) during in situ electron donor amendment (Anderson et al. 2003, Williams et al. 2011). In parallel, in situ desorption tracer tests using bicarbonate amendment demonstrated rate-limited U(VI) desorption (Fox et al. 2012). These results and prior laboratory studies underscored the importance of enzymatic U(VI)-reduction and suggestedmore » the ability to combine desorption and bioreduction of U(VI). Here we report the results of a new field experiment in which bicarbonate-promoted uranium desorption and acetate amendment were combined and compared to an acetate amendment-only experiment in the same experimental plot. Results confirm that bicarbonate amendment to alluvial aquifer desorbs U(VI) and increases the abundance of Ca-uranyl-carbonato complexes. At the same time, that the rate of acetate-promoted enzymatic U(VI) reduction was greater in the presence of added bicarbonate in spite of the increased dominance of Ca-uranyl-carbonato aqueous complexes. A model-simulated peak rate of U(VI) reduction was ~3.8 times higher during acetate-bicarbonate treatment than under acetate-only conditions. Lack of consistent differences in microbial community structure between acetate-bicarbonate and acetate-only treatments suggest that a significantly higher rate of U(VI) reduction the bicarbonate-impacted sediment may be due to a higher intrinsic rate of microbial reduction induced by elevated concentrations of the bicarbonate oxyanion. The findings indicate that bicarbonate amendment may be useful in improving the engineered bioremediation of uranium in aquifers.« less

Bicarbonate impact on U(VI) bioreduction in a shallow alluvial aquifer

NASA Astrophysics Data System (ADS)

Long, Philip E.; Williams, Kenneth H.; Davis, James A.; Fox, Patricia M.; Wilkins, Michael J.; Yabusaki, Steven B.; Fang, Yilin; Waichler, Scott R.; Berman, Elena S. F.; Gupta, Manish; Chandler, Darrell P.; Murray, Chris; Peacock, Aaron D.; Giloteaux, Ludovic; Handley, Kim M.; Lovley, Derek R.; Banfield, Jillian F.

2015-02-01

Field-scale biostimulation and desorption tracer experiments conducted in a uranium (U) contaminated, shallow alluvial aquifer have provided insight into the coupling of microbiology, biogeochemistry, and hydrogeology that control U mobility in the subsurface. Initial experiments successfully tested the concept that Fe-reducing bacteria such as Geobacter sp. could enzymatically reduce soluble U(VI) to insoluble U(IV) during in situ electron donor amendment (Anderson et al., 2003; Williams et al., 2011). In parallel, in situ desorption tracer tests using bicarbonate amendment demonstrated rate-limited U(VI) desorption (Fox et al., 2012). These results and prior laboratory studies underscored the importance of enzymatic U(VI)-reduction and suggested the ability to combine desorption and bioreduction of U(VI). Here we report the results of a new field experiment in which bicarbonate-promoted uranium desorption and acetate amendment were combined and compared to an acetate amendment-only experiment in the same experimental plot. Results confirm that bicarbonate amendment to alluvial aquifer sediments desorbs U(VI) and increases the abundance of Ca-uranyl-carbonato complexes. At the same time, the rate of acetate-promoted enzymatic U(VI) reduction was greater in the presence of added bicarbonate in spite of the increased dominance of Ca-uranyl-carbonato aqueous complexes. A model-simulated peak rate of U(VI) reduction was ∼3.8 times higher during acetate-bicarbonate treatment than under acetate-only conditions. Lack of consistent differences in microbial community structure between acetate-bicarbonate and acetate-only treatments suggest that a significantly higher rate of U(VI) reduction in the bicarbonate-impacted sediment may be due to a higher intrinsic rate of microbial reduction induced by elevated concentrations of the bicarbonate oxyanion. The findings indicate that bicarbonate amendment may be useful in improving the engineered bioremediation of uranium in aquifers.

The short-term reduction of uranium by nanoscale zero-valent iron (nZVI): role of oxide shell, reduction mechanism and the formation of U( v )-carbonate phases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsarev, Sergey; Collins, Richard N.; Ilton, Eugene S.

Nanoscale zero-valent iron (nZVI) is a potential remediation agent for uranium-contaminated groundwaters, however, a complete mechanistic understanding of the processes that lead to uranium immobilization has yet to be achieved. In this study, the short-term anoxic reaction of U(VI) with fresh, (anoxic) aged and corroded nZVI particles was investigated under aqueous conditions conducive to the formation of thermodynamically stable U(VI)-Ca-CO3 ternary aqueous complexes. The first stage of the reaction between U(VI) and nZVI was assigned to sorption processes with the formation of surface U(VI)-carbonate complexes. Aged nZVI removed U(VI) faster than either fresh or corroded nZVI and it is hypothesizedmore » that U reduction initially occurs through the transfer of one electron from Fe(II) in the nZVI surface oxide layer. Evidence for reduction to U(V) was obtained through X-ray photoelectron spectroscopy and by determination of U-O bond distances of ~2.05 Å and 2.27 Å by U LIII-edge X-ray absorption spectroscopy detection of U-O bond distances at ~2.05 Å and 2.27 Å with these distances , similar to thoseat observed for the U(V) site in the mixed U(V)/U(VI) carbonate mineral wyartite. Scanning transmission electron microscopy also demonstrated that U was present as a nanoparticulate phase after one day of reaction, rather than a surface complex. Further reduction to U(IV), as observed in previous studies, would appear to be rate-limiting and coincident with the transformation of this meta-stable U-carbonate phase to uraninite (UO2).« less

Metals other than uranium affected microbial community composition in a historical uranium-mining site.

PubMed

Sitte, Jana; Löffler, Sylvia; Burkhardt, Eva-Maria; Goldfarb, Katherine C; Büchel, Georg; Hazen, Terry C; Küsel, Kirsten

2015-12-01

To understand the links between the long-term impact of uranium and other metals on microbial community composition, ground- and surface water-influenced soils varying greatly in uranium and metal concentrations were investigated at the former uranium-mining district in Ronneburg, Germany. A soil-based 16S PhyloChip approach revealed 2358 bacterial and 35 archaeal operational taxonomic units (OTU) within diverse phylogenetic groups with higher OTU numbers than at other uranium-contaminated sites, e.g., at Oak Ridge. Iron- and sulfate-reducing bacteria (FeRB and SRB), which have the potential to attenuate uranium and other metals by the enzymatic and/or abiotic reduction of metal ions, were found at all sites. Although soil concentrations of solid-phase uranium were high, ranging from 5 to 1569 μg·g (dry weight) soil(-1), redundancy analysis (RDA) and forward selection indicated that neither total nor bio-available uranium concentrations contributed significantly to the observed OTU distribution. Instead, microbial community composition appeared to be influenced more by redox potential. Bacterial communities were also influenced by bio-available manganese and total cobalt and cadmium concentrations. Bio-available cadmium impacted FeRB distribution while bio-available manganese and copper as well as solid-phase zinc concentrations in the soil affected SRB composition. Archaeal communities were influenced by the bio-available lead as well as total zinc and cobalt concentrations. These results suggest that (i) microbial richness was not impacted by heavy metals and radionuclides and that (ii) redox potential and secondary metal contaminants had the strongest effect on microbial community composition, as opposed to uranium, the primary source of contamination.

Effects of nitrate on the stability of uranium in a bioreduced region of the subsurface.

PubMed

Wu, Wei-Min; Carley, Jack; Green, Stefan J; Luo, Jian; Kelly, Shelly D; Van Nostrand, Joy; Lowe, Kenneth; Mehlhorn, Tonia; Carroll, Sue; Boonchayanant, Benjaporn; Löfller, Frank E; Watson, David; Kemner, Kenneth M; Zhou, Jizhong; Kitanidis, Peter K; Kostka, Joel E; Jardine, Philip M; Criddle, Craig S

2010-07-01

The effects of nitrate on the stability of reduced, immobilized uranium were evaluated in field experiments at a U.S. Department of Energy site in Oak Ridge, TN. Nitrate (2.0 mM) was injected into a reduced region of the subsurface containing high levels of previously immobilized U(IV). The nitrate was reduced to nitrite, ammonium, and nitrogen gas; sulfide levels decreased; and Fe(II) levels increased then deceased. Uranium remobilization occurred concomitant with nitrite formation, suggesting nitrate-dependent, iron-accelerated oxidation of U(IV). Bromide tracer results indicated changes in subsurface flowpaths likely due to gas formation and/or precipitate. Desorption-adsorption of uranium by the iron-rich sediment impacted uranium mobilization and sequestration. After rereduction of the subsurface through ethanol additions, background groundwater containing high levels of nitrate was allowed to enter the reduced test zone. Aqueous uranium concentrations increased then decreased. Clone library analyses of sediment samples revealed the presence of denitrifying bacteria that can oxidize elemental sulfur, H(2)S, Fe(II), and U(IV) (e.g., Thiobacillus spp.), and a decrease in relative abundance of bacteria that can reduce Fe(III) and sulfate. XANES analyses of sediment samples confirmed changes in uranium oxidation state. Addition of ethanol restored reduced conditions and triggered a short-term increase in Fe(II) and aqueous uranium, likely due to reductive dissolution of Fe(III) oxides and release of sorbed U(VI). After two months of intermittent ethanol addition, sulfide levels increased, and aqueous uranium concentrations gradually decreased to <0.1 microM.

Efficacy of acetate-amended biostimulation for uranium sequestration: Combined analysis of sediment/groundwater geochemistry and bacterial community structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Jie; Veeramani, Harish; Qafoku, Nikolla P.

Systematic flow-through column experiments were conducted using sediments and ground water collected from different subsurface localities at the U.S. Department of Energy's Integrated Field Research Challenge site in Rifle, Colorado. The principal purpose of this study is to gain a better understanding of the interactive effects of groundwater geochemistry, sediment mineralogy, and indigenous bacterial community structures on the efficacy of uranium removal from the groundwater with/without acetate amendment. Overall, we find that the subtle variations in the sediments' mineralogy, redox conditions, as well as contents of metal(loid) co-contaminants showed a pronounced effect on the associated bacterial population and composition, whichmore » mainly determines the system's performance with respect to uranium removal. Positive relationship was identified between the abundance of dissimilatory sulfate-reduction genes (i.e., drsA), markers of sulfate-reducing bacteria, and the sediments' propensity to sequester aqueous uranium. In contrast, no obvious connections were observed between the abundance of common iron-reducing bacteria, e.g., Geobacter spp., and the sediments' ability to sequester uranium. In the sediments with low bacterial biomass and the absence of sulfate-reducing conditions, abiotic adsorption onto mineral surfaces such as phyllosilicates likely played a relatively major role in the attenuation of aqueous uranium; however, in these scenarios, acetate amendment induced detectable rebounds in the effluent uranium concentrations. Lastly, the results of this study suggest that immobilization of uranium can be achieved under predominantly sulfate-reducing conditions, and provide insight into the integrated roles of various biogeochemical components in long-term uranium sequestration.« less

Efficacy of acetate-amended biostimulation for uranium sequestration: Combined analysis of sediment/groundwater geochemistry and bacterial community structure

DOE PAGES

Xu, Jie; Veeramani, Harish; Qafoku, Nikolla P.; ...

2016-12-29

Systematic flow-through column experiments were conducted using sediments and ground water collected from different subsurface localities at the U.S. Department of Energy's Integrated Field Research Challenge site in Rifle, Colorado. The principal purpose of this study is to gain a better understanding of the interactive effects of groundwater geochemistry, sediment mineralogy, and indigenous bacterial community structures on the efficacy of uranium removal from the groundwater with/without acetate amendment. Overall, we find that the subtle variations in the sediments' mineralogy, redox conditions, as well as contents of metal(loid) co-contaminants showed a pronounced effect on the associated bacterial population and composition, whichmore » mainly determines the system's performance with respect to uranium removal. Positive relationship was identified between the abundance of dissimilatory sulfate-reduction genes (i.e., drsA), markers of sulfate-reducing bacteria, and the sediments' propensity to sequester aqueous uranium. In contrast, no obvious connections were observed between the abundance of common iron-reducing bacteria, e.g., Geobacter spp., and the sediments' ability to sequester uranium. In the sediments with low bacterial biomass and the absence of sulfate-reducing conditions, abiotic adsorption onto mineral surfaces such as phyllosilicates likely played a relatively major role in the attenuation of aqueous uranium; however, in these scenarios, acetate amendment induced detectable rebounds in the effluent uranium concentrations. Lastly, the results of this study suggest that immobilization of uranium can be achieved under predominantly sulfate-reducing conditions, and provide insight into the integrated roles of various biogeochemical components in long-term uranium sequestration.« less

40 CFR 471.71 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2010 CFR

2010-07-01

... CATEGORY Uranium Forming Subcategory § 471.71 Effluent limitations representing the degree of effluent... uranium extruded Cadium 0.117 0.052 Chromium 0.152 0.062 Copper 0.654 0.344 Lead 0.145 0.069 Nickel 0.661 0.437 Fluoride 20.5 9.08 Molybdenum 2.28 1.18 Oil and grease 6.88 4.13 TSS 14.1 6.71 pH (1) (1) 1...

40 CFR 471.71 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2011 CFR

2011-07-01

... CATEGORY Uranium Forming Subcategory § 471.71 Effluent limitations representing the degree of effluent... uranium extruded Cadium 0.117 0.052 Chromium 0.152 0.062 Copper 0.654 0.344 Lead 0.145 0.069 Nickel 0.661 0.437 Fluoride 20.5 9.08 Molybdenum 2.28 1.18 Oil and grease 6.88 4.13 TSS 14.1 6.71 pH (1) (1) 1...

High-Quality Draft Genome Sequence of Desulfovibrio carbinoliphilus FW-101-2B, an Organic Acid-Oxidizing Sulfate-Reducing Bacterium Isolated from Uranium(VI)-Contaminated Groundwater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ramsay, Bradley D.; Hwang, Chiachi; Woo, Hannah L.

2015-03-12

Desulfovibrio carbinoliphilus subsp. oakridgensis FW-101-2B is an anaerobic, organic acid/alcohol-oxidizing, sulfate-reducing δ-proteobacterium. FW-101-2B was isolated from contaminated groundwater at The Field Research Center at Oak Ridge National Lab after in situ stimulation for heavy metal-reducing conditions. The genome will help elucidate the metabolic potential of sulfate-reducing bacteria during uranium reduction.

Actinide Oxidation State and O/M Ratio in Hypostoichiometric Uranium-Plutonium-Americium U0.750Pu0.246Am0.004O2-x Mixed Oxides.

PubMed

Vauchy, Romain; Belin, Renaud C; Robisson, Anne-Charlotte; Lebreton, Florent; Aufore, Laurence; Scheinost, Andreas C; Martin, Philippe M

2016-03-07

Innovative americium-bearing uranium-plutonium mixed oxides U1-yPuyO2-x are envisioned as nuclear fuel for sodium-cooled fast neutron reactors (SFRs). The oxygen-to-metal (O/M) ratio, directly related to the oxidation state of cations, affects many of the fuel properties. Thus, a thorough knowledge of its variation with the sintering conditions is essential. The aim of this work is to follow the oxidation state of uranium, plutonium, and americium, and so the O/M ratio, in U0.750Pu0.246Am0.004O2-x samples sintered for 4 h at 2023 K in various Ar + 5% H2 + z vpm H2O (z = ∼ 15, ∼ 90, and ∼ 200) gas mixtures. The O/M ratios were determined by gravimetry, XAS, and XRD and evidenced a partial oxidation of the samples at room temperature. Finally, by comparing XANES and EXAFS results to that of a previous study, we demonstrate that the presence of uranium does not influence the interactions between americium and plutonium and that the differences in the O/M ratio between the investigated conditions is controlled by the reduction of plutonium. We also discuss the role of the homogeneity of cation distribution, as determined by EPMA, on the mechanisms involved in the reduction process.

Progress in understanding uranium(IV) speciation and dynamics in biologically reduced sediments: Research at molecular to centimeter scales by the SLAC SFA program

NASA Astrophysics Data System (ADS)

Bargar, J.; Williams, K. H.; Campbell, K. M.; Stubbs, J. E.; Suvorova, E.; Lezama-Pacheco, J. S.; Alessi, D.; Stylo, M.; Handley, K. M.; Bernier-Latmani, R.; Cerrato, J.; Davis, J. A.; Fox, P. M.; Giammar, D.; Long, P. E.

2011-12-01

The chemical and physical forms of U(IV) in reduced sediments, as well as the biogeochemical processes by which they form and transform, profoundly influence the stability of reduced U(IV) species and the behavior of uranium in biostimulated aquifers. Obtaining such information in field sediments is important because biogeochemical field conditions and their time dependence are difficult to replicate in the laboratory. The majority of contaminated aquifers in which bioremediation is of potential interest, including the Old Rifle, CO IFRC site, exhibit relatively low uranium sediment concentrations, i.e., < 10 ppm, presenting a formidable challenge to the use of spectroscopy and microscopy techniques that typically require 10-fold or higher uranium loadings. We have developed an in-situ column technique to study U(IV) species and evolving microbial communities in the Old Rifle aquifer and to correlate them with changes in trace and major ion groundwater composition during biostimulation treatments. Sediments were examined using x-ray and electron microscopy, x-ray absorption spectroscopy (XAS), and chemical extractions. XAS analysis showed that U(IV) occurred predominantly or exclusively as monomeric U(IV) complexes coordinated to oxo (or similar N/C) neighbors, and is associated with biomass or Fe sulfides. Even in the latter case, U(IV) was not coordinated directly to S neighbors. Sediment-hosted monomeric U(IV) complexes were found to partially transform into uraninite in the aquifer over a subsequent 12 month period. This work establishes the importance of monomeric U(IV) complexes in subsurface sediments at the Old Rifle site and provides a conceptual framework in which previously observed U(IV) reduction products can be related. These experiments also establish that U(IV) species are dynamic in aquifers and can undergo non-oxidative transformation reactions. These new results have important implications for uranium reactive transport models, long-term assessment of remediation technologies, and understanding natural uranium reduction in aquifers.

Assessment for advanced fuel cycle options in CANDU

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morreale, A.C.; Luxat, J.C.; Friedlander, Y.

2013-07-01

The possible options for advanced fuel cycles in CANDU reactors including actinide burning options and thorium cycles were explored and are feasible options to increase the efficiency of uranium utilization and help close the fuel cycle. The actinide burning TRUMOX approach uses a mixed oxide fuel of reprocessed transuranic actinides from PWR spent fuel blended with natural uranium in the CANDU-900 reactor. This system reduced actinide content by 35% and decreased natural uranium consumption by 24% over a PWR once through cycle. The thorium cycles evaluated used two CANDU-900 units, a generator and a burner unit along with a drivermore » fuel feedstock. The driver fuels included plutonium reprocessed from PWR, from CANDU and low enriched uranium (LEU). All three cycles were effective options and reduced natural uranium consumption over a PWR once through cycle. The LEU driven system saw the largest reduction with a 94% savings while the plutonium driven cycles achieved 75% savings for PWR and 87% for CANDU. The high neutron economy, online fuelling and flexible compact fuel make the CANDU system an ideal reactor platform for many advanced fuel cycles.« less

Different biosorption mechanisms of Uranium(VI) by live and heat-killed Saccharomyces cerevisiae under environmentally relevant conditions.

PubMed

Wang, Tieshan; Zheng, Xinyan; Wang, Xiaoyu; Lu, Xia; Shen, Yanghao

2017-02-01

Uranium adsorption mechanisms of live and heat-killed Saccharomyces cerevisiae in different pH values and biomass concentrations were studied under environmentally relevant conditions. Compared with live cells, the adsorption capacity of heat-killed cells is almost one order of magnitude higher in low biomass concentration and highly acidic pH conditions. To explore the mesoscopic surface interactions between uranium and cells, the characteristic of uranium deposition was investigated by SEM-EDX, XPS and FTIR. Biosorption process of live cells was considered to be metabolism-dependent. Under stimulation by uranyl ions, live cells could gradually release phosphorus and reduce uranium from U(VI) to U(IV) to alleviate uranium toxicity. The uranyl-phosphate complexes were formed in scale-like shapes on cell surface. The metabolic detoxification mechanisms such as reduction and "self-protection" are of significance to the migration of radionuclides. In the metabolism-independent biosorption process of heat-killed cells: the cells cytomembrane was damaged by autoclaving which led to the free diffusion of phosphorous from intracellular, and the rough surface and nano-holes indicated that the dead cells provided larger contact area to precipitate U(VI) as spherical nano-particles. The high biosorption capacity of heat-killed cells makes it become a suitable biological adsorbent for uranium removal. Copyright © 2016 Elsevier Ltd. All rights reserved.

Reaction-Based Reactive Transport Modeling of Iron Reduction and Uranium Immobilization at Area 2 of the NABIR Field Research Center

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burgos, W.D.

2009-09-02

This report summarizes research conducted in conjunction with a project entitled “Reaction-Based Reactive Transport Modeling of Iron Reduction and Uranium Immobilization at Area 2 of the NABIR Field Research Center”, which was funded through the Integrative Studies Element of the former NABIR Program (now the Environmental Remediation Sciences Program) within the Office of Biological and Environmental Research. Dr. William Burgos (The Pennsylvania State University) was the overall PI/PD for the project, which included Brian Dempsey (Penn State), Gour-Tsyh (George) Yeh (Central Florida University), and Eric Roden (formerly at The University of Alabama, now at the University of Wisconsin) as separately-fundedmore » co-PIs. The project focused on development of a mechanistic understanding and quantitative models of coupled Fe(III)/U(VI) reduction in FRC Area 2 sediments. The work builds on our previous studies of microbial Fe(III) and U(VI) reduction, and was directly aligned with the Scheibe et al. ORNL FRC Field Project at Area 2.« less

Microbial reduction of U(VI) under alkaline conditions: implications for radioactive waste geodisposal.

PubMed

Williamson, Adam J; Morris, Katherine; Law, Gareth T W; Rizoulis, Athanasios; Charnock, John M; Lloyd, Jonathan R

2014-11-18

Although there is consensus that microorganisms significantly influence uranium speciation and mobility in the subsurface under circumneutral conditions, microbiologically mediated U(VI) redox cycling under alkaline conditions relevant to the geological disposal of cementitious intermediate level radioactive waste, remains unexplored. Here, we describe microcosm experiments that investigate the biogeochemical fate of U(VI) at pH 10-10.5, using sediments from a legacy lime working site, stimulated with an added electron donor, and incubated in the presence and absence of added Fe(III) as ferrihydrite. In systems without added Fe(III), partial U(VI) reduction occurred, forming a U(IV)-bearing non-uraninite phase which underwent reoxidation in the presence of air (O2) and to some extent nitrate. By contrast, in the presence of added Fe(III), U(VI) was first removed from solution by sorption to the Fe(III) mineral, followed by bioreduction and (bio)magnetite formation coupled to formation of a complex U(IV)-bearing phase with uraninite present, which also underwent air (O2) and partial nitrate reoxidation. 16S rRNA gene pyrosequencing showed that Gram-positive bacteria affiliated with the Firmicutes and Bacteroidetes dominated in the post-reduction sediments. These data provide the first insights into uranium biogeochemistry at high pH and have significant implications for the long-term fate of uranium in geological disposal in both engineered barrier systems and the alkaline, chemically disturbed geosphere.

National Uranium Resource Evaluation: Aztec quadrangle, New Mexico and Colorado

DOE Office of Scientific and Technical Information (OSTI.GOV)

Green, M.W.

1982-09-01

Areas and formations within the Aztec 1/sup 0/ x 2/sup 0/ Quadrangle, New Mexico and Colorado considered favorable for uranium endowment of specified minimum grade and tonnage include, in decreasing order of favorability: (1) the Early Cretaceous Burro Canyon Formation in the southeastern part of the Chama Basin; (2) the Tertiary Ojo Alamo Sandstone in the east-central part of the San Juan Basin; and (3) the Jurassic Westwater Canyon and Brushy Basin Members of the Morrison Formation in the southwestern part of the quadrangle. Favorability of the Burro Canyon is based on the presence of favorable host-rock facies, carbonaceous materialmore » and pyrite to act as a reductant for uranium, and the presence of mineralized ground in the subsurface of the Chama Basin. The Ojo Alamo Sandstone is considered favorable because of favorable host-rock facies, the presence of carbonaceous material and pyrite to act as a reductant for uranium, and the presence of a relatively large subsurface area in which low-grade mineralization has been encountered in exploration activity. The Morrison Formation, located within the San Juan Basin adjacent to the northern edge of the Grants mineral belt, is considered favorable because of mineralization in several drill holes at depths near 1500 m (5000 ft) and because of favorable facies relationships extending into the Aztec Quadrangle from the Grants mineral belt which lies in the adjacent Albuquerque and Gallup Quadrangles. Formations considered unfavorable for uranium deposits of specified tonnage and grade include the remainder of sedimentary and igneous formations ranging from Precambrian to Quaternary in age. Included under the unfavorable category are the Cutler Formation of Permian age, and Dakota Sandstone of Late Cretaceous age, and the Nacimiento and San Jose Formations of Tertiary age.« less

Effects of dietary uranium on reproductive endpoints--fecundity, survival, reproductive success--of the fish Danio rerio.

PubMed

Simon, Olivier; Mottin, Elmina; Geffroy, Benjamin; Hinton, Thomas

2011-01-01

Exposure to metal-contaminated water has been shown to result in a number of reproductive abnormalities in adult and larvae fish, such as failure of oocyte maturation and teratogenic effects. Recently, dietary uptake of metals by fish has been recognized as a critical route of exposure, however, the mechanisms of metal uptake and toxicity are poorly understood and in need of further investigation. The objectives of the present study are to quantify uranium (U dietary transfers from spiked artificial diets) in Danio rerio tissues and embryos, as well as establish its effect on reproduction and embryonic development. Uranium's environmental prominence is currently increasing because of new mining and milling activities. Uranium concentrations range from 0.02 µg/L in natural waters to 2 mg/L. The focus of this study was to examine the trophic transfer and effects of U following exposure modalities (dose, exposure duration 1 to 20 d). Two different isotopes were used to distinguish between chemical and radioactivity toxicity of U. Results showed that U trophic transfer was low (0.52%). Uranium tissue distributions showed that accumulation occurred in digestive organs (liver, digestive tract) following dietary exposure. High levels of U were measured in the gonads (female in particular, >20% of relative burden). High U accumulation levels in eggs indicated maternal transfer of the contaminant. Moreover, U trophic exposure led to a reduction in reproduction success as a function of U accumulated levels. High U exposure conditions strongly reduced the total number of eggs (50%) and their viability at 10 d (reduction of the clutch number, low quality of eggs). © 2010 SETAC.

Effects of uranium concentration on microbial community structure and functional potential.

PubMed

Sutcliffe, Brodie; Chariton, Anthony A; Harford, Andrew J; Hose, Grant C; Greenfield, Paul; Elbourne, Liam D H; Oytam, Yalchin; Stephenson, Sarah; Midgley, David J; Paulsen, Ian T

2017-08-01

Located in the Northern Territory of Australia, Ranger uranium mine is directly adjacent to the UNESCO World Heritage listed Kakadu National Park, with rehabilitation targets needed to ensure the site can be incorporated into the park following the mine's closure in 2026. This study aimed to understand the impact of uranium concentration on microbial communities, in order to identify and describe potential breakpoints in microbial ecosystem services. This is the first study to report in situ deployment of uranium-spiked sediments along a concentration gradient (0-4000 mg U kg -1 ), with the study design maximising the advantages of both field surveys and laboratory manipulative studies. Changes to microbial communities were characterised through the use of amplicon and shotgun metagenomic next-generation sequencing. Significant changes to taxonomic and functional community assembly occurred at a concentration of 1500 mg U kg -1 sediment and above. At uranium concentrations of ≥ 1500 mg U kg -1 , genes associated with methanogenic consortia and processes increased in relative abundance, while numerous significant changes were also seen in the relative abundances of genes involved in nitrogen cycling. Such alterations in carbon and nitrogen cycling pathways suggest that taxonomic and functional changes to microbial communities may result in changes in ecosystem processes and resilience. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

METHOD OF PRODUCING URANIUM

DOEpatents

Foster, L.S.; Magel, T.T.

1958-05-13

A modified process is described for the production of uranium metal by means of a bomb reduction of UF/sub 4/. Difficulty is sometimes experienced in obtaining complete separation of the uranium from the slag when the process is carried out on a snnall scale, i.e., for the production of 10 grams of U or less. Complete separation may be obtained by incorporating in the reaction mixture a quantity of MnCl/sub 2/, so that this compound is reduced along with the UF/sub 4/ . As a result a U--Mn alloy is formed which has a melting point lower than that of pure U, and consequently the metal remains molten for a longer period allowing more complete separation from the slag.

PROCESS FOR RECOVERY OF URANIUM AND VANADIUM FROM CARBONATE SOLUTIONS BY REDUCTION-PRECIPITATION

DOEpatents

Ellis, D.A.; Lindblom, R.O.

1957-09-24

A process employing carbonate leaching of ores and an advantageous methcd of recovering the uranium and vanadium from the leach solution is described. The uranium and vanadium can be precipitated from carbonate leach solutions by reaction with sodium amalgam leaving the leach solution in such a condition that it is economical to replenish for recycling. Such a carbonate leach solution is treated with a dilute sodium amalgam having a sodium concentration within a range of about 0.01 to 0.5% of sodium. Efficiency of the treatment is dependent on at least three additional factors, intimacy of contact of the amalgam with the leach solution, rate of addition of the amalgam and exclusion of oxygen (air).

Richland five-year O2 R and D Program. Integrated site operation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1966-07-11

The technical feasibility of using an electrolytic reduction process to reduce metal scrap and oxide to usable uranium metal is being studied. The incentives for using electrolytic reduction at Richland may be summarized as follows: (1) reduce the unit and total costs of producing plutonium; (2) increase the flexibility of the Richland reactors for producing isotopes, particularly U-236; and (3) simplify the present fuel cycle complex. The scope of the mission is limited to the evaluation of hollow extruded I and E cores, the evaluation of electro-reduced uranium, an investigation of the solution rate of UO{sub 2} in the electrolyte,more » and small-scale irradiations of UO{sub 2} fuels in the N and K Reactors. Progress during FY 1966 is summarized.« less

A novel molten-salt electrochemical cell for investigating the reduction of uranium dioxide to uranium metal by lithium using in situ synchrotron radiation

PubMed Central

Brown, Leon D.; Abdulaziz, Rema; Jervis, Rhodri; Bharath, Vidal; Mason, Thomas J.; Reinhard, Christina; Connor, Leigh D.; Inman, Douglas; Brett, Daniel J. L.; Shearing, Paul R.

2017-01-01

A novel electrochemical cell has been designed and built to allow for in situ energy-dispersive X-ray diffraction measurements to be made during reduction of UO2 to U metal in LiCl–KCl at 500°C. The electrochemical cell contains a recessed well at the bottom of the cell into which the working electrode sits, reducing the beam path for the X-rays through the molten-salt and maximizing the signal-to-noise ratio from the sample. Lithium metal was electrodeposited onto the UO2 working electrode by exposing the working electrode to more negative potentials than the Li deposition potential of the LiCl–KCl eutectic electrolyte. The Li metal acts as a reducing agent for the chemical reduction of UO2 to U, which appears to proceed to completion. All phases were fitted using Le Bail refinement. The cell is expected to be widely applicable to many studies involving molten-salt systems. PMID:28244437

A novel molten-salt electrochemical cell for investigating the reduction of uranium dioxide to uranium metal by lithium using in situ synchrotron radiation.

PubMed

Brown, Leon D; Abdulaziz, Rema; Jervis, Rhodri; Bharath, Vidal; Mason, Thomas J; Atwood, Robert C; Reinhard, Christina; Connor, Leigh D; Inman, Douglas; Brett, Daniel J L; Shearing, Paul R

2017-03-01

A novel electrochemical cell has been designed and built to allow for in situ energy-dispersive X-ray diffraction measurements to be made during reduction of UO 2 to U metal in LiCl-KCl at 500°C. The electrochemical cell contains a recessed well at the bottom of the cell into which the working electrode sits, reducing the beam path for the X-rays through the molten-salt and maximizing the signal-to-noise ratio from the sample. Lithium metal was electrodeposited onto the UO 2 working electrode by exposing the working electrode to more negative potentials than the Li deposition potential of the LiCl-KCl eutectic electrolyte. The Li metal acts as a reducing agent for the chemical reduction of UO 2 to U, which appears to proceed to completion. All phases were fitted using Le Bail refinement. The cell is expected to be widely applicable to many studies involving molten-salt systems.

Using a relative health indicator (RHI) metric to estimate health risk reductions in drinking water.

PubMed

Alfredo, Katherine A; Seidel, Chad; Ghosh, Amlan; Roberson, J Alan

2017-03-01

When a new drinking water regulation is being developed, the USEPA conducts a health risk reduction and cost analysis to, in part, estimate quantifiable and non-quantifiable cost and benefits of the various regulatory alternatives. Numerous methodologies are available for cumulative risk assessment ranging from primarily qualitative to primarily quantitative. This research developed a summary metric of relative cumulative health impacts resulting from drinking water, the relative health indicator (RHI). An intermediate level of quantification and modeling was chosen, one which retains the concept of an aggregated metric of public health impact and hence allows for comparisons to be made across "cups of water," but avoids the need for development and use of complex models that are beyond the existing state of the science. Using the USEPA Six-Year Review data and available national occurrence surveys of drinking water contaminants, the metric is used to test risk reduction as it pertains to the implementation of the arsenic and uranium maximum contaminant levels and quantify "meaningful" risk reduction. Uranium represented the threshold risk reduction against which national non-compliance risk reduction was compared for arsenic, nitrate, and radium. Arsenic non-compliance is most significant and efforts focused on bringing those non-compliant utilities into compliance with the 10 μg/L maximum contaminant level would meet the threshold for meaningful risk reduction.

Total electron acceptor loading and composition affect hexavalent uranium reduction and microbial community structure in a membrane biofilm reactor.

PubMed

Ontiveros-Valencia, Aura; Zhou, Chen; Ilhan, Zehra Esra; de Saint Cyr, Louis Cornette; Krajmalnik-Brown, Rosa; Rittmann, Bruce E

2017-11-15

Molecular microbiology tools (i.e., 16S rDNA gene sequencing) were employed to elucidate changes in the microbial community structure according to the total electron acceptor loading (controlled by influent flow rate and/or medium composition) in a H 2 -based membrane biofilm reactor evaluated for removal of hexavalent uranium. Once nitrate, sulfate, and dissolved oxygen were replaced by U(VI) and bicarbonate and the total acceptor loading was lowered, slow-growing bacteria capable of reducing U(VI) to U(IV) dominated in the biofilm community: Replacing denitrifying bacteria Rhodocyclales and Burkholderiales were spore-producing Clostridiales and Natranaerobiales. Though potentially competing for electrons with U(VI) reducers, homo-acetogens helped attain steady U(VI) reduction, while methanogenesis inhibited U(VI) reduction. U(VI) reduction was reinstated through suppression of methanogenesis by addition of bromoethanesulfonate or by competition from SRB when sulfate was re-introduced. Predictive metagenome analysis further points out community changes in response to alterations in the electron-acceptor loading: Sporulation and homo-acetogenesis were critical factors for strengthening stable microbial U(VI) reduction. This study documents that sporulation was important to long-term U(VI) reduction, whether or not microorganisms that carry out U(VI) reduction mediated by cytochrome c 3 , such as SRB and ferric-iron-reducers, were inhibited. Copyright © 2017 Elsevier Ltd. All rights reserved.

Novel Approaches for Delineating and Studying "Hotspots" and "Hot Moments" in Fluvial Environments

NASA Astrophysics Data System (ADS)

Williams, K. H.; Bücker, M.; Flores Orozco, A.; Hobson, C.; Robbins, M.

2014-12-01

Experiments at the Department of Energy's Rifle, CO (USA) field site have long focused on stimulated biogeochemical pathways arising from organic carbon injection. While reductive pathways and their relation to uranium immobilization have been a focus since 2002, ongoing studies are exploring oxidative pathways and their role in mediating fluxes of C, N, S, and aqueous metals. Insights gained from 'stimulation' experiments are providing insight into analogous natural biogeochemical pathways that mediate elemental cycling in the absence of exogenous carbon. Such reactions are instead mediated by endogenous pools of natural organic matter (NOM) deposited during aggradation of aquifer sediments associated with fluvial processes within the Colorado River floodplain. Discrete lenses of fine-grained, organic-rich sediments enriched in reduced species, such as Fe(II) and iron sulfides have been identified along the active margin of the floodplain. Referred to as "naturally reduced zones" (NRZs), these localities constitute a distinct facies type within an otherwise gravel-dominated, largely NOM-deficient matrix. NRZs represent 'hotspots' of seasonally intense C, N, S, and U cycling during excursions in groundwater elevation. Air bubble imbibition within the capillary fringe is inferred to contribute to seasonally oxic groundwater, with its puntuated, 'hot moment' like impact on redox-mediated reactions exhibiting close correspondence to those induced through the intentional introduction of oxidants. Reactions induce sharp gradients in nitrate and sulfate resulting from elevated rates of nitrification and oxidation of reduced sulfur as dissolved oxygen becomes non-limiting. Given their outsized role in constraining the location and timing of critcal element cycling pathways, delineating the distribution of NRZs across scales of relevance to natural field systems is of great importance. Novel mapping approaches borrowed from the field of exploration geophysics provide one means for identifying such 'hotspots' across a variety of environments where their formation is favored. Drilling activities and deployment of monitoring approaches to study cycling pathways of interest and as a function of hydrologic perturbation may then be performed in a targeted and scientificlally-informed manner.

Anaerobic U(IV) Bio-oxidation and the Resultant Remobilization of Uranium in Contaminated Sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coates, John D.

2005-06-01

A proposed strategy for the remediation of uranium (U) contaminated sites is based on immobilizing U by reducing the oxidized soluble U, U(VI), to form a reduced insoluble end product, U(IV). Due to the use of nitric acid in the processing of nuclear fuels, nitrate is often a co-contaminant found in many of the environments contaminated with uranium. Recent studies indicate that nitrate inhibits U(VI) reduction in sediment slurries. However, the mechanism responsible for the apparent inhibition of U(VI) reduction is unknown, i.e. preferential utilization of nitrate as an electron acceptor, direct biological oxidation of U(IV) coupled to nitrate reduction,more » and/or abiotic oxidation by intermediates of nitrate reduction. Recent studies indicates that direct biological oxidation of U(IV) coupled to nitrate reduction may exist in situ, however, to date no organisms have been identified that can grow by this metabolism. In an effort to evaluate the potential for nitrate-dependent bio-oxidation of U(IV) in anaerobic sedimentary environments, we have initiated the enumeration of nitrate-dependent U(IV) oxidizing bacteria. Sediments, soils, and groundwater from uranium (U) contaminated sites, including subsurface sediments from the NABIR Field Research Center (FRC), as well as uncontaminated sites, including subsurface sediments from the NABIR FRC and Longhorn Army Ammunition Plant, Texas, lake sediments, and agricultural field soil, sites served as the inoculum source. Enumeration of the nitrate-dependent U(IV) oxidizing microbial population in sedimentary environments by most probable number technique have revealed sedimentary microbial populations ranging from 9.3 x 101 - 2.4 x 103 cells (g sediment)-1 in both contaminated and uncontaminated sites. Interestingly uncontaminated subsurface sediments (NABIR FRC Background core FB618 and Longhorn Texas Core BH2-18) both harbored the most numerous nitrate-dependent U(IV) oxidizing population 2.4 x 103 cells (g sediment)-1. The nitrate-dependent U(IV) oxidizing microbial population in groundwaters is less numerous ranging from 0 cells mL-1 (Well FW300, Uncontaminated Background NABIR FRC) to 4.3 x 102 cells mL-1 (Well TPB16, Contaminated Area 2 NABIR FRC). The presence of nitrate-dependent U(IV) oxidizing bacteria supports our hypothesis that bacteria capable of anaerobic U(IV) oxidation are ubiquitous and indigenous to sedimentary and groundwater environments.« less

Retention and chemical speciation of uranium in an oxidized wetland sediment from the Savannah River Site.

PubMed

Li, Dien; Seaman, John C; Chang, Hyun-Shik; Jaffe, Peter R; Koster van Groos, Paul; Jiang, De-Tong; Chen, Ning; Lin, Jinru; Arthur, Zachary; Pan, Yuanming; Scheckel, Kirk G; Newville, Matthew; Lanzirotti, Antonio; Kaplan, Daniel I

2014-05-01

Uranium speciation and retention mechanisms onto Savannah River Site (SRS) wetland sediments was studied using batch (ad)sorption experiments, sequential extraction, U L3-edge X-ray absorption near-edge structure (XANES) spectroscopy, fluorescence mapping and μ-XANES. Under oxidized conditions, U was highly retained by the SRS wetland sediments. In contrast to other similar but much lower natural organic matter (NOM) sediments, significant sorption of U onto the SRS sediments was observed at pH < 4 and pH > 8. Sequential extraction indicated that the U species were primarily associated with the acid soluble fraction (weak acetic acid extractable) and organic fraction (Na-pyrophosphate extractable). Uranium L3-edge XANES spectra of the U-bound sediments were nearly identical to that of uranyl acetate. Based on fluorescence mapping, U and Fe distributions in the sediment were poorly correlated, U was distributed throughout the sample and did not appear as isolated U mineral phases. The primary oxidation state of U in these oxidized sediments was U(VI), and there was little evidence that the high sorptive capacity of the sediments could be ascribed to abiotic or biotic reduction to the less soluble U(IV) species or to secondary mineral formation. Collectively, this study suggests that U may be strongly bound to wetland sediments, not only under reducing conditions by reductive precipitation, but also under oxidizing conditions through NOM-uranium bonding. Published by Elsevier Ltd.

Microbial Reduction of Fe(III) and U(VI) in Aquifers: Simulations Exploring Coupled Effects of Heterogeneity and Fe(II) Sorption

NASA Astrophysics Data System (ADS)

Scheibe, T. D.; Fang, Y.; Roden, E. E.; Brooks, S. C.; Chien, Y.; Murray, C. J.

2004-05-01

Uranium is a significant groundwater contaminant at many former mining and processing sites. In its oxidized state, U(VI) is soluble and mobile, although strongly retarded by sorption to natural iron oxide surfaces. It has been demonstrated that commonly occurring subsurface microorganisms can reduce uranium and other metals when provided sufficient carbon as an electron donor. Reduced U(IV) precipitates as a solid phase; therefore biostimulation provides a potential strategy for in situ removal from contaminated groundwater. However, these biogeochemical reactions occur in the context of a complex heterogeneous environment in which flow and transport dynamics and abiotic reactions can have significant impacts. We have constructed a high-resolution numerical model of groundwater flow and multicomponent reactive transport that incorporates heterogeneity in hydraulic conductivity and initial Fe(III) distribution, microbial growth and transport dynamics, and effects of sorption or precipitation of biogenic Fe(II) on availability of Fe(III) as an electron acceptor. The biogeochemical reaction models and their parameters are based on laboratory experiments; the heterogeneous field-scale property distributions are based on interpretations of geophysical and other observations at a highly characterized field site. The model is being run in Monte Carlo mode to examine the controls that these factors exert on 1) the initial distribution of sorbed uranium in an oxic environment and 2) the reduction and immobilization of uranium upon introduction of a soluble electron donor.

Different pattern of brain pro-/anti-oxidant activity between depleted and enriched uranium in chronically exposed rats.

PubMed

Lestaevel, P; Romero, E; Dhieux, B; Ben Soussan, H; Berradi, H; Dublineau, I; Voisin, P; Gourmelon, P

2009-04-05

Uranium is not only a heavy metal but also an alpha particle emitter. The main toxicity of uranium is expected to be due to chemiotoxicity rather than to radiotoxicity. Some studies have demonstrated that uranium induced some neurological disturbances, but without clear explanations. A possible mechanism of this neurotoxicity could be the oxidative stress induced by reactive oxygen species imbalance. The aim of the present study was to determine whether a chronic ingestion of uranium induced anti-oxidative defence mechanisms in the brain of rats. Rats received depleted (DU) or 4% enriched (EU) uranyl nitrate in the drinking water at 2mg(-1)kg(-1)day(-1) for 9 months. Cerebral cortex analyses were made by measuring mRNA and protein levels and enzymatic activities. Lipid peroxidation, an oxidative stress marker, was significantly enhanced after EU exposure, but not after DU. The gene expression or activity of the main antioxidant enzymes, i.e. superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPx), increased significantly after chronic exposure to DU. On the contrary, oral EU administration induced a decrease of these antioxidant enzymes. The NO-ergic pathway was almost not perturbed by DU or EU exposure. Finally, DU exposure increased significantly the transporters (Divalent-Metal-Transporter1; DMT1), the storage molecule (ferritin) and the ferroxidase enzyme (ceruloplasmin), but not EU. These results illustrate that oxidative stress plays a key role in the mechanism of uranium neurotoxicity. They showed that chronic exposure to DU, but not EU, seems to induce an increase of several antioxidant agents in order to counteract the oxidative stress. Finally, these results demonstrate the importance of the double toxicity, chemical and radiological, of uranium.

MICROSCALE METABOLIC, REDOX AND ABIOTIC REACTIONS IN HANFORD 300 AREA SUBSURFACE SEDIMENTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beyenal, Haluk; McLEan, Jeff; Majors, Paul

2013-11-14

The Hanford 300 Area is a unique site due to periodic hydrologic influence of river water resulting in changes in groundwater elevation and flow direction. This area is also highly subject to uranium remobilization, the source of which is currently believed to be the region at the base of the vadose zone that is subject to period saturation due to the changes in the water levels in the Columbia River. We found that microbial processes and redox and abiotic reactions which operate at the microscale were critical to understanding factors controlling the macroscopic fate and transport of contaminants in themore » subsurface. The combined laboratory and field research showed how microscale conditions control uranium mobility and how biotic, abiotic and redox reactions relate to each other. Our findings extended the current knowledge to examine U(VI) reduction and immobilization using natural 300 Area communities as well as selected model organisms on redox-sensitive and redox-insensitive minerals. Using innovative techniques developed specifically to probe biogeochemical processes at the microscale, our research expanded our current understanding of the roles played by mineral surfaces, bacterial competition, and local biotic, abiotic and redox reaction rates on the reduction and immobilization of uranium.« less

Mineral solubility and free energy controls on microbial reaction kinetics: Application to contaminant transport in the subsurface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taillefert, Martial; Van Cappellen, Philippe

Recent developments in the theoretical treatment of geomicrobial reaction processes have resulted in the formulation of kinetic models that directly link the rates of microbial respiration and growth to the corresponding thermodynamic driving forces. The overall objective of this project was to verify and calibrate these kinetic models for the microbial reduction of uranium(VI) in geochemical conditions that mimic as much as possible field conditions. The approach combined modeling of bacterial processes using new bioenergetic rate laws, laboratory experiments to determine the bioavailability of uranium during uranium bioreduction, evaluation of microbial growth yield under energy-limited conditions using bioreactor experiments, competitionmore » experiments between metabolic processes in environmentally relevant conditions, and model applications at the field scale. The new kinetic descriptions of microbial U(VI) and Fe(III) reduction should replace those currently used in reactive transport models that couple catabolic energy generation and growth of microbial populations to the rates of biogeochemical redox processes. The above work was carried out in collaboration between the groups of Taillefert (batch reactor experiments and reaction modeling) at Georgia Tech and Van Cappellen (retentostat experiments and reactive transport modeling) at University of Waterloo (Canada).« less

Homologation and functionalization of carbon monoxide by a recyclable uranium complex.

PubMed

Gardner, Benedict M; Stewart, John C; Davis, Adrienne L; McMaster, Jonathan; Lewis, William; Blake, Alexander J; Liddle, Stephen T

2012-06-12

Carbon monoxide (CO) is in principle an excellent resource from which to produce industrial hydrocarbon feedstocks as alternatives to crude oil; however, CO has proven remarkably resistant to selective homologation, and the few complexes that can effect this transformation cannot be recycled because liberation of the homologated product destroys the complexes or they are substitutionally inert. Here, we show that under mild conditions a simple triamidoamine uranium(III) complex can reductively homologate CO and be recycled for reuse. Following treatment with organosilyl halides, bis(organosiloxy)acetylenes, which readily convert to furanones, are produced, and this was confirmed by the use of isotopically (13)C-labeled CO. The precursor to the triamido uranium(III) complex is formed concomitantly. These findings establish that, under appropriate conditions, uranium(III) can mediate a complete synthetic cycle for the homologation of CO to higher derivatives. This work may prove useful in spurring wider efforts in CO homologation, and the simplicity of this system suggests that catalytic CO functionalization may soon be within reach.

METHOD FOR SEPARATION OF PLUTONIUM FROM URANIUM AND FISSION PRODUCTS BY SOLVENT EXTRACTION

DOEpatents

Seaborg, G.T.; Blaedel, W.J.; Walling, M.T. Jr.

1960-08-23

A process is given for separating from each other uranium, plutonium, and fission products in an aqueous nitric acid solution by the so-called Redox process. The plutonium is first oxidized to the hexavalent state, e.g., with a water-soluble dichromate or sodium bismuthate, preferably together with a holding oxidant such as potassium bromate. potassium permanganate, or an excess of the oxidizing agent. The solution is then contacted with a water-immiscible organic solvent, preferably hexone. whereby uranium and plutonium are extracted while the fission products remain in the aqueous solution. The separated organic phase is then contacted with an aqueous solution of a reducing agent, with or without a holding reductant (e.g., with a ferrous salt plus hydrazine or with ferrous sulfamate), whereby plutonium is reduced to the trivalent state and back- extracted into the aqueous solution. The uranium may finally be back-extracted from the organic solvent (e.g., with a 0.1 N nitric acid).

Reactivity of uranium(iii) with H2E (E = S, Se, Te): synthesis of a series of mononuclear and dinuclear uranium(iv) hydrochalcogenido complexes.

PubMed

Franke, Sebastian M; Rosenzweig, Michael W; Heinemann, Frank W; Meyer, Karsten

2015-01-01

We report the syntheses, electronic properties, and molecular structures of a series of mono- and dinuclear uranium(iv) hydrochalcogenido complexes supported by the sterically demanding but very flexible, single N-anchored tris(aryloxide) ligand ( Ad ArO) 3 N) 3- . The mononuclear complexes [(( Ad ArO) 3 N)U(DME)(EH)] (E = S, Se, Te) can be obtained from the reaction of the uranium(iii) starting material [(( Ad ArO) 3 N)U III (DME)] in DME via reduction of H 2 E and the elimination of 0.5 equivalents of H 2 . The dinuclear complexes [{(( Ad ArO) 3 N)U} 2 (μ-EH) 2 ] can be obtained by dissolving their mononuclear counterparts in non-coordinating solvents such as benzene. In order to facilitate the work with the highly toxic gases, we created concentrated THF solutions that can be handled using simple glovebox techniques and can be stored at -35 °C for several weeks.

Homologation and functionalization of carbon monoxide by a recyclable uranium complex

PubMed Central

Gardner, Benedict M.; Stewart, John C.; Davis, Adrienne L.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.

2012-01-01

Carbon monoxide (CO) is in principle an excellent resource from which to produce industrial hydrocarbon feedstocks as alternatives to crude oil; however, CO has proven remarkably resistant to selective homologation, and the few complexes that can effect this transformation cannot be recycled because liberation of the homologated product destroys the complexes or they are substitutionally inert. Here, we show that under mild conditions a simple triamidoamine uranium(III) complex can reductively homologate CO and be recycled for reuse. Following treatment with organosilyl halides, bis(organosiloxy)acetylenes, which readily convert to furanones, are produced, and this was confirmed by the use of isotopically 13C-labeled CO. The precursor to the triamido uranium(III) complex is formed concomitantly. These findings establish that, under appropriate conditions, uranium(III) can mediate a complete synthetic cycle for the homologation of CO to higher derivatives. This work may prove useful in spurring wider efforts in CO homologation, and the simplicity of this system suggests that catalytic CO functionalization may soon be within reach. PMID:22652572

High-Resolution Mineralogical Characterization and Biogeochemical Modeling of Uranium Reduction Pathways at the NABIR Field-Research Center

DOE Office of Scientific and Technical Information (OSTI.GOV)

David R. Veblen; Chen Zhu; Lee Krumholz

The effectiveness and feasibility of bioremediation at the field scale cannot be fully assessed until the mechanisms of immobilization and U speciation in the solid matrix are resolved. However, characterization of the immobilized U and its valence states is extremely difficult, because microbially mediated mineral precipitates are generally nanometer (nm)-sized, poorly crystalline, or amorphous. We are developing combined field emission gun--scanning electron microscopy (FEG-SEM, at Indiana University) and FEG transmission electron microscopy (TEM, at Hopkins) to detect and isolate uranium containing phases; (1) method developments for TEM sample preparations and parallel electron energy loss spectroscopy (EELS) determination of uranium valence;more » and (2) to determine the speciation, fate, reactivity, valence states of immobilized uranium, using the state-of-the-art 300-kV, FEG-TEM. We have obtained preliminary results on contaminated sediments from Area 3 at the Oak Ridge Field Research Center (FRC). TEM results show that the sediments contain numerous minerals, including quartz, mica/clay (muscovite and/or illite), rutile, ilmenite, zircon, and an Al-Sr-Ce-Ca phosphate mineral, none of which contain uranium above the EDS detection limit. Substantial U (up to {approx}2 wt.%) is, however, clearly associated with two materials: (1) the Fe oxyhydroxide and (2) clots of a chemically complex material that is likely a mixture of several nm-scale phases. The Fe oxyhydroxide was identified as goethite from its polycrystalline SAED pattern and EDS analysis showing it to be very Fe-rich; the aggregate also displays one of several morphologies that are common for goethite. U is strongly sorbed to goethite in the FRC sediment, and the ubiquitous association with phosphorous suggests that complexes containing both U and P may play an important role in that sorption. Results from bulk analysis and SEM had previously demonstrated the association of U with Fe and thus suggested that U may be sorbed by Fe oxide or oxyhydroxide (Dr. Roh, image presented by David Watson). However, rigorous identification of the host minerals for U requires TEM results such as these involving imaging, electron diffraction, and spectroscopic analysis. An even higher concentration of U occurs in the chemically complex material noted above. These ''clots'' are high in Fe but also contain C, O, Mg, Al, Si, P, S, Cl, K, Ca, Mn, and U. This chemical complexity strongly suggests that they consist of aggregates of carbonate, silicate, phosphate, and sulfate phases, and TEM images also suggest that they may be intergrowths of numerous exceedingly small nanoparticles. EELS and EFTEM studies should be able to resolve these various components and identify precisely where the uranium is in these complex materials. From the results, it is clear that the FEG-SEM and FEG-TEM can readily detect uranium in the FRC samples. The FEG-SEM allows a wide field of view of the samples and can detect U-rich aggregates as small as 20-30 nm. The FEG-TEM can then focus on these aggregates and use SAED, EDS, EFTEM, and PEELS techniques to determine the valence states, structures, and compositional data for these aggregates. This research will provide a crucial component for a complete understanding of the efficacy of uranium bioremediation.« less

The Uranium Controversy

ERIC Educational Resources Information Center

McCarthy, I. E.

1975-01-01

Cites many hazards pertaining to nuclear-fueled energy and outlines many alternatives to this type of energy, such as the development of solar energy and existing coal reserves, and the worldwide reduction in energy consumption. (MLH)

Thermochemistry of rare earth doped uranium oxides LnxU1-xO2-0.5x+y (Ln = La, Y, Nd)

NASA Astrophysics Data System (ADS)

Zhang, Lei; Navrotsky, Alexandra

2015-10-01

Lanthanum, yttrium, and neodymium doped uranium dioxide samples in the fluorite structure have been synthesized, characterized in terms of metal ratio and oxygen content, and their enthalpies of formation measured by high temperature oxide melt solution calorimetry. For oxides doped with 10-50 mol % rare earth (Ln) cations, the formation enthalpies from constituent oxides (LnO1.5, UO2 and UO3 in a reaction not involving oxidation or reduction) become increasingly exothermic with increasing rare earth content, while showing no significant dependence on the varying uranium oxidation state. The oxidation enthalpy of LnxU1-xO2-0.5x+y is similar to that of UO2 to UO3 for all three rare earth doped systems. Though this may suggest that the oxidized uranium in these systems is energetically similar to that in the hexavalent state, thermochemical data alone can not constrain whether the uranium is present as U5+, U6+, or a mixture of oxidation states. The formation enthalpies from elements calculated from the calorimetric data are generally consistent with those from free energy measurements.

Why Nuclear Forensics Needs New Plasma Chemistry Data

NASA Astrophysics Data System (ADS)

Rose, T.; Armstrong, M.; Chernov, A.; Crowhurst, J.; Dai, Z.; Knight, K.; Koroglu, B.; Radousky, H.; Stavrou, E.; Weisz, D.; Zaug, J.; Azer, M.; Finko, M.; Curreli, D.

2016-10-01

The mechanisms that control the distribution of radionuclides in fallout after a nuclear detonation are not adequately constrained. Current capabilities for assessing post-detonation scenarios often rely on empirical observations and approximations. Deeper insight into chemical condensation requires a coupled experimental, theoretical, and modeling approach. The behavior of uranium during plasma condensation is perplexing. Two independent methods are being developed to investigate gas phase uranium chemistry and speciation during plasma condensation: (1) laser-induced breakdown spectroscopy and (2) a unique steady-state ICP flow reactor. Both methods use laser absorption spectroscopy to obtain in situ data for vapor phase molecular species as they form. We are developing a kinetic model to describe the relative abundance of uranium species in the evolving plasma. Characterization of the uranium-oxygen system will be followed by other chemical components, including `carrier' materials such as silica. The goal is to develop a semi-empirical model to describe the chemical fractionation of uranium during fallout formation. Prepared by LLNL under Contract DE-AC52-07NA27344. This project was sponsored in part by the Department of the Defense, Defense Threat Reduction Agency, under Grant Number HDTRA1-16-1-0020.

A high converter concept for fuel management with blanket fuel assemblies in boiling water reactors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martinez-Frances, N.; Timm, W.; Rossbach, D.

2012-07-01

Studies on the natural Uranium saving and waste reduction potential of a multiple-plant BWR system were performed. The BWR High Converter system should enable a multiple recycling of MOX fuel in current BWR plants by introducing blanket fuel assemblies and burning Uranium and MOX fuel separately. The feasibility of Uranium cores with blankets and full-MOX cores with Plutonium qualities as low as 40% were studied. The power concentration due to blanket insertion is manageable with modern fuel and acceptable values for the thermal limits and reactivity coefficients were obtained. While challenges remain, full-MOX cores also complied with the main designmore » criteria. The combination of Uranium and Plutonium burners in appropriate proportions could enable obtaining as much as 40% more energy out of Uranium ore. Moreover, a proper adjustment of blanket average stay and Plutonium qualities could lead to a system with nearly no Plutonium left for final disposal. The achievement of such goals with current light water technology makes the BWR HC concept an attractive option to improve the fuel cycle until Gen-IV designs are mature. (authors)« less

RERTR 2009 (Reduced Enrichment for Research and Test Reactors)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Totev, T.; Stevens, J.; Kim, Y. S.

2010-03-01

The U.S. Department of Energy/National Nuclear Security Administration's Office of Global Threat Reduction in cooperation with the China Atomic Energy Authority and International Atomic Energy Agency hosted the 'RERTR 2009 International Meeting on Reduced Enrichment for Research and Test Reactors.' The meeting was organized by Argonne National Laboratory, China Institute of Atomic Energy and Idaho National Laboratory and was held in Beijing, China from November 1-5, 2009. This was the 31st annual meeting in a series on the same general subject regarding the conversion of reactors within the Global Threat Reduction Initiative (GTRI). The Reduced Enrichment for Research and Testmore » Reactors (RERTR) Program develops technology necessary to enable the conversion of civilian facilities using high enriched uranium (HEU) to low enriched uranium (LEU) fuels and targets.« less

Origin of coffinite in sedimentary rocks by a sequential adsorption-reduction mechanism.

USGS Publications Warehouse

Goldhaber, M.B.; Hemingway, B.S.; Mohagheghi, A.; Reynolds, R.L.; Northrop, H.R.

1987-01-01

Coffinite is the dominant ore mineral in the V-U ores of the Tony-M mine in the Henry Mts mineral belt of the Colorado Plateau. This orebody was formed at a density-stratified solution interface between uranyl-ion-bearing meteoric water and a saline fluid which was locally reducing. The localization of U at this solution interface occurred by adsorption onto the surfaces of detrital minerals, this adsorption being related to the pH difference between the two fluids. Experimental evidence is presented showing that the adsorption facilitated the reduction of uranium to U(IV). This adsorbed, reduced uranium bonded with aqueous silica in the ore zone to form coffinite. The high concentration of silica (as a monomeric species) in the ore-forming solution stabilized coffinite in preference to uraninite.-R.A.H.

Metabolomics identifies a biological response to chronic low-dose natural uranium contamination in urine samples.

PubMed

Grison, Stéphane; Favé, Gaëlle; Maillot, Matthieu; Manens, Line; Delissen, Olivia; Blanchardon, Eric; Banzet, Nathalie; Defoort, Catherine; Bott, Romain; Dublineau, Isabelle; Aigueperse, Jocelyne; Gourmelon, Patrick; Martin, Jean-Charles; Souidi, Maâmar

2013-01-01

Because uranium is a natural element present in the earth's crust, the population may be chronically exposed to low doses of it through drinking water. Additionally, the military and civil uses of uranium can also lead to environmental dispersion that can result in high or low doses of acute or chronic exposure. Recent experimental data suggest this might lead to relatively innocuous biological reactions. The aim of this study was to assess the biological changes in rats caused by ingestion of natural uranium in drinking water with a mean daily intake of 2.7 mg/kg for 9 months and to identify potential biomarkers related to such a contamination. Subsequently, we observed no pathology and standard clinical tests were unable to distinguish between treated and untreated animals. Conversely, LC-MS metabolomics identified urine as an appropriate biofluid for discriminating the experimental groups. Of the 1,376 features detected in urine, the most discriminant were metabolites involved in tryptophan, nicotinate, and nicotinamide metabolic pathways. In particular, N -methylnicotinamide, which was found at a level seven times higher in untreated than in contaminated rats, had the greatest discriminating power. These novel results establish a proof of principle for using metabolomics to address chronic low-dose uranium contamination. They open interesting perspectives for understanding the underlying biological mechanisms and designing a diagnostic test of exposure.

Process for converting magnesium fluoride to calcium fluoride

DOEpatents

Kreuzmann, A.B.; Palmer, D.A.

1984-12-21

This invention is a process for the conversion of magnesium fluoride to calcium fluoride whereby magnesium fluoride is decomposed by heating in the presence of calcium carbonate, calcium oxide or calcium hydroxide. Magnesium fluoride is a by-product of the reduction of uranium tetrafluoride to form uranium metal and has no known commercial use, thus its production creates a significant storage problem. The advantage of this invention is that the quality of calcium fluoride produced is sufficient to be used in the industrial manufacture of anhydrous hydrogen fluoride, steel mill flux or ceramic applications.

Uranium reduction and resistance to reoxidation under iron-reducing and sulfate-reducing conditions.

PubMed

Boonchayaanant, Benjaporn; Nayak, Dipti; Du, Xin; Criddle, Craig S

2009-10-01

Oxidation and mobilization of microbially-generated U(IV) is of great concern for in situ uranium bioremediation. This study investigated the reoxidation of uranium by oxygen and nitrate in a sulfate-reducing enrichment and an iron-reducing enrichment derived from sediment and groundwater from the Field Research Center in Oak Ridge, Tennessee. Both enrichments were capable of reducing U(VI) rapidly. 16S rRNA gene clone libraries of the two enrichments revealed that Desulfovibrio spp. are dominant in the sulfate-reducing enrichment, and Clostridium spp. are dominant in the iron-reducing enrichment. In both the sulfate-reducing enrichment and the iron-reducing enrichment, oxygen reoxidized the previously reduced uranium but to a lesser extent in the iron-reducing enrichment. Moreover, in the iron-reducing enrichment, the reoxidized U(VI) was eventually re-reduced to its previous level. In both, the sulfate-reducing enrichment and the iron-reducing enrichment, uranium reoxidation did not occur in the presence of nitrate. The results indicate that the Clostridium-dominated iron-reducing communities created conditions that were more favorable for uranium stability with respect to reoxidation despite the fact that fewer electron equivalents were added to these systems. The likely reason is that more of the added electrons are present in a form that can reduce oxygen to water and U(VI) back to U(IV).

Diversity and Characterization of Sulfate-Reducing Bacteria in Groundwater at a Uranium Mill Tailings Site

PubMed Central

Chang, Yun-Juan; Peacock, Aaron D.; Long, Philip E.; Stephen, John R.; McKinley, James P.; Macnaughton, Sarah J.; Hussain, A. K. M. Anwar; Saxton, Arnold M.; White, David C.

2001-01-01

Microbially mediated reduction and immobilization of U(VI) to U(IV) plays a role in both natural attenuation and accelerated bioremediation of uranium-contaminated sites. To realize bioremediation potential and accurately predict natural attenuation, it is important to first understand the microbial diversity of such sites. In this paper, the distribution of sulfate-reducing bacteria (SRB) in contaminated groundwater associated with a uranium mill tailings disposal site at Shiprock, N.Mex., was investigated. Two culture-independent analyses were employed: sequencing of clone libraries of PCR-amplified dissimilatory sulfite reductase (DSR) gene fragments and phospholipid fatty acid (PLFA) biomarker analysis. A remarkable diversity among the DSR sequences was revealed, including sequences from δ-Proteobacteria, gram-positive organisms, and the Nitrospira division. PLFA analysis detected at least 52 different mid-chain-branched saturate PLFA and included a high proportion of 10me16:0. Desulfotomaculum and Desulfotomaculum-like sequences were the most dominant DSR genes detected. Those belonging to SRB within δ-Proteobacteria were mainly recovered from low-uranium (≤302 ppb) samples. One Desulfotomaculum-like sequence cluster overwhelmingly dominated high-U (>1,500 ppb) sites. Logistic regression showed a significant influence of uranium concentration over the dominance of this cluster of sequences (P = 0.0001). This strong association indicates that Desulfotomaculum has remarkable tolerance and adaptation to high levels of uranium and suggests the organism's possible involvement in natural attenuation of uranium. The in situ activity level of Desulfotomaculum in uranium-contaminated environments and its comparison to the activities of other SRB and other functional groups should be an important area for future research. PMID:11425735

Preliminary study of uranium favorability of the Boulder batholith, Montana

DOE Office of Scientific and Technical Information (OSTI.GOV)

Castor, S.B.; Robins, J.W.

1978-01-01

The Boulder batholith of southwestern Montana is a composite Late Cretaceous intrusive mass, mostly composed of quartz monzonite and granodiorite. This study was not restricted to the plutonic rocks; it also includes younger rocks that overlie the batholith, and older rocks that it intrudes. The Boulder batholith area has good overall potential for economic uranium deposits, because its geology is similar to that of areas that contain economic deposits elsewhere in the world, and because at least 35 uranium occurrences of several different types are present. Potential is greatest for the occurrence of small uranium deposits in chalcedony veins andmore » base-metal sulfide veins. Three areas may be favorable for large, low-grade deposits consisting of a number of closely spaced chalcedony veins and enriched wall rock; the Mooney claims, the Boulder area, and the Clancy area. In addition, there is a good possibility of by-product uranium production from phosphatic black shales in the project area. The potential for uranium deposits in breccia masses that cut prebatholith rocks, in manganese-quartz veins near Butte, and in a shear zone that cuts Tertiary rhyolite near Helena cannot be determined on the basis of available information. Low-grade, disseminated, primary uranium concentrations similar to porphyry deposits proposed by Armstrong (1974) may exist in the Boulder batholith, but the primary uranium content of most batholith rocks is low. The geologic environment adjacent to the Boulder batholith is similar in places to that at the Midnite mine in Washington. Some igneous rocks in the project area contain more than 10 ppM U/sub 3/O/sub 8/, and some metasedimentary rocks near the batholith contain reductants such as sulfides and carbonaceous material.« less

Origin of the Mariano Lake uranium deposit, McKinley County, New Mexico

USGS Publications Warehouse

Fishman, Neil S.; Reynolds, Richard L.

1982-01-01

The Mariano Lake uranium deposit, hosted by the Brushy Basin Member of the Jurassic Morrison Formation, occurs in the trough of an east-west trending syncline at the western end of the Smith Lake-Mariano Lake group of uranium deposits near Crownpoint, New Mexico. The orebody, which contains abundant amorphous organic material, is situated on the reduced side of a regional reduction-oxidation (redox) interface. The presence of amorphous organic material suggests the orebody may represent a tabular (primary) deposit, whereas the close proximity of the orebody to the redox interface is suggestive that uranium was secondarily redistributed by oxidative processes from pre-existing tabular orebodies. Uranium contents correlate positively with both organic carbon and vanadium contents. Petrographic evidence and scanning electron microscope-energy dispersive analyses point to uranium residence in the epigentically introduced amorphous organic material, which coats detrital grains and fills voids. Uranium mineralization was preceded by the following diagenetic alterations: precipitation of pyrite (d34S values ranging from-11.0 to-38.2 per mil); precipitation of mixed-layer smectite-illite clays; partial dissolution of some of the detrital feldspar population; and precipitation of quartz and adularia overgrowths. Alterations associated with uranium mineralization include emplacement of amorphous organic material (possibly uranium bearing); destruction of detrital iron-titanium oxide grains; coprecipitation of chlorite and microcrystalline quartz, and precipitation of pyrite and marcasite (d34S values for these sulfides ranging from -29.4 to -41.6 per mil). After mineralization, calcite, dolomite, barite, and kaolinite precipitated, and authigenic iron disulfides were replaced by ferric oxides and hydroxides. Geochemical data (primarily the positive correlation of uranium content to both organic carbon and vanadium contents) and petrographic observations (epigentically introduced amorphous organic matter and uranium residence in this organic matter) indicate that the Mariano Lake orebody is a tabular-type uranium deposit. Oxidative processes have not noticeably redistributed and reconcentrated primary uranium in the immediate vicinity of the deposit nor have they greatly modified geochemical characteristics in the ore. Preservation of the Mariano Lake deposit may not only be related to its position along the synclinal trough, where oxidative destruction of the orebody has been inhibited by stagnation of oxidizing ground waters by the structure, but also due to the deflection of ground waters (resulting from low orebody porosity) around the orebody.

Identification of simultaneous U(VI) sorption complexes and U(IV) nanoprecipitates on the magnetite (111) surface.

PubMed

Singer, David M; Chatman, Shawn M; Ilton, Eugene S; Rosso, Kevin M; Banfield, Jillian F; Waychunas, Glenn A

2012-04-03

Sequestration of uranium (U) by magnetite is a potentially important sink for U in natural and contaminated environments. However, molecular-scale controls that favor U(VI) uptake including both adsorption of U(VI) and reduction to U(IV) by magnetite remain poorly understood, in particular, the role of U(VI)-CO(3)-Ca complexes in inhibiting U(VI) reduction. To investigate U uptake pathways on magnetite as a function of U(VI) aqueous speciation, we performed batch sorption experiments on (111) surfaces of natural single crystals under a range of solution conditions (pH 5 and 10; 0.1 mM U(VI); 1 mM NaNO(3); and with or without 0.5 mM CO(3) and 0.1 mM Ca) and characterized surface-associated U using grazing incidence extended X-ray absorption fine structure spectroscopy (GI-EXAFS), grazing incidence X-ray diffraction (GI-XRD), and scanning electron microscopy (SEM). In the absence of both carbonate ([CO(3)](T), denoted here as CO(3)) and calcium (Ca), or in the presence of CO(3) only, coexisting adsorption of U(VI) surface species and reduction to U(IV) occurs at both pH 5 and 10. In the presence of both Ca and CO(3), only U(VI) adsorption (VI) occurs. When U reduction occurs, nanoparticulate UO(2) forms only within and adjacent to surface microtopographic features such as crystal boundaries and cracks. This result suggests that U reduction is limited to defect-rich surface regions. Further, at both pH 5 and 10 in the presence of both CO(3) and Ca, U(VI)-CO(3)-Ca ternary surface species develop and U reduction is inhibited. These findings extend the range of conditions under which U(VI)-CO(3)-Ca complexes inhibit U reduction.

Investigating microstructural evolution during the electroreduction of UO2 to U in LiCl-KCl eutectic using focused ion beam tomography

NASA Astrophysics Data System (ADS)

Brown, L. D.; Abdulaziz, R.; Tjaden, B.; Inman, D.; Brett, D. J. L.; Shearing, P. R.

2016-11-01

Reprocessing of spent nuclear fuels using molten salt media is an attractive alternative to liquid-liquid extraction techniques. Pyroelectrochemical processing utilizes direct, selective, electrochemical reduction of uranium dioxide, followed by selective electroplating of a uranium metal. Thermodynamic prediction of the electrochemical reduction of UO2 to U in LiCl-KCl eutectic has shown to be a function of the oxide ion activity. The pO2- of the salt may be affected by the microstructure of the UO2 electrode. A uranium dioxide filled "micro-bucket" electrode has been partially electroreduced to uranium metal in molten lithium chloride-potassium chloride eutectic. This partial electroreduction resulted in two distinct microstructures: a dense UO2 and a porous U metal structure were characterised by energy dispersive X-ray spectroscopy. Focused ion beam tomography was performed on five regions of this electrode which revealed an overall porosity ranging from 17.36% at the outer edge to 3.91% towards the centre, commensurate with the expected extent of reaction in each location. The pore connectivity was also seen to reduce from 88.32% to 17.86% in the same regions and the tortuosity through the sample was modelled along the axis of propagation of the electroreduction, which was seen to increase from a value of 4.42 to a value of infinity (disconnected pores). These microstructural characteristics could impede the transport of O2- ions resulting in a change in the local pO2- which could result in the inability to perform the electroreduction.

Molybdenum Availability Is Key to Nitrate Removal in Contaminated Groundwater Environments

PubMed Central

Thorgersen, Michael P.; Lancaster, W. Andrew; Vaccaro, Brian J.; Poole, Farris L.; Rocha, Andrea M.; Mehlhorn, Tonia; Pettenato, Angelica; Ray, Jayashree; Waters, R. Jordan; Melnyk, Ryan A.; Chakraborty, Romy; Deutschbauer, Adam M.; Arkin, Adam P.

2015-01-01

The concentrations of molybdenum (Mo) and 25 other metals were measured in groundwater samples from 80 wells on the Oak Ridge Reservation (ORR) (Oak Ridge, TN), many of which are contaminated with nitrate, as well as uranium and various other metals. The concentrations of nitrate and uranium were in the ranges of 0.1 μM to 230 mM and <0.2 nM to 580 μM, respectively. Almost all metals examined had significantly greater median concentrations in a subset of wells that were highly contaminated with uranium (≥126 nM). They included cadmium, manganese, and cobalt, which were 1,300- to 2,700-fold higher. A notable exception, however, was Mo, which had a lower median concentration in the uranium-contaminated wells. This is significant, because Mo is essential in the dissimilatory nitrate reduction branch of the global nitrogen cycle. It is required at the catalytic site of nitrate reductase, the enzyme that reduces nitrate to nitrite. Moreover, more than 85% of the groundwater samples contained less than 10 nM Mo, whereas concentrations of 10 to 100 nM Mo were required for efficient growth by nitrate reduction for two Pseudomonas strains isolated from ORR wells and by a model denitrifier, Pseudomonas stutzeri RCH2. Higher concentrations of Mo tended to inhibit the growth of these strains due to the accumulation of toxic concentrations of nitrite, and this effect was exacerbated at high nitrate concentrations. The relevance of these results to a Mo-based nitrate removal strategy and the potential community-driving role that Mo plays in contaminated environments are discussed. PMID:25979890

Microscopic Fuel Particles Produced by Self-Assembly of Actinide Nanoclusters on Carbon Nanomaterials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Na, Chongzheng

2016-10-17

Many consider further development of nuclear power to be essential for sustained development of society; however, the fuel forms currently used are expensive to recycle. In this project, we sought to create the knowledge and knowhow that are needed to produce nanocomposite materials by directly depositing uranium nanoclusters on networks of carbon-­ based nanomaterials. The objectives of the proposed work were to (1) determine the control of uranium nanocluster surface chemistry on nanocomposite formation, (2) determine the control of carbon nanomaterial surface chemistry on nanocomposite formation, and (3) develop protocols for synthesizing uranium-­carbon nanomaterials. After examining a wide variety ofmore » synthetic methods, we show that synthesizing graphene-­supported UO 2 nanocrystals in polar ethylene glycol compounds by polyol reduction under boiling reflux can enable the use of an inexpensive graphene precursor graphene oxide in the production of uranium-carbon nanocomposites in a one-­pot process. We further show that triethylene glycol is the most suitable solvent for producing nanometer-­sized UO 2 crystals compared to monoethylene glycol, diethylene glycol, and polyethylene glycol. Graphene-­supported UO 2 nanocrystals synthesized with triethylene glycol show evidence of heteroepitaxy, which can be beneficial for facilitating heat transfer in nuclear fuel particles. Furthermore, we show that graphene-supported UO 2 nanocrystals synthesized by polyol reduction can be readily stored in alcohols, preventing oxidation from the prevalent oxygen in air. Together, these methods provide a facile approach for preparing and storing graphene-supported UO nanocrystals for further investigation and development under ambient conditions.« less

Microbially catalyzed nitrate-dependent metal/radionuclide oxidation in shallow subsurface sediments

NASA Astrophysics Data System (ADS)

Weber, K.; Healy, O.; Spanbauer, T. L.; Snow, D. D.

2011-12-01

Anaerobic, microbially catalyzed nitrate-dependent metal/radionuclide oxidation has been demonstrated in a variety of sediments, soils, and groundwater. To date, studies evaluating U bio-oxidation and mobilization have primarily focused on anthropogenically U contaminated sites. In the Platte River Basin U originating from weathering of uranium-rich igneous rocks in the Rocky Mountains was deposited in shallow alluvial sediments as insoluble reduced uranium minerals. These reduced U minerals are subject to reoxidation by available oxidants, such nitrate, in situ. Soluble uranium (U) from natural sources is a recognized contaminant in public water supplies throughout the state of Nebraska and Colorado. Here we evaluate the potential of anaerobic, nitrate-dependent microbially catalyzed metal/radionuclide oxidation in subsurface sediments near Alda, NE. Subsurface sediments and groundwater (20-64ft.) were collected from a shallow aquifer containing nitrate (from fertilizer) and natural iron and uranium. The reduction potential revealed a reduced environment and was confirmed by the presence of Fe(II) and U(IV) in sediments. Although sediments were reduced, nitrate persisted in the groundwater. Nitrate concentrations decreased, 38 mg/L to 30 mg/L, with increasing concentrations of Fe(II) and U(IV). Dissolved U, primarily as U(VI), increased with depth, 30.3 μg/L to 302 μg/L. Analysis of sequentially extracted U(VI) and U(IV) revealed that virtually all U in sediments existed as U(IV). The presence of U(IV) is consistent with reduced Fe (Fe(II)) and low reduction potential. The increase in aqueous U concentrations with depth suggests active U cycling may occur at this site. Tetravalent U (U(IV)) phases are stable in reduced environments, however the input of an oxidant such as oxygen or nitrate into these systems would result in oxidation. Thus co-occurrence of nitrate suggests that nitrate could be used by bacteria as a U(IV) oxidant. Most probable number enumeration of nitrate-dependent U(IV) oxidizing microorganisms demonstrated an abundant community ranging from 1.61x104 to 2.74x104 cells g-1 sediment. Enrichments initiated verified microbial U reduction and U oxidation coupled to nitrate reduction. Sediment slurries were serially diluted and incubated over a period of eight weeks and compared to uninoculated controls. Oxidation (0-4,554 μg/L) and reduction (0-55 μg/L) of U exceeded uninoculated controls further providing evidence of a U biogeochemical cycling in these subsurface sediments. The oxidation of U(IV) could contribute to U mobilization in the groundwater and result in decreased water quality. Not only could nitrate serve as an oxidant, but Fe(III) could also contribute to U mobilization. Nitrate-dependent Fe(II) oxidation is an environmentally ubiquitous process facilitated by a diversity of microorganisms. Additional research is necessary in order to establish a role of biogenic Fe(III) oxides in U geochemical cycling at this site. These microbially mediated processes could also have a confounding effect on uranium mobility in subsurface environments.

Catalytic Reduction of Hexavalent Uranium by Formic Acid; RIDUZIONE CATALITICA DELL'URANIO ESAVALENTE MEDIANTE ACIDO FORMICO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cogliati, G.; Lanz, R.; Lepscky, C.

1963-10-01

S>The catalytic reduction of U(VI) to U(IV) by means of formic acid has been studied, considering particularly the uranyl nltrate solutions, This process will be applied in the urania--thoria mixed fuel reprocessing plant, (PCUT). Various catalysts have been tested and the influence of formic acid concentration, temperature and catalyst concentration on the reaction rate have been determined. A possible reduction mechanism coherent with Ihe experimental data is discussed. (auth)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stillman, J. A.; Feldman, E. E.; Wilson, E. H.

This report contains the results of reactor accident analyses for the University of Missouri Research Reactor (MURR). The calculations were performed as part of the conversion from the use of highly-enriched uranium (HEU) fuel to the use of low-enriched uranium (LEU) fuel. The analyses were performed by staff members of the Global Threat Reduction Initiative (GTRI) Reactor Conversion Program at the Argonne National Laboratory (ANL), the MURR Facility, and the Nuclear Engineering Program – College of Engineering, University of Missouri-Columbia. The core conversion to LEU is being performed with financial support from the U. S. government. This report contains themore » results of reactor accident analyses for the University of Missouri Research Reactor (MURR). The calculations were performed as part of the conversion from the use of highly-enriched uranium (HEU) fuel to the use of low-enriched uranium (LEU) fuel. The analyses were performed by staff members of the Global Threat Reduction Initiative (GTRI) Reactor Conversion Program at the Argonne National Laboratory (ANL), the MURR Facility, and the Nuclear Engineering Program – College of Engineering, University of Missouri-Columbia. The core conversion to LEU is being performed with financial support from the U. S. government. In the framework of non-proliferation policies, the international community presently aims to minimize the amount of nuclear material available that could be used for nuclear weapons. In this geopolitical context most research and test reactors, both domestic and international, have started a program of conversion to the use of LEU fuel. A new type of LEU fuel based on an alloy of uranium and molybdenum (U-Mo) is expected to allow the conversion of U.S. domestic high performance reactors like MURR. This report presents the results of a study of core behavior under a set of accident conditions for MURR cores fueled with HEU U-Alx dispersion fuel or LEU monolithic U-Mo alloy fuel with 10 wt% Mo (U-10Mo).« less

Biological reduction of uranium coupled with oxidation of ammonium by Acidimicrobiaceae bacterium A6 under iron reducing conditions.

PubMed

Gilson, Emily R; Huang, Shan; Jaffé, Peter R

2015-11-01

This study investigated the possibility of links between the biological immobilization of uranium (U) and ammonium oxidation under iron (Fe) reducing conditions. The recently-identified Acidimicrobiaceae bacterium A6 (ATCC, PTA-122488) derives energy from ammonium oxidation coupled with Fe reduction. This bacterium has been found in various soil and wetland environments, including U-contaminated wetland sediments. Incubations of Acidimicrobiaceae bacteria A6 with nontronite, an Fe(III)-rich clay, and approximately 10 µM U indicate that these bacteria can use U(VI) in addition to Fe(III) as an electron acceptor in the presence of ammonium. Measurements of Fe(II) production and ammonium oxidation support this interpretation. Concentrations of approximately 100 µM U were found to entirely inhibit Acidimicrobiaceae bacteria A6 activity. These results suggest that natural sites of active ammonium oxidation under Fe reducing conditions by Acidimicrobiaceae bacteria A6 could be hotspots of U immobilization by bioreduction. This is the first report of biological U reduction that is not coupled to carbon oxidation.

Field Demonstration of a Novel Biotreatment Process for Perchlorate Reduction in Groundwater

DTIC Science & Technology

2010-06-01

biological reduction and/or reaction with ZVI, and arsenic hexavalent chromium and/or uranium by adsorption on corrosion products. • Simple rugged...problems and troubleshooting measures ................................... 22 5.2 Laboratory Evaluation of Porosity Decrease and Corrosion Products...reactor when it was dismantled showing the heavy deposits of iron corrosion products and quasi total loss of porosity. Figure 5.14 Picture of the column

40 CFR 440.35 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2012 CFR

2012-07-01

... (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS (CONTINUED) ORE MINING AND DRESSING POINT SOURCE CATEGORY Uranium, Radium and Vanadium Ores Subcategory § 440.35 Effluent limitations representing the degree of...

40 CFR 440.35 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2013 CFR

2013-07-01

... (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS (CONTINUED) ORE MINING AND DRESSING POINT SOURCE CATEGORY Uranium, Radium and Vanadium Ores Subcategory § 440.35 Effluent limitations representing the degree of...

40 CFR 440.35 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2010 CFR

2010-07-01

... (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORE MINING AND DRESSING POINT SOURCE CATEGORY Uranium, Radium and Vanadium Ores Subcategory § 440.35 Effluent limitations representing the degree of effluent...

40 CFR 440.35 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2011 CFR

2011-07-01

... (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS ORE MINING AND DRESSING POINT SOURCE CATEGORY Uranium, Radium and Vanadium Ores Subcategory § 440.35 Effluent limitations representing the degree of effluent...

40 CFR 440.35 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2014 CFR

2014-07-01

... (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS (CONTINUED) ORE MINING AND DRESSING POINT SOURCE CATEGORY Uranium, Radium and Vanadium Ores Subcategory § 440.35 Effluent limitations representing the degree of...

U redox fronts and kaolinisation in basement-hosted unconformity-related U ores of the Athabasca Basin (Canada): late U remobilisation by meteoric fluids

NASA Astrophysics Data System (ADS)

Mercadier, Julien; Cuney, Michel; Cathelineau, Michel; Lacorde, Mathieu

2011-02-01

Proterozoic basement-hosted unconformity-related uranium deposits of the Athabasca Basin (Saskatchewan, Canada) were affected by significant uranium redistribution along oxidation-reduction redox fronts related to cold and late meteoric fluid infiltration. These redox fronts exhibit the same mineralogical and geochemical features as the well-studied uranium roll-front deposits in siliclastic rocks. The primary hydrothermal uranium mineralisation (1.6-1.3 Ga) of basement-hosted deposits is strongly reworked to new disseminated ores comprising three distinctly coloured zones: a white-green zone corresponding to the previous clay-rich alteration halo contemporaneous with hydrothermal ores, a uranium front corresponding to the uranium deposition zone of the redox front (brownish zone, rich in goethite) and a hematite-rich red zone marking the front progression. The three zones directly reflect the mineralogical zonation related to uranium oxides (pitchblende), sulphides, iron minerals (hematite and goethite) and alumino-phosphate-sulphate (APS) minerals. The zoning can be explained by processes of dissolution-precipitation along a redox interface and was produced by the infiltration of cold (<50°C) meteoric fluids to the hydrothermally altered areas. U, Fe, Ca, Pb, S, REE, V, Y, W, Mo and Se were the main mobile elements in this process, and their distribution within the three zones was, for most of them, directly dependent on their redox potential. The elements concentrated in the redox fronts were sourced by the alteration of previously crystallised hydrothermal minerals, such as uranium oxides and light rare earth element (LREE)-rich APS. The uranium oxides from the redox front are characterised by LREE-enriched patterns, which differ from those of unconformity-related ores and clearly demonstrate their distinct conditions of formation. Uranium redox front formation is thought to be linked to fluid circulation episodes initiated during the 400-300 Ma period during uplift and erosion of the Athabasca Basin when it was near the Equator and to have been still active during the last million years. A major kaolinisation event was caused by changes in the fluid circulation regime, reworking the primary uranium redox fronts and causing the redistribution of elements originally concentrated in the uranium-enriched meteoric-related redox fronts.

Influence of season growth, soils and irrigation water composition on the concentration of uranium in two lettuce (Lactuca sativa L.) varieties. Field experiments

NASA Astrophysics Data System (ADS)

Abreu, M. M.; Neves, O.; Marcelino, M.

2012-04-01

Former uranium mines areas are frequently the sources of environmental radionuclides problems even many years after the closure of mining operations. A concern for inhabitants from mining areas is the use of contaminated land or irrigation water for agriculture, and the potential transfer of metals from soils to vegetables, and to humans through the food chain. The main aim of this study was to compare the uranium concentration in lettuce (Lactuca sativa L. varieties Marady and Romana) grown in different seasons (autumn and summer) and exposed to high and low uranium concentrations both in irrigation water and agricultural soil. The content of uranium in irrigation water, soil (total and available fraction) and in lettuce leaf samples was analyzed in a certified laboratory. In the field experiments, two agricultural soils were divided into two plots (four replicates each); one of them was irrigated with uranium contaminated water (0.94 to 1.14 mg/L) and the other with uncontaminated water (< 0.02 mg/L). Irrigation with contaminated water together with highest soil uranium available concentration (10 to 13 mg/kg) had negative effects on both studied lettuce varieties, namely yield reduction (up to 53% and 87% in autumn and summer experiments, respectively) and increase of uranium leaf concentration (up to 1.4 and 7 fold in autumn and summer, respectively). Effect on lettuce yield was mainly due to the high soil salinity (1.01 to 6.31 mS/cm) as a consequence of high irrigation water electrical conductivity (up to 1.82 mS/cm) and low lettuce soil salinity tolerance (1 to 3 mS/cm). The highest lettuce uranium concentration (dry weight) observed was 2.13 and 5.37 mg/kg for Marady and Romana variety, respectively. The highest uranium lettuce concentration in Romana variety was also the effect of its growing in summer season when it was subject to greatest frequency and amount of water irrigation. The consumption by an adult of the lettuce that concentrate more uranium, represents only 16.7% of the tolerable daily limit intake set by World Health Organisation for this element (0.6 mg/kg body weight daily), suggesting that lettuce uranium intake had a low contribution and do not represent a potential health risk for Cunha Baixa's residents.

Efficacy of a solution-based approach for making sodalite waste forms for an oxide reduction salt utilized in the reprocessing of used uranium oxide fuel

NASA Astrophysics Data System (ADS)

Riley, Brian J.; Pierce, David A.; Frank, Steven M.; Matyáš, Josef; Burns, Carolyne A.

2015-04-01

This paper describes the various approaches evaluated for making solution-derived sodalite with a LiCl-Li2O oxide reduction salt selected to dissolve used uranium oxide fuel so the uranium can be recovered and recycled. The approaches include modified sol-gel and solution-based synthesis processes. As-made products were mixed with 5 and 10 mass% of a Na2O-B2O3-SiO2 glass binder and these, along with product without a binder, were heated using either a cold-press-and-sinter method or hot uniaxial pressing. The results demonstrate the limitation of sodalite yield due to the fast intermediate reactions between Na+ and Cl- to form halite in solution and Li2O and SiO2 to form lithium silicates (e.g., Li2SiO3 or Li2Si2O5) in the calcined and sintered pellets. The results show that pellets can be made with high sodalite fractions in the crystalline product (∼92 mass%) and low porosities using a solution-based approach and this LiCl-Li2O salt but that the incorporation of Li into the sodalite is low.

Bioimmobilization of uranium-practical tools for field applications

NASA Astrophysics Data System (ADS)

Istok, J. D.

2011-12-01

Extensive laboratory and field research has conclusively demonstrated that it is possible to stimulate indigenous microbial activity and create conditions favorable for the reductive precipitation of uranium from groundwater, reducing aqueous U concentrations below regulatory levels. A wide variety of complex and coupled biogeochemical processes have been identified and specific reaction mechanisms and parameters have been quantified for a variety of experimental systems including pure, mixed, and natural microbial cultures, and single mineral, artificial, and natural sediments, and groundwater aquifers at scales ranging from very small (10s nm) to very large (10s m). Multicomponent coupled reactive transport models have also been developed to simulate various aspects of this process in 3D heterogeneous environments. Nevertheless, full-scale application of reductive bioimmobilization of uranium (and other radionuclides and metals) remains problematical because of the technical and logistical difficulties in creating and maintaining reducing environment in the many large U contaminated groundwater aquifers currently under aerobic and oxidizing conditions and often containing high concentrations of competing and more energetically favorable electron acceptors (esp. nitrate). This talk will discuss how simple tools, including small-scale in situ testing and geochemical reaction path modeling, can be used to quickly assess the feasibility of applying bioimmobilization to remediate U contaminated groundwater aquifers and provide data needed for full-scale design.

Efficacy of a solution-based approach for making sodalite waste forms for an oxide reduction salt utilized in the reprocessing of used uranium oxide fuel

DOE PAGES

Riley, Brian J.; Pierce, David A.; Frank, Steven M.; ...

2015-04-01

This paper describes the various approaches attempted to make solution-derived sodalite with a LiCl-Li 2O oxide reduction salt used to dissolve used uranium oxide fuel so the uranium can be recovered and recycled. The approaches include modified sol-gel and solutionbased synthesis processes. As-made products were mixed with 5 and 10 mass% of a Na 2O-B 2O 3- SiO 2 glass binder and these, along with product without a binder, were heated using either a cold-press-and-sinter method or hot uniaxial pressing. The results demonstrate the limitation of sodalite yield due to the fast intermediate reactions between Na+ and Cl- to formmore » halite in solution and Li 2O and SiO 2 to form lithium silicates (e.g., Li 2SiO 3 or Li 2Si 2O 5) in the calcined and sintered pellets. The results show that pellets can be made with high sodalite fractions in the crystalline product (~92 mass%) and low porosities using a solution-based approach and this LiCl-Li 2O salt but that the incorporation of Li into the sodalite is low.« less

Bacterial diversity and composition of an alkaline uranium mine tailings-water interface.

PubMed

Khan, Nurul H; Bondici, Viorica F; Medihala, Prabhakara G; Lawrence, John R; Wolfaardt, Gideon M; Warner, Jeff; Korber, Darren R

2013-10-01

The microbial diversity and biogeochemical potential associated with a northern Saskatchewan uranium mine water-tailings interface was examined using culture-dependent and -independent techniques. Morphologically-distinct colonies from uranium mine water-tailings and a reference lake (MC) obtained using selective and non-selective media were selected for 16S rRNA gene sequencing and identification, revealing that culturable organisms from the uranium tailings interface were dominated by Firmicutes and Betaproteobacteria; whereas, MC organisms mainly consisted of Bacteroidetes and Gammaproteobacteria. Ion Torrent (IT) 16S rRNA metagenomic analysis carried out on extracted DNA from tailings and MC interfaces demonstrated the dominance of Firmicutes in both of the systems. Overall, the tailings-water interface environment harbored a distinct bacterial community relative to the MC, reflective of the ambient conditions (i.e., total dissolved solids, pH, salinity, conductivity, heavy metals) dominating the uranium tailings system. Significant correlations among the physicochemical data and the major bacterial groups present in the tailings and MC were also observed. Presence of sulfate reducing bacteria demonstrated by culture-dependent analyses and the dominance of Desulfosporosinus spp. indicated by Ion Torrent analyses within the tailings-water interface suggests the existence of anaerobic microenvironments along with the potential for reductive metabolic processes.

National Uranium Resource Evaluation: Marfa Quadrangle, Texas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Henry, C D; Duex, T W; Wilbert, W P

1982-09-01

The uranium favorability of the Marfa 1/sup 0/ by 2/sup 0/ Quadrangle, Texas, was evaluated in accordance with criteria established for the National Uranium Resource Evaluation. Surface and subsurface studies, to a 1500 m (5000 ft) depth, and chemical, petrologic, hydrogeochemical, and airborne radiometric data were employed. The entire quadrangle is in the Basin and Range Province and is characterized by Tertiary silicic volcanic rocks overlying mainly Cretaceous carbonate rocks and sandstones. Strand-plain sandstones of the Upper Cretaceous San Carlos Formation and El Picacho Formation possess many favorable characteristics and are tentatively judged as favorable for sandstone-type deposits. The Tertiarymore » Buckshot Ignimbrite contains uranium mineralization at the Mammoth Mine. This deposit may be an example of the hydroauthigenic class; alternatively, it may have formed by reduction of uranium-bearing ground water produced during diagenesis of tuffaceous sediments of the Vieja Group. Although the presence of the deposit indicates favorability, the uncertainty in the process that formed the mineralization makes delineation of a favorable environment or area difficult. The Allen intrusions are favorable for authigenic deposits. Basin fill in several bolsons possesses characteristics that suggest favorability but which are classified as unevaluated because of insufficient data. All Precambrian, Paleozoic, other Mesozoic, and other Cenozoic environments are unfavorable.« less

In Situ Immobilization of Uranium in Structured Porous Media (Invited)

NASA Astrophysics Data System (ADS)

Brooks, S. C.; Gu, B.; Wu, W.; Spalding, B. P.; Watson, D. B.; Jardine, P.

2009-12-01

Defense related activities have resulted in broad areas of uranium contaminated groundwater across the U. S. Department of Energy complex. For example, past waste disposal practices at the DOE’s Y-12 site generated a plume of uranium and nitrate contamination in the underlying vadose and saturated zones which extends more than 120 meters deep and thousands of meters along geologic strike. Several DOE sponsored research programs have enabled the study of multiple biotic and abiotic methods of immobilizing uranium in situ at the site. These include biostimulation of metal reducing bacteria to promote reduction of the more soluble U(VI) to the sparingly soluble U(IV) and pH manipulation to immobilize U(VI) through its interactions (e.g., sorption, coprecipitation) with incipient aluminum oxyhydroxide minerals. The application of laboratory based results to the field site must also account for (i) the structured media which can impose incomplete mixing conditions and (ii) steep geochemical gradients or transition zones which differ significantly from the typically well mixed laboratory conditions. In this presentation results of several of these studies will be reviewed and lessons learned summarized.

Formation and Geological Sequestration of Uranium Nanoparticles in Deep Granitic Aquifer

PubMed Central

Suzuki, Yohey; Mukai, Hiroki; Ishimura, Toyoho; Yokoyama, Takaomi D.; Sakata, Shuhei; Hirata, Takafumi; Iwatsuki, Teruki; Mizuno, Takashi

2016-01-01

The stimulation of bacterial activities that convert hexavalent uranium, U(VI), to tetravalent uranium, U(IV), appears to be feasible for cost-effective remediation of contaminated aquifers. However, U(VI) reduction typically results in the precipitation of U(IV) particles less than 5 nanometers in diameter, except for environmental conditions enriched with iron. Because these tiny particles are mobile and susceptible to oxidative dissolution after the termination of nutrient injection, in situ bioremediation remains to be impractical. Here we show that U(IV) nanoparticles of coffinite (U(SiO4)1−x(OH)4x) formed in fracture-filling calcium carbonate in a granitic aquifer. In situ U-Pb isotope dating demonstrates that U(IV) nanoparticles have been sequestered in the calcium carbonate for at least 1 million years. As the microbiologically induced precipitation of calcium carbonate in aquifer systems worldwide is extremely common, we anticipate simultaneous stimulation of microbial activities for precipitation reactions of calcium carbonate and U(IV) nanoparticles, which leads to long-term sequestration of uranium and other radionuclides in contaminated aquifers and deep geological repositories. PMID:26948389

Formation and Geological Sequestration of Uranium Nanoparticles in Deep Granitic Aquifer.

PubMed

Suzuki, Yohey; Mukai, Hiroki; Ishimura, Toyoho; Yokoyama, Takaomi D; Sakata, Shuhei; Hirata, Takafumi; Iwatsuki, Teruki; Mizuno, Takashi

2016-03-07

The stimulation of bacterial activities that convert hexavalent uranium, U(VI), to tetravalent uranium, U(IV), appears to be feasible for cost-effective remediation of contaminated aquifers. However, U(VI) reduction typically results in the precipitation of U(IV) particles less than 5 nanometers in diameter, except for environmental conditions enriched with iron. Because these tiny particles are mobile and susceptible to oxidative dissolution after the termination of nutrient injection, in situ bioremediation remains to be impractical. Here we show that U(IV) nanoparticles of coffinite (U(SiO4)1-x(OH)4x) formed in fracture-filling calcium carbonate in a granitic aquifer. In situ U-Pb isotope dating demonstrates that U(IV) nanoparticles have been sequestered in the calcium carbonate for at least 1 million years. As the microbiologically induced precipitation of calcium carbonate in aquifer systems worldwide is extremely common, we anticipate simultaneous stimulation of microbial activities for precipitation reactions of calcium carbonate and U(IV) nanoparticles, which leads to long-term sequestration of uranium and other radionuclides in contaminated aquifers and deep geological repositories.

Performance Indicators for Uranium Bioremediation in the Subsurface: Basis and Assessment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Long, Philip E.; Yabusaki, Steven B.

2006-12-29

The purpose of this letter report is to identify performance indicators for in situ engineered bioremediation of subsurface uranium (U) contamination. This report focuses on in situ treatment of groundwater by biostimulation of extant in situ microbial populations (see http://128.3.7.51/NABIR/generalinfo/primers_guides/03_NABIR_primer.pdf for background information on bioremediation of metals and radionuclides). The treatment process involves amendment of the subsurface with an electron donor such as acetate, lactate, ethanol or other organic compound such that in situ microorganisms mediate the reduction of U(VI) to U(IV). U(VI) precipitates as uraninite or other insoluble U phase. Uranium is thus immobilized in place by such processesmore » and is subject to reoxidation that may remobilize the reduced uranium. Related processes include augmenting the extant subsurface microbial populations, addition of electron acceptors, and introduction of chemically reducing materials such as zero-valent Fe. While metrics for such processes may be similar to those for in situ biostimulation, these related processes are not directly in the scope of this letter report.« less

Simulation of in situ uranium bioremediation with slow-release organic amendment injection

NASA Astrophysics Data System (ADS)

Zhang, F.; Parker, J.; Ye, M.; Tang, G.; Wu, W.; Mehlhorn, T.; Gihring, T. M.; Schadt, C.; Watson, D. B.; Brooks, S. C.

2010-12-01

In situ bioremediation of a highly uranium-contaminated gravel aquifer with a slow-release electron donor (emulsified edible oil) has been investigated at the US DOE Oak Ridge Integrated Field Research Challenge (ORIFRC) site in east Tennessee. Groundwater at the study location has pH ~6.7 and contains high concentrations of U (5-6 μM), sulfate (1.0-1.2) mM and Ca (3-4 mM). Diluted emulsified oil (20% solution) was injected into three injection wells within 1.5 hrs. Geochemical analysis of site groundwater demonstrated the sequential reduction of nitrate, Mn, Fe(III) and sulfate. The oil was degraded by indigenous microorganisms with acetate as a major product. Rapid removal of U(VI) from the aqueous phase occurred concurrently with acetate production and sulfate reduction. The field test data were analyzed using a reaction network with a kinetic model for lipid hydrolysis and glycerol fermentation and equilibrium reactions representing microbial reduction of sulfate, nitrate, iron, uranium, manganese and carbon dioxide based on the thermodynamic approach of Istok et al. (2010) using the parallelized HGC5 code. Model-simulated chemical concentrations and relative abundance of functional microbial populations are compared with field measurements. Application of the thermodynamically-based modeling approach instead of the widely used multi-Monod kinetic rate law to formulate bioreduction reactions substantially reduces the number of reaction parameters that need to be calibrated thus facilitating a more comprehensive representation of microbial community dynamics. The model developed through this study is expected to aid the design of future bioremediation strategies for the site.

Removing oxygen from a solvent extractant in an uranium recovery process

DOEpatents

Hurst, Fred J.; Brown, Gilbert M.; Posey, Franz A.

1984-01-01

An improvement in effecting uranium recovery from phosphoric acid solutions is provided by sparging dissolved oxygen contained in solutions and solvents used in a reductive stripping stage with an effective volume of a nonoxidizing gas before the introduction of the solutions and solvents into the stage. Effective volumes of nonoxidizing gases, selected from the group consisting of argon, carbon dioxide, carbon monoxide, helium, hydrogen, nitrogen, sulfur dioxide, and mixtures thereof, displace oxygen from the solutions and solvents thereby reduce deleterious effects of oxygen such as excessive consumption of elemental or ferrous and accumulation of complex iron phosphates or cruds.

Proteogenomic insights into uranium tolerance of a Chernobyl's Microbacterium bacterial isolate.

PubMed

Gallois, Nicolas; Alpha-Bazin, Béatrice; Ortet, Philippe; Barakat, Mohamed; Piette, Laurie; Long, Justine; Berthomieu, Catherine; Armengaud, Jean; Chapon, Virginie

2018-04-15

Microbacterium oleivorans A9 is a uranium-tolerant actinobacteria isolated from the trench T22 located near the Chernobyl nuclear power plant. This site is contaminated with different radionuclides including uranium. To observe the molecular changes at the proteome level occurring in this strain upon uranyl exposure and understand molecular mechanisms explaining its uranium tolerance, we established its draft genome and used this raw information to perform an in-depth proteogenomics study. High-throughput proteomics were performed on cells exposed or not to 10μM uranyl nitrate sampled at three previously identified phases of uranyl tolerance. We experimentally detected and annotated 1532 proteins and highlighted a total of 591 proteins for which abundances were significantly differing between conditions. Notably, proteins involved in phosphate and iron metabolisms show high dynamics. A large ratio of proteins more abundant upon uranyl stress, are distant from functionally-annotated known proteins, highlighting the lack of fundamental knowledge regarding numerous key molecular players from soil bacteria. Microbacterium oleivorans A9 is an interesting environmental model to understand biological processes engaged in tolerance to radionuclides. Using an innovative proteogenomics approach, we explored its molecular mechanisms involved in uranium tolerance. We sequenced its genome, interpreted high-throughput proteomic data against a six-reading frame ORF database deduced from the draft genome, annotated the identified proteins and compared protein abundances from cells exposed or not to uranyl stress after a cascade search. These data show that a complex cellular response to uranium occurs in Microbacterium oleivorans A9, where one third of the experimental proteome is modified. In particular, the uranyl stress perturbed the phosphate and iron metabolic pathways. Furthermore, several transporters have been identified to be specifically associated to uranyl stress, paving the way to the development of biotechnological tools for uranium decontamination. Copyright © 2017. Published by Elsevier B.V.

Uranium vacancy mobility at the Σ5 symmetric tilt and Σ5 twist grain boundaries in UO₂

DOE PAGES

Uberuaga, Blas Pedro; Andersson, David A.

2015-10-01

Ionic transport at grain boundaries in oxides dictates a number of important phenomena, from ionic conductivity to sintering to creep. For nuclear fuels, it also influences fission gas bubble nucleation and growth. Here, using a combination of atomistic calculations and object kinetic Monte Carlo (okMC) simulations, we examine the kinetic pathways associated with uranium vacancies at two model grain boundaries in UO 2. The barriers for vacancy motion were calculated using the nudged elastic band method at all uranium sites at each grain boundary and were used as the basis of the okMC simulations. For both boundaries considered – amore » simple tilt and a simple twist boundary – the mobility of uranium vacancies is significantly higher than in the bulk. For the tilt boundary, there is clearly preferred migration along the tilt axis as opposed to in the perpendicular direction while, for the twist boundary, migration is essentially isotropic within the boundary plane. These results show that cation defect mobility in fluorite-structured materials is enhanced at certain types of grain boundaries and is dependent on the boundary structure with the tilt boundary exhibiting higher rates of migration than the twist boundary.« less

Spectroscopic confirmation of uranium(VI)-carbonato adsorption complexes on hematite

USGS Publications Warehouse

Bargar, John R.; Reitmeyer, Rebecca; Davis, James A.

1999-01-01

Evaluating societal risks posed by uranium contamination from waste management facilities, mining sites, and heavy industry requires knowledge about uranium transport in groundwater, often the most significant pathway of exposure to humans. It has been proposed that uranium mobility in aquifers may be controlled by adsorption of U(VI)−carbonato complexes on oxide minerals. The existence of such complexes has not been demonstrated, and little is known about their compositions and reaction stoichiometries. We have used attenuated total reflectance Fourier transform infrared (ATR-FTIR) and extended X-ray absorption fine structure (EXAFS) spectroscopies to probe the existence, structures, and compositions of ≡FeOsurface−U(VI)−carbonato complexes on hematite throughout the pH range of uranyl uptake under conditions relevant to aquifers. U(VI)−carbonato complexes were found to be the predominant adsorbed U(VI) species at all pH values examined, a much wider pH range than previously postulated based on analogy to aqueous U(VI)−carbonato complexes, which are trace constituents at pH < 6. This result indicates the inadequacy of the common modeling assumption that the compositions and predominance of adsorbed species can be inferred from aqueous species. By extension, adsorbed carbonato complexes may be of major importance to the groundwater transport of similar actinide contaminants such as neptunium and plutonium.

Fate of Uranium During Transport Across the Groundwater-Surface Water Interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jaffe, Peter R.; Kaplan, Daniel I.

Discharge of contaminated groundwater to surface waters is of concern at many DOE facilities. For example, at F-Area and TNX-Area on the Savannah River Site, contaminated groundwater, including uranium, is already discharging into natural wetlands. It is at this interface where contaminants come into contact with the biosphere. These this research addressed a critical knowledge gap focusing on the geochemistry of uranium (or for that matter, any redox-active contaminant) in wetland systems. Understanding the interactions between hydrological, microbial, and chemical processes will make it possible to provide a more accurate conceptual and quantitative understanding of radionuclide fate and transport undermore » these unique conditions. Understanding these processes will permit better long-term management and the necessary technical justification for invoking Monitored Natural Attenuation of contaminated wetland areas. Specifically, this research did provide new insights on how plant-induced alterations to the sediment biogeochemical processes affect the key uranium reducing microorganisms, the uranium reduction, its spatial distribution, the speciation of the immobilized uranium, and its long-term stability. This was achieved by conducting laboratory mesocosm wetland experiments as well as field measurements at the SRNL. Results have shown that uranium can be immobilized in wetland systems. To a degree some of the soluble U(VI) was reduced to insoluble U(IV), but the majority of the immobilized U was incorporated into iron oxyhydroxides that precipitated onto the root surfaces of wetland plants. This U was immobilized mostly as U(VI). Because it was immobilized in its oxidized form, results showed that dry spells, resulting in the lowering of the water table and the exposure of the U to oxic conditions, did not result in U remobilization.« less

Natural uranium and thorium isotopes in sediment cores off Malaysian ports

NASA Astrophysics Data System (ADS)

Yusoff, Abdul Hafidz; Sabuti, Asnor Azrin; Mohamed, Che Abd Rahim

2015-06-01

Sediment cores collected from three Malaysian marine ports, namely, Kota Kinabalu, Labuan and Klang were analyzed to determine the radioactivities of 234U, 238U, 230Th, 232Th and total organic carbon (TOC) content. The objectives of this study were to determine the factors that control the activity of uranium isotopes and identify the possible origin of uranium and thorium in these areas. The activities of 234U and 238U show high positive correlation with TOC at the middle of sediment core from Kota Kinabalu port. This result suggests that activity of uranium at Kota Kinabalu port was influenced by organic carbon. The 234U/238U value at the upper layer of Kota Kinabalu port was ≥1.14 while the ratio value at Labuan and Klang port was ≤ 1.14. These results suggest a reduction process occurred at Kota Kinabalu port where mobile U(VI) was converted to immobile U(IV) by organic carbon. Therefore, it can be concluded that the major input of uranium at Kota Kinabalu port is by sorptive uptake of authigenic uranium from the water column whereas the major inputs of uranium to Labuan and Klang port are of detrital origin. The ratio of 230Th/232Th was used to estimate the origin of thorium. Low ratio value (lt; 1.5) at Labuan and Klang ports support the suggestion that thorium from both areas were come from detrital input while the high ratio (> 1.5) of 230Th/232Th at Kota Kinabalu port suggest the anthropogenic input of 230Th to this area. The source of 230Th is probably from phosphate fertilizers used in the oil-palm cultivation in Kota Kinabalu that is adjacent to the Kota Kinabalu port.

Successful Completion of the Largest Shipment of Russian Research Reactor High-Enriched Uranium Spent Nuclear Fuel from Czech Republic to Russian Federation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Michael Tyacke; Dr. Igor Bolshinsky; Jeff Chamberlin

On December 8, 2007, the largest shipment of high-enriched uranium spent nuclear fuel was successfully made from a Russian-designed nuclear research reactor in the Czech Republic to the Russian Federation. This accomplishment is the culmination of years of planning, negotiations, and hard work. The United States, Russian Federation, and the International Atomic Energy Agency have been working together on the Russian Research Reactor Fuel Return (RRRFR) Program in support of the Global Threat Reduction Initiative. In February 2003, RRRFR Program representatives met with the Nuclear Research Institute in Rež, Czech Republic, and discussed the return of their high-enriched uranium spentmore » nuclear fuel to the Russian Federation for reprocessing. Nearly 5 years later, the shipment was made. This paper discusses the planning, preparations, coordination, and cooperation required to make this important international shipment.« less

Significant Association between Sulfate-Reducing Bacteria and Uranium-Reducing Microbial Communities as Revealed by a Combined Massively Parallel Sequencing-Indicator Species Approach▿ †

PubMed Central

Cardenas, Erick; Wu, Wei-Min; Leigh, Mary Beth; Carley, Jack; Carroll, Sue; Gentry, Terry; Luo, Jian; Watson, David; Gu, Baohua; Ginder-Vogel, Matthew; Kitanidis, Peter K.; Jardine, Philip M.; Zhou, Jizhong; Criddle, Craig S.; Marsh, Terence L.; Tiedje, James M.

2010-01-01

Massively parallel sequencing has provided a more affordable and high-throughput method to study microbial communities, although it has mostly been used in an exploratory fashion. We combined pyrosequencing with a strict indicator species statistical analysis to test if bacteria specifically responded to ethanol injection that successfully promoted dissimilatory uranium(VI) reduction in the subsurface of a uranium contamination plume at the Oak Ridge Field Research Center in Tennessee. Remediation was achieved with a hydraulic flow control consisting of an inner loop, where ethanol was injected, and an outer loop for flow-field protection. This strategy reduced uranium concentrations in groundwater to levels below 0.126 μM and created geochemical gradients in electron donors from the inner-loop injection well toward the outer loop and downgradient flow path. Our analysis with 15 sediment samples from the entire test area found significant indicator species that showed a high degree of adaptation to the three different hydrochemical-created conditions. Castellaniella and Rhodanobacter characterized areas with low pH, heavy metals, and low bioactivity, while sulfate-, Fe(III)-, and U(VI)-reducing bacteria (Desulfovibrio, Anaeromyxobacter, and Desulfosporosinus) were indicators of areas where U(VI) reduction occurred. The abundance of these bacteria, as well as the Fe(III) and U(VI) reducer Geobacter, correlated with the hydraulic connectivity to the substrate injection site, suggesting that the selected populations were a direct response to electron donor addition by the groundwater flow path. A false-discovery-rate approach was implemented to discard false-positive results by chance, given the large amount of data compared. PMID:20729318

Significant association between sulfate-reducing bacteria and uranium-reducing microbial communities as revealed by a combined massively parallel sequencing-indicator species approach.

PubMed

Cardenas, Erick; Wu, Wei-Min; Leigh, Mary Beth; Carley, Jack; Carroll, Sue; Gentry, Terry; Luo, Jian; Watson, David; Gu, Baohua; Ginder-Vogel, Matthew; Kitanidis, Peter K; Jardine, Philip M; Zhou, Jizhong; Criddle, Craig S; Marsh, Terence L; Tiedje, James M

2010-10-01

Massively parallel sequencing has provided a more affordable and high-throughput method to study microbial communities, although it has mostly been used in an exploratory fashion. We combined pyrosequencing with a strict indicator species statistical analysis to test if bacteria specifically responded to ethanol injection that successfully promoted dissimilatory uranium(VI) reduction in the subsurface of a uranium contamination plume at the Oak Ridge Field Research Center in Tennessee. Remediation was achieved with a hydraulic flow control consisting of an inner loop, where ethanol was injected, and an outer loop for flow-field protection. This strategy reduced uranium concentrations in groundwater to levels below 0.126 μM and created geochemical gradients in electron donors from the inner-loop injection well toward the outer loop and downgradient flow path. Our analysis with 15 sediment samples from the entire test area found significant indicator species that showed a high degree of adaptation to the three different hydrochemical-created conditions. Castellaniella and Rhodanobacter characterized areas with low pH, heavy metals, and low bioactivity, while sulfate-, Fe(III)-, and U(VI)-reducing bacteria (Desulfovibrio, Anaeromyxobacter, and Desulfosporosinus) were indicators of areas where U(VI) reduction occurred. The abundance of these bacteria, as well as the Fe(III) and U(VI) reducer Geobacter, correlated with the hydraulic connectivity to the substrate injection site, suggesting that the selected populations were a direct response to electron donor addition by the groundwater flow path. A false-discovery-rate approach was implemented to discard false-positive results by chance, given the large amount of data compared.

Molybdenum Availability Is Key to Nitrate Removal in Contaminated Groundwater Environments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thorgersen, Michael P.; Lancaster, W. Andrew; Vaccaro, Brian J.

2015-05-15

The concentrations of molybdenum (Mo) and 25 other metals were measured in groundwater samples from 80 wells on the Oak Ridge Reservation (ORR) (Oak Ridge, TN), many of which are contaminated with nitrate, as well as uranium and various other metals. Moreover, the concentrations of nitrate and uranium were in the ranges of 0.1 μM to 230 mM and <0.2 nM to 580 μM, respectively. Most metals examined had significantly greater median concentrations in a subset of wells that were highly contaminated with uranium (≥126 nM). They included cadmium, manganese, and cobalt, which were 1,300- to 2,700-fold higher. A notablemore » exception, however, was Mo, which had a lower median concentration in the uranium-contaminated wells. This is significant, because Mo is essential in the dissimilatory nitrate reduction branch of the global nitrogen cycle. It is required at the catalytic site of nitrate reductase, the enzyme that reduces nitrate to nitrite. Furthermore, more than 85% of the groundwater samples contained less than 10 nM Mo, whereas concentrations of 10 to 100 nM Mo were required for efficient growth by nitrate reduction for twoPseudomonasstrains isolated from ORR wells and by a model denitrifier,Pseudomonas stutzeriRCH2. Higher concentrations of Mo tended to inhibit the growth of these strains due to the accumulation of toxic concentrations of nitrite, and this effect was exacerbated at high nitrate concentrations. The relevance of these results to a Mo-based nitrate removal strategy and the potential community-driving role that Mo plays in contaminated environments are discussed.« less

National Uranium Resource Evaluation: Lewistown Quadrangle, Montana

DOE Office of Scientific and Technical Information (OSTI.GOV)

Culver, J.C.

1982-09-01

Uranium resources in the Lewistown Quadrangle, Montana, were evaluated to a depth of 1500 m (5000 ft). All existing geologic data were considered, including geologic surveys, literature, theses, radiometric surveys, oil- and water-well logs. Additional data were generated during the course of two field seasons, including the collection of more than 350 water, rock, crude oil and panned concentrate samples for analyses, sedimentary facies maps, structural geology and isopach maps, and field examination of reported areas of anomalous radioactivity. Three environments with potential for the occurrence of a minimum of 100 t of 0.01% U/sub 3/O/sub 8/ were delineated. Themore » most favorable environment is located in the southeastern portion of the quadrangle; here, Tertiary felsic dikes intrude four potential sandstone host rocks in the Kootenai Formation and the Colorado Shale. Structural-chemical traps for allogenic uranium are provided by the juxtaposition of oil-bearing domes. A second potential environment is located in the Eagle Sandstone in the northwestern and western portions of the quadrangle; here, anomalous water samples were obtained downtip from oxidized outcrops that are structurally related to Tertiary intrusive rocks of the Bearpaw and Highwood Mountains. Lignitic lenses and carbonaceous sandstones deposited in a near-shore lagoonal and deltaic environment provide potential reductants for hexavalent uranium in this environment. A third environment, in the Judith River Formation, was selected as favorable on the basis of water-well and gamma-ray log anomalies and their structural relationship with the Bearpaw Mountains. Organic materials are present in the Judith River Formation as potential reductants. They were deposited in a near-shore fluvial and lagoonal system similar to the depositional environment of the Jackson Group of the Texas Gulf Coast.« less

Steven's orbital reduction factor in ionic clusters

NASA Astrophysics Data System (ADS)

Gajek, Z.; Mulak, J.

1985-11-01

General expressions for reduction coefficients of matrix elements of angular momentum operator in ionic clusters or molecular systems have been derived. The reduction in this approach results from overlap and covalency effects and plays an important role in the reconciling of magnetic and spectroscopic experimental data. The formulated expressions make possible a phenomenological description of the effect with two independent parameters for typical equidistant clusters. Some detailed calculations also suggest the possibility of a one-parameter description. The results of these calculations for some ionic uranium compounds are presented as an example.

Investigating Uranium Mobility Using Stable Isotope Partitioning of 238U/235U and a Reactive Transport Model

NASA Astrophysics Data System (ADS)

Bizjack, M.; Johnson, T. M.; Druhan, J. L.; Shiel, A. E.

2015-12-01

We report a numerical reactive transport model which explicitly incorporates the effectively stable isotopes of uranium (U) and the factors that influence their partitioning in bioactive systems. The model reproduces trends observed in U isotope ratios and concentration measurements from a field experiment, thereby improving interpretations of U isotope ratios as a tracer for U reactive transport. A major factor contributing to U storage and transport is its redox state, which is commonly influenced by the availability of organic carbon to support metal-reducing microbial communities. Both laboratory and field experiments have demonstrated that biogenic reduction of U(VI) fractionates the stable isotope ratio 238U/235U, producing an isotopically heavy solid U(IV) product. It has also been shown that other common reactive transport processes involving U do not fractionate isotopes to a consistently measurable level, which suggests the capacity to quantify the extent of bioreduction occurring in groundwater containing U using 238U/235U ratios. A recent study of a U bioremediation experiment at the Rifle IFRC site (Colorado, USA) applied Rayleigh distillation models to quantify U stable isotope fractionation observed during acetate amendment. The application of these simplified models were fit to the observations only by invoking a "memory-effect," or a constant source of low-concentration, unfractionated U(VI). In order to more accurately interpret the measured U isotope ratios, we present a multi-component reactive transport model using the CrunchTope software. This approach is capable of quantifying the cycling and partitioning of individual U isotopes through a realistic network of transport and reaction pathways including reduction, oxidation, and microbial growth. The model incorporates physical heterogeneity of the aquifer sediments through zones of decreased permeability, which replicate the observed bromide tracer, major ion chemistry, U concentration, and U isotope ratios. These results suggest that the rate-limited transport properties of U in the Rifle aquifer are governed by the presence of low-permeability regions in the modeling domain and that these zones are responsible for the suggested "memory" effect observed in previous U isotope studies at this site.

Nuclear Fuel Reprocessing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harold F. McFarlane; Terry Todd

2013-11-01

Reprocessing is essential to closing nuclear fuel cycle. Natural uranium contains only 0.7 percent 235U, the fissile (see glossary for technical terms) isotope that produces most of the fission energy in a nuclear power plant. Prior to being used in commercial nuclear fuel, uranium is typically enriched to 3–5% in 235U. If the enrichment process discards depleted uranium at 0.2 percent 235U, it takes more than seven tonnes of uranium feed to produce one tonne of 4%-enriched uranium. Nuclear fuel discharged at the end of its economic lifetime contains less one percent 235U, but still more than the natural ore.more » Less than one percent of the uranium that enters the fuel cycle is actually used in a single pass through the reactor. The other naturally occurring isotope, 238U, directly contributes in a minor way to power generation. However, its main role is to transmute into plutoniumby neutron capture and subsequent radioactive decay of unstable uraniumand neptuniumisotopes. 239Pu and 241Pu are fissile isotopes that produce more than 40% of the fission energy in commercially deployed reactors. It is recovery of the plutonium (and to a lesser extent the uranium) for use in recycled nuclear fuel that has been the primary focus of commercial reprocessing. Uraniumtargets irradiated in special purpose reactors are also reprocessed to obtain the fission product 99Mo, the parent isotope of technetium, which is widely used inmedical procedures. Among the fission products, recovery of such expensive metals as platinum and rhodium is technically achievable, but not economically viable in current market and regulatory conditions. During the past 60 years, many different techniques for reprocessing used nuclear fuel have been proposed and tested in the laboratory. However, commercial reprocessing has been implemented along a single line of aqueous solvent extraction technology called plutonium uranium reduction extraction process (PUREX). Similarly, hundreds of types of reactor fuels have been irradiated for different purposes, but the vast majority of commercial fuel is uranium oxide clad in zirconium alloy tubing. As a result, commercial reprocessing plants have relatively narrow technical requirements for used nuclear that is accepted for processing.« less

Acetate availability and its influence on sustainable bioremediation of Uranium-contaminated groundwater

USGS Publications Warehouse

Williams, K.H.; Long, P.E.; Davis, J.A.; Wilkins, M.J.; N'Guessan, A. L.; Steefel, Carl; Yang, L.; Newcomer, D.; Spane, F.A.; Kerkhof, L.J.; Mcguinness, L.; Dayvault, R.; Lovley, D.R.

2011-01-01

Field biostimulation experiments at the U.S. Department of Energy's Integrated Field Research Challenge (IFRC) site in Rifle, Colorado, have demonstrated that uranium concentrations in groundwater can be decreased to levels below the U.S. Environmental Protection Agency's (EPA) drinking water standard (0.126??M).During successive summer experiments - referred to as "Winchester" (2007) and "Big Rusty" (2008) - acetate was added to the aquifer to stimulate the activity of indigenous dissimilatory metal reducing bacteria capable of reductively immobilizing uranium. The two experiments differed in the length of injection (31 vs. 110 days), the maximum concentration of acetate (5 vs. 30 mM),and the extent to which iron reduction ("Winchester") or sulfate reduction("Big Rusty") was the predominant metabolic process. In both cases, rapid removal of U(VI) from groundwater occurred at calcium concentrations (6 mM) and carbonate alkalinities (8 meq/L) where Ca-UO2-CO3 ternary complexes constitute >90% of uranyl species in groundwater. Complete consumption of acetate and increased alkalinity (>30 meq/L) accompanying the onset of sulfate reduction corresponded to temporary increases in U(VI);however, by increasing acetate concentrations in excess of available sulfate (10 mM), low U(VI) concentrations (0.1-0.05 ??M) were achieved for extended periods of time (>140 days). Uniform delivery of acetate during "Big Rusty" was impeded due to decreases in injection well permeability, likely resulting from biomass accumulation and carbonate and sulfide mineral precipitation. Such decreases were not observed during the short-duration "Winchester" experiment. Terminal restriction fragment length polymorphism (TRFLP) analysis of 16S rRNA genes demonstrated that Geobacter sp. and Geobacter-like strains dominated the groundwater community profile during iron reduction, with 13C stable isotope probing (SIP) results confirming these strains were actively utilizing acetate to replicate their genome during the period of optimal U(VI) removal. Gene transcript levels during "Big Rusty" were quantified for Geobacter-specific citrate synthase (gltA), with ongoing transcription during sulfate reduction indicating that members of the Geobacteraceae were still active and likely contributing to U(VI) removal. The persistence of reducible Fe(III) in sediments recovered from an area of prolonged (110-day) sulfate reduction is consistent with this conclusion. These results indicate that acetate availability and its ability to sustain the activity of iron- and uranyl-respiring Geobacter strains during sulfate reduction exerts a primary control on optimized U(VI) removal from groundwater at the Rifle IFRC site over extended time scales (>50 days). ?? Taylor & Francis Group, LLC.

Vanadium Respiration by Geobacter metallireducens: Novel Strategy for In Situ Removal of Vanadium from Groundwater

PubMed Central

Ortiz-Bernad, Irene; Anderson, Robert T.; Vrionis, Helen A.; Lovley, Derek R.

2004-01-01

Vanadium can be an important contaminant in groundwaters impacted by mining activities. In order to determine if microorganisms of the Geobacteraceae, the predominant dissimilatory metal reducers in many subsurface environments, were capable of reducing vanadium(V), Geobacter metallireducens was inoculated into a medium in which acetate was the electron donor and vanadium(V) was the sole electron acceptor. Reduction of vanadium(V) resulted in the production of vanadium(IV), which subsequently precipitated. Reduction of vanadium(V) was associated with cell growth with a generation time of 15 h. No vanadium(V) was reduced and no precipitate was formed in heat-killed or abiotic controls. Acetate was the most effective of all the electron donors evaluated. When acetate was injected into the subsurface to enhance the growth and activity of Geobacteraceae in an aquifer contaminated with uranium and vanadium, vanadium was removed from the groundwater even more effectively than uranium. These studies demonstrate that G. metallireducens can grow via vanadium(V) respiration and that stimulating the activity of Geobacteraceae, and hence vanadium(V) reduction, can be an effective strategy for in situ immobilization of vanadium in contaminated subsurface environments. PMID:15128571

REDUCTION OF INORGANIC COMPOUNDS WITH MOLECULAR HYDROGEN BY MICROCOCCUS LACTILYTICUS I.

PubMed Central

Woolfolk, C. A.; Whiteley, H. R.

1962-01-01

Woolfolk, C. A. (University of Washington, Seattle) and H. R. Whiteley. Reduction of inorganic compounds with molecular hydrogen by Micrococcus lactilyticus. I. Stoichiometry with compounds of arsenic, selenium, tellurium, transition and other elements. J. Bacteriol. 84:647–658. 1962.—Extracts of Micrococcus lactilyticus (Veillonella alcalescens) oxidize molecular hydrogen at the expense of certain compounds of arsenic, bismuth, selenium, tellurium, lead, thallium, vanadium, manganese, iron, copper, molybdenum, tungsten, osmium, ruthenium, gold, silver, and uranium, as well as molecular oxygen. Chemical and manometric data indicate that the following reductions are essentially quantitative: arsenate to arsenite, pentavalent and trivalent bismuth to the free element, selenite via elemental selenium to selenide, tellurate and tellurite to tellurium, lead dioxide and manganese dioxide to the divalent state, ferric to ferrous iron, osmium tetroxide to osmate ion, osmium dioxide and trivalent osmium to the metal, uranyl uranium to the tetravalent state, vanadate to the level of vanadyl, and polymolybdate ions to molybdenum blues with an average valence for molybdenum of +5. The results of a study of certain other hydrogenase-containing bacteria with respect to their ability to carry out some of the same reactions are also presented. PMID:14001842

Studies on the Composition of the Solids in the Fumes Released in the Calciometric Process for Uranium Production; ESTUDIOS SOBRE LA COMPOSICION DE LOS SOLIDOS EN LOS HUMOS DESPRENDIDOS EN EL PROCESO CALCIOTERMICO DE OBTENCION DE URANIO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Travesi, A.; de la Cruz, F.; Cellini, R.F.

1958-01-01

In the dust produced during the thermal reduction of uranium tetrafluoride with calcium, the existence of a beta activity which decays with time was confirmed. The activity was assigned to Th/sup 234/. An enrichment in Th/sup 234/ of approximately 68% over the equilibrium value was found in the dust. An anomalous enrichment in the dust was found for the trace elements Zn, Sn, Pb, and Cu. No enrichment was detected for Fe and Ni. (tr-auth)

The Synechocystis PCC6803 MerA-like enzyme operates in the reduction of both mercury and uranium under the control of the glutaredoxin 1 enzyme.

PubMed

Marteyn, Benoit; Sakr, Samer; Farci, Sandrine; Bedhomme, Mariette; Chardonnet, Solenne; Decottignies, Paulette; Lemaire, Stéphane D; Cassier-Chauvat, Corinne; Chauvat, Franck

2013-09-01

In a continuing effort to analyze the selectivity/redundancy of the three glutaredoxin (Grx) enzymes of the model cyanobacterium Synechocystis PCC6803, we have characterized an enzyme system that plays a crucial role in protection against two toxic metal pollutants, mercury and uranium. The present data show that Grx1 (Slr1562 in CyanoBase) selectively interacts with the presumptive mercuric reductase protein (Slr1849). This MerA enzyme plays a crucial role in cell defense against both mercuric and uranyl ions, in catalyzing their NADPH-driven reduction. Like MerA, Grx1 operates in cell protection against both mercury and uranium. The Grx1-MerA interaction requires cysteine 86 (C86) of Grx1 and C78 of MerA, which is critical for its reductase activity. MerA can be inhibited by glutathionylation and subsequently reactivated by Grx1, likely through deglutathionylation. The two Grx1 residues C31, which belongs to the redox active site (CX(2)C), and C86, which operates in MerA interactions, are both required for reactivation of MerA. These novel findings emphasize the role of glutaredoxins in tolerance to metal stress as well as the evolutionary conservation of the glutathionylation process, so far described mostly for eukaryotes.

The Synechocystis PCC6803 MerA-Like Enzyme Operates in the Reduction of Both Mercury and Uranium under the Control of the Glutaredoxin 1 Enzyme

PubMed Central

Marteyn, Benoit; Sakr, Samer; Farci, Sandrine; Bedhomme, Mariette; Chardonnet, Solenne; Decottignies, Paulette; Lemaire, Stéphane D.; Cassier-Chauvat, Corinne

2013-01-01

In a continuing effort to analyze the selectivity/redundancy of the three glutaredoxin (Grx) enzymes of the model cyanobacterium Synechocystis PCC6803, we have characterized an enzyme system that plays a crucial role in protection against two toxic metal pollutants, mercury and uranium. The present data show that Grx1 (Slr1562 in CyanoBase) selectively interacts with the presumptive mercuric reductase protein (Slr1849). This MerA enzyme plays a crucial role in cell defense against both mercuric and uranyl ions, in catalyzing their NADPH-driven reduction. Like MerA, Grx1 operates in cell protection against both mercury and uranium. The Grx1-MerA interaction requires cysteine 86 (C86) of Grx1 and C78 of MerA, which is critical for its reductase activity. MerA can be inhibited by glutathionylation and subsequently reactivated by Grx1, likely through deglutathionylation. The two Grx1 residues C31, which belongs to the redox active site (CX2C), and C86, which operates in MerA interactions, are both required for reactivation of MerA. These novel findings emphasize the role of glutaredoxins in tolerance to metal stress as well as the evolutionary conservation of the glutathionylation process, so far described mostly for eukaryotes. PMID:23852862

Geology and recognition criteria for sandstone uranium deposits in mixed fluvial-shallow marine sedimentary sequences, South Texas. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adams, S.S.; Smith, R.B.

1981-01-01

Uranium deposits in the South Texas Uranium Region are classical roll-type deposits that formed at the margin of tongues of altered sandstone by the encroachment of oxidizing, uraniferous solutions into reduced aquifers containing pyrite and, in a few cases, carbonaceous plant material. Many of the uranium deposits in South Texas are dissimilar from the roll fronts of the Wyoming basins. The host sands for many of the deposits contain essentially no carbonaceous plant material, only abundant disseminated pyrite. Many of the deposits do not occur at the margin of altered (ferric oxide-bearing) sandstone tongues but rather occur entirely within reduced,more » pyurite-bearing sandstone. The abundance of pyrite within the sands probably reflects the introduction of H/sub 2/S up along faults from hydrocarbon accumulations at depth. Such introductions before ore formation prepared the sands for roll-front development, whereas post-ore introductions produced re-reduction of portions of the altered tongue, leaving the deposit suspended in reduced sandstone. Evidence from three deposits suggests that ore formation was not accompanied by the introduction of significant amounts of H/sub 2/S.« less

Hydrologic and geochemical data assimilation at the Hanford 300 Area

NASA Astrophysics Data System (ADS)

Chen, X.; Hammond, G. E.; Murray, C. J.; Zachara, J. M.

2012-12-01

In modeling the uranium migration within the Integrated Field Research Challenge (IFRC) site at the Hanford 300 Area, uncertainties arise from both hydrologic and geochemical sources. The hydrologic uncertainty includes the transient flow boundary conditions induced by dynamic variations in Columbia River stage and the underlying heterogeneous hydraulic conductivity field, while the geochemical uncertainty is a result of limited knowledge of the geochemical reaction processes and parameters, as well as heterogeneity in uranium source terms. In this work, multiple types of data, including the results from constant-injection tests, borehole flowmeter profiling, and conservative tracer tests, are sequentially assimilated across scales within a Bayesian framework to reduce the hydrologic uncertainty. The hydrologic data assimilation is then followed by geochemical data assimilation, where the goal is to infer the heterogeneous distribution of uranium sources using uranium breakthrough curves from a desorption test that took place at high spring water table. We demonstrate in our study that Ensemble-based data assimilation techniques (Ensemble Kalman filter and smoother) are efficient in integrating multiple types of data sequentially for uncertainty reduction. The computational demand is managed by using the multi-realization capability within the parallel PFLOTRAN simulator.

Variably Saturated Flow and Multicomponent Biogeochemical Reactive Transport Modeling of a Uranium Bioremediation Field Experiment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yabusaki, Steven B.; Fang, Yilin; Williams, Kenneth H.

2011-11-01

Field experiments at a former uranium mill tailings site have identified the potential for stimulating indigenous bacteria to catalyze the conversion of aqueous uranium in the +6 oxidation state to immobile solid-associated uranium in the +4 oxidation state. This effectively removes uranium from solution resulting in groundwater concentrations below actionable standards. Three-dimensional, coupled variably-saturated flow and biogeochemical reactive transport modeling of a 2008 in situ uranium bioremediation field experiment is used to better understand the interplay of transport rates and biogeochemical reaction rates that determine the location and magnitude of key reaction products. A comprehensive reaction network, developed largely throughmore » previous 1-D modeling studies, was used to simulate the impacts on uranium behavior of pulsed acetate amendment, seasonal water table variation, spatially-variable physical (hydraulic conductivity, porosity) and geochemical (reactive surface area) material properties. A principal challenge is the mechanistic representation of biologically-mediated terminal electron acceptor process (TEAP) reactions whose products significantly alter geochemical controls on uranium mobility through increases in pH, alkalinity, exchangeable cations, and highly reactive reduction products. In general, these simulations of the 2008 Big Rusty acetate biostimulation field experiment in Rifle, Colorado confirmed previously identified behaviors including (1) initial dominance by iron reducing bacteria that concomitantly reduce aqueous U(VI), (2) sulfate reducing bacteria that become dominant after {approx}30 days and outcompete iron reducers for the acetate electron donor, (3) continuing iron-reducer activity and U(VI) bioreduction during dominantly sulfate reducing conditions, and (4) lower apparent U(VI) removal from groundwater during dominantly sulfate reducing conditions. New knowledge on simultaneously active metal and sulfate reducers has been incorporated into the modeling. In this case, an initially small population of slow growing sulfate reducers is active from the initiation of biostimulation. Three-dimensional, variably saturated flow modeling was used to address impacts of a falling water table during acetate injection. These impacts included a significant reduction in aquifer saturated thickness and isolation of residual reactants and products, as well as unmitigated uranium, in the newly unsaturated vadose zone. High permeability sandy gravel structures resulted in locally high flow rates in the vicinity of injection wells that increased acetate dilution. In downgradient locations, these structures created preferential flow paths for acetate delivery that enhanced local zones of TEAP reactivity and subsidiary reactions. Conversely, smaller transport rates associated with the lower permeability lithofacies (e.g., fine) and vadose zone were shown to limit acetate access and reaction. Once accessed by acetate, however, these same zones limited subsequent acetate dilution and provided longer residence times that resulted in higher concentrations of TEAP products when terminal electron donors and acceptors were not limiting. Finally, facies-based porosity and reactive surface area variations were shown to affect aqueous uranium concentration distributions; however, the ranges were sufficiently small to preserve general trends. Large computer memory and high computational performance were required to simulate the detailed coupled process models for multiple biogeochemical components in highly resolved heterogeneous materials for the 110-day field experiment and 50 days of post-biostimulation behavior. In this case, a highly-scalable subsurface simulator operating on 128 processor cores for 12 hours was used to simulate each realization. An equivalent simulation without parallel processing would have taken 60 days, assuming sufficient memory was available.« less

MURMoT. Design and Application of Microbial Uranium Reduction Monitoring Tools

DOE Office of Scientific and Technical Information (OSTI.GOV)

Loeffler, Frank E.

2014-12-31

Uranium (U) contamination in the subsurface is a major remediation challenge at many DOE sites. Traditional site remedies present enormous costs to DOE; hence, enhanced bioremediation technologies (i.e., biostimulation and bioaugmentation) combined with monitoring efforts are being considered as cost-effective corrective actions to address subsurface contamination. This research effort improved understanding of the microbial U reduction process and developed new tools for monitoring microbial activities. Application of these tools will promote science-based site management decisions that achieve contaminant detoxification, plume control, and long-term stewardship in the most efficient manner. The overarching hypothesis was that the design, validation and application ofmore » a suite of new molecular and biogeochemical tools advance process understanding, and improve environmental monitoring regimes to assess and predict in situ U immobilization. Accomplishments: This project (i) advanced nucleic acid-based approaches to elucidate the presence, abundance, dynamics, spatial distribution, and activity of metal- and radionuclide-detoxifying bacteria; (ii) developed proteomics workflows for detection of metal reduction biomarker proteins in laboratory cultures and contaminated site groundwater; (iii) developed and demonstrated the utility of U isotopic fractionation using high precision mass spectrometry to quantify U(VI) reduction for a range of reduction mechanisms and environmental conditions; and (iv) validated the new tools using field samples from U-contaminated IFRC sites, and demonstrated their prognostic and diagnostic capabilities in guiding decision making for environmental remediation and long-term site stewardship.« less

Radionuclide inventories : ORIGEN2.2 isotopic depletion calculation for high burnup low-enriched uranium and weapons-grade mixed-oxide pressurized-water reactor fuel assemblies.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gauntt, Randall O.; Ross, Kyle W.; Smith, James Dean

2010-04-01

The Oak Ridge National Laboratory computer code, ORIGEN2.2 (CCC-371, 2002), was used to obtain the elemental composition of irradiated low-enriched uranium (LEU)/mixed-oxide (MOX) pressurized-water reactor fuel assemblies. Described in this report are the input parameters for the ORIGEN2.2 calculations. The rationale for performing the ORIGEN2.2 calculation was to generate inventories to be used to populate MELCOR radionuclide classes. Therefore the ORIGEN2.2 output was subsequently manipulated. The procedures performed in this data reduction process are also described herein. A listing of the ORIGEN2.2 input deck for two-cycle MOX is provided in the appendix. The final output from this data reduction processmore » was three tables containing the radionuclide inventories for LEU/MOX in elemental form. Masses, thermal powers, and activities were reported for each category.« less

Fabrication of thorium bearing carbide fuels

DOEpatents

Gutierrez, R.L.; Herbst, R.J.; Johnson, K.W.R.

Thorium-uranium carbide and thorium-plutonium carbide fuel pellets have been fabricated by the carbothermic reduction process. Temperatures of 1750/sup 0/C and 2000/sup 0/C were used during the reduction cycle. Sintering temperatures of 1800/sup 0/C and 2000/sup 0/C were used to prepare fuel pellet densities of 87% and > 94% of theoretical, respectively. The process allows the fabrication of kilogram quantities of fuel with good reproductibility of chemical and phase composition.

Application of remote sensor data to geologic analysis of the Bonanza test site Colorado

NASA Technical Reports Server (NTRS)

Lee, K. (Compiler); Butler, R. W.; Fisher, J. C.; Huntley, D.; Hulstrom, R. L.; Knepper, D. H., Jr.; Muhm, J. R.; Sawatzky, D. L.; Worman, K. E.; Wychgram, D.

1973-01-01

Research activities on geologic remote sensing applications for Colorado are summarized. Projects include: regional and detailed geologic mapping, surficial and engineering geology, fracture studies, uranium exploration, hydrology, and data reduction and enhancement. The acquisition of remote sensor data is also discussed.

Studying Legacy Uranium Contamination On Navajo, Laguna, and Isleta Lands In Collaboration With Native American Undergraduate Researchers

NASA Astrophysics Data System (ADS)

Cadol, D. D.; Frey, B.; Chee, C.

2017-12-01

Personally relevant research experiences at key points in a student's education are potentially powerful influences on their long-term career path. With this in mind, New Mexico EPSCoR created the STEM Advancement Program (STEMAP) to provide a summer research experience for students from the non-graduate-degree granting institutions in New Mexico. Recruitment focused on underrepresented minorities, primarily Native American and Hispanic students, who applied to work with one of six research components. Our research component focused on understanding the fate and transport of environmental uranium in the Four Corners region. The geosciences are especially amenable to providing meaningful research experiences, particularly for groups that have a strong cultural connection with the land. Uranium mining activities were extensive on several reservations in the 1950s to 1980s, and many of the sites have not been remediated. The impact of mining likely contributed to the high interest among Native American (especially Navajo) STEMAP applicants in this research topic. In four years of summer research we mentored four Native American students (two male and two female) and one white non-Hispanic female. Following their work in our research group, one student extended her research, three graduated, and one transferred to a research institution. This success likely reflects a combination of recruitment efforts, which built on community connections, as well as efforts to provide personal mentoring and to create an inclusive environment. The work of these students has advanced our understanding of fluvial transport of uranium from inactive mining districts, an important pathway given the role of these streams in providing water for agriculture and aggregate for construction. Findings demonstrate an affinity of uranium to sorb to fine-grained sediment, meaning standing water in stock ponds is of particular concern. The students also studied uranium-bearing dust generated from legacy sites, documenting dissolution of uranium in two contrasting simulated lung fluids. Student presentations in the affected communities closed the communication loop, presenting findings in an accessible format. Ideally these presentations also planted seeds of interest in the geosciences for younger community members.

Characterization of cores from an in-situ recovery mined uranium deposit in Wyoming: Implications for post-mining restoration

DOE Office of Scientific and Technical Information (OSTI.GOV)

WoldeGabriel, G.; Boukhalfa, H.; Ware, S. D.

In-situ recovery (ISR) of uranium (U) from sandstone-type roll-front deposits is a technology that involves the injection of solutions that consist of ground water fortified with oxygen and carbonate to promote the oxidative dissolution of U, which is pumped to recovery facilities located at the surface that capture the dissolved U and recycle the treated water. The ISR process alters the geochemical conditions in the subsurface creating conditions that are more favorable to the migration of uranium and other metals associated with the uranium deposit. There is a lack of clear understanding of the impact of ISR mining on themore » aquifer and host rocks of the post-mined site and the fate of residual U and other metals within the mined ore zone. We performed detailed petrographic, mineralogical, and geochemical analyses of several samples taken from about 7 m of core of the formerly the ISR-mined Smith Ranch–Highland uranium deposit in Wyoming. We show that previously mined cores contain significant residual uranium (U) present as coatings on pyrite and carbonaceous fragments. Coffinite was identified in three samples. Core samples with higher organic (> 1 wt.%) and clay (> 6–17 wt.%) contents yielded higher 234U/ 238U activity ratios (1.0–1.48) than those with lower organic and clay fractions. The ISR mining was inefficient in mobilizing U from the carbonaceous materials, which retained considerable U concentrations (374–11,534 ppm). This is in contrast with the deeper part of the ore zone, which was highly depleted in U and had very low 234U/ 238U activity ratios. This probably is due to greater contact with the lixiviant (leaching solution) during ISR mining. EXAFS analyses performed on grains with the highest U and Fe concentrations reveal that Fe is present in a reduced form as pyrite and U occurs mostly as U(IV) complexed by organic matter or as U(IV) phases of carbonate complexes. Moreover, U–O distances of ~ 2.05 Å were noted, indicating the potential formation of other poorly defined U(IV/VI) species. We also noted a small contribution from Udouble bond; length as m-dashO at 1.79 Å, which indicates that U is partially oxidized. There is no apparent U–S or U–Fe interaction in any of the U spectra analyzed. However, SEM analysis of thin sections prepared from the same core material reveals surficial U associated with pyrite which is probably a minor fraction of the total U present as thin coatings on the surface of pyrite. Our data show the presence of different structurally variable uranium forms associated with the mined cores. U associated with carbonaceous materials is probably from the original U mobilization that accumulated in the organic matter-rich areas under reducing conditions during shallow burial diagenesis. U associated with pyrite represents a small fraction of the total U and was likely deposited as a result of chemical reduction by pyrite. Our data suggest that areas rich in carbonaceous materials had limited exposure to the lixiviant solution, continue to be reducing, and still hold significant U resources. Because of their limited access to fluid flow, these areas might not contribute significantly to post-mining U release or attenuation. Areas with pyrite that are accessible to fluids seem to be more reactive and could act as reductants and facilitate U reduction and accumulation, limiting its migration.« less

Characterization of cores from an in-situ recovery mined uranium deposit in Wyoming: Implications for post-mining restoration

DOE PAGES

WoldeGabriel, G.; Boukhalfa, H.; Ware, S. D.; ...

2014-10-08

In-situ recovery (ISR) of uranium (U) from sandstone-type roll-front deposits is a technology that involves the injection of solutions that consist of ground water fortified with oxygen and carbonate to promote the oxidative dissolution of U, which is pumped to recovery facilities located at the surface that capture the dissolved U and recycle the treated water. The ISR process alters the geochemical conditions in the subsurface creating conditions that are more favorable to the migration of uranium and other metals associated with the uranium deposit. There is a lack of clear understanding of the impact of ISR mining on themore » aquifer and host rocks of the post-mined site and the fate of residual U and other metals within the mined ore zone. We performed detailed petrographic, mineralogical, and geochemical analyses of several samples taken from about 7 m of core of the formerly the ISR-mined Smith Ranch–Highland uranium deposit in Wyoming. We show that previously mined cores contain significant residual uranium (U) present as coatings on pyrite and carbonaceous fragments. Coffinite was identified in three samples. Core samples with higher organic (> 1 wt.%) and clay (> 6–17 wt.%) contents yielded higher 234U/ 238U activity ratios (1.0–1.48) than those with lower organic and clay fractions. The ISR mining was inefficient in mobilizing U from the carbonaceous materials, which retained considerable U concentrations (374–11,534 ppm). This is in contrast with the deeper part of the ore zone, which was highly depleted in U and had very low 234U/ 238U activity ratios. This probably is due to greater contact with the lixiviant (leaching solution) during ISR mining. EXAFS analyses performed on grains with the highest U and Fe concentrations reveal that Fe is present in a reduced form as pyrite and U occurs mostly as U(IV) complexed by organic matter or as U(IV) phases of carbonate complexes. Moreover, U–O distances of ~ 2.05 Å were noted, indicating the potential formation of other poorly defined U(IV/VI) species. We also noted a small contribution from Udouble bond; length as m-dashO at 1.79 Å, which indicates that U is partially oxidized. There is no apparent U–S or U–Fe interaction in any of the U spectra analyzed. However, SEM analysis of thin sections prepared from the same core material reveals surficial U associated with pyrite which is probably a minor fraction of the total U present as thin coatings on the surface of pyrite. Our data show the presence of different structurally variable uranium forms associated with the mined cores. U associated with carbonaceous materials is probably from the original U mobilization that accumulated in the organic matter-rich areas under reducing conditions during shallow burial diagenesis. U associated with pyrite represents a small fraction of the total U and was likely deposited as a result of chemical reduction by pyrite. Our data suggest that areas rich in carbonaceous materials had limited exposure to the lixiviant solution, continue to be reducing, and still hold significant U resources. Because of their limited access to fluid flow, these areas might not contribute significantly to post-mining U release or attenuation. Areas with pyrite that are accessible to fluids seem to be more reactive and could act as reductants and facilitate U reduction and accumulation, limiting its migration.« less

DNA methylation and potential multigenerational epigenetic effects linked to uranium chronic low-dose exposure in gonads of males and females rats.

PubMed

Elmhiri, G; Gloaguen, C; Grison, S; Kereselidze, D; Elie, C; Tack, K; Benderitter, M; Lestaevel, P; Legendre, A; Souidi, M

2018-01-05

An increased health problem in industrialised countries is the contemporary concern of public and scientific community as well. This has been attributed in part to accumulated environmental pollutants especially radioactive substances and the use of nuclear power plants worldwide. However, the outcome of chronic exposure to low doses of a radionuclide such as uranium remains unknown. Recently, a paradigm shift in the perception of risk of radiotoxicology has emerged through investigating the possibility of transmission of biological effects over generations, in particular by epigenetic pathways. These processes are known for their crucial roles associated with the development of several diseases. The current work investigates the epigenetic effect of chronic exposure to low doses of uranium and its inheritance across generations. Materials and Methods To test this proposition, a rodent multigenerational model, males and females, were exposed to a non-toxic concentration of uranium (40mgL -1 drinking water) for nine months. The uranium effects on were evaluated over three generations (F0, F1 and F2) by analysing the DNA methylation profile and DNMT genes expression in ovaries and testes tissues. Here we report a significant hypermethylation of testes DNA (p <0.005) whereas ovaries showed hypomethylated DNA (p <0.005). Interestingly, this DNA methylation profile was significantly maintained across generations F0, F1 and F2. Furthermore, qPCR results of both tissues imply a significant change in the expression of DNA methyltransferase genes (DNMT 1 and DNMT3a/b) as well. Altogether, our work demonstrates for the first time a sex-dependance and inheritance of epigenetic marks, DNA methylation, as a biological response to the exposure to low doses of uranium. However, it is not clear which type of reproductive cell type is more responsive in this context. Copyright © 2017 Elsevier B.V. All rights reserved.

Bridging the gap between tribal risk perceptions and scientific decision-making for uranium legacy sites located in Native American communities

NASA Astrophysics Data System (ADS)

Joseph, C.; Waugh, W.; Glenn, E.; Chief, K.

2017-12-01

There are approximately 15,000 abandoned uranium mines (AUM) in the western United States, of which 500 AUMs are located in the Colorado Plateau Four-Corners region. Uranium mill tailings, referred to as legacy waste, compromise the largest volume of any category of radioactive waste in the nation. Today, the Department of Energy Legacy Management is responsible for long-term stewardship and maintenance of inactive uranium processing sites that have been remediated to prevent further migration and exposure of tailings to the environment and surrounding communities. In collaboration with the DOE-LM, I am investigating the impact of climate change and community adaptation on the long-term performance of disposal cell covers for uranium mill tailings located in Native American communities, as well as how these communities have adapted to and perceive these areas. I am interested in how abiotic engineered cell covers may be candidate sites for future conversion to vegetated evapotranspirative caps for arid to semi-arid climates. The objectives are to: 1) assess above-ground tissue of plants encroaching engineered cell covers for concentrations of uranium, radium, selenium, molybdenum, thorium, arsenic, lead, and manganese and compare them to control sites; 2) determine if above-cell plant tissue is accumulating to toxic levels that may create an exposure pathway, 3) identify climate scenarios for site locations and determine how short-and long-scale climate projections will influence spatial and temporal plant distribution for specific woody species; and 4) evaluate the risk perceptions of Hopi villages located five miles downstream of one site location. To date, risk perception and stakeholder outreach to the Hopi communities has been absent. This study will help inform how land use, water use, and sustenance practices may contribute to environmental health disparities for one of the few tribes that has maintained physical continuity within their ancestral homeland.

Uranium biogeochemistry across the redox transition zone of a permanently stratified fjord: Framvaren, Norway

USGS Publications Warehouse

Swarzenski, P.W.; McKee, B.A.; Skei, J.M.; Todd, J.F.

1999-01-01

During August 1995, the vertical concentration profile of dissolved and particulate uranium exhibited strong non-conservative characteristics in the upper 30 m of Framvaren Fjord. There was a pronounced peak in both particulate (> 0.2 ??m; 1.09 nM) and dissolved (< 0.2 ??m; 17.06 nM) uranium in the finely stratified waters at the O2/H2S interface which is positioned well within the euphotic zone at about 20-21 m. Such concentration maxima at the redox boundary are also observed for dissolved organic carbon (DEC), Sr and Ba. Dissolved U levels seen in the water column from 18 m down to 30 m exceeded the high salinity (salinity = 35) U concentrations (13.63 ?? 0.84 nM; Chen, J.H., Edwards, R.L., Wasserburg, G.L., 1986. 238U, 234U and 232Th in seawater. Earth Planet Sci. Lett. 80, 241-251.) observed uniformly in the open ocean. A prolific population of S microbes (e.g., Chromatium, Chlorobium sp.) flourishes at the O2/H2S interface. The source of elevated U at the redox boundary must be due to microbial uptake and subsequent release processes rather than dilution from oceanic uranium. Uranium oxidation state determinations in waters from 1, 22 and 30 m depth reveal that reduced U(IV) is not present in significant abundance, and that the chemical and/or biological reduction of hexavalent uranium is largely inhibited. Our results suggest that U and other trace constituents such as DOC, Sr, Ba, Fe(II), Mn(II) are greatly modified by direct and indirect microbial transformation reactions which are most concentrated across the redox transition zone in Framvaren Fjord.

Geochemical, mineralogical and microbiological characteristics of sediment from a naturally reduced zone in a uranium-contaminated aquifer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Campbell, Kate M.; Kukkadapu, Ravi K.; Qafoku, Nikolla

2012-05-23

Localized zones or lenses of naturally reduced sediments have the potential to play a significant role in the fate and transport of redox-sensitive metals and metalloids in aquifers. To assess the mineralogy, microbiology, and redox processes that occur in these zones, we examined several cores from a region of naturally occurring reducing conditions in a uranium-contaminated aquifer (Rifle, CO). Sediment samples from a transect of cores ranging from oxic/suboxic Rifle aquifer sediment to naturally reduced sediment were analyzed for uranium and iron content, oxidation state, and mineralogy, reduced sulfur phases, and solid phase organic carbon content using a suite ofmore » analytical and spectroscopic techniques on bulk sediment and size fractions. Solid-phase uranium concentrations were higher in the naturally reduced zone, with a high proportion of the uranium present as reduced U(IV). The sediments were also elevated in reduced sulfur phases and Fe(II), indicating it is very likely that U(VI), Fe(III), and sulfate reduction occurred or is occurring in the sediment. The microbial community was assessed using lipid- and DNA-based techniques, and statistical redundancy analysis was performed to determine correlations between the microbial community and the geochemistry. Increased concentration of solid phase organic carbon and biomass in the naturally reduced sediment suggests that natural bioreduction is stimulated by a zone of increased organic carbon concentration associated with fine-grained material and lower permeability to groundwater flow. Characterization of the naturally bioreduced sediment provides an understanding of the natural processes that occur in the sediment under reducing conditions and how they may impact natural attenuation of radionuclides and other redox sensitive materials. Results also suggest the importance of recalcitrant organic carbon for maintaining reducing conditions and uranium immobilization.« less

Oxidation of naturally reduced uranium in aquifer sediments by dissolved oxygen and its potential significance to uranium plume persistence

NASA Astrophysics Data System (ADS)

Davis, J. A.; Smith, R. L.; Bohlke, J. K.; Jemison, N.; Xiang, H.; Repert, D. A.; Yuan, X.; Williams, K. H.

2015-12-01

The occurrence of naturally reduced zones is common in alluvial aquifers in the western U.S.A. due to the burial of woody debris in flood plains. Such reduced zones are usually heterogeneously dispersed in these aquifers and characterized by high concentrations of organic carbon, reduced mineral phases, and reduced forms of metals, including uranium(IV). The persistence of high concentrations of dissolved uranium(VI) at uranium-contaminated aquifers on the Colorado Plateau has been attributed to slow oxidation of insoluble uranium(IV) mineral phases found in association with these reducing zones, although there is little understanding of the relative importance of various potential oxidants. Four field experiments were conducted within an alluvial aquifer adjacent to the Colorado River near Rifle, CO, wherein groundwater associated with the naturally reduced zones was pumped into a gas-impermeable tank, mixed with a conservative tracer (Br-), bubbled with a gas phase composed of 97% O2 and 3% CO2, and then returned to the subsurface in the same well from which it was withdrawn. Within minutes of re-injection of the oxygenated groundwater, dissolved uranium(VI) concentrations increased from less than 1 μM to greater than 2.5 μM, demonstrating that oxygen can be an important oxidant for uranium in such field systems if supplied to the naturally reduced zones. Dissolved Fe(II) concentrations decreased to the detection limit, but increases in sulfate could not be detected due to high background concentrations. Changes in nitrogen species concentrations were variable. The results contrast with other laboratory and field results in which oxygen was introduced to systems containing high concentrations of mackinawite (FeS), rather than the more crystalline iron sulfides found in aged, naturally reduced zones. The flux of oxygen to the naturally reduced zones in the alluvial aquifers occurs mainly through interactions between groundwater and gas phases at the water table. Seasonal variations of the water table at the Rifle, CO site may play an important role in introducing oxygen into the system. Although oxygen was introduced directly to the naturally reduced zones in these experiments, delivery of oxidants to the system may also be controlled by other oxidative pathways in which oxygen plays an indirect role.

Geological conditions of safe long-term storage and disposal of depleted uranium hexafluoride

NASA Astrophysics Data System (ADS)

Laverov, N. P.; Velichkin, V. I.; Omel'Yanenko, B. I.; Yudintsev, S. V.; Tagirov, B. R.

2010-08-01

The production of enriched uranium used in nuclear weapons and fuel for atomic power plants is accompanied by the formation of depleted uranium (DU), the amount of which annually increases by 35-40 kt. To date, more than 1.6 Mt DU has accumulated in the world. The main DU mass is stored as environ-mentally hazardous uranium hexafluoride (UF6), which is highly volatile and soluble in water with the formation of hydrofluoric acid. To ensure safe UF6 storage, it is necessary to convert this compound in chemically stable phases. The industrial reprocessing of UF6 into U3O8 and HF implemented in France is highly expensive. We substantiate the expediency of long-term storage of depleted uranium hexafluoride in underground repositories localized in limestone. On the basis of geochemical data and thermodynamic calculations, we show that interaction in the steel container-UF6-limestone-groundwater system gives rise to the development of a slightly alkaline reductive medium favorable for chemical reaction with formation of uraninite (UO2) and fluorite (CaF2). The proposed engineering solution not only ensures safe DU storage but also makes it possible to produce uraninite, which can be utilized, if necessary, in fast-neutron reactors. In the course of further investigations aimed at safe maintenance of DU, it is necessary to study the kinetics of conversion of UF6 into stable phases, involving laboratory and field experiments.

A multi-instrumental geochemical study of anomalous uranium enrichment in coal.

PubMed

Havelcová, Martina; Machovič, Vladimír; Mizera, Jiří; Sýkorová, Ivana; Borecká, Lenka; Kopecký, Lubomír

2014-11-01

Contents of uranium in coals from Odeř in the northernmost part of the Sokolov Basin, Czech Republic, in the vicinity of the well known St. Joachimsthal uranium ore deposits, reach extremely high values. In the present work, coal samples with contents of uranium ranging from 0.02 to 6 wt.% were studied. The study employing a whole complex of analytical techniques has been aimed at identification of changes in the structure of coal organic matter, which are associated with the high contents of uranium in coal. The study includes proximate and ultimate analyses, multielement analysis by instrumental neutron and photon activation analyses, micropetrographic analysis by optical microscopy, ESEM/EDX analysis of mineral matter, infrared and Raman spectroscopies, solvent extraction followed by gas chromatography with mass spectroscopy (GC/MS), and analytical pyrolysis (Py-GC/MS). The study has confirmed previously proposed explanation of uraniferous mineralization in sedimentary carboniferous substances by the mechanism of reduction and fixation of soluble U(VI) (uranyl, UO2(2+)) species (e.g., humic, carbonate/hydroxo/phosphate complexes) by sedimentary organic matter under diagenetic or hydrothermal conditions, and formation of insoluble U(IV) species as phosphate minerals and uraninite. The process is accompanied with alteration and destruction of the coal organic matter. The changes in the structure of coal organic matter involve dehydrogenation and oxidation mainly in the aliphatic, aromatic and hydroxyl structures, and an increase in aromaticity, content of ether bonds, and the degree of coalification. Copyright © 2014 Elsevier Ltd. All rights reserved.

In situ bioremediation of uranium with emulsified vegetable oil as the electron donor.

PubMed

Watson, David B; Wu, Wei-Min; Mehlhorn, Tonia; Tang, Guoping; Earles, Jennifer; Lowe, Kenneth; Gihring, Thomas M; Zhang, Gengxin; Phillips, Jana; Boyanov, Maxim I; Spalding, Brian P; Schadt, Christopher; Kemner, Kenneth M; Criddle, Craig S; Jardine, Philip M; Brooks, Scott C

2013-06-18

A field test with a one-time emulsified vegetable oil (EVO) injection was conducted to assess the capacity of EVO to sustain uranium bioreduction in a high-permeability gravel layer with groundwater concentrations of (mM) U, 0.0055; Ca, 2.98; NO3(-), 0.11; HCO3(-), 5.07; and SO4(2-), 1.23. Comparison of bromide and EVO migration and distribution indicated that a majority of the injected EVO was retained in the subsurface from the injection wells to 50 m downgradient. Nitrate, uranium, and sulfate were sequentially removed from the groundwater within 1-2 weeks, accompanied by an increase in acetate, Mn, Fe, and methane concentrations. Due to the slow release and degradation of EVO with time, reducing conditions were sustained for approximately one year, and daily U discharge to a creek, located approximately 50 m from the injection wells, decreased by 80% within 100 days. Total U discharge was reduced by 50% over the one-year period. Reduction of U(VI) to U(IV) was confirmed by synchrotron analysis of recovered aquifer solids. Oxidants (e.g., dissolved oxygen, nitrate) flowing in from upgradient appeared to reoxidize and remobilize uranium after the EVO was exhausted as evidenced by a transient increase of U concentration above ambient values. Occasional (e.g., annual) EVO injection into a permeable Ca and bicarbonate-containing aquifer can sustain uranium bioreduction/immobilization and decrease U migration/discharge.

Mechanism for transient migration of xenon in UO{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, X.-Y.; Uberuaga, B. P.; Andersson, D. A.

2011-04-11

In this letter, we report recent work on atomistic modeling of diffusion migration events of the fission gas product xenon in UO{sub 2} nuclear fuel. Under nonequilibrium conditions, Xe atoms can occupy the octahedral interstitial site, in contrast to the thermodynamically most stable uranium substitutional site. A transient migration mechanism involving Xe and two oxygen atoms is identified using basin constrained molecular dynamics employing a Buckingham type interatomic potential. This mechanism is then validated using density functional theory calculations using the nudged elastic band method. An overall reduction in the migration barrier of 1.6-2.7 eV is obtained compared to vacancy-mediatedmore » diffusion on the uranium sublattice.« less

METAL PLATING PROCESS

DOEpatents

Walker, D.E.; Noland, R.A.

1958-08-12

A process ts described for obtaining a closely bonded coating of steel or iron on uranium. The process consists of providing, between the steel and uramium. a layer of silver. amd then pressure rolling tbe assembly at about 600 deg C until a reduction of from l0 to 50% has been obtained.

Optimizing Metalloporphyrin-Catalyzed Reduction Reactions for In Situ Remediation of DOE Contaminants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schlautman, Mark A.

2013-07-14

Past activities have resulted in a legacy of contaminated soil and groundwater at Department of Energy facilities nationwide. Uranium and chromium are among the most frequently encountered and highest-priority metal and radionuclide contaminants at DOE installations. Abiotic chemical reduction of uranium and chromium at contaminated DOE sites can be beneficial because the reduced metal species are less soluble in water, less mobile in the environment, and less toxic to humans and ecosystems. Although direct biological reduction has been reported for U(VI) and Cr(VI) in laboratory studies and at some field sites, the reactions can sometimes be slow or even inhibitedmore » due to unfavorable environmental conditions. One promising approach for the in-situ remediation of DOE contaminants is to develop electron shuttle catalysts that can be delivered precisely to the specific subsurface locations where contaminants reside. Previous research has shown that reduction of oxidized organic and inorganic contaminants often can be catalyzed by electron shuttle systems. Metalloporphyrins and their derivatives are well known electron shuttles for many biogeochemical systems, and thus were selected to study their catalytic capabilities for the reduction of chromium and uranium in the presence of reducing agents. Zero valent iron (ZVI) was chosen as the primary electron donor in most experimental systems. Research proceeded in three phases and the key findings of each phase are reported here. Phase I examined Cr(VI) reduction and utilized micro- and nano-sized ZVI as the electron donors. Electron shuttle catalysts tested were cobalt- and iron-containing metalloporphyrins and Vitamin B12. To aid in the recycle and reuse of the nano-sized ZVI and soluble catalysts, sol-gels and calcium-alginate gel beads were tested as immobilization/support matrices. Although the nano-sized ZVI could be incorporated within the alginate gel beads, preliminary attempts to trap it in sol-gels were not successful. Conversely, the water-soluble catalysts could be trapped within sol-gel matrices but they tended to leach out of the alginate gel beads during use. In general, immobilization of the nano-sized ZVI in gel beads and of the catalysts in sol-gels tended to result in slower rates of Cr(VI) reduction, but these effects could be overcome to some extent by using higher reactant/catalyst concentrations. In addition, the lowering of their effectiveness would likely be offset by the benefits obtained when recycling and reusing the materials because they were immobilized. Addition of the catalytic electron shuttles will be most useful when the micro-sized or nano-sized ZVI becomes less reactive with reaction time. Continued work in Phase II in the area of nano-sized ZVI immobilization led to procedures that were successful in incorporating the iron particles in sol-gel matrices. The water-soluble reductants sodium dithionite and L-ascorbic acid were also tested, but their use appeared to lead to formation of complexes with the uranyl cation which limited their effectiveness. Also, although the sol-gel supported nano-sized ZVI showed some promise at reducing uranium, the fluoride used in the sol-gel synthesis protocol appeared to lead to formation of uranyl-fluoride complexes that were less reactive. Because hexavalent chromium is an anion which does not form complexes with fluoride, it was used to demonstrate the intrinsic reactivity of the sol-gel immobilized nano-sized ZVI. Consistent with our observations in Phase I, the sol-gel matrix once again slowed down the reduction reaction but the expected benefits of recycle/reuse should outweigh this adverse effect. The major emphasis in Phase III of this study was to simultaneously incorporate nano-sized ZVI and water-soluble catalysts in the same sol-gel matrix. The catalysts utilized were cobalt complexes of uroporphyrin and protoporphyrin and Cr(VI) reduction was used to test the efficacy of the combined "catalyst + reductant" sol-gel matrix. When enough catalyst was added to the sol-gels, enhancement of the Cr(VI) reduction reaction was observed. At the lowest levels of catalyst addition, however, the rates of Cr(VI) reduction were similar to those systems which only used sol-gel immobilized nano-sized ZVI without any catalyst present. These findings suggest future areas of research that should be pursued to further optimize abiotic reduction reactions of metals with combined "catalyst + reductant" matrices.« less

Enzymatic iron and uranium reduction by sulfate-reducing bacteria

USGS Publications Warehouse

Lovley, D.R.; Roden, E.E.; Phillips, E.J.P.; Woodward, J.C.

1993-01-01

The potential for sulfate-reducing bacteria (SRB) to enzymatically reduce Fe(III) and U(VI) was investigated. Five species of Desulfovibrio as well as Desulfobacterium autotrophicum and Desulfobulbus propionicus reduced Fe(III) chelated with nitrilotriacetic acid as well as insoluble Fe(III) oxide. Fe(III) oxide reduction resulted in the accumulation of magnetite and siderite. Desulfobacter postgatei reduced the chelated Fe(III) but not Fe(III) oxide. Desulfobacter curvatus, Desulfomonile tiedjei, and Desulfotomaculum acetoxidans did not reduce Fe(III). Only Desulfovibrio species reduced U(VI). U(VI) reduction resulted in the precipitation of uraninite. None of the SRB that reduced Fe(III) or U(VI) appeared to conserve enough energy to support growth from this reaction. However, Desulfovibrio desulfuricans metabolized H2 down to lower concentrations with Fe(III) or U(VI) as the electron acceptor than with sulfate, suggesting that these metals may be preferred electron acceptors at the low H2 concentrations present in most marine sediments. Molybdate did not inhibit Fe(III) reduction by D. desulfuricans. This indicates that the inability of molybdate to inhibit Fe(III) reduction in marine sediments does not rule out the possibility that SRB are important catalysts for Fe(III) reduction. The results demonstrate that although SRB were previously considered to reduce Fe(III) and U(VI) indirectly through the production of sulfide, they may also directly reduce Fe(III) and U(VI) through enzymatic mechanisms. These findings, as well as our recent discovery that the So-reducing microorganism Desulfuromonas acetoxidans can reduce Fe(III), demonstrate that there are close links between the microbial sulfur, iron, and uranium cycles in anaerobic marine sediments. ?? 1993.

Pyroprocessing of oxidized sodium-bonded fast reactor fuel - An experimental study of treatment options for degraded EBR-II fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hermann, S.D.; Gese, N.J.; Wurth, L.A.

An experimental study was conducted to assess pyrochemical treatment options for degraded EBR-II fuel. As oxidized material, the degraded fuel would need to be converted back to metal to enable electrorefining within an existing electro-metallurgical treatment process. A lithium-based electrolytic reduction process was studied to assess the efficacy of converting oxide materials to metal with a particular focus on the impact of zirconium oxide and sodium oxide on this process. Bench-scale electrolytic reduction experiments were performed in LiCl-Li{sub 2}O at 650 C. degrees with combinations of manganese oxide (used as a surrogate for uranium oxide), zirconium oxide, and sodium oxide.more » In the absence of zirconium or sodium oxide, the electrolytic reduction of MnO showed nearly complete conversion to metal. The electrolytic reduction of a blend of MnO-ZrO{sub 2} in LiCl - 1 wt% Li{sub 2}O showed substantial reduction of manganese, but only 8.5% of the zirconium was found in the metal phase. The electrolytic reduction of the same blend of MnO-ZrO{sub 2} in LiCl - 1 wt% Li{sub 2}O - 6.2 wt% Na{sub 2}O showed substantial reduction of manganese, but zirconium reduction was even less at 2.4%. This study concluded that ZrO{sub 2} cannot be substantially reduced to metal in an electrolytic reduction system with LiCl - 1 wt% Li{sub 2}O at 650 C. degrees due to the perceived preferential formation of lithium zirconate. This study also identified a possible interference that sodium oxide may have on the same system by introducing a parasitic and cyclic reaction of dissolved sodium metal between oxidation at the anode and reduction at the cathode. When applied to oxidized sodium-bonded EBR-II fuel (e.g., U-10Zr), the prescribed electrolytic reduction system would not be expected to substantially reduce zirconium oxide, and the accumulation of sodium in the electrolyte could interfere with the reduction of uranium oxide, or at least render it less efficient.« less

Characterization of U(VI) reduction in contaminated sediments with slow-degrading electron donor source

NASA Astrophysics Data System (ADS)

Wu, W.; Watson, D. B.; Zhang, G.; Mehlhorn, T.; Lowe, K.; Earles, J.; Phillips, J.; Kelly, S. D.; Boyanov, M.; Kemner, K. M.; Schadt, C.; Criddle, C. S.; Jardine, P. M.; Brooks, S. C.

2011-12-01

In order to select sustainable, high efficiency and cost effective electron donor source, oleate and emulsified vegetable oil (EVO) were tested uranium (VI) reduction in comparison with ethanol in microcosms using uranium contaminated sediments and groundwater from the US DOE Oak Ridge Integrated Field Research Challenge (ORIFRC) site. The effect of initial sulfate concentration on U(VI) reduction was also tested. Both oleate and EVO were effective electron donor sources for U(VI) reduction. Accumulation of acetate as a major product and the removal of aqueous U(VI) were observed and were associated with sulfate reduction. Both oleate and EVO supported U(VI) reduction but at slower rates with a comparable but slightly lower extent of reduction than ethanol. X-ray absorption near-edge spectroscopy (XANES) analysis confirmed reduction of U(VI) to U(IV). The extent of U(VI) reduction in solid phase was negatively influenced by aqueous calcium concentration. The majority of electrons of the three substrates were consumed by sulfate reduction, Fe(III) reduction, and methanogenesis. Initial U(VI) concentration in the aqueous phase increased with increased sulfate concentration (1 versus 5 mM), likely due to U(VI) desorption from the solid phase. At the higher initial sulfate concentration more U(VI) was reduced and fewer electrons were used in methanogenesis. Analysis of bacterial and archeal populations using 16S rRNA gene libraries showed a significant increase in Deltaproteobacteria after biostimulation. The microbial community structures developed with oleate and EVO were significantly distinct from those developed with ethanol. Bacteria similar to Desulforegula spp. was predominant for oleate and EVO degradation but were not observed in ethanol-amended microcosms. Known U(VI)-reducing bacteria in the microcosms amended with the three electron donor sources included iron(III) reducing Geobacter spp. but in lower abundances than sulfate-reducing Desulfovibrio spp. The test results were used for the design a field test by one-time injection of EVO to the subsurface for U(VI) reduction in Area 2 of the ORIFRC site.

Deep liquid-chromatographic purification of uranium extract from technetium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Volk, V.; Dvoeglazov, K; Podrezova, L.

The recycling of uranium in the nuclear fuel cycle requires the removal of a number of radioactive and stable impurities like {sup 99}Tc from spent fuels. In order to improve the grade of uranium extract purification from technetium the method of liquid chromatography and the apparatus for its performance have been developed. Process of technetium extraction and concentrating in aqueous solution containing reducing agent has been studied on simulated solutions (U-Tc-HNO{sub 3}-30% TBP-isoparM). The dynamic tests of the method have been carried out on the laboratory unit. Solution of diformyl-hydrazine in nitric acid was used as a stationary phase. Silicamore » gel with specific surface of 186 m{sup 2}/g was used as a carrier of the stationary phase. It is shown that the volume of purified extract increases as the solution temperature increases, concentration of reducing agent increases and extract flow rate decreases. It is established that the technetium content in uranium by this method could achieve a value below 0.3 ppm. Some variants of overload and composition of the stationary phase containing the extracted technetium have been offered and tested. It is defined that the method provides reduction of processing medium-active wastes by more than 10 times during finish refining process. (authors)« less

Impact of biostimulated redox processes on metal dynamics in an iron-rich creek soil of a former uranium mining area.

PubMed

Burkhardt, Eva-Maria; Akob, Denise M; Bischoff, Sebastian; Sitte, Jana; Kostka, Joel E; Banerjee, Dipanjan; Scheinost, Andreas C; Küsel, Kirsten

2010-01-01

Understanding the dynamics of metals and radionuclides in soil environments is necessary for evaluating risks to pristine sites. An iron-rich creek soil of a former uranium-mining district (Ronneburg, Germany) showed high porewater concentrations of heavy metals and radionuclides. Thus, this study aims to (i) evaluate metal dynamics during terminal electron accepting processes (TEAPs) and (ii) characterize active microbial populations in biostimulated soil microcosms using a stable isotope probing (SIP) approach. In biostimulated soil slurries, concentrations of soluble Co, Ni, Zn, As, and unexpectedly U increased during Fe(III)-reduction. This suggests that there was a release of sorbed metals and As during reductive dissolution of Fe(III)-oxides. Subsequent sulfate-reduction was concurrent with a decrease of U, Co, Ni, and Zn concentrations. The relative contribution of U(IV) in the solid phase changed from 18.5 to 88.7% after incubation. The active Fe(III)-reducing population was dominated by delta-Proteobacteria (Geobacter) in (13)C-ethanol amended microcosms. A more diverse community was present in (13)C-lactate amended microcosms including taxa related to Acidobacteria, Firmicutes, delta-Proteobacteria, and beta-Proteobacteria. Our results suggested that biostimulated Fe(III)-reducing communities facilitated the release of metals including U to groundwater which is in contrast to other studies.

Direct vs. indirect pathway for nitrobenzene reduction reaction on a Ni catalyst surface: a density functional study.

PubMed

Mahata, Arup; Rai, Rohit K; Choudhuri, Indrani; Singh, Sanjay K; Pathak, Biswarup

2014-12-21

Density functional theory (DFT) calculations are performed to understand and address the previous experimental results that showed the reduction of nitrobenzene to aniline prefers direct over indirect reaction pathways irrespective of the catalyst surface. Nitrobenzene to aniline conversion occurs via the hydroxyl amine intermediate (direct pathway) or via the azoxybenzene intermediate (indirect pathway). Through our computational study we calculated the spin polarized and dispersion corrected reaction energies and activation barriers corresponding to various reaction pathways for the reduction of nitrobenzene to aniline over a Ni catalyst surface. The adsorption behaviour of the substrate, nitrobenzene, on the catalyst surface was also considered and the energetically most preferable structural orientation was elucidated. Our study indicates that the parallel adsorption behaviour of the molecules over a catalyst surface is preferable over vertical adsorption behaviour. Based on the reaction energies and activation barrier of the various elementary steps involved in direct or indirect reaction pathways, we find that the direct reduction pathway of nitrobenzene over the Ni(111) catalyst surface is more favourable than the indirect reaction pathway.

Cost-Reduction Roadmap Outlines Two Pathways to Meet DOE Residential Solar

Science.gov Websites

Cost Target for 2030 | News | NREL Cost-Reduction Roadmap Outlines Two Pathways to Meet DOE Residential Solar Cost Target for 2030 News Release: Cost-Reduction Roadmap Outlines Two Pathways to Meet DOE Residential Solar Cost Target for 2030 Installing photovoltaics at the time of roof replacement or as part of

Geology, geochemistry, and geophysics of the Fry Canyon uranium/copper project site, southeastern Utah - Indications of contaminant migration

USGS Publications Warehouse

Otton, James K.; Zielinski, Robert A.; Horton, Robert J.

2010-01-01

The Fry Canyon uranium/copper project site in San Juan County, southeastern Utah, was affected by the historical (1957-68) processing of uranium and copper-uranium ores. Relict uranium tailings and related ponds, and a large copper heap-leach pile at the site represent point sources of uranium and copper to local soils, surface water, and groundwater. This study was designed to establish the nature, extent, and pathways of contaminant dispersion. The methods used in this study are applicable at other sites of uranium mining, milling, or processing. The uranium tailings and associated ponds sit on a bench that is as much as 4.25 meters above the level of the adjacent modern channel of Fry Creek. The copper heap leach pile sits on bedrock just south of this bench. Contaminated groundwater from the ponds and other nearby sites moves downvalley and enters the modern alluvium of adjacent Fry Creek, its surface water, and also a broader, deeper paleochannel that underlies the modern creek channel and adjacent benches and stream terraces. The northern extent of contaminated groundwater is uncertain from geochemical data beyond an area of monitoring wells about 300 meters north of the site. Contaminated surface water extends to the State highway bridge. Some uranium-contaminated groundwater may also enter underlying bedrock of the Permian Cedar Mesa Sandstone along fracture zones. Four dc-resistivity surveys perpendicular to the valley trend were run across the channel and its adjacent stream terraces north of the heap-leach pile and ponds. Two surveys were done in a small field of monitoring wells and two in areas untested by borings to the north of the well field. Bedrock intercepts, salt distribution, and lithologic information from the wells and surface observations in the well field aided interpretation of the geophysical profiles there and allowed interpretation of the two profiles not tested by wells. The geophysical data for the two profiles to the north of the well field suggest that the paleochannel persists at least 900 m to the north of the heap leach and pond sites. Contamination of groundwater beneath the stream terraces may extend at least that far. Fry Creek surface water (six samples), seeps and springs (six samples), and wells (eight samples) were collected during a dry period of April 16-19, 2007. The most uranium-rich (18.7 milligrams per liter) well water on the site displays distinctive Ca-Mg-SO4-dominant chemistry indicating the legacy of heap leaching copper-uranium ores with sulfuric acid. This same water has strongly negative d34S of sulfate (-13.3 per mil) compared to most local waters of -2.4 to -5.4 per mil. Dissolved uranium species in all sampled waters are dominantly U(VI)-carbonate complexes. All waters are undersaturated with respect to U(VI) minerals. The average 234U/238U activity ratio (AR) in four well waters from the site (0.939 + or ? 0.011) is different from that of seven upstream waters (1.235 + or ? 0.069). This isotopic contrast permits quantitative estimates of mixing of site-derived uranium with natural uranium in waters collected downstream. At the time of sampling, uranium in downstream surface water was mostly (about 67 percent) site-derived and subject to further concentration by evaporation. Three monitoring wells located approximately 0.4 kilometer downstream contained dominantly (78-87 percent) site-derived uranium. Distinctive particles of chalcopyrite (CuFeS) and variably weathered pyrite (FeS2) are present in tailings at the stream edge on the site and are identified in stream sediments 1.3 kilometers downstream, based on inspection of polished grain mounts of magnetic mineral separates.

Genetic and grade and tonnage models for sandstone-hosted roll-type uranium deposits, Texas Coastal Plain, USA

USGS Publications Warehouse

Hall, Susan M.; Mihalasky, Mark J.; Tureck, Kathleen; Hammarstrom, Jane M.; Hannon, Mark

2017-01-01

The coincidence of a number of geologic and climatic factors combined to create conditions favorable for the development of mineable concentrations of uranium hosted by Eocene through Pliocene sandstones in the Texas Coastal Plain. Here 254 uranium occurrences, including 169 deposits, 73 prospects, 6 showings and 4 anomalies, have been identified. About 80 million pounds of U3O8 have been produced and about 60 million pounds of identified producible U3O8 remain in place. The development of economic roll-type uranium deposits requires a source, large-scale transport of uranium in groundwater, and deposition in reducing zones within a sedimentary sequence. The weight of the evidence supports a source from thick sequences of volcanic ash and volcaniclastic sediment derived mostly from the Trans-Pecos volcanic field and Sierra Madre Occidental that lie west of the region. The thickest accumulations of source material were deposited and preserved south and west of the San Marcos arch in the Catahoula Formation. By the early Oligocene, a formerly uniformly subtropical climate along the Gulf Coast transitioned to a zoned climate in which the southwestern portion of Texas Coastal Plain was dry, and the eastern portion humid. The more arid climate in the southwestern area supported weathering of volcanic ash source rocks during pedogenesis and early diagenesis, concentration of uranium in groundwater and movement through host sediments. During the middle Tertiary Era, abundant clastic sediments were deposited in thick sequences by bed-load dominated fluvial systems in long-lived channel complexes that provided transmissive conduits favoring transport of uranium-rich groundwater. Groundwater transported uranium through permeable sandstones that were hydrologically connected with source rocks, commonly across formation boundaries driven by isostatic loading and eustatic sea level changes. Uranium roll fronts formed as a result of the interaction of uranium-rich groundwater with either (1) organic-rich debris adjacent to large long-lived fluvial channels and barrier–bar sequences or (2) extrinsic reductants entrained in formation water or discrete gas that migrated into host units via faults and along the flanks of salt domes and shale diapirs. The southwestern portion of the region, the Rio Grande embayment, contains all the necessary factors required for roll-type uranium deposits. However, the eastern portion of the region, the Houston embayment, is challenged by a humid environment and a lack of source rock and transmissive units, which may combine to preclude the deposition of economic deposits. A grade and tonnage model for the Texas Coastal Plain shows that the Texas deposits represent a lower tonnage subset of roll-type deposits that occur around the world, and required aggregation of production centers into deposits based on geologic interpretation for the purpose of conducting a quantitative mineral resource assessment.

Bacterial Community Succession During in situ Uranium Bioremediation: Spatial Similarities Along Controlled Flow Paths

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hwang, Chiachi; Wu, Weimin; Gentry, Terry J.

2009-05-22

Bacterial community succession was investigated in a field-scale subsurface reactor formed by a series of wells that received weekly ethanol additions to re-circulating groundwater. Ethanol additions stimulated denitrification, metal reduction, sulfate reduction, and U(VI) reduction to sparingly soluble U(IV). Clone libraries of SSU rRNA gene sequences from groundwater samples enabled tracking of spatial and temporal changes over a 1.5 y period. Analyses showed that the communities changed in a manner consistent with geochemical variations that occurred along temporal and spatial scales. Canonical correspondence analysis revealed that the levels of nitrate, uranium, sulfide, sulfate, and ethanol strongly correlated with particular bacterialmore » populations. As sulfate and U(VI) levels declined, sequences representative of sulfate-reducers and metal-reducers were detected at high levels. Ultimately, sequences associated with sulfate-reducing populations predominated, and sulfate levels declined as U(VI) remained at low levels. When engineering controls were compared to the population variation via canonical ordination, changes could be related to dissolved oxygen control and ethanol addition. The data also indicated that the indigenous populations responded differently to stimulation for bio-reduction; however, the two bio-stimulated communities became more similar after different transitions in an idiosyncratic manner. The strong associations between particular environmental variables and certain populations provide insight into the establishment of practical and successful remediation strategies in radionuclide-contaminated environments with respect to engineering controls and microbial ecology.« less

Kinetics of triscarbonato uranyl reduction by aqueous ferrous iron: a theoretical study.

PubMed

Wander, Matthew C F; Kerisit, Sebastien; Rosso, Kevin M; Schoonen, Martin A A

2006-08-10

Uranium is a pollutant whose mobility is strongly dependent on its oxidation state. While U(VI) in the form of the uranyl cation is readily reduced by a range of natural reductants, by contrast complexation of uranyl by carbonate greatly reduces its reduction potential and imposes increased electron transfer (ET) distances. Very little is known about the elementary processes involved in uranium reduction from U(VI) to U(V) to U(IV) in general. In this study, we examine the theoretical kinetics of ET from ferrous iron to triscarbonato uranyl in aqueous solution. A combination of molecular dynamics (MD) simulations and density functional theory (DFT) electronic structure calculations is employed to compute the parameters that enter into Marcus' ET model, including the thermodynamic driving forces, reorganization energies, and electronic coupling matrix elements. MD simulations predict that two ferrous iron atoms will bind in an inner-sphere fashion to the three-membered carbonate ring of triscarbonato uranyl, forming the charge-neutral ternary Fe(2)UO(2)(CO(3))(3)(H(2)O)(8) complex. Through a sequential proton-coupled electron-transfer mechanism (PCET), the first ET step converting U(VI) to U(V) is predicted by DFT to occur with an electronic barrier that corresponds to a rate on the order of approximately 1 s(-1). The second ET step converting U(V) to U(IV) is predicted to be significantly endergonic. Therefore, U(V) is a stabilized end product in this ET system, in agreement with experiment.

Phase formation during the carbothermic reduction of eudialyte concentrate

NASA Astrophysics Data System (ADS)

Krasikov, S. A.; Upolovnikova, A. G.; Sitnikova, O. A.; Ponomarenko, A. A.; Agafonov, S. N.; Zhidovinova, S. V.; Maiorov, D. V.

2013-07-01

The phase transformations of eudialyte concentrate during the carbothermic reduction in the temperature range 25-2000°C are studied by thermodynamic simulation, differential thermal analysis, and X-ray diffraction. As the temperature increases to 1500°C, the following phases are found to form sequentially: iron and manganese carbides, free iron, niobium carbide, iron silicides, silicon and titanium carbides, and free silicon. Strontium, yttrium, and uranium in the temperature range under study are not reduced and are retained in an oxide form, and insignificant reduction of zirconium oxides with the formation of carbide ZrC is possible only at temperatures above 1500°C.

Method for preparing actinide nitrides

DOEpatents

Bryan, G.H.; Cleveland, J.M.; Heiple, C.R.

1975-12-01

Actinide nitrides, and particularly plutonium and uranium nitrides, are prepared by reacting an ammonia solution of an actinide compound with an ammonia solution of a reactant or reductant metal, to form finely divided actinide nitride precipitate which may then be appropriately separated from the solution. The actinide nitride precipitate is particularly suitable for forming nuclear fuels.

Efficacy of a Solution-Based Approach for Making Sodalite Waste Forms for an Oxide Reduction Salt Utilized in the Reprocessing of Used Uranium Oxide Fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Riley, Brian J.; Pierce, David A.; Frank, Steven M.

2015-04-01

This paper describes various approaches for making sodalite with a LiCl-Li2O oxide reduction salt used to recover uranium from used oxide fuel. The approaches include sol-gel and solution-based synthesis processes. As-made products were mixed with 5 and 10 mass% of a Na2O-B2O3-SiO2 glass binder and these, along with product without a binder, were heated using either a cold-press-and-sinter method or hot uniaxial pressing. The results demonstrate the limitation of sodalite yield due to the fast intermediate reactions between Na+ and Cl- to form halite in solution and Li2O and SiO2 to form lithium silicates (e.g., Li2SiO3 or Li2Si2O5) in themore » calcined and sintered pellets. The results show that pellets can be made with high sodalite fractions (~92 mass%) and low porosities using a solution-based approach and this LiCl-Li2O salt.« less

Apparatus and process for the electrolytic reduction of uranium and plutonium oxides

DOEpatents

Poa, David S.; Burris, Leslie; Steunenberg, Robert K.; Tomczuk, Zygmunt

1991-01-01

An apparatus and process for reducing uranium and/or plutonium oxides to produce a solid, high-purity metal. The apparatus is an electrolyte cell consisting of a first container, and a smaller second container within the first container. An electrolyte fills both containers, the level of the electrolyte in the first container being above the top of the second container so that the electrolyte can be circulated between the containers. The anode is positioned in the first container while the cathode is located in the second container. Means are provided for passing an inert gas into the electrolyte near the lower end of the anode to sparge the electrolyte and to remove gases which form on the anode during the reduction operation. Means are also provided for mixing and stirring the electrolyte in the first container to solubilize the metal oxide in the electrolyte and to transport the electrolyte containing dissolved oxide into contact with the cathode in the second container. The cell is operated at a temperature below the melting temperature of the metal product so that the metal forms as a solid on the cathode.

Roadmap for disposal of Electrorefiner Salt as Transuranic Waste.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rechard, Robert P.; Trone, Janis R.; Kalinina, Elena Arkadievna

The experimental breeder reactor (EBR-II) used fuel with a layer of sodium surrounding the uranium-zirconium fuel to improve heat transfer. Disposing of EBR-II fuel in a geologic repository without treatment is not prudent because of the potentially energetic reaction of the sodium with water. In 2000, the US Department of Energy (DOE) decided to treat the sodium-bonded fuel with an electrorefiner (ER), which produces metallic uranium product, a metallic waste, mostly from the cladding, and the salt waste in the ER, which contains most of the actinides and fission products. Two waste forms were proposed for disposal in a minedmore » repository; the metallic waste, which was to be cast into ingots, and the ER salt waste, which was to be further treated to produce a ceramic waste form. However, alternative disposal pathways for metallic and salt waste streams may reduce the complexity. For example, performance assessments show that geologic repositories can easily accommodate the ER salt waste without treating it to form a ceramic waste form. Because EBR-II was used for atomic energy defense activities, the treated waste likely meets the definition of transuranic waste. Hence, disposal at the Waste Isolation Pilot Plant (WIPP) in southern New Mexico, may be feasible. This report reviews the direct disposal pathway for ER salt waste and describes eleven tasks necessary for implementing disposal at WIPP, provided space is available, DOE decides to use this alternative disposal pathway in an updated environmental impact statement, and the State of New Mexico grants permission.« less

The biomineralization process of uranium(VI) by Saccharomyces cerevisiae - transformation from amorphous U(VI) to crystalline chernikovite.

PubMed

Shen, Yanghao; Zheng, Xinyan; Wang, Xiaoyu; Wang, Tieshan

2018-05-01

Microorganisms play a significant role in uranium(VI) biogeochemistry and influence U(VI) transformation through biomineralization. In the present work, the process of uranium mineralization was investigated by Saccharomyces cerevisiae. The toxicity experiments showed that the viability of cell was not significantly affected by 100 mg L -1 U(VI) under 4 days of exposure time. The batch experiments showed that the phosphate concentration and pH value increased over time during U(VI) adsorption. Meanwhile, thermodynamic calculations demonstrated that the adsorption system was supersaturated with respect to UO 2 HPO 4 . The X-ray powder diffraction spectroscopy (XRD), field emission scanning electron microscopy (FE-SEM) equipped with energy dispersive spectroscopy (EDX), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) analyses indicated that the U(VI) was first attached onto the cell surface and reacted with hydroxyl, carboxyl, and phosphate groups through electrostatic interactions and complexation. As the immobilization of U(VI) transformed it from the ionic to the amorphous state, lamellar uranium precipitate was formed on the cell surface. With the prolongation of time, the amorphous uranium compound disappeared, and there were some crystalline substances observed extracellularly, which were well-characterized as tetragonal-chernikovite. Furthermore, the size of chernikovite was regulated at nano-level by cells, and the perfect crystal was formed finally. These findings provided an understanding of the non-reductive transformation process of U(VI) from the amorphous to crystalline state within microbe systems, which would be beneficial for the U(VI) treatment and reuse of nuclides and heavy metals.

Gum-compliant uncertainty propagations for Pu and U concentration measurements using the 1st-prototype XOS/LANL hiRX instrument; an SRNL H-Canyon Test Bed performance evaluation project

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holland, Michael K.; O'Rourke, Patrick E.

An SRNL H-Canyon Test Bed performance evaluation project was completed jointly by SRNL and LANL on a prototype monochromatic energy dispersive x-ray fluorescence instrument, the hiRX. A series of uncertainty propagations were generated based upon plutonium and uranium measurements performed using the alpha-prototype hiRX instrument. Data reduction and uncertainty modeling provided in this report were performed by the SRNL authors. Observations and lessons learned from this evaluation were also used to predict the expected uncertainties that should be achievable at multiple plutonium and uranium concentration levels provided instrument hardware and software upgrades being recommended by LANL and SRNL are performed.

Surface catalysis of uranium(VI) reduction by iron(II)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liger, E.; Charlet, L.; Van Cappellen, P.

1999-10-01

Colloidal hematite ({alpha}-Fe{sub 2}O{sub 3}) is used as model solid to investigate the kinetic effect of specific adsorption interactions on the chemical reduction of uranyl (U{sup VI}O{sub 2}{sup 2+}) by ferrous iron. Acid-base titrations and Fe(II) and uranyl adsorption experiments are performed on hematite suspensions, under O{sub 2}- and CO{sub 2}-free conditions. The results are explained in terms of a constant capacitance surface complexation model of the hematite-aqueous solution interface. Two distinct Fe(II) surface complexes are required to reproduce the data: ({equivalent{underscore}to}Fe{sup III}OFe{sup II}){sup +} (or {equivalent{underscore}to}Fe{sup III}OFe{sup II}(OH{sub 2}){sub n}{sup +}) and {equivalent{underscore}to}Fe{sup III}OFe{sup II}OH{sup 0} (or {equivalent{underscore}to}Fe{sup III}OFe{supmore » II}(OH{sub 2}){sub n{minus}1}OH{sup 0}). The latter complex represents a significant fraction of total adsorbed Fe(II) at pH {gt} 6.5. Uranyl binding to the hematite particles is characterized by a sharp adsorption edge between pH 4 and pH 5.5. Because of the absence of competing aqueous carbonate complexes, uranyl remains completely adsorbed at pH {gt} 7. A single mononuclear surface complex accounts for the adsorption of uranyl over the entire range of experimental conditions. Although thermodynamically feasible, no reaction between uranyl and Fe(II) is observed in homogeneous solution at pH 7.5, for periods of up to three days. In hematite suspensions, however, surface-bound uranyl reacts on a time scale of hours. Based on Fourier Transformed Infrared spectra, chemical reduction of U(VI) is inferred to be the mechanism responsible for the disappearance of uranyl. The kinetics of uranyl reduction are quantified by measuring the decrease with time of the concentration of U(VI) extractable from the hematite particles by NaHCO{sub 3}. In the presence of excess Fe(II), the initial rate of U(VI) reduction exhibits a first-order dependence on the concentration of adsorbed uranyl. The pseudo-first-order rate constant varies with pH (range, 6--7.5) and the total (dissolved + adsorbed) concentration of Fe(II) (range, 2--160 {micro}M). When analyzing the rate data in terms of the calculated surface speciation, the variability of the rate constant can be accounted for entirely by changes in the concentration of the Fe(II) monohydroxo surface complex {equivalent{underscore}to}Fe{sup III}OFe{sup II}OH{sup 0}. Therefore, the rate law is derived for the hematite-catalyzed reduction of uranyl by Fe(II), where the bimolecular rate constant {kappa} has a value of 399 {+-} 25 M{sup {minus}1} min{sup {minus}1} at 25 C. The hydroxo surface complex is the rate-controlling reductant species, because it provides the most favorable coordination environment in which electrons are removed from Fe(II). Natural particulate matter collected in the hypolimnion of a seasonally stratified lake also causes the rapid reduction of uranyl by Fe(II), Ferrihydrite, identified in the particulate matter by X-ray diffraction, is one possible mineral phase accelerating the reaction between U(VI) and Fe(II). At near-neutral pH and total Fe(II) levels less than 1 mM, the pseudo-first-order rate constants of chemical U(VI) reduction, measured in the presence of the hematite and lake particles, are of the same order of magnitude as the highest corresponding rate coefficients for enzymatic U(VI) reduction in bacterial cultures. Hence, based on the results of this study, surface-catalyzed U(VI) reduction by Fe(II) is expected to be a major pathway of uranium immobilization in a wide range of redox-stratified environments.« less

Redox potential as a master variable controlling pathways of metal reduction by Geobacter sulfurreducens

PubMed Central

Levar, Caleb E; Hoffman, Colleen L; Dunshee, Aubrey J; Toner, Brandy M; Bond, Daniel R

2017-01-01

Geobacter sulfurreducens uses at least two different pathways to transport electrons out of the inner membrane quinone pool before reducing acceptors beyond the outer membrane. When growing on electrodes poised at oxidizing potentials, the CbcL-dependent pathway operates at or below redox potentials of –0.10 V vs the standard hydrogen electrode, whereas the ImcH-dependent pathway operates only above this value. Here, we provide evidence that G. sulfurreducens also requires different electron transfer proteins for reduction of a wide range of Fe(III)- and Mn(IV)-(oxyhydr)oxides, and must transition from a high- to low-potential pathway during reduction of commonly studied soluble and insoluble metal electron acceptors. Freshly precipitated Fe(III)-(oxyhydr)oxides could not be reduced by mutants lacking the high-potential pathway. Aging these minerals by autoclaving did not change their powder X-ray diffraction pattern, but restored reduction by mutants lacking the high-potential pathway. Mutants lacking the low-potential, CbcL-dependent pathway had higher growth yields with both soluble and insoluble Fe(III). Together, these data suggest that the ImcH-dependent pathway exists to harvest additional energy when conditions permit, and CbcL switches on to allow respiration closer to thermodynamic equilibrium conditions. With evidence of multiple pathways within a single organism, the study of extracellular respiration should consider not only the crystal structure or solubility of a mineral electron acceptor, but rather the redox potential, as this variable determines the energetic reward affecting reduction rates, extents, and final microbial growth yields in the environment. PMID:28045456

Hydrocarbon-mediated gold and uranium concentration in the Witwatersrand Basin, South Africa

NASA Astrophysics Data System (ADS)

Fuchs, Sebastian; Williams-Jones, Anthony; Schumann, Dirk; Couillard, Martin; Murray, Andrew

2016-04-01

The Witwatersrand deposits in South Africa represent the largest repository of gold in the World and a major resource of uranium. The genesis of the gold and uranium ores in the quartz-pebble conglomerates (reefs), however, is still a matter of considerable discussion. Opinion has been divided over whether they represent paleo-placers that have been partly remobilised by hydrothermal fluids or if the mineralisation is entirely hydrothermal in origin. In addition, recently published models have proposed a syngenetic origin for the gold involving bacterially-mediated precipitation from meteoric water and shallow seawater. An important feature of the gold and uranium mineralisation in the reefs is the strong spatial association with organic matter. In some reefs, up to 70% of the gold and almost the entire uranium resource is spatially associated with pyrobitumen seams, suggesting a genetic relationship of the gold-uranium mineralisation with hydrocarbons. Here we report results of a study of the Carbon Leader Reef, using high-resolution scanning and transmission electron microscopy (SEM / TEM) and LA-ICP-MS that provide new insights into the role of hydrocarbons in the concentration of the gold and uranium. A detailed examination revealed gold monocrystals containing numerous rounded or elliptical inclusions filled with pyrobitumen. We interpret these inclusions to record the crystallisation of the gold around droplets of a hydrocarbon liquid that migrated through the Witwatersrand basin, and was converted to pyrobitumen by being heated. We propose that the gold was transported in a hydrothermal fluid as a bisulphide complex and that this fluid mixed with the hydrocarbon liquid to form a water-oil emulsion. The interaction between the two fluids caused a sharp reduction in fO2 at the water-oil interface, which destabilised the gold-bisulphide complexes, causing gold monocrystals to precipitate around the oil droplets. In contrast to the gold, uraninite, the principal uranium mineral, occurs as complex-shaped grains that represent aggregates containing billions of uraninite nanocrystals (5 - 7 nm in diameter), which grew in situ in the pyrobitumen matrix or more likely its liquid precursor (Fuchs et al., 2015). This in situ growth of isolated nanocrystalline aggregates shows that uranium was mobilised and concentrated by liquid hydrocarbons, and that uraninite nanocrystals were released from the oils during the conversion of oil to pyrobitumen. Our study provides new insights into the complex mechanisms of ore formation in the Witwatersrand Supergroup and compelling evidence that hydrocarbons played a major role in the concentration of the gold and uranium. It does not rule out the possibility that gold and uranium were introduced into the Witwatersrand Basin as detrital grains but shows that mobilisation of gold and uranium by hydrothermal fluids and hydrocarbon liquids, respectively, and the mixing of these fluids, were essential to ore formation. Fuchs, S., Schumann, D., Williams-Jones, A.E., Vali, H., 2015. The growth and concentration of uranium and titanium minerals in hydrocarbons of the Carbon Leader Reef, Witwatersrand Supergroup, South Africa. Chemical Geology 393-394, 55-66.

Electrochemistry suggests proton access from the exit site to the binuclear center in Paracoccus denitrificans cytochrome c oxidase pathway variants.

PubMed

Meyer, Thomas; Melin, Frédéric; Richter, Oliver-M H; Ludwig, Bernd; Kannt, Aimo; Müller, Hanne; Michel, Hartmut; Hellwig, Petra

2015-02-27

Two different pathways through which protons access cytochrome c oxidase operate during oxygen reduction from the mitochondrial matrix, or the bacterial cytoplasm. Here, we use electrocatalytic current measurements to follow oxygen reduction coupled to proton uptake in cytochrome c oxidase isolated from Paracoccus denitrificans. Wild type enzyme and site-specific variants with defects in both proton uptake pathways (K354M, D124N and K354M/D124N) were immobilized on gold nanoparticles, and oxygen reduction was probed electrochemically in the presence of varying concentrations of Zn(2+) ions, which are known to inhibit both the entry and the exit proton pathways in the enzyme. Our data suggest that under these conditions substrate protons gain access to the oxygen reduction site via the exit pathway. Copyright © 2015 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

A theoretical probe of high-valence uranium and transuranium silylamides: Structural and redox properties

NASA Astrophysics Data System (ADS)

Zhong, Yu-Xi; Guo, Yuan-Ru; Pan, Qing-Jiang

2016-02-01

Relativistic density functional theory was used to explore the structural and redox properties of 18 prototypical actinyl silylamides including a variation of metals (U, Np and Pu), metal oxidation states (VI and V) and equatorial ligands. A theoretical approach associated with implicit solvation and spin-orbit/multiplet corrections was proved to be reliable. A marked shift of reduction potentials of actinyl silylamides caused by changes of equatorial coordination ligands and implicit solvation was elucidated by analyses of electronic structures and single-electron reduction mechanism.

A review of the high temperature oxidation of uranium oxides in molten salts and in the solid state to form alkali metal uranates, and their composition and properties

NASA Astrophysics Data System (ADS)

Griffiths, Trevor R.; Volkovich, Vladimir A.

An extensive review of the literature on the high temperature reactions (both in melts and in the solid state) of uranium oxides (UO 2, U 3O 8 and UO 3) resulting in the formation of insoluble alkali metal (Li to Cs) uranates is presented. Their uranate(VI) and uranate(V) compounds are examined, together with mixed and oxygen-deficient uranates. The reactions of uranium oxides with carbonates, oxides, per- and superoxides, chlorides, sulfates, nitrates and nitrites under both oxidising and non-oxidising conditions are critically examined and systematised, and the established compositions of a range of uranate(VI) and (V) compounds formed are discussed. Alkali metal uranates(VI) are examined in detail and their structural, physical, thermodynamic and spectroscopic properties considered. Chemical properties of alkali metal uranates(VI), including various methods for their reduction, are also reported. Errors in the current theoretical treatment of uranate(VI) spectra are identified and the need to develop routes for the preparation of single crystals is stressed.

Linking Chaotic Advection with Subsurface Biogeochemical Processes

NASA Astrophysics Data System (ADS)

Mays, D. C.; Freedman, V. L.; White, S. K.; Fang, Y.; Neupauer, R.

2017-12-01

This work investigates the extent to which groundwater flow kinematics drive subsurface biogeochemical processes. In terms of groundwater flow kinematics, we consider chaotic advection, whose essential ingredient is stretching and folding of plumes. Chaotic advection is appealing within the context of groundwater remediation because it has been shown to optimize plume spreading in the laminar flows characteristic of aquifers. In terms of subsurface biogeochemical processes, we consider an existing model for microbially-mediated reduction of relatively mobile uranium(VI) to relatively immobile uranium(IV) following injection of acetate into a floodplain aquifer beneath a former uranium mill in Rifle, Colorado. This model has been implemented in the reactive transport code eSTOMP, the massively parallel version of STOMP (Subsurface Transport Over Multiple Phases). This presentation will report preliminary numerical simulations in which the hydraulic boundary conditions in the eSTOMP model are manipulated to simulate chaotic advection resulting from engineered injection and extraction of water through a manifold of wells surrounding the plume of injected acetate. This approach provides an avenue to simulate the impact of chaotic advection within the existing framework of the eSTOMP code.

Feasibility Study of Economics and Performance of Geothermal Power Generation at the Lakeview Uranium Mill Site in Lakeview, Oregon. A Study Prepared in Partnership with the Environmental Protection Agency for the RE-Powering America's Land Initiative: Siting Renewable Energy on Potentially Contaminated Land and Mine Sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hillesheim, M.; Mosey, G.

2013-11-01

The U.S. Environmental Protection Agency (EPA), in accordance with the RE-Powering America's Land initiative, selected the Lakeview Uranium Mill site in Lakeview, Oregon, for a feasibility study of renewable energy production. The EPA contracted with the National Renewable Energy Laboratory (NREL) to provide technical assistance for the project. The purpose of this report is to describe an assessment of the site for possible development of a geothermal power generation facility and to estimate the cost, performance, and site impacts for the facility. In addition, the report recommends development pathways that could assist in the implementation of a geothermal power systemmore » at the site.« less

Oxygen diffusion model of the mixed (U,Pu)O2 ± x: Assessment and application

NASA Astrophysics Data System (ADS)

Moore, Emily; Guéneau, Christine; Crocombette, Jean-Paul

2017-03-01

The uranium-plutonium (U,Pu)O2 ± x mixed oxide (MOX) is used as a nuclear fuel in some light water reactors and considered for future reactor generations. To gain insight into fuel restructuring, which occurs during the fuel lifetime as well as possible accident scenarios understanding of the thermodynamic and kinetic behavior is crucial. A comprehensive evaluation of thermo-kinetic properties is incorporated in a computational CALPHAD type model. The present DICTRA based model describes oxygen diffusion across the whole range of plutonium, uranium and oxygen compositions and temperatures by incorporating vacancy and interstitial migration pathways for oxygen. The self and chemical diffusion coefficients are assessed for the binary UO2 ± x and PuO2 - x systems and the description is extended to the ternary mixed oxide (U,Pu)O2 ± x by extrapolation. A simulation to validate the applicability of this model is considered.

Uranium from Seawater Program Review; Fuel Resources Uranium from Seawater Program DOE Office of Nuclear Energy

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

2013-07-01

For nuclear energy to remain sustainable in the United States, economically viable sources of uranium beyond terrestrial ores must be developed. The goal of this program is to develop advanced adsorbents that can extract uranium from seawater at twice the capacity of the best adsorbent developed by researchers at the Japan Atomic Energy Agency (JAEA), 1.5 mg U/g adsorbent. A multidisciplinary team from Oak Ridge National Laboratory, Lawrence Berkeley National Laboratory, Pacific Northwest National Laboratory, and the University of Texas at Austin was assembled to address this challenging problem. Polymeric adsorbents, based on the radiation grafting of acrylonitrile and methacrylicmore » acid onto high surface-area polyethylene fibers followed by conversion of the nitriles to amidoximes, have been developed. These poly(acrylamidoxime-co-methacrylic acid) fibers showed uranium adsorption capacities for the extraction of uranium from seawater that exceed 3 mg U/g adsorbent in testing at the Pacific Northwest National Laboratory Marine Sciences Laboratory. The essence of this novel technology lies in the unique high surface-area trunk material that considerably increases the grafting yield of functional groups without compromising its mechanical properties. This technology received an R&D100 Award in 2012. In addition, high surface area nanomaterial adsorbents are under development with the goal of increasing uranium adsorption capacity by taking advantage of the high surface areas and tunable porosity of carbon-based nanomaterials. Simultaneously, de novo structure-based computational design methods are being used to design more selective and stable ligands and the most promising candidates are being synthesized, tested and evaluated for incorporation onto a support matrix. Fundamental thermodynamic and kinetic studies are being carried out to improve the adsorption efficiency, the selectivity of uranium over other metals, and the stability of the adsorbents. Understanding the rate-limiting step of uranium uptake from seawater is also essential in designing an effective uranium recovery system. Finally, economic analyses have been used to guide these studies and highlight what parameters, such as capacity, recyclability, and stability, have the largest impact on the cost of extraction of uranium from seawater. Initially, the cost estimates by the JAEA for extraction of uranium from seawater with braided polymeric fibers functionalized with amidoxime ligands were evaluated and updated. The economic analyses were subsequently updated to reflect the results of this project while providing insight for cost reductions in the adsorbent development through “cradle-to-grave” case studies for the extraction process. This report highlights the progress made over the last three years on the design, synthesis, and testing of new materials to extract uranium for seawater. This report is organized into sections that highlight the major research activities in this project: (1) Chelate Design and Modeling, (2) Thermodynamics, Kinetics and Structure, (3) Advanced Polymeric Adsorbents by Radiation Induced Grafting, (4) Advanced Nanomaterial Adsorbents, (5) Adsorbent Screening and Modeling, (6) Marine Testing, and (7) Cost and Energy Assessment. At the end of each section, future research directions are briefly discussed to highlight the challenges that still remain to reduce the cost of extractions of uranium for seawater. Finally, contributions from the Nuclear Energy University Programs (NEUP), which complement this research program, are included at the end of this report.« less

Isotopic evidence for reductive immobilization of uranium across a roll-front mineral deposit

DOE PAGES

Brown, Shaun T.; Basu, Anirban; Christensen, John N.; ...

2016-05-20

We use uranium (U) isotope ratios to detect and quantify the extent of natural U reduction in groundwater across a roll front redox gradient. Our study was conducted at the Smith Ranch-Highland in situ recovery (ISR) U mine in eastern Wyoming, USA, where economic U deposits occur in the Paleocene Fort Union formation. To evaluate the fate of aqueous U in and adjacent to the ore body, we investigated the chemical composition and isotope ratios of groundwater samples from the roll-front type ore body and surrounding monitoring wells of a previously mined area. The 238U/ 235U of groundwater varies bymore » approximately 3‰ and is correlated with U concentrations. Fluid samples down-gradient of the ore zone are the most depleted in 238U and have the lowest U concentrations. Activity ratios of 234U/ 238U are ~5.5 up-gradient of the ore zone, ~1.0 in the ore zone, and between 2.3 and 3.7 in the down-gradient monitoring wells. High-precision measurements of 234U/ 238U and 238U/ 235U allow for development of a conceptual model that evaluates both the migration of U from the ore body and the extent of natural attenuation due to reduction. We find that the premining migration of U down-gradient of the delineated ore body is minimal along eight transects due to reduction in or adjacent to the ore body, whereas two other transects show little or no sign of reduction in the down-gradient region. Lastly, these results suggest that characterization of U isotopic ratios at the mine planning stage, in conjunction with routine geochemical analyses, can be used to identify where more or less postmining remediation will be necessary.« less

Top Ten Reasons for DEOX as a Front End to Pyroprocessing

DOE Office of Scientific and Technical Information (OSTI.GOV)

B.R. Westphal; K.J. Bateman; S.D. Herrmann

A front end step is being considered to augment chopping during the treatment of spent oxide fuel by pyroprocessing. The front end step, termed DEOX for its emphasis on decladding via oxidation, employs high temperatures to promote the oxidation of UO2 to U3O8 via an oxygen carrier gas. During oxidation, the spent fuel experiences a 30% increase in lattice structure volume resulting in the separation of fuel from cladding with a reduced particle size. A potential added benefit of DEOX is the removal of fission products, either via direct release from the broken fuel structure or via oxidation and volatilizationmore » by the high temperature process. Fuel element chopping is the baseline operation to prepare spent oxide fuel for an electrolytic reduction step. Typical chopping lengths range from 1 to 5 mm for both individual elements and entire assemblies. During electrolytic reduction, uranium oxide is reduced to metallic uranium via a lithium molten salt. An electrorefining step is then performed to separate a majority of the fission products from the recoverable uranium. Although DEOX is based on a low temperature oxidation cycle near 500oC, additional conditions have been tested to distinguish their effects on the process.[1] Both oxygen and air have been utilized during the oxidation portion followed by vacuum conditions to temperatures as high as 1200oC. In addition, the effects of cladding on fission product removal have also been investigated with released fuel to temperatures greater than 500oC.« less

Field Testing of Downgradient Uranium Mobility at an In-Situ Recovery Uranium Mine

NASA Astrophysics Data System (ADS)

Reimus, P. W.; Clay, J. T.; Rearick, M.; Perkins, G.; Brown, S. T.; Basu, A.; Chamberlain, K.

2015-12-01

In-situ recovery (ISR) mining of uranium involves the injection of O2 and CO2 (or NaHCO3) into saturated roll-front deposits to oxidize and solubilize the uranium, which is then removed by ion exchange at the surface and processed into U3O8. While ISR is economical and environmentally-friendly relative to conventional mining, one of the challenges of extracting uranium by this process is that it leaves behind a geochemically-altered aquifer that is exceedingly difficult to restore to pre-mining geochemical conditions, a regulatory objective. In this research, we evaluated the ability of the aquifer downgradient of an ISR mining area to attenuate the transport of uranium and other problem constituents that are mobilized by the mining process. Such an evaluation can help inform both regulators and the mining industry as to how much restoration of the mined ore zone is necessary to achieve regulatory compliance at various distances downgradient of the mining zone even if complete restoration of the ore zone proves to be difficult or impossible. Three single-well push-pull tests and one cross-well test were conducted in which water from an unrestored, previously-mined ore zone was injected into an unmined ore zone that served as a geochemical proxy for the downgradient aquifer. In all tests, non-reactive tracers were injected with the previously-mined ore zone water to allow the transport of uranium and other constituents to be compared to that of the nonreactive species. In the single-well tests, it was shown that the recovery of uranium relative to the nonreactive tracers ranged from 12-25%, suggesting significant attenuation capacity of the aquifer. In the cross-well test, selenate, molybdate and metavanadate were injected with the unrestored water to provide information on the transport of these potentially-problematic anionic constituents. In addition to the species-specific transport information, this test provided valuable constraints on redox conditions within the system, as redox couples involving these species collectively bracket the predicted transition redox potential for the U(VI)/U(IV) couple. Reduction should provide much longer-lasting immobilization of constituents than adsorption, especially given the inherent reducing characteristics of roll-front systems.

Developmental dysplasia of the hip: A computational biomechanical model of the path of least energy for closed reduction.

PubMed

Zwawi, Mohammed A; Moslehy, Faissal A; Rose, Christopher; Huayamave, Victor; Kassab, Alain J; Divo, Eduardo; Jones, Brendan J; Price, Charles T

2017-08-01

This study utilized a computational biomechanical model and applied the least energy path principle to investigate two pathways for closed reduction of high grade infantile hip dislocation. The principle of least energy when applied to moving the femoral head from an initial to a final position considers all possible paths that connect them and identifies the path of least resistance. Clinical reports of severe hip dysplasia have concluded that reduction of the femoral head into the acetabulum may occur by a direct pathway over the posterior rim of the acetabulum when using the Pavlik harness, or by an indirect pathway with reduction through the acetabular notch when using the modified Hoffman-Daimler method. This computational study also compared the energy requirements for both pathways. The anatomical and muscular aspects of the model were derived using a combination of MRI and OpenSim data. Results of this study indicate that the path of least energy closely approximates the indirect pathway of the modified Hoffman-Daimler method. The direct pathway over the posterior rim of the acetabulum required more energy for reduction. This biomechanical analysis confirms the clinical observations of the two pathways for closed reduction of severe hip dysplasia. The path of least energy closely approximated the modified Hoffman-Daimler method. Further study of the modified Hoffman-Daimler method for reduction of severe hip dysplasia may be warranted based on this computational biomechanical analysis. © 2016 The Authors. Journal of Orthopaedic Research Published by Wiley Periodicals, Inc. on behalf of Orthopaedic Research Society. J Orthop Res 35:1799-1805, 2017. © 2016 The Authors. Journal of Orthopaedic Research Published by Wiley Periodicals, Inc. on behalf of Orthopaedic Research Society.

Sorption and bioreduction of hexavalent uranium at a military facility by the Chesapeake Bay.

PubMed

Dong, Wenming; Xie, Guibo; Miller, Todd R; Franklin, Mark P; Oxenberg, Tanya Palmateer; Bouwer, Edward J; Ball, William P; Halden, Rolf U

2006-07-01

Directly adjacent to the Chesapeake Bay lies the Aberdeen Proving Ground, a U.S. Army facility where testing of armor-piercing ammunitions has resulted in the deposition of >70,000 kg of depleted uranium (DU) to local soils and sediments. Results of previous environmental monitoring suggested limited mobilization in the impact area and no transport of DU into the nation's largest estuary. To determine if physical and biological reactions constitute mechanisms involved in limiting contaminant transport, the sorption and biotransformation behavior of the radionuclide was studied using geochemical modeling and laboratory microcosms (500 ppb U(VI) initially). An immediate decline in dissolved U(VI) concentrations was observed under both sterile and non-sterile conditions due to rapid association of U(VI) with natural organic matter in the sediment. Reduction of U(VI) to U(IV) occurred only in non-sterile microcosms. In the non-sterile samples, intrinsic bioreduction of uranium involved bacteria of the order Clostridiales and was only moderately enhanced by the addition of acetate (41% vs. 56% in 121 days). Overall, this study demonstrates that the migration of depleted uranium from the APG site into the Chesapeake Bay may be limited by a combination of processes that include rapid sorption of U(VI) species to natural organic matter, followed by slow, intrinsic bioreduction to U(IV).

Microbial Functional Gene Diversity with a Shift of Subsurface Redox Conditions during In Situ Uranium Reduction

PubMed Central

Liang, Yuting; Van Nostrand, Joy D.; N′Guessan, Lucie A.; Peacock, Aaron D.; Deng, Ye; Long, Philip E.; Resch, C. Tom; Wu, Liyou; He, Zhili; Li, Guanghe; Hazen, Terry C.; Lovley, Derek R.

2012-01-01

To better understand the microbial functional diversity changes with subsurface redox conditions during in situ uranium bioremediation, key functional genes were studied with GeoChip, a comprehensive functional gene microarray, in field experiments at a uranium mill tailings remedial action (UMTRA) site (Rifle, CO). The results indicated that functional microbial communities altered with a shift in the dominant metabolic process, as documented by hierarchical cluster and ordination analyses of all detected functional genes. The abundance of dsrAB genes (dissimilatory sulfite reductase genes) and methane generation-related mcr genes (methyl coenzyme M reductase coding genes) increased when redox conditions shifted from Fe-reducing to sulfate-reducing conditions. The cytochrome genes detected were primarily from Geobacter sp. and decreased with lower subsurface redox conditions. Statistical analysis of environmental parameters and functional genes indicated that acetate, U(VI), and redox potential (Eh) were the most significant geochemical variables linked to microbial functional gene structures, and changes in microbial functional diversity were strongly related to the dominant terminal electron-accepting process following acetate addition. The study indicates that the microbial functional genes clearly reflect the in situ redox conditions and the dominant microbial processes, which in turn influence uranium bioreduction. Microbial functional genes thus could be very useful for tracking microbial community structure and dynamics during bioremediation. PMID:22327592

Spent nuclear fuel recycling with plasma reduction and etching

DOEpatents

Kim, Yong Ho

2012-06-05

A method of extracting uranium from spent nuclear fuel (SNF) particles is disclosed. Spent nuclear fuel (SNF) (containing oxides of uranium, oxides of fission products (FP) and oxides of transuranic (TRU) elements (including plutonium)) are subjected to a hydrogen plasma and a fluorine plasma. The hydrogen plasma reduces the uranium and plutonium oxides from their oxide state. The fluorine plasma etches the SNF metals to form UF₆ and PuF₄. During subjection of the SNF particles to the fluorine plasma, the temperature is maintained in the range of 1200-2000 deg K to: a) allow any PuF₆ (gas) that is formed to decompose back to PuF₄ (solid), and b) to maintain stability of the UF₆. Uranium (in the form of gaseous UF₆) is easily extracted and separated from the plutonium (in the form of solid PuF₄). The use of plasmas instead of high temperature reactors or flames mitigates the high temperature corrosive atmosphere and the production of PuF₆ (as a final product). Use of plasmas provide faster reaction rates, greater control over the individual electron and ion temperatures, and allow the use of CF₄ or NF₃ as the fluorine sources instead of F₂ or HF.

Uranium Biomineralization By Natural Microbial Phosphatase Activities in the Subsurface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taillefert, Martial

This project investigated the geochemical and microbial processes associated with the biomineralization of radionuclides in subsurface soils. During this study, it was determined that microbial communities from the Oak Ridge Field Research subsurface are able to express phosphatase activities that hydrolyze exogenous organophosphate compounds and result in the non-reductive bioimmobilization of U(VI) phosphate minerals in both aerobic and anaerobic conditions. The changes of the microbial community structure associated with the biomineralization of U(VI) was determined to identify the main organisms involved in the biomineralization process, and the complete genome of two isolates was sequenced. In addition, it was determined thatmore » both phytate, the main source of natural organophosphate compounds in natural environments, and polyphosphate accumulated in cells could also be hydrolyzed by native microbial population to liberate enough orthophosphate and precipitate uranium phosphate minerals. Finally, the minerals produced during this process are stable in low pH conditions or environments where the production of dissolved inorganic carbon is moderate. These findings suggest that the biomineralization of U(VI) phosphate minerals is an attractive bioremediation strategy to uranium bioreduction in low pH uranium-contaminated environments. These efforts support the goals of the SBR long-term performance measure by providing key information on "biological processes influencing the form and mobility of DOE contaminants in the subsurface".« less

The Use of Chemical Probes for the Characterization of the Predominant Abiotic Reductants in Anaerobic Sediments

EPA Science Inventory

Identifying the predominant chemical reductants and pathways for electron transfer in anaerobic systems is paramount to the development of environmental fate models that incorporate pathways for abiotic reductive transformations. Currently, such models do not exist. In this chapt...

Spectroscopic properties of some borate glasses containg uranium

NASA Astrophysics Data System (ADS)

Culea, E.; Milea, I.; Bratu, I.

1993-03-01

Spectroscopic properties of some borate glasses containing 1-5%UO 3 have been studied in the fields of 700-1200 cm -1 and 10,000-30,000 cm -1 Absorption bands specific for U 6+ and U 4+ ions were observed. The increase of the melting time produces the reduction of U 6+ ions to U 4+.

HANDBOOK: SUB-SLAB DEPRESSURIZATION FOR LOW PERMEABILITY FILL MATERIAL DESIGN AND INSTALLATION OF A HOME RADON REDUCTION SYSTEM

EPA Science Inventory

Radon, a radioactive gas, comes from the natural decay of uranium. It moves to the earth's surface through tiny openings and cracks in soil and rocks. In outdoor air, radon is diluted to such low concentrations that it is usually nothing to worry about. However, radon can accumul...

40 CFR 440.33 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2012 CFR

2012-07-01

...) The concentration of pollutants discharged in mine drainage from mines, either open-pit or underground, that produce uranium ore, including mines using in-situ leach methods, shall not exceed: Effluent...). Except as provided in subpart L of this part and 40 CFR 125.30 through 125.32, any existing point source...

40 CFR 440.32 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2013 CFR

2013-07-01

... using in-situ leach methods shall not exceed: Effluent characteristic Effluent limitations Maximum for... uranium, radium and vanadium including mill-mine facilities and mines using in-situ leach methods shall... available (BPT). Except as provided in subpart L of this part and 40 CFR 125.30 through 125.32, any existing...

40 CFR 440.33 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2011 CFR

2011-07-01

... concentration of pollutants discharged in mine drainage from mines, either open-pit or underground, that produce uranium ore, including mines using in-situ leach methods, shall not exceed: Effluent characteristic... provided in subpart L of this part and 40 CFR 125.30 through 125.32, any existing point source subject to...

40 CFR 440.32 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2014 CFR

2014-07-01

... using in-situ leach methods shall not exceed: Effluent characteristic Effluent limitations Maximum for... uranium, radium and vanadium including mill-mine facilities and mines using in-situ leach methods shall... available (BPT). Except as provided in subpart L of this part and 40 CFR 125.30 through 125.32, any existing...

40 CFR 440.33 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2014 CFR

2014-07-01

...) The concentration of pollutants discharged in mine drainage from mines, either open-pit or underground, that produce uranium ore, including mines using in-situ leach methods, shall not exceed: Effluent...). Except as provided in subpart L of this part and 40 CFR 125.30 through 125.32, any existing point source...

40 CFR 440.33 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2010 CFR

2010-07-01

... concentration of pollutants discharged in mine drainage from mines, either open-pit or underground, that produce uranium ore, including mines using in-situ leach methods, shall not exceed: Effluent characteristic... provided in subpart L of this part and 40 CFR 125.30 through 125.32, any existing point source subject to...

40 CFR 440.32 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2012 CFR

2012-07-01

... using in-situ leach methods shall not exceed: Effluent characteristic Effluent limitations Maximum for... uranium, radium and vanadium including mill-mine facilities and mines using in-situ leach methods shall... available (BPT). Except as provided in subpart L of this part and 40 CFR 125.30 through 125.32, any existing...

Uptake of Uranium and Other Elements of Concern by Plants Growing on Uranium Mill Tailings Disposal Cells

NASA Astrophysics Data System (ADS)

Joseph, C. N.; Waugh, W.; Glenn, E.

2015-12-01

The U.S. Department of Energy (DOE) is responsible for long-term stewardship of disposal cells for uranium mill tailings throughout the United States. Rock-armored disposal cell covers create favorable habitat for deep-rooted plants by reducing soil evaporation, increasing soil water storage, and trapping windblown dust, thereby providing water and nutrients for plant germination and establishment. DOE is studying the tradeoffs of potential detrimental and beneficial effects of plants growing on disposal cell covers to develop a rational and consistent vegetation management policy. Plant roots often extend vertically through disposal cell covers into underlying tailings, therefore, uptake of tailings contaminants and dissemination through animals foraging on stems and leaves is a possible exposure pathway. The literature shows that plant uptake of contaminants in uranium mill tailings occurs, but levels can vary widely depending on plant species, tailings and soil chemistry, and cover soil hydrology. Our empirical field study measured concentrations of uranium, radium, thorium, molybdenum, selenium, manganese, lead, and arsenic in above ground tissues harvested from plants growing on disposal cells near Native American communities in western states that represent a range of climates, cover designs, cover soil types, and vegetation types. For risk screening, contaminant levels in above ground tissues harvested from plants on disposal cells were compared to Maximum Tolerance Levels (MTLs) set for livestock by the National Research Council, and to tissue levels in the same plant species growing in reference areas near disposal cells. Although tailings were covered with uncontaminated soils, for 14 of 46 comparisons, levels of uranium and other contaminants were higher in plants growing on disposal cells compared to reference area plants, indicating possible mobilization of these elements from the tailing into plant tissues. However, with one exception, all plant levels were well below MTLs. Selenium, the only element that exceeded its MTL, likely originated in local seleniferous soil found both at reference areas and in disposal cell covers, and not in the underlying tailings. Our screening risk assessment suggests that allowing plants to grow on disposal cells appears to be safe.

OPTIMIZATION OF HETEROGENEOUS UTILIZATION OF THORIUM IN PWRS TO ENHANCE PROLIFERATION RESISTANCE AND REDUCE WASTE.

DOE Office of Scientific and Technical Information (OSTI.GOV)

TODOSOW,M.; KAZIMI,M.

2004-08-01

Issues affecting the implementation, public perception and acceptance of nuclear power include: proliferation, radioactive waste, safety, and economics. The thorium cycle directly addresses the proliferation and waste issues, but optimization studies of core design and fuel management are needed to ensure that it fits within acceptable safety and economic margins. Typical pressurized water reactors, although loaded with uranium fuel, produce 225 to 275 kg of plutonium per gigawatt-year of operation. Although the spent fuel is highly radioactive, it nevertheless offers a potential proliferation pathway because the plutonium is relatively easy to separate, amounts to many critical masses, and does notmore » present any significant intrinsic barrier to weapon assembly. Uranium 233, on the other hand, produced by the irradiation of thorium, although it too can be used in weapons, may be ''denatured'' by the addition of natural, depleted or low enriched uranium. Furthermore, it appears that the chemical behavior of thoria or thoria-urania fuel makes it a more stable medium for the geological disposal of the spent fuel. It is therefore particularly well suited for a once-through fuel cycle. The use of thorium as a fertile material in nuclear fuel has been of interest since the dawn of nuclear power technology due to its abundance and to potential neutronic advantages. Early projects include homogeneous mixtures of thorium and uranium oxides in the BORAX-IV, Indian Point I, and Elk River reactors, as well as heterogeneous mixtures in the Shippingport seed-blanket reactor. However these projects were developed under considerably different circumstances than those which prevail at present. The earlier applications preceded the current proscription, for non-proliferation purposes, of the use of uranium enriched to more than 20 w/o in {sup 235}U, and has in practice generally prohibited the use of uranium highly enriched in {sup 235}U. They were designed when the expected burnup of light water fuel was on the order of 25 MWD/kgU--about half the present day value--and when it was expected that the spent fuel would be recycled to recover its fissile content.« less

Evaluation of Settler Tank Thermal Stability during Solidification and Disposition to ERDF

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stephenson, David E.; Delegard, Calvin H.; Schmidt, Andrew J.

2015-03-30

Ten 16-foot-long and 20-inch diameter horizontal tanks currently reside in a stacked 2×5 (high) array in the ~20,000-gallon water-filled Weasel Pit of the 105-KW Fuel Storage Basin on the US-DOE Hanford Site. These ten tanks are part of the Integrated Water Treatment System used to manage water quality in the KW Basin and are called “settler” tanks because of their application in removing particles from the KW Basin waters. Based on process knowledge, the settler tanks are estimated to contain about 124 kilograms of finely divided uranium metal, 22 kg of uranium dioxide, and another 55 kg of other radioactivemore » sludge. The Sludge Treatment Project (STP), managed by CH2MHill Plateau Remediation Company (CHPRC) is charged with managing the settler tanks and arranging for their ultimate disposal by burial in ERDF. The presence of finely divided uranium metal in the sludge is of concern because of the potential for thermal runaway reaction of the uranium metal with water and the formation of flammable hydrogen gas as a product of the uranium-water reaction. Thermal runaway can be instigated by external heating. The STP commissioned a formal Decision Support Board (DSB) to consider options and provide recommendations to manage and dispose of the settler tanks and their contents. Decision criteria included consideration of the project schedule and longer-term deactivation, decontamination, decommissioning, and demolition (D4) of the KW Basin. The DSB compared the alternatives and recommended in-situ grouting, size-reduction, and ERDF disposal as the best of six candidate options for settler tank treatment and disposal. It is important to note that most grouts contain a complement of Portland cement as the binding agent and that Portland cement curing reactions generate heat. Therefore, concern is raised that the grouting of the settler tank contents may produce heating sufficient to instigate thermal runaway reactions in the contained uranium metal sludge.« less

Microbial communities associated with uranium in-situ recovery mining process are related to acid mine drainage assemblages.

PubMed

Coral, Thomas; Descostes, Michaël; De Boissezon, Hélène; Bernier-Latmani, Rizlan; de Alencastro, Luiz Felippe; Rossi, Pierre

2018-07-01

A large fraction (47%) of the world's uranium is mined by a technique called "In Situ Recovery" (ISR). This mining technique involves the injection of a leaching fluid (acidic or alkaline) into a uranium-bearing aquifer and the pumping of the resulting solution through cation exchange columns for the recovery of dissolved uranium. The present study reports the in-depth alterations brought to autochthonous microbial communities during acidic ISR activities. Water samples were collected from a uranium roll-front deposit that is part of an ISR mine in operation (Tortkuduk, Kazakhstan). Water samples were obtained at a depth of ca 500 m below ground level from several zones of the Uyuk aquifer following the natural redox zonation inherited from the roll front deposit, including the native mineralized orebody and both upstream and downstream adjacent locations. Samples were collected equally from both the entrance and the exit of the uranium concentration plant. Next-generation sequencing data showed that the redox gradient shaped the community structures, within the anaerobic, reduced, and oligotrophic habitats of the native aquifer zones. Acid injection induced drastic changes in the structures of these communities, with a large decrease in both cell numbers and diversity. Communities present in the acidified (pH values < 2) mining areas exhibited similarities to those present in acid mine drainage, with the dominance of Sulfobacillus sp., Leptospirillum sp. and Acidithiobacillus sp., as well as the archaean Ferroplasma sp. Communities located up- and downstream of the mineralized zone under ISR and affected by acidic fluids were blended with additional facultative anaerobic and acidophilic microorganisms. These mixed biomes may be suitable communities for the natural attenuation of ISR mining-affected subsurface through the reduction of metals and sulfate. Assessing the effect of acidification on the microbial community is critical to evaluating the potential for natural attenuation or active bioremediation strategies. Copyright © 2018 Elsevier B.V. All rights reserved.

Bacterial community succession during in situ uranium bioremediation: spatial similarities along controlled flow paths.

PubMed

Hwang, Chiachi; Wu, Weimin; Gentry, Terry J; Carley, Jack; Corbin, Gail A; Carroll, Sue L; Watson, David B; Jardine, Phil M; Zhou, Jizhong; Criddle, Craig S; Fields, Matthew W

2009-01-01

Bacterial community succession was investigated in a field-scale subsurface reactor formed by a series of wells that received weekly ethanol additions to re-circulating groundwater. Ethanol additions stimulated denitrification, metal reduction, sulfate reduction and U(VI) reduction to sparingly soluble U(IV). Clone libraries of SSU rRNA gene sequences from groundwater samples enabled tracking of spatial and temporal changes over a 1.5-year period. Analyses showed that the communities changed in a manner consistent with geochemical variations that occurred along temporal and spatial scales. Canonical correspondence analysis revealed that the levels of nitrate, uranium, sulfide, sulfate and ethanol were strongly correlated with particular bacterial populations. As sulfate and U(VI) levels declined, sequences representative of sulfate reducers and metal reducers were detected at high levels. Ultimately, sequences associated with sulfate-reducing populations predominated, and sulfate levels declined as U(VI) remained at low levels. When engineering controls were compared with the population variation through canonical ordination, changes could be related to dissolved oxygen control and ethanol addition. The data also indicated that the indigenous populations responded differently to stimulation for bioreduction; however, the two biostimulated communities became more similar after different transitions in an idiosyncratic manner. The strong associations between particular environmental variables and certain populations provide insight into the establishment of practical and successful remediation strategies in radionuclide-contaminated environments with respect to engineering controls and microbial ecology.

Leaching under Oxygen Pressure with Carbonate Solution Reduction by Hydrogen; LIXIVIATION OXYDANTE DES PECHBLENDES ET PRECIPITATION DE L'URANIUM PAR L'HYDROGENE. APPLICATION AUX MINERAIS PAUVRES FRANCAIS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balaceanu, J.C.; Coussemant, F.; Mouret, P.

1959-10-31

A study was made of the basic characteristics of the leaching with carbonate solution under oxygen pressure and of the catalytic hydrogen reduction of low-grade French ores. Pure U/sub 3/O/sub 8/ was used in the investigations on leaching. The effects of oxygen pressure, temperature, initial surface of the oxide, surfuce during the course of the reaction, and concentration of the carbonate solution were determined. It was shown that the heterogeneous reactions involve a constant surface and two steps. A pilot plant experiment was made on a number of low-grade French ores. With ores the leaching is not sensitive to oxygenmore » pressure. Dilute solutions of sodium uranyl carbonate are obtained from the leaching. The uranium can be precipitated as an oxide of a lower valent state by catalytic reduction with hydrogen. The study of this step was made on pure solutions of sodium uranyl carbonate in the presence of nickel and platinum catalysts. The reaction is strongly modified by the presence of even low concentrations of sodium bicarbonate. The reaction velocity increases with hydrogen pressure up to 5 atm, but then becomes independent of the pressure. The precipitation is accelerated by an increase in temperature. (J.S.R.)« less

Adsorption of Fe(II) and U(VI) to carboxyl-functionalized microspheres: The influence of speciation on uranyl reduction studied by titration and XAFS

NASA Astrophysics Data System (ADS)

Boyanov, Maxim I.; O'Loughlin, Edward J.; Roden, Eric E.; Fein, Jeremy B.; Kemner, Kenneth M.

2007-04-01

The chemical reduction of U(VI) by Fe(II) is a potentially important pathway for immobilization of uranium in subsurface environments. Although the presence of surfaces has been shown to catalyze the reaction between Fe(II) and U(VI) aqueous species, the mechanism(s) responsible for the enhanced reactivity remain ambiguous. To gain further insight into the U-Fe redox process at a complexing, non-conducting surface that is relevant to common organic phases in the environment, we studied suspensions containing combinations of 0.1 mM U(VI), 1.0 mM Fe(II), and 4.2 g/L carboxyl-functionalized polystyrene microspheres. Acid-base titrations were used to monitor protolytic reactions, and Fe K-edge and U L-edge X-ray absorption fine structure spectroscopy was used to determine the valence and atomic environment of the adsorbed Fe and U species. In the Fe + surface carboxyl system, a transition from monomeric to oligomeric Fe(II) surface species was observed between pH 7.5 and pH 8.4. In the U + surface carboxyl system, the U(VI) cation was adsorbed as a mononuclear uranyl-carboxyl complex at both pH 7.5 and 8.4. In the ternary U + Fe + surface carboxyl system, U(VI) was not reduced by the solvated or adsorbed Fe(II) at pH 7.5 over a 4-month period, whereas complete and rapid reduction to U(IV) nanoparticles occurred at pH 8.4. The U(IV) product reoxidized rapidly upon exposure to air, but it was stable over a 4-month period under anoxic conditions. Fe atoms were found in the local environment of the reduced U(IV) atoms at a distance of 3.56 Å. The U(IV)-Fe coordination is consistent with an inner-sphere electron transfer mechanism between the redox centers and involvement of Fe(II) atoms in both steps of the reduction from U(VI) to U(IV). The inability of Fe(II) to reduce U(VI) in solution and at pH 7.5 in the U + Fe + carboxyl system is explained by the formation of a transient, "dead-end" U(V)-Fe(III) complex that blocks the U(V) disproportionation pathway after the first electron transfer. The increased reactivity at pH 8.4 relative to pH 7.5 is explained by the reaction of U(VI) with an Fe(II) oligomer, whereby the bonds between Fe atoms facilitate the transfer of a second electron to the hypothetical U(V)-Fe(III) intermediate. We discuss how this mechanism may explain the commonly observed higher efficiency of uranyl reduction by adsorbed or structural Fe(II) relative to aqueous Fe(II).

Pyroprocessing of Light Water Reactor Spent Fuels Based on an Electrochemical Reduction Technology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ohta, Hirokazu; Inoue, Tadashi; Sakamura, Yoshiharu

A concept of pyroprocessing light water reactor (LWR) spent fuels based on an electrochemical reduction technology is proposed, and the material balance of the processing of mixed oxide (MOX) or high-burnup uranium oxide (UO{sub 2}) spent fuel is evaluated. Furthermore, a burnup analysis for metal fuel fast breeder reactors (FBRs) is conducted on low-decontamination materials recovered by pyroprocessing. In the case of processing MOX spent fuel (40 GWd/t), UO{sub 2} is separately collected for {approx}60 wt% of the spent fuel in advance of the electrochemical reduction step, and the product recovered through the rare earth (RE) removal step, which hasmore » the composition uranium:plutonium:minor actinides:fission products (FPs) = 76.4:18.4:1.7:3.5, can be applied as an ingredient of FBR metal fuel without a further decontamination process. On the other hand, the electroreduced alloy of high-burnup UO{sub 2} spent fuel (48 GWd/t) requires further decontamination of residual FPs by an additional process such as electrorefining even if RE FPs are removed from the alloy because the recovered plutonium (Pu) is accompanied by almost the same amount of FPs in addition to RE. However, the amount of treated materials in the electrorefining step is reduced to {approx}10 wt% of the total spent fuel owing to the prior UO{sub 2} recovery step. These results reveal that the application of electrochemical reduction technology to LWR spent oxide fuel is a promising concept for providing FBR metal fuel by a rationalized process.« less

RUSSIAN-ORIGIN HIGHLY ENRICHED URANIUM SPENT NUCLEAR FUEL SHIPMENT FROM BULGARIA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kelly Cummins; Igor Bolshinsky; Ken Allen

2009-07-01

In July 2008, the Global Threat Reduction Initiative and the IRT 2000 research reactor in Sofia, Bulgaria, operated by the Institute for Nuclear Research and Nuclear Energy (INRNE), safely shipped 6.4 kilograms of Russian origin highly enriched uranium (HEU) spent nuclear fuel (SNF) to the Russian Federation. The shipment, which resulted in the removal of all HEU from Bulgaria, was conducted by truck, barge, and rail modes of transport across two transit countries before reaching the final destination at the Production Association Mayak facility in Chelyabinsk, Russia. This paper describes the work, equipment, organizations, and approvals that were required tomore » complete the spent fuel shipment and provides lessons learned that might assist other research reactor operators with their own spent nuclear fuel shipments.« less

Returning HEU Fuel from the Czech Republic to Russia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Michael Tyacke; Dr. Igor Bolshinsky

In December 1999, representatives from the United States, Russian Federation, and International Atomic Energy Agency began working on a program to return Russian supplied, highly enriched, uranium fuel stored at foreign research reactors to Russia. Now, under the Global Threat Reduction Initiative’s Russian Research Reactor Fuel Return Program, this effort has repatriated over 800 kg of highly enriched uranium to Russia from over 10 countries. In May 2004, the “Agreement Between the Government of the United States of America and the Government of the Russian Federation Concerning Cooperation for the Transfer of Russian Produced Research Reactor Nuclear Fuel to themore » Russian Federation” was signed. This agreement provides legal authority for the Russian Research Reactor Fuel Return Program and establishes parameters whereby eligible countries may return highly enriched uranium spent and fresh fuel assemblies and other fissile materials to Russia. On December 8, 2007, one of the largest shipments of highly enriched uranium spent nuclear fuel was successfully made from a Russian-designed nuclear research reactor in the Czech Republic to the Russian Federation. This accomplishment is the culmination of years of planning, negotiations, and hard work. The United States, Russian Federation, and the International Atomic Energy Agency have been working together. In February 2003, Russian Research Reactor Fuel Return Program representatives met with the Nuclear Research Institute in Rež, Czech Republic, and discussed the return of their highly enriched uranium spent nuclear fuel to the Russian Federation for reprocessing. Nearly 5 years later, the shipment was made. This article discusses the planning, preparations, coordination, and cooperation required to make this important international shipment.« less

Hydrothermal Testing of K Basin Sludge and N Reactor Fuel at Sludge Treatment Project Operating Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Delegard, Calvin H.; Schmidt, Andrew J.; Thornton, Brenda M.

The Sludge Treatment Project (STP), managed for the U. S. DOE by Fluor Hanford (FH), was created to design and operate a process to eliminate uranium metal from K Basin sludge prior to packaging for Waste Isolation Pilot Plant (WIPP). The STP process uses high temperature liquid water to accelerate the reaction, produce uranium dioxide from the uranium metal, and safely discharge the hydrogen. Under nominal process conditions, the sludge will be heated in pressurized water at 185°C for as long as 72 hours to assure the complete reaction (corrosion) of up to 0.25-inch diameter uranium metal pieces. Under contractmore » to FH, the Pacific Northwest National Laboratory (PNNL) conducted bench-scale testing of the STP hydrothermal process in November and December 2006. Five tests (~50 ml each) were conducted in sealed, un-agitated reaction vessels under the hydrothermal conditions (e.g., 7 to 72 h at 185°C) of the STP corrosion process using radioactive sludge samples collected from the K East Basin and particles/coupons of N Reactor fuel also taken from the K Basins. The tests were designed to evaluate and understand the chemical changes that may be occurring and the effects that any changes would have on sludge rheological properties. The tests were not designed to evaluate engineering aspects of the process. The hydrothermal treatment affected the chemical and physical properties of the sludge. In each test, significant uranium compound phase changes were identified, resulting from dehydration and chemical reduction reactions. Physical properties of the sludge were significantly altered from their initial, as-settled sludge values, including, shear strength, settled density, weight percent water, and gas retention.« less

The Use of Thorium within the Nuclear Power Industry - 13472

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, Keith

2013-07-01

Thorium is 3 to 4 times more abundant than uranium and is widely distributed in nature as an easily exploitable resource in many countries. Unlike natural uranium, which contains ∼0.7% fissile {sup 235}U isotope, natural thorium does not contain any fissile material and is made up of the fertile {sup 232}Th isotope only. Therefore thorium and thorium-based fuel as metal, oxide or carbide, has been utilized in combination with fissile {sup 235}U or {sup 239}Pu in nuclear research and power reactors for conversion to fissile {sup 233}U, thereby enlarging fissile material resources. During the pioneering years of nuclear energy, frommore » the mid 1950's to mid 1970's, there was considerable interest worldwide to develop thorium fuels and fuel cycles in order to supplement uranium reserves. Thorium fuels and fuel cycles are particularly relevant to countries having large thorium deposits but very limited uranium reserves for their long term nuclear power programme. The feasibility of thorium utilization in high temperature gas cooled reactors (HTGR), light water reactors (LWR), pressurized heavy water reactors (PHWRs), liquid metal cooled fast breeder reactors (LMFBR) and molten salt breeder reactors (MSBR) were demonstrated. The initial enthusiasm for thorium fuels and fuel cycles was not sustained among the developing countries later, due to new discovery of uranium deposits and their improved availability. However, in recent times, the need for proliferation-resistance, longer fuel cycles, higher burnup, and improved waste form characteristics, reduction of plutonium inventories and in situ use of bred-in fissile material has led to renewed interest in thorium-based fuels and fuel cycles. (authors)« less

Carbothermic reduction of uranium oxides into solvent metallic baths

NASA Astrophysics Data System (ADS)

Guisard Restivo, Thomaz A.; Capocchi, José D. T.

2004-09-01

The carbothermic reduction of UO 2 and U 3O 8 is studied employing tin and silicon solvent metallic baths in thermal analysis equipment, under Ar inert and N 2 reactive atmospheres. The metallic solvents are expected to lower the U activity by several orders of magnitude owing to strong interactions among the metals. The reduction products are composed of the solvent metal matrix and intermetallic U compounds. Silicon is more effective in driving the reduction since there is no residual UO 2 after the reaction. The gaseous product detected by mass spectrometer (MS) during the reduction is CO. A kinetic study for the Si case was accomplished by the stepwise isothermal analysis (SAI) method, leading to the identification of the controlling mechanisms as chemical reaction at the surface and nucleation, for UO 2 and U 3O 8 charges, respectively. One example for another system containing Al 2O 3 is also shown.

Microbial physiology-based model of ethanol metabolism in subsurface sediments

NASA Astrophysics Data System (ADS)

Jin, Qusheng; Roden, Eric E.

2011-07-01

A biogeochemical reaction model was developed based on microbial physiology to simulate ethanol metabolism and its influence on the chemistry of anoxic subsurface environments. The model accounts for potential microbial metabolisms that degrade ethanol, including those that oxidize ethanol directly or syntrophically by reducing different electron acceptors. Out of the potential metabolisms, those that are active in the environment can be inferred by fitting the model to experimental observations. This approach was applied to a batch sediment slurry experiment that examined ethanol metabolism in uranium-contaminated aquifer sediments from Area 2 at the U.S. Department of Energy Field Research Center in Oak Ridge, TN. According to the simulation results, complete ethanol oxidation by denitrification, incomplete ethanol oxidation by ferric iron reduction, ethanol fermentation to acetate and H 2, hydrogenotrophic sulfate reduction, and acetoclastic methanogenesis: all contributed significantly to the degradation of ethanol in the aquifer sediments. The assemblage of the active metabolisms provides a frame work to explore how ethanol amendment impacts the chemistry of the environment, including the occurrence and levels of uranium. The results can also be applied to explore how diverse microbial metabolisms impact the progress and efficacy of bioremediation strategies.

Uranium potential of the Burro Canyon Formation in western Colorado

USGS Publications Warehouse

Craig, L.C.

1982-01-01

The Burro Canyon Formation of Early Cretaceous age overlies the Morrison Formation (Late Jurassic) and underlies the Dakota Sandstone (Late Cretaceous) over most of southeastern Utah and southwestern Colorado. It consists mainly of alternating beds of fluvial sandstone and overbank mudstone with sandstone dominating in the lower part of the formation and mudstone in the upper part. At the outcrop, the sandstones in the formation exhibit almost all the characteristics that are considered favorable for the occurrence of sandstone-type uranium deposits, but only a few small deposits have been discovered in the Colorado-Utah area. The major deficiency of the Burro Canyon in these outcrop areas is the absence of a reductant such as carbonaceous debris, humic or humate materials, or pyrite. Reductants were probably removed during a period of extensive oxidation at the time of deposition and during a subsequent erosional episode prior to deposition of the Dakota Sandstone. The formation reaches a lobate, inexactly located eastern margin that extends from near Meeker, Colorado, southward through the Piceance basin to near Aztec, New Mexico, in the northwestern part of the San Juan Basin. Along much of this distance, the formation is in the subsurface and has been penetrated by only a few drill holes. Along this eastern margin, the lobes project eastward where fluvial distributary streams built minor alluvial fans of relatively high-energy deposits out from the main axis of Burro Canyon stream deposition. The lower and distal reaches of these lobes may have survived the period of post depositional erosion and oxidation in a reduced condition because of low relief and the protection of a high water table. If so, the peripheral and distal parts of these lobes may have retained the precipitants necessary to form a uranium deposit. Two of the lobes extend into the southwest margin of the Piceance Basin and are considered the possible location of uranium deposits. Two additional lobes extend into the northwestern part of the San Juan Basin but have not been evaluated in this study.

A two-fold reduction in measurement time for neutron assay: Initial tests of a prototype dual-gated shift register

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stewart, J.E.; Bourret, S.C.; Krick, M.S.

1996-09-01

Neutron coincidence counting (NCC) is used routinely around the world for nondestructive mass assay of uranium and plutonium in many forms, including waste. Compared with other methods, NCC is generally the most flexible, economic, and rapid. Many applications of NCC would benefit from a reduction in counting time required for a fixed random error. We have developed and tested the first prototype of a dual- gated, shift-register-based electronics unit that offers the potential of decreased measurement time for all passive and active NCC applications.

A two-fold reduction in measurement time for neutron assay: Initial tests of a prototype dual-gated shift register

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stewart, J.E.; Bourret, S.C.; Krick, M.S.

1996-12-31

Neutron coincidence counting (NCC) is used routinely around the world for nondestructive mass assay of uranium and plutonium in many forms, including waste. Compared with other methods, NCC is generally the most flexible, economic, and rapid. Many applications of NCC would benefit from a reduction in counting time required for a fixed random error. The authors have developed and tested the first prototype of a dual-gated, shift-register-based electronics unit that offers the potential of decreased measurement time for all passive and active NCC applications.

Redox properties of biscyclopentadienyl uranium(V) imido-halide complexes: a relativistic DFT study.

PubMed

Elkechai, Aziz; Kias, Farida; Talbi, Fazia; Boucekkine, Abdou

2014-06-01

Calculations of ionization energies (IE) and electron affinities (EA) of a series of biscyclopentadienyl imido-halide uranium(V) complexes Cp*2U(=N-2,6-(i)Pr2-C6H3)(X) with X =  F, Cl, Br, and I, related to the U(IV)/U(V) and U(V)/U(VI) redox systems, were carried out, for the first time, using density functional theory (DFT) in the framework of the relativistic zeroth order regular approximation (ZORA) coupled with the conductor-like screening model (COSMO) solvation approach. A very good linear correlation (R(2) =  0.993) was obtained, between calculated ionization energies at the ZORA/BP86/TZP level, and the experimental half-wave oxidation potentials E1/2. A similar linear correlation between the computed electron affinities and the electrochemical reduction U(IV)/U(III) potentials (R(2) =  0.996) is obtained. The importance of solvent effects and of spin-orbit coupling is definitively confirmed. The molecular orbital analysis underlines the crucial role played by the 5f orbitals of the central metal whereas the Nalewajski-Mrozek (N-M) bond indices explain well the bond distances variations following the redox processes. The IE variation of the complexes, i.e., IE(F) < IE(Cl) < IE(Br) < IE(I) is also well rationalized considering the frontier MO diagrams of these species. Finally, this work confirms the relevance of the Hirshfeld charges analysis which bring to light an excellent linear correlation (R(2) =  0.999) between the variations of the uranium charges and E1/2 in the reduction process of the U(V) species.

Preliminary Assessment of the Impact on Reactor Vessel dpa Rates Due to Installation of a Proposed Low Enriched Uranium (LEU) Core in the High Flux Isotope Reactor (HFIR)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daily, Charles R.

2015-10-01

An assessment of the impact on the High Flux Isotope Reactor (HFIR) reactor vessel (RV) displacements-per-atom (dpa) rates due to operations with the proposed low enriched uranium (LEU) core described by Ilas and Primm has been performed and is presented herein. The analyses documented herein support the conclusion that conversion of HFIR to low-enriched uranium (LEU) core operations using the LEU core design of Ilas and Primm will have no negative impact on HFIR RV dpa rates. Since its inception, HFIR has been operated with highly enriched uranium (HEU) cores. As part of an effort sponsored by the National Nuclearmore » Security Administration (NNSA), conversion to LEU cores is being considered for future HFIR operations. The HFIR LEU configurations analyzed are consistent with the LEU core models used by Ilas and Primm and the HEU balance-of-plant models used by Risner and Blakeman in the latest analyses performed to support the HFIR materials surveillance program. The Risner and Blakeman analyses, as well as the studies documented herein, are the first to apply the hybrid transport methods available in the Automated Variance reduction Generator (ADVANTG) code to HFIR RV dpa rate calculations. These calculations have been performed on the Oak Ridge National Laboratory (ORNL) Institutional Cluster (OIC) with version 1.60 of the Monte Carlo N-Particle 5 (MCNP5) computer code.« less

Research Reactor Preparations for the Air Shipment of Highly Enriched Uranium from Romania

DOE Office of Scientific and Technical Information (OSTI.GOV)

K. J. Allen; I. Bolshinsky; L. L. Biro

2010-03-01

In June 2009 two air shipments transported both unirradiated (fresh) and irradiated (spent) Russian-origin highly enriched uranium (HEU) nuclear fuel from two research reactors in Romania to the Russian Federation for conversion to low enriched uranium. The Institute for Nuclear Research at Pitesti (SCN Pitesti) shipped 30.1 kg of HEU fresh fuel pellets to Dimitrovgrad, Russia and the Horia Hulubei National Institute of Physics and Nuclear Engineering (IFIN-HH) shipped 23.7 kilograms of HEU spent fuel assemblies from the VVR S research reactor at Magurele, Romania, to Chelyabinsk, Russia. Both HEU shipments were coordinated by the Russian Research Reactor Fuel Returnmore » Program (RRRFR) as part of the U.S. Department of Energy Global Threat Reduction Initiative (GTRI), were managed in Romania by the National Commission for Nuclear Activities Control (CNCAN), and were conducted in cooperation with the Russian Federation State Corporation Rosatom and the International Atomic Energy Agency. Both shipments were transported by truck to and from respective commercial airports in Romania and the Russian Federation and stored at secure nuclear facilities in Russia until the material is converted into low enriched uranium. These shipments resulted in Romania becoming the 3rd country under the RRRFR program and the 14th country under the GTRI program to remove all HEU. This paper describes the research reactor preparations and license approvals that were necessary to safely and securely complete these air shipments of nuclear fuel.« less

Radon as a natural tracer for gas transport within uranium waste rock piles.

PubMed

Silva, N C; Chagas, E G L; Abreu, C B; Dias, D C S; Lopez, D; Guerreiro, E T Z; Alberti, H L C; Braz, M L; Branco, O; Fleming, P

2014-07-01

Acid mine drainage (AMD) has been identified as the main cause for outflow of acid water and radioactive/non-radioactive contaminants. AMD encompasses pyrites oxidation when water and oxygen are available. AMD was identified in uranium waste rock piles (WRPs) of Indústrias Nucleares do Brasil-Caldas facility (Brazilian uranium mine), resulting in high costs for water treatment. AMD reduction is the main challenge, and scientific investigation has been conducted to understand oxygen and water transportation within WRPs, where 222Rn is used as natural tracer for oxygen transportation. The study consists of soil radon gas mapping in the top layer of WRP4 using active soil gas pumping, radon adsorption in active charcoal and 222Rn determination using high-resolution gamma-ray spectrometry. A sampling network of 71 points was built where samples were collected at a depth of 40 cm. Soil radon gas concentration ranged from 33.7 to 1484.2 kBq m(-3) with mean concentration of 320.7±263.3 kBq m(-3). © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Oxidative dissolution of biogenic uraninite in groundwater at Old Rifle, CO

USGS Publications Warehouse

Campbell, Kate M.; Veeramani, Harish; Ulrich, Kai-Uwe; Blue, Lisa Y.; Giammar, Dianiel E.; Bernier-Latmani, Rizlan; Stubbs, Joanne E.; Suvorova, Elena; Yabusaki, Steve; Lezama-Pacheco, Juan S.; Mehta, Apurva; Long, Philip E.; Bargar, John R.

2011-01-01

Reductive bioremediation is currently being explored as a possible strategy for uranium-contaminated aquifers such as the Old Rifle site (Colorado). The stability of U(IV) phases under oxidizing conditions is key to the performance of this procedure. An in situ method was developed to study oxidative dissolution of biogenic uraninite (UO2), a desirable U(VI) bioreduction product, in the Old Rifle, CO, aquifer under different variable oxygen conditions. Overall uranium loss rates were 50–100 times slower than laboratory rates. After accounting for molecular diffusion through the sample holders, a reactive transport model using laboratory dissolution rates was able to predict overall uranium loss. The presence of biomass further retarded diffusion and oxidation rates. These results confirm the importance of diffusion in controlling in-aquifer U(IV) oxidation rates. Upon retrieval, uraninite was found to be free of U(VI), indicating dissolution occurred via oxidation and removal of surface atoms. Interaction of groundwater solutes such as Ca2+ or silicate with uraninite surfaces also may retard in-aquifer U loss rates. These results indicate that the prolonged stability of U(IV) species in aquifers is strongly influenced by permeability, the presence of bacterial cells and cell exudates, and groundwater geochemistry.

Disguised as a Sulfate Reducer: Growth of the Deltaproteobacterium Desulfurivibrio alkaliphilus by Sulfide Oxidation with Nitrate.

PubMed

Thorup, Casper; Schramm, Andreas; Findlay, Alyssa J; Finster, Kai W; Schreiber, Lars

2017-07-18

This study demonstrates that the deltaproteobacterium Desulfurivibrio alkaliphilus can grow chemolithotrophically by coupling sulfide oxidation to the dissimilatory reduction of nitrate and nitrite to ammonium. Key genes of known sulfide oxidation pathways are absent from the genome of D. alkaliphilus Instead, the genome contains all of the genes necessary for sulfate reduction, including a gene for a reductive-type dissimilatory bisulfite reductase (DSR). Despite this, growth by sulfate reduction was not observed. Transcriptomic analysis revealed a very high expression level of sulfate-reduction genes during growth by sulfide oxidation, while inhibition experiments with molybdate pointed to elemental sulfur/polysulfides as intermediates. Consequently, we propose that D. alkaliphilus initially oxidizes sulfide to elemental sulfur, which is then either disproportionated, or oxidized by a reversal of the sulfate reduction pathway. This is the first study providing evidence that a reductive-type DSR is involved in a sulfide oxidation pathway. Transcriptome sequencing further suggests that nitrate reduction to ammonium is performed by a novel type of periplasmic nitrate reductase and an unusual membrane-anchored nitrite reductase. IMPORTANCE Sulfide oxidation and sulfate reduction, the two major branches of the sulfur cycle, are usually ascribed to distinct sets of microbes with distinct diagnostic genes. Here we show a more complex picture, as D. alkaliphilus , with the genomic setup of a sulfate reducer, grows by sulfide oxidation. The high expression of genes typically involved in the sulfate reduction pathway suggests that these genes, including the reductive-type dissimilatory bisulfite reductases, are also involved in as-yet-unresolved sulfide oxidation pathways. Finally, D. alkaliphilus is closely related to cable bacteria, which grow by electrogenic sulfide oxidation. Since there are no pure cultures of cable bacteria, D. alkaliphilus may represent an exciting model organism in which to study the physiology of this process. Copyright © 2017 Thorup et al.

An Exploratory Study on the Pathways of Cr (VI) Reduction in Sulfate-reducing Up-flow Anaerobic Sludge Bed (UASB) Reactor

PubMed Central

Qian, Jin; Wei, Li; Liu, Rulong; Jiang, Feng; Hao, Xiaodi; Chen, Guang-Hao

2016-01-01

Electroplating wastewater contains both Cr (VI) and sulfate. So Cr (VI) removal under sulfate-rich condition is quite complicated. This study mainly investigates the pathways for Cr (VI) removal under biological sulfate-reducing condition in the up-flow anaerobic sludge bed (UASB) reactor. Two potential pathways are found for the removal of Cr (VI). The first one is the sulfidogenesis-induced Cr (VI) reduction pathway (for 90% Cr (VI) removal), in which Cr (VI) is reduced by sulfide generated from biological reduction of sulfate. The second one leads to direct reduction of Cr (VI) which is utilized by bacteria as the electron acceptor (for 10% Cr (VI) removal). Batch test results confirmed that sulfide was oxidized to elemental sulfur instead of sulfate during Cr (VI) reduction. The produced extracellular polymeric substances (EPS) provided protection to the microbes, resulting in effective removal of Cr (VI). Sulfate-reducing bacteria (SRB) genera accounted for 11.1% of the total bacterial community; thus they could be the major organisms mediating the sulfidogenesis-induced reduction of Cr (VI). In addition, chromate-utilizing genera (e.g. Microbacterium) were also detected, which were possibly responsible for the direct reduction of Cr (VI) using organics as the electron donor and Cr (VI) as the electron acceptor. PMID:27021522

Trimolecular reactions of uranium hexafluoride with water.

PubMed

Lind, Maria C; Garrison, Stephen L; Becnel, James M

2010-04-08

The hydrolysis reaction of uranium hexafluoride (UF(6)) is a key step in the synthesis of uranium dioxide (UO(2)) powder for nuclear fuels. Mechanisms for the hydrolysis reactions are studied here with density functional theory and the Stuttgart small-core scalar relativistic pseudopotential and associated basis set for uranium. The reaction of a single UF(6) molecule with a water molecule in the gas phase has been previously predicted to proceed over a relatively sizable barrier of 78.2 kJ x mol(-1), indicating this reaction is only feasible at elevated temperatures. Given the observed formation of a second morphology for the UO(2) product coupled with the observations of rapid, spontaneous hydrolysis at ambient conditions, an alternate reaction pathway must exist. In the present work, two trimolecular hydrolysis mechanisms are studied with density functional theory: (1) the reaction between two UF(6) molecules and one water molecule, and (2) the reaction of two water molecules with a single UF(6) molecule. The predicted reaction of two UF(6) molecules with one water molecule displays an interesting "fluorine-shuttle" mechanism, a significant energy barrier of 69.0 kJ x mol(-1) to the formation of UF(5)OH, and an enthalpy of reaction (DeltaH(298)) of +17.9 kJ x mol(-1). The reaction of a single UF(6) molecule with two water molecules displays a "proton-shuttle" mechanism, and is more favorable, having a slightly lower computed energy barrier of 58.9 kJ x mol(-1) and an exothermic enthalpy of reaction (DeltaH(298)) of -13.9 kJ x mol(-1). The exothermic nature of the overall UF(6) + 2H(2)O trimolecular reaction and the lowering of the barrier height with respect to the bimolecular reaction are encouraging.

Physical setting and natural sources of exposure to carcinogenic trace elements and radionuclides in Lahontan Valley, Nevada

USGS Publications Warehouse

Seiler, Ralph L.

2012-01-01

In Lahontan Valley, Nevada, arsenic, cobalt, tungsten, uranium, radon, and polonium-210 are carcinogens that occur naturally in sediments and groundwater. Arsenic and cobalt are principally derived from erosion of volcanic rocks in the local mountains and tungsten and uranium are derived from erosion of granitic rocks in headwater reaches of the Carson River. Radon and 210Po originate from radioactive decay of uranium in the sediments. Arsenic, aluminum, cobalt, iron, and manganese concentrations in household dust suggest it is derived from the local soils. Excess zinc and chromium in the dust are probably derived from the vacuum cleaner used to collect the dust, or household sources such as the furnace. Some samples have more than 5 times more cobalt in the dust than in the local soil, but whether the source of the excess cobalt is anthropogenic or natural cannot be determined with the available data. Cobalt concentrations are low in groundwater, but arsenic, uranium, radon, and 210Po concentrations often exceed human-health standards, and sometime greatly exceed them. Exposure to radon and its decay products in drinking water can vary significantly depending on when during the day that the water is consumed. Although the data suggests there have been no long term changes in groundwater chemistry that corresponds to the Lahontan Valley leukemia cluster, the occurrence of the very unusual leukemia cluster in an area with numerous 210Po and arsenic contaminated wells is striking, particularly in conjunction with the exceptionally high levels of urinary tungsten in Lahontan Valley residents. Additional research is needed on potential exposure pathways involving food or inhalation, and on synergistic effects of mixtures of these natural contaminants on susceptibility to development of leukemia.

Physical setting and natural sources of exposure to carcinogenic trace elements and radionuclides in Lahontan Valley, Nevada.

PubMed

Seiler, Ralph

2012-04-05

In Lahontan Valley, Nevada, arsenic, cobalt, tungsten, uranium, radon, and polonium-210 are carcinogens that occur naturally in sediments and groundwater. Arsenic and cobalt are principally derived from erosion of volcanic rocks in the local mountains and tungsten and uranium are derived from erosion of granitic rocks in headwater reaches of the Carson River. Radon and 210Po originate from radioactive decay of uranium in the sediments. Arsenic, aluminum, cobalt, iron, and manganese concentrations in household dust suggest it is derived from the local soils. Excess zinc and chromium in the dust are probably derived from the vacuum cleaner used to collect the dust, or household sources such as the furnace. Some samples have more than 5 times more cobalt in the dust than in the local soil, but whether the source of the excess cobalt is anthropogenic or natural cannot be determined with the available data. Cobalt concentrations are low in groundwater, but arsenic, uranium, radon, and 210Po concentrations often exceed human-health standards, and sometime greatly exceed them. Exposure to radon and its decay products in drinking water can vary significantly depending on when during the day that the water is consumed. Although the data suggests there have been no long term changes in groundwater chemistry that corresponds to the Lahontan Valley leukemia cluster, the occurrence of the very unusual leukemia cluster in an area with numerous 210Po and arsenic contaminated wells is striking, particularly in conjunction with the exceptionally high levels of urinary tungsten in Lahontan Valley residents. Additional research is needed on potential exposure pathways involving food or inhalation, and on synergistic effects of mixtures of these natural contaminants on susceptibility to development of leukemia. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

U(VI) Reduction by Biogenic and Abiotic Hydroxycarbonate Green Rusts: Impacts on U(IV) Speciation and Stability Over Time

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan, Sen; Boyanov, Maxim I.; Mishra, Bhoopesh

Green rusts (GRs) are redox active Fe II-Fe III minerals that form in the environment via various biotic and abiotic processes. Although both biogenic (BioGR) and abiotic (ChemGR) GRs have been shown to reduce U VI, the dynamics of the transformations and the speciation and stability of the resulting U IV phases are poorly understood. We used carbonate extraction and XAFS spectroscopy to investigate the products of U VI reduction by BioGR and ChemGR. The results show that both GRs can rapidly remove U VI from synthetic groundwater via reduction to U IV. The initial products in the ChemGR systemmore » are solids-associated U IV-carbonate complexes that gradually transform to nanocrystalline uraninite over time, leading to a decrease in the proportion of carbonate-extractable U from ~95% to ~10%. In contrast, solid-phase U IV atoms in the BioGR system remain relatively extractable, non-uraninite U IV species over the same reaction period. The presence of calcium and carbonate in groundwater significantly increase the extractability of U IV in the BioGR system. Furthermore, these data provide new insights into the transformations of U under anoxic conditions in groundwater that contains calcium and carbonate, and have major implications for predicting uranium stability within redox dynamic environments and designing approaches for the remediation of uranium-contaminated groundwater.« less

U(VI) Reduction by Biogenic and Abiotic Hydroxycarbonate Green Rusts: Impacts on U(IV) Speciation and Stability Over Time

DOE PAGES

Yan, Sen; Boyanov, Maxim I.; Mishra, Bhoopesh; ...

2018-04-09

Green rusts (GRs) are redox active Fe II-Fe III minerals that form in the environment via various biotic and abiotic processes. Although both biogenic (BioGR) and abiotic (ChemGR) GRs have been shown to reduce U VI, the dynamics of the transformations and the speciation and stability of the resulting U IV phases are poorly understood. We used carbonate extraction and XAFS spectroscopy to investigate the products of U VI reduction by BioGR and ChemGR. The results show that both GRs can rapidly remove U VI from synthetic groundwater via reduction to U IV. The initial products in the ChemGR systemmore » are solids-associated U IV-carbonate complexes that gradually transform to nanocrystalline uraninite over time, leading to a decrease in the proportion of carbonate-extractable U from ~95% to ~10%. In contrast, solid-phase U IV atoms in the BioGR system remain relatively extractable, non-uraninite U IV species over the same reaction period. The presence of calcium and carbonate in groundwater significantly increase the extractability of U IV in the BioGR system. Furthermore, these data provide new insights into the transformations of U under anoxic conditions in groundwater that contains calcium and carbonate, and have major implications for predicting uranium stability within redox dynamic environments and designing approaches for the remediation of uranium-contaminated groundwater.« less

Towards A Modern Calibration Of The 238U/235U Paleoredox Proxy: Apparent Uranium Isotope Fractionation Factor During U(VI)-U(IV) Reduction In The Black Sea

NASA Astrophysics Data System (ADS)

Rolison, J. M.; Stirling, C. H.; Middag, R.; Rijkenberg, M. J. A.; De Baar, H. J. W.

2015-12-01

The isotopic compositions of redox-sensitive metals, including uranium (U), in marine sediments have recently emerged as powerful diagnostic tracers of the redox state of the ancient ocean-atmosphere system. Interpretation of sedimentary isotopic information requires a thorough understating of the environmental controls on isotopic fractionation in modern anoxic environments before being applied to the paleo-record. In this study, the relationship between ocean anoxia and the isotopic fractionation of U was investigated in the water column and sediments of the Black Sea. The Black Sea is the world's largest anoxic basin and significant removal of U from the water column and high U accumulation rates in modern underlying sediments have been documented. Removal of U from the water column occurs during the redox transition of soluble U(VI) to relatively insoluble U(IV). The primary results of this study are two-fold. First, significant 238U/235U fractionation was observed in the water column of the Black Sea, suggesting the reduction of U induces 238U/235U fractionation with the preferential removal of 238U from the aqueous phase. Second, the 238U/235U of underlying sediments is related to the water column through the isotope fractionation factor of the reduction reaction but is influenced by mass transport processes. These results provide important constraints on the use of 238U/235U as a proxy of the redox state of ancient oceans.

Mechanistic Explanation of the pH Dependence and Onset Potentials for Hydrocarbon Products from Electrochemical Reduction of CO on Cu (111)

DOE PAGES

Xiao, Hai; Cheng, Tao; Goddard, William A.; ...

2015-12-30

Energy and environmental concerns demand development of more efficient and selective electrodes for electrochemical reduction of CO 2 to form fuels and chemicals. Since Cu is the only pure metal exhibiting reduction to form hydrocarbon chemicals, we focus here on the Cu (111) electrode. We present a methodology for density functional theory calculations to obtain accurate onset electrochemical potentials with explicit constant electrochemical potential and pH effects using implicit solvation. We predict the atomistic mechanisms underlying electrochemical reduction of CO, finding that (1) at acidic pH, the C 1 pathway proceeds through COH to CHOH to form CH 4 whilemore » C 2 (C 3) pathways are kinetically blocked; (2) at neutral pH, the C 1 and C 2 (C 3) pathways share the COH common intermediate, where the branch to C-C coupling is realized by a novel CO-COH pathway; and (3) at high pH, early C-C coupling through adsorbed CO dimerization dominates, suppressing the C 1 pathways by kinetics, thereby boosting selectivity for multi-carbon products.« less

Evaluation of N,N-dialkylamides as promising process extractants

NASA Astrophysics Data System (ADS)

Pathak, P. N.; Prabhu, D. R.; Kanekar, A. S.; Manchanda, V. K.

2010-03-01

Studies carried out at BARC, India on the development of new extractants for reprocessing of spent fuel suggested that while straight chain N,N-dihexyloctanamide (DHOA) is promising alternative to TBP for the reprocessing of irradiated uranium based fuels, branched chain N,N-di(2-ethylhexyl)isobutyramide (D2EHIBA) is suitable for the selective recovery of 233U from irradiated Th. In advanced fuel cycle scenarios, the coprocessing of U/Pu stream appears attractive particularly with respect to development of proliferation resistant technologies. DHOA extracted Pu(IV) more efficiently than TBP, both at trace-level concentration as well as under uranium/plutonium loading conditions. Uranium extraction behavior of DHOA was however, similar to that of TBP during the extraction cycle. Stripping behavior of U and Pu (without any reductant) was better for DHOA than that of TBP. It was observed during batch studies that whereas 99% Pu is stripped in four stages in case of DHOA, only 89% Pu is stripped in case of TBP under identical experimental conditions. DHOA offered better fission product decontamination than that of TBP. GANEX (Group ActiNide EXtraction) and ARTIST (Amide-based Radio-resources Treatment with Interim Storage of Transuranics) processes proposed for actinide partitioning use branched chain amides for the selective extraction of uranium from spent fuel feed solutions. The branched-alkyl monoamide (BAMA) proposed to be used in ARTIST process is N,N-di-(2-ethylhexyl)butyramide (D2EHBA). In this context, the extraction behavior of U(VI) and Pu(IV) were compared using D2EHIBA, TBP, and D2EHBA under similar concentration of nitric acid (0.5 — 6M) and of uranium (0-50g/L). These studies suggested that D2EHIBA is a promising extractant for selective extraction of uranium over plutonium in process streams. Similarly, D2EHIBA offered distinctly better decontamination of 233U over Th and fission products under THOREX feed conditions. The possibility of simultaneous stripping and precipitation of thorium (as oxalate) from loaded organic phase was explored using 0.05M oxalic acid. Ammonium diuranate (ADU) precipitation was performed on the oxalate supernatant for the recovery of uranium. Quantitative recovery (>99.9%) of Th as well as of U was achieved. Radiolytic studies suggested that irradiated DHOA and D2EHIBA behaved better with respect to fission product decontamination as compared to that of TBP.

Occupational dose reduction at Department of Energy contractor facilities: Bibliography of selected readings in radiation protection and ALARA; Volume 5

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dionne, B.J.; Sullivan, S.G.; Baum, J.W.

1994-01-01

Promoting the exchange of information related to implementation of the As Low as Reasonably Achievable (ALARA) philosophy is a continuing objective for the Department of Energy (DOE). This report was prepared by the Brookhaven National Laboratory (BNL) ALARA Center for the DOE Office of Health. It contains the fifth in a series of bibliographies on dose reduction at DOE facilities. The BNL ALARA Center was originally established in 1983 under the sponsorship of the Nuclear Regulatory Commission to monitor dose-reduction research and ALARA activities at nuclear power plants. This effort was expanded in 1988 by the DOE`s Office of Environment,more » Safety and Health, to include DOE nuclear facilities. This bibliography contains abstracts relating to various aspects of ALARA program implementation and dose-reduction activities, with a specific focus on DOE facilities. Abstracts included in this bibliography were selected from proceedings of technical meetings, journals, research reports, searches of the DOE Energy, Science and Technology Database (in general, the citation and abstract information is presented as obtained from this database), and reprints of published articles provided by the authors. Facility types and activities covered in the scope of this report include: radioactive waste, uranium enrichment, fuel fabrication, spent fuel storage and reprocessing, facility decommissioning, hot laboratories, tritium production, research, test and production reactors, weapons fabrication and testing, fusion, uranium and plutonium processing, radiography, and accelerators. Information on improved shielding design, decontamination, containments, robotics, source prevention and control, job planning, improved operational and design techniques, as well as on other topics, has been included. In addition, DOE/EH reports not included in previous volumes of the bibliography are in this volume (abstracts 611 to 684). This volume (Volume 5 of the series) contains 217 abstracts.« less

Using 238U/235U ratios to understand the formation and oxidation of reduced uranium solids in naturally reduced zones

NASA Astrophysics Data System (ADS)

Jemison, N.; Johnson, T. M.; Druhan, J. L.; Davis, J. A.

2016-12-01

Uranium occurs in groundwater primarily as soluble and mobile U(VI), which can be reduced to immobile U(IV), often observed in sediments as uraninite. Numerous U(VI)-contaminated sites, such as the DOE field site in Rifle, CO, contain naturally reduced zones (NRZ's) that have relatively high concentrations of organic matter. Reduction of heavy metals occurs within NRZ's, producing elevated concentrations of iron sulfides and U(IV). Slow, natural oxidation of U(IV) from NRZ's may prolong U(VI) contamination of groundwater. The reduction of U(VI) produces U(IV) with a higher 238U/235U ratio. Samples from two NRZ sediment cores recovered from the Rifle site revealed that the outer fringes of the NRZ contain U(IV) with a high 238U/235U ratio, while lower values are observed in the center . We suggest that as aqueous U(VI) was reduced in the NRZ, it was driven to lower 238U/235U values, such that U(IV) formed in the core of the NRZ reflects a lower 238U/235U. Two oxidation experiments were conducted by injecting groundwater containing between 14.9 and 21.2 mg/L dissolved O2 as an oxidant into the NRZ. The oxidation of U(IV) from this NRZ increased aqueous U(VI) concentrations and caused a shift to higher 238U/235U in groundwater as U(IV) was oxidized primarily on the outer fringes of the NRZ. In total these observations suggest that the stability of solid phase uranium is governed by coupled reaction and transport processes. To better understand various reactive transport scenarios we developed a model for the formation and oxidation of NRZ's utilizing the reactive transport software CrunchTope. These simulations suggest that the development of isotopically heterogeneous U(IV) within NRZ's is largely controlled by permeability of the NRZ and the U(VI) reduction rate. Oxidation of U(IV) from the NRZ's is constrained by the oxidation rate of U(IV) as well as iron sulfides, which can prevent oxidation of U(IV) by scavenging dissolved oxygen.

Disguised as a Sulfate Reducer: Growth of the Deltaproteobacterium Desulfurivibrio alkaliphilus by Sulfide Oxidation with Nitrate

PubMed Central

Thorup, Casper; Schramm, Andreas

2017-01-01

ABSTRACT This study demonstrates that the deltaproteobacterium Desulfurivibrio alkaliphilus can grow chemolithotrophically by coupling sulfide oxidation to the dissimilatory reduction of nitrate and nitrite to ammonium. Key genes of known sulfide oxidation pathways are absent from the genome of D. alkaliphilus. Instead, the genome contains all of the genes necessary for sulfate reduction, including a gene for a reductive-type dissimilatory bisulfite reductase (DSR). Despite this, growth by sulfate reduction was not observed. Transcriptomic analysis revealed a very high expression level of sulfate-reduction genes during growth by sulfide oxidation, while inhibition experiments with molybdate pointed to elemental sulfur/polysulfides as intermediates. Consequently, we propose that D. alkaliphilus initially oxidizes sulfide to elemental sulfur, which is then either disproportionated, or oxidized by a reversal of the sulfate reduction pathway. This is the first study providing evidence that a reductive-type DSR is involved in a sulfide oxidation pathway. Transcriptome sequencing further suggests that nitrate reduction to ammonium is performed by a novel type of periplasmic nitrate reductase and an unusual membrane-anchored nitrite reductase. PMID:28720728

Remediation of subsurface and groundwater contamination with uranium from fuel fabrication facilities at Hanau (Germany)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nitzsche, Olaf; Thierfeldt, Stefan; Hummel, Lothar

2013-07-01

This paper presents aspects of site decommissioning and clearance of a former fuel fabrication facility (development and production of fuel assemblies for research reactors and HTR) at Hanau (Germany). The main pathways for environmental contamination were deposition on soil surface and topsoil and pollution of deep soil and the aquifer by waste water channel leakage. Soil excavation could be done by classical excavator techniques. An effective removal of material from the saturated zone was possible by using advanced drilling techniques. A large amount of demolished building structure and excavated soil had to be classified. Therefore the use of conveyor detectormore » was necessary. Nearly 100000 Mg of material (excavated soil and demolished building material) were disposed of at an underground mine. A remaining volume of 700 m{sup 3} was classified as radioactive waste. Site clearance started in 2006. Groundwater remediation and monitoring is still ongoing, but has already provided excellent results by reducing the remaining Uranium considerably. (authors)« less

Fast Oxidation Processes in a Naturally Reduced Aquifer Zone Caused by Dissolved Oxygen

NASA Astrophysics Data System (ADS)

Davis, J. A.; Jemison, N. E.; Williams, K. H.; Hobson, C.; Bush, R. P.

2014-12-01

The occurrence of naturally reduced zones is quite common in alluvial aquifers in the western U.S.A. due to the burial of woody debris in flood plains. The naturally reduced zones are heterogeneously dispersed in such aquifers and are characterized by high concentrations of organic carbon and reduced phases, including iron sulfides and reduced forms of metals, including uranium(IV). The persistence of high concentrations of dissolved uranium(VI) at uranium-contaminated aquifers on the Colorado Plateau has been attributed to slow oxidation of insoluble uranium(IV) mineral phases that are found in association with these natural reducing zones, although there is little understanding of the relative importance of various potential oxidants. Three field experiments were conducted within an alluvial aquifer adjacent to the Colorado River near Rifle, CO wherein groundwater associated with naturally reduced zones was pumped into a gas-impermeable tank, mixed with a conservative tracer (Br-), bubbled with a gas phase composed of 97% O2 and 3% CO2, and then returned to the subsurface in the same well from which it was withdrawn. Within minutes of re-injection of the oxygenated groundwater, dissolved uranium(VI) concentrations increased from less than 1 μM to greater than 2.5 μM, demonstrating that oxygen can be an important oxidant for uranium in these field systems if supplied to the naturally reduced zones. Small concentrations of nitrate were also observed in the previously nitrate-free groundwater, and Fe(II) decreased to the detection limit. These results contrast with other laboratory and field results in which oxygen was introduced to systems containing high concentrations of mackinawite (FeS) rather than the more crystalline iron sulfides found in aged, naturally reduced zones. The flux of oxygen to the naturally reduced zones in the alluvial aquifers occurs mainly through interactions between groundwater and gas phases at the water table, and seasonal variations of the water table at the Rifle, CO site may play an important role in introducing oxygen into the system. Although oxygen was introduced directly to the naturally reduced zones in these experiments, delivery of oxidants to the system may normally be controlled by other oxidative pathways in which oxygen plays an indirect role.

Corrosion Evaluation of RERTR Uranium Molybdenum Fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

A K Wertsching

2012-09-01

As part of the National Nuclear Security Agency (NNSA) mandate to replace the use of highly enriched uranium (HEU) fuel for low enriched uranium (LEU) fuel, research into the development of LEU fuel for research reactors has been active since the late 1970’s. Originally referred to as the Reduced Enrichment for Research and Test Reactor (RERTR) program the new effort named Global Threat Reduction Initiative (GTRI) is nearing the goal of replacing the standard aluminum clad dispersion highly enriched uranium aluminide fuel with a new LEU fuel. The five domestic high performance research reactors undergoing this conversion are High Fluxmore » Isotope reactor (HFIR), Advanced Test Reactor (ATR), National Institute of Standards and Technology (NIST) Reactor, Missouri University Research Reactor (MURR) and the Massachusetts Institute of Technology Reactor II (MITR-II). The design of these reactors requires a higher neutron flux than other international research reactors, which to this point has posed unique challenges in the design and development of the new mandated LEU fuel. The new design utilizes a monolithic fuel configuration in order to obtain sufficient 235U within the LEU stoichoimetry to maintain the fission reaction within the domestic test reactors. The change from uranium aluminide dispersion fuel type to uranium molybdenum (UMo) monolithic configuration requires examination of possible corrosion issues associated with the new fuel meat. A focused analysis of the UMo fuel under potential corrosion conditions, within the ATR and under aqueous storage indicates a slow and predictable corrosion rate. Additional corrosion testing is recommended for the highest burn-up fuels to confirm observed corrosion rate trends. This corrosion analysis will focus only on the UMo fuel and will address corrosion of ancillary components such as cladding only in terms of how it affects the fuel. The calculations and corrosion scenarios are weighted with a conservative bias to provide additional confidence with the results. The actual corrosion rates of UMo fuel is very likely to be lower than assumed within this report which can be confirmed with additional testing.« less

Assay for uranium and determination of disequilibrium by means of in situ high resolution gamma-ray spectrometry

USGS Publications Warehouse

Tanner, Allan B.; Moxham, Robert M.; Senftle, F.E.

1977-01-01

Two sealed sondes, using germanium gamma-ray detectors cooled by melting propane, have been field tested to depths of 79 m in water-filled boreholes at the Pawnee Uranium Mine in Bee Co., Texas. When, used as total-count devices, the sondes are comparable in logging speed and counting rate with conventional scintillation detectors for locating zones of high radioactivity. When used with a multichannel analyzer, the sondes are detectors with such high resolution that individual lines from the complex spectra of the uranium and thorium series can be distinguished. Gamma rays from each group of the uranium series can be measured in ore zones permitting determination of the state of equilibrium at each measurement point. Series of 10-minute spectra taken at 0.3- to 0.5-m intervals in several holes showed zones where maxima from the uranium group and from the 222Rn group were displaced relative to each other. Apparent excesses of 230Th at some locations suggest that uranium-group concentrations at those locations were severalfold greater some tens of kiloyears, ago. At the current state of development a 10-minute count yields a sensitivity of about 80 ppm U308. Data reduction could in practice be accomplished in about 5 minutes. The result is practically unaffected by disequilibrium or radon contamination. In comparison with core assay, high-resolution spectrometry samples a larger volume; avoids problems due to incomplete core recovery, loss of friable material to drilling fluids, and errors in depth and marking; and permits use of less expensive drilling methods. Because gamma rays from the radionuclides are accumulated simultaneously, it also avoids the problems inherent in trying to correlate logs made in separate runs with different equipment. Continuous-motion delayed-gamma activation by a 163-?g 252Cf neutron source attached to the sonde yielded poor sensitivity. A better neutron-activation method, in which the sonde is moved in steps so as to place the detector at the previous activation point, could not be evaluated because of equipment failure.

Influence of Reactive Transport on the Reduction of U(VI) in the Presence of Fe(III) and Nitrate: Implications for U(VI) Immobilization by Bioremediation / Biobarriers- Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

B.D. Wood

2007-01-01

Subsurface contamination by metals and radionuclides represent some of the most challenging remediation problems confronting the Department of Energy (DOE) complex. In situ remediation of these contaminants by dissimilatory metal reducing bacteria (DMRB) has been proposed as a potential cost effective remediation strategy. The primary focus of this research is to determine the mechanisms by which the fluxes of electron acceptors, electron donors, and other species can be controlled to maximize the transfer of reductive equivalents to the aqueous and solid phases. The proposed research is unique in the NABIR portfolio in that it focuses on (i) the role ofmore » flow and transport in the initiation of biostimulation and the successful sequestration of metals and radionuclides [specifically U(VI)], (ii) the subsequent reductive capacity and stability of the reduced sediments produced by the biostimulation process, and (iii) the potential for altering the growth of biomass in the subsurface by the addition of specific metabolic uncoupling compounds. A scientifically-based understanding of these phenomena are critical to the ability to design successful bioremediation schemes. The laboratory research will employ Shewanella putrefaciens (CN32), a facultative DMRB that can use Fe(III) oxides as a terminal electron acceptor. Sediment-packed columns will be inoculated with this organism, and the reduction of U(VI) by the DMRB will be stimulated by the addition of a carbon and energy source in the presence of Fe(III). Separate column experiments will be conducted to independently examine: (1) the importance of the abiotic reduction of U(VI) by biogenic Fe(II); (2) the influence of the transport process on Fe(III) reduction and U(VI) immobilization, with emphasis on methods for controlling the fluxes of aqueous species to maximize uranium reduction; (3) the reductive capacity of biologically-reduced sediments (with respect to re-oxidation by convective fluxes of O2 and NO3-) and the long-term stability of immobilized uranium mineral phases after bioremediation processes are complete, and (4) the ability for metabolic uncoupling compounds to maintain microbial growth while limiting biomass production. The results of the laboratory experiments will be used to develop mathematical descriptive models for the coupled transport and reduction processes.« less

Remediation strategy, capping construction and ongoing monitoring for the mill tailings pond, Ningyo-Toge uranium mine, Japan

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hiroshi Saito; Tomihiro Taki

2013-07-01

Ningyo-toge Uranium Mine is subject to the environmental remediation. The main purposes are to take measures to ensure the radiation protection from the exposure pathways to humans in future, and to prevent the occurrence of mining pollution. The Yotsugi Mill Tailings Pond in the Ningyo-toge Uranium Mine has deposited mining waste and impounded water as a buffer reservoir before it is transferred to the Water Treatment Facility. It is located at the upstream of the water-source river and as the impact on its environment in case of earthquake is estimated significant, the highest priority has been put to it amongmore » mine-related facilities in the Mine. So far, basic concept has been examined and a great number of data has been acquired, and using the data, some remediation activities have already done, including capping construction for the upstream part of the Mill Tailings Pond. The capping is to reduce rainwater penetration to lower the burden of water treatment, and to reduce radon exhalation and dose rates. Only natural materials are used to alleviate the future maintenance. Data, including settlement amount and underground temperature is now being acquired and accumulated to verify the effectiveness of the capping, and used for the future remediation of the Downstream with revision of its specifications if necessary. (authors)« less

Spectral pathways for exploration of secondary uranium: An investigation in the desertic tracts of Rajasthan and Gujarat, India

NASA Astrophysics Data System (ADS)

Bharti, Rishikesh; Kalimuthu, R.; Ramakrishnan, D.

2015-10-01

This study aims at identifying potential zones of secondary uranium enrichment using hyperspectral remote sensing, γ-ray spectrometry, fluorimetry and geochemical techniques in the western Rajasthan and northern Gujarat, India. The investigated area has suitable source rocks, conducive past-, and present-climate that can facilitate such enrichment. This enrichment process involves extensive weathering of uranium bearing source rocks, leaching of uranyl compounds in groundwater, and their precipitation in chemical deltas along with duricrusts like calcretes and gypcretes. Spatial distribution of groundwater calcretes (that are rich in Mg-calcite) and gypcretes (that are rich in gypsum) along palaeochannels and chemical deltas were mapped using hyperspectral remote sensing data based on spectral absorptions in 1.70 μm, 2.16 μm, 2.21 μm, 2.33 μm, 2.44 μm wavelength regions. Subsequently based on field radiometric survey, zones of U anomalies were identified and samples of duricrusts and groundwater were collected for geochemical analyses. Anomalous concentration of U (2345.7 Bq/kg) and Th (142.3 Bq/kg) are observed in both duricrusts and groundwater (U-1791 μg/l, Th-34 μg/l) within the palaeo-delta and river confluence. The estimated carnotite Solubility Index also indicates the secondary enrichment of U and the likelihood of occurrence of an unconventional deposit.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Catalano, Jeffrey G.; Giammar, Daniel E.; Wang, Zheming

Phosphate addition is an in situ remediation approach that may enhance the sequestration of uranium without requiring sustained reducing conditions. However, the geochemical factors that determine the dominant immobilization mechanisms upon phosphate addition are insufficiently understood to design efficient remediation strategies or accurately predict U(VI) transport. The overall objective of our project is to determine the dominant mechanisms of U(VI)-phosphate reactions in subsurface environments. Our research approach seeks to determine the U(VI)-phosphate solid that form in the presence of different groundwater cations, characterize the effects of phosphate on U(VI) adsorption and precipitation on smectite and iron oxide minerals, examples ofmore » two major reactive mineral phases in contaminated sediments, and investigate how phosphate affects U(VI) speciation and fate during water flow through sediments from contaminated sites. The research activities conducted for this project have generated a series of major findings. U(VI) phosphate solids from the autunite mineral family are the sole phases to form during precipitation, with uranyl orthophosphate not occurring despite its predicted greater stability. Calcium phosphates may take up substantial quantities of U(VI) through three different removal processes (adsorption, coprecipitation, and precipitation) but the dominance of each process varies with the pathway of reaction. Phosphate co-adsorbs with U(VI) onto smectite mineral surfaces, forming a mixed uranium-phosphate surface complex over a wide range of conditions. However, this molecular-scale association of uranium and phosphate has not effect on the overall extent of uptake. In contrast, phosphate enhanced U(VI) adsorption to iron oxide minerals at acidic pH conditions but suppresses such adsorption at neutral and alkaline pH, despite forming mixed uranium-phosphate surface complexes during adsorption. Nucleation barriers exist that inhibit U(VI) phosphate solids from precipitating in the presence of smectite and iron oxide minerals as well as sediments from contaminated sites. Phosphate addition enhances retention of U(VI) by sediments from the Rifle, CO and Hanford, WA field research sites, areas containing substantial uranium contamination of groundwater. This enhanced retention is through adsorption processes. Both fast and slow uptake and release behavior is observed, indicating that diffusion of uranium between sediment grains has a substantial effect of U(VI) fate in flowing groundwater systems. This project has revealed the complexity of U(VI)-phosphate reactions in subsurface systems. Distinct chemical processes occur in acidic and alkaline groundwater systems. For the latter, calcium phosphate formation, solution complexation, and competition between phosphate and uranium for adsorption sites may serve to either enhance or inhibit U(VI) removal from groundwater. Under the groundwater conditions present at many contaminated sites in the U.S., phosphate appears to general enhance U(VI) retention and limit transport. However, formation of low-solubility uranium phosphate solids does not occur under field-relevant conditions, despite this being the desired product of phosphate-based remediation approaches. In addition, simple equilibrium approaches fail to well-predict uranium fate in contaminated sediments amended with phosphate, with reactive transport models that include reaction rates and mass transport through occluded domains needed to properly describe the system. Phosphate addition faces challenges to being effective as a stand-alone groundwater treatment approach but would prove beneficial as an add-on to other treatment methods that will further limit uranium migration in the subsurface.« less

PROCESS OF REDUCING PLUTONIUM TO TETRAVALENT TRIVALENT STATE

DOEpatents

Mastick, D.F.

1960-05-10

The reduction of hexavalent and tetravalert plutonium ions to the trivalent state in strong nitric acid can be accomplished with hydrogen peroxide. The trivalent state may be stabilized as a precipitate by including oxalate or fluoride ions in the solution. The acid should be strong to encourage the reduction from the plutonyl to the trivalent state (and discourage the opposed oxidation reaction) and prevent the precipitation of plutonium peroxide, although the latter may be digested by increasing the acid concentration. Although excess hydrogen peroxide will oxidize plutonlum to the plutonyl state, complete reduction is insured by gently warming the solution to break down such excess H/ sub 2/O/sub 2/. The particular advantage of hydrogen peroxide as a reductant lies in the precipitation technique, where it introduces no contaminating ions. The process is adaptable to separate plutonium from uranium and impurities by proper adjustment of the sequence of insoluble anion additions and the hydrogen peroxide addition.

31 CFR 540.317 - Uranium feed; natural uranium feed.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 31 Money and Finance:Treasury 3 2011-07-01 2011-07-01 false Uranium feed; natural uranium feed...) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.317 Uranium feed; natural uranium feed. The term uranium feed or natural uranium feed means natural uranium in the form of UF6 suitable for uranium...

31 CFR 540.317 - Uranium feed; natural uranium feed.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 31 Money and Finance: Treasury 3 2010-07-01 2010-07-01 false Uranium feed; natural uranium feed...) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.317 Uranium feed; natural uranium feed. The term uranium feed or natural uranium feed means natural uranium in the form of UF6 suitable for uranium...

The nitric-oxide reductase from Paracoccus denitrificans uses a single specific proton pathway.

PubMed

ter Beek, Josy; Krause, Nils; Reimann, Joachim; Lachmann, Peter; Ädelroth, Pia

2013-10-18

The NO reductase from Paracoccus denitrificans reduces NO to N2O (2NO + 2H(+) + 2e(-) → N2O + H2O) with electrons donated by periplasmic cytochrome c (cytochrome c-dependent NO reductase; cNOR). cNORs are members of the heme-copper oxidase superfamily of integral membrane proteins, comprising the O2-reducing, proton-pumping respiratory enzymes. In contrast, although NO reduction is as exergonic as O2 reduction, there are no protons pumped in cNOR, and in addition, protons needed for NO reduction are derived from the periplasmic solution (no contribution to the electrochemical gradient is made). cNOR thus only needs to transport protons from the periplasm into the active site without the requirement to control the timing of opening and closing (gating) of proton pathways as is needed in a proton pump. Based on the crystal structure of a closely related cNOR and molecular dynamics simulations, several proton transfer pathways were suggested, and in principle, these could all be functional. In this work, we show that residues in one of the suggested pathways (denoted pathway 1) are sensitive to site-directed mutation, whereas residues in the other proposed pathways (pathways 2 and 3) could be exchanged without severe effects on turnover activity with either NO or O2. We further show that electron transfer during single-turnover reduction of O2 is limited by proton transfer and can thus be used to study alterations in proton transfer rates. The exchange of residues along pathway 1 showed specific slowing of this proton-coupled electron transfer as well as changes in its pH dependence. Our results indicate that only pathway 1 is used to transfer protons in cNOR.

Criticality safety evaluation for the Advanced Test Reactor enhanced low enriched uranium fuel elements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Montierth, Leland M.

2016-07-19

The Global Threat Reduction Initiative (GTRI) convert program is developing a high uranium density fuel based on a low enriched uranium (LEU) uranium-molybdenum alloy. Testing of prototypic GTRI fuel elements is necessary to demonstrate integrated fuel performance behavior and scale-up of fabrication techniques. GTRI Enhanced LEU Fuel (ELF) elements based on the ATR-Standard Size elements (all plates fueled) are to be fabricated for testing in the Advanced Test Reactor (ATR). While a specific ELF element design will eventually be provided for detailed analyses and in-core testing, this criticality safety evaluation (CSE) is intended to evaluate a hypothetical ELF element designmore » for criticality safety purposes. Existing criticality analyses have analyzed Standard (HEU) ATR elements from which controls have been derived. This CSE documents analysis that determines the reactivity of the hypothetical ELF fuel elements relative to HEU ATR elements and whether the existing HEU ATR element controls bound the ELF element. The initial calculations presented in this CSE analyzed the original ELF design, now referred to as Mod 0.1. In addition, as part of a fuel meat thickness optimization effort for reactor performance, other designs have been evaluated. As of early 2014 the most current conceptual designs are Mk1A and Mk1B, that were previously referred to as conceptual designs Mod 0.10 and Mod 0.11, respectively. Revision 1 evaluates the reactivity of the ATR HEU Mark IV elements for a comparison with the Mark VII elements.« less

Phanerozoic extensional faulting and alteration control on uranium mineralization in trachytes of the Central Eastern Desert of Egypt

NASA Astrophysics Data System (ADS)

Hamdy, Mohamed M.; Waheeb, Anton G.; Aly, Samir M.; Farag, Nagdy M.; Sadek, Adel F.

2017-12-01

The Gabal Nasb El Atshan Upper Carboniferous-Lower Permian altered trachytes include uranium up to 3165 ppm. The paleostress and resolved shear stress analyses of the deformation systems in Gabal Nasb El Atshan area indicate that the trachyte was subjected to WNW-ESE to E-W tensile shear stress directed extensional regimes. The low-stress regions in the vicinity of extensional faults and their associated joints were favorable locations for fluid flow and the consequence alteration and U-mineralization. This occurred more extensively along the contacts between the sills of trachyte and the Hammamat sedimentary rocks; where the latter acted as a physical barrier for the alteration fluids migration outward. Alteration styles include albitization, aegirinization, arfvedsonization, chloritization and ferruginisation. The albitization is the most common sodic metasomatism, giving sanidine from Or98.8Ab0.7 to Or62.3Ab37.6, anorthoclase from Or51.4Ab48.0 to Or12.2Ab87.6 and albite from Or11.0Ab89.0 to Or0.8Ab99.2. Aegirine and arfvedsonite formed due to decreasing sodium activity in the metasomatic fluids. Sodic metasomatism may be the source of uranium-enrichment, taking place during the late magmatic to deuteric processes. This was followed by a retrograde alteration of chloritization between 175 and 42 °C toward precipitation of Fe-oxides and alteration of primary uranium. Surficial low-temperature alteration remobilized and redistributed the produced uranylhydroxides and ferruginisation caused the reduction and adsorption of U forming betafite, uranophane, soddyite, umohoite, uranotile and uranopilite.

Conversion Preliminary Safety Analysis Report for the NIST Research Reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Diamond, D. J.; Baek, J. S.; Hanson, A. L.

The NIST Center for Neutron Research (NCNR) is a reactor-laboratory complex providing the National Institute of Standards and Technology (NIST) and the nation with a world-class facility for the performance of neutron-based research. The heart of this facility is the NIST research reactor (aka NBSR); a heavy water moderated and cooled reactor operating at 20 MW. It is fueled with high-enriched uranium (HEU) fuel elements. A Global Threat Reduction Initiative (GTRI) program is underway to convert the reactor to low-enriched uranium (LEU) fuel. This program includes the qualification of the proposed fuel, uranium and molybdenum alloy foil clad in anmore » aluminum alloy, and the development of the fabrication techniques. This report is a preliminary version of the Safety Analysis Report (SAR) that would be submitted to the U.S. Nuclear Regulatory Commission (NRC) for approval prior to conversion. The report follows the recommended format and content from the NRC codified in NUREG-1537, “Guidelines for Preparing and Reviewing Applications for the Licensing of Non-power Reactors,” Chapter 18, “Highly Enriched to Low-Enriched Uranium Conversions.” The emphasis in any conversion SAR is to explain the differences between the LEU and HEU cores and to show the acceptability of the new design; there is no need to repeat information regarding the current reactor that will not change upon conversion. Hence, as seen in the report, the bulk of the SAR is devoted to Chapter 4, Reactor Description, and Chapter 13, Safety Analysis.« less

Determination of actinides in urine and fecal samples

DOEpatents

McKibbin, Terry T.

1993-01-01

A method of determining the radioactivity of specific actinides that are carried in urine or fecal sample material is disclosed. The samples are ashed in a muffle furnace, dissolved in an acid, and then treated in a series of steps of reduction, oxidation, dissolution, and precipitation, including a unique step of passing a solution through a chloride form anion exchange resin for separation of uranium and plutonium from americium.

Determination of actinides in urine and fecal samples

DOEpatents

McKibbin, T.T.

1993-03-02

A method of determining the radioactivity of specific actinides that are carried in urine or fecal sample material is disclosed. The samples are ashed in a muffle furnace, dissolved in an acid, and then treated in a series of steps of reduction, oxidation, dissolution, and precipitation, including a unique step of passing a solution through a chloride form anion exchange resin for separation of uranium and plutonium from americium.

Predicting Large Deflections of Multiplate Fuel Elements Using a Monolithic FSI Approach

DOE PAGES

Curtis, Franklin G.; Freels, James D.; Ekici, Kivanc

2017-10-26

As part of the Global Threat Reduction Initiative, the Oak Ridge National Laboratory is evaluating conversion of fuel for the High Flux Isotope Reactor (HFIR) from high-enriched uranium to low-enriched uranium. Currently, multiphysics simulations that model fluid-structure interaction phenomena are being performed to ensure the safety of the reactor with the new fuel type. A monolithic solver that fully couples fluid and structural dynamics is used to model deflections in the new design. A classical experiment is chosen to validate the capabilities of the current solver and the method. Here, a single-plate simulation with various boundary conditions as well asmore » a five-plate simulation are presented. Finally, use of the monolithic solver provides stable solutions for the large deflections and the tight coupling of the fluid and structure and the maximum deflections are captured accurately.« less

Production of Low Enriched Uranium Nitride Kernels for TRISO Particle Irradiation Testing

DOE Office of Scientific and Technical Information (OSTI.GOV)

McMurray, J. W.; Silva, C. M.; Helmreich, G. W.

2016-06-01

A large batch of UN microspheres to be used as kernels for TRISO particle fuel was produced using carbothermic reduction and nitriding of a sol-gel feedstock bearing tailored amounts of low-enriched uranium (LEU) oxide and carbon. The process parameters, established in a previous study, produced phasepure NaCl structure UN with dissolved C on the N sublattice. The composition, calculated by refinement of the lattice parameter from X-ray diffraction, was determined to be UC 0.27N 0.73. The final accepted product weighed 197.4 g. The microspheres had an average diameter of 797±1.35 μm and a composite mean theoretical density of 89.9±0.5% formore » a solid solution of UC and UN with the same atomic ratio; both values are reported with their corresponding calculated standard error.« less

Electron binding energy of uranium-ligand and uranyl-ligand anions

NASA Astrophysics Data System (ADS)

Wang, Lei; Horowitz, Steven; Marston, Brad

2012-02-01

Electron binding energies of the early actinide element uranium in gas-phase anion complexes are calculated by relativistic density functional theory (DFT) with two different exchange-correlation functions (RPBE and B3LYP) and also in the Hartree-Fock (HF) approximationootnotetextADF2010.02, SCM.com. Scalar and spin-orbit calculations are performed, and the calculated energies are compared to available experimental measurements and shown to disagree by energies of order 1 eV. Strong correlations that are poorly treated in DFT and HF can be included by a hybrid approach in which a generalized Anderson impurity model is numerically diagonalized. Reduction-oxidation (redox) potentials of aqueous actinide ions show improved agreement with measured values in the hybrid approachootnotetextS. E. Horowitz and J. B. Marston, J. Chem. Phys 134 064510 (2011).. We test whether or not similar improvements are found in the gas-phase.

Estimating Environmental Co-benefits of U.S. GHG Reduction Pathways Using the GCAM-USA Integrated Assessment Model

EPA Science Inventory

Previous studies have shown that mitigating climate change through curbing greenhouse gas (GHG) emissions can bring about substantial environmental co-benefits, such as for air quality and reductions in energy-related water demand. A variety of pathways are available for reducing...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiao, Hai; Cheng, Tao; Goddard, William A.

Energy and environmental concerns demand development of more efficient and selective electrodes for electrochemical reduction of CO 2 to form fuels and chemicals. Since Cu is the only pure metal exhibiting reduction to form hydrocarbon chemicals, we focus here on the Cu (111) electrode. We present a methodology for density functional theory calculations to obtain accurate onset electrochemical potentials with explicit constant electrochemical potential and pH effects using implicit solvation. We predict the atomistic mechanisms underlying electrochemical reduction of CO, finding that (1) at acidic pH, the C 1 pathway proceeds through COH to CHOH to form CH 4 whilemore » C 2 (C 3) pathways are kinetically blocked; (2) at neutral pH, the C 1 and C 2 (C 3) pathways share the COH common intermediate, where the branch to C-C coupling is realized by a novel CO-COH pathway; and (3) at high pH, early C-C coupling through adsorbed CO dimerization dominates, suppressing the C 1 pathways by kinetics, thereby boosting selectivity for multi-carbon products.« less

The chemical biology of methanogenesis

NASA Astrophysics Data System (ADS)

Ferry, James G.

2010-12-01

Two distinct pathways account for most of the CH 4 produced in the majority of the diverse and vast anaerobic environments of Earth's biosphere by microbes that are classified in the Archaea domain of life: conversion of the methyl group of acetate to CH 4 in the aceticlastic pathway and reduction of CO 2 with electrons derived from H 2, formate or CO in the CO 2 reduction pathway. Minor, albeit ecologically important, amounts of CH 4 are produced by conversion of methylotrophic substrates methanol, methylamines and methyl sulfides. Although all pathways have terminal steps in common, they deviate in the initial steps leading to CH 4 and mechanisms for synthesizing ATP for growth. Hydrogen gas is the major reductant for CO 2-reducing methanogens in the deep subsurface, although H 2 is also utilized by CO 2-reducing microbes from the Bacteria domain that produce acetate for the aceticlastic methanogens. This review presents fundamentals of the two major CH 4-producing pathways with a focus on understanding the potential for biologically-produced CH 4 on Mars.

Oxidative Uranium Release from Anoxic Sediments under Diffusion-Limited Conditions.

PubMed

Bone, Sharon E; Cahill, Melanie R; Jones, Morris E; Fendorf, Scott; Davis, James; Williams, Kenneth H; Bargar, John R

2017-10-03

Uranium (U) contamination occurs as a result of mining and ore processing; often in alluvial aquifers that contain organic-rich, reduced sediments that accumulate tetravalent U, U(IV). Uranium(IV) is sparingly soluble, but may be mobilized upon exposure to nitrate (NO 3 - ) and oxygen (O 2 ), which become elevated in groundwater due to seasonal fluctuations in the water table. The extent to which oxidative U mobilization can occur depends upon the transport properties of the sediments, the rate of U(IV) oxidation, and the availability of inorganic reductants and organic electron donors that consume oxidants. We investigated the processes governing U release upon exposure of reduced sediments to artificial groundwater containing O 2 or NO 3 - under diffusion-limited conditions. Little U was mobilized during the 85-day reaction, despite rapid diffusion of groundwater within the sediments and the presence of nonuraninite U(IV) species. The production of ferrous iron and sulfide in conjunction with rapid oxidant consumption suggested that the sediments harbored large concentrations of bioavailable organic carbon that fueled anaerobic microbial respiration and stabilized U(IV). Our results suggest that seasonal influxes of O 2 and NO 3 - may cause only localized mobilization of U without leading to export of U from the reducing sediments when ample organic carbon is present.

Rolling Process Modeling Report. Finite-Element Model Validation and Parametric Study on various Rolling Process parameters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soulami, Ayoub; Lavender, Curt A.; Paxton, Dean M.

2015-06-15

Pacific Northwest National Laboratory (PNNL) has been investigating manufacturing processes for the uranium-10% molybdenum alloy plate-type fuel for high-performance research reactors in the United States. This work supports the U.S. Department of Energy National Nuclear Security Administration’s Office of Material Management and Minimization Reactor Conversion Program. This report documents modeling results of PNNL’s efforts to perform finite-element simulations to predict roll-separating forces for various rolling mill geometries for PNNL, Babcock & Wilcox Co., Y-12 National Security Complex, Los Alamos National Laboratory, and Idaho National Laboratory. The model developed and presented in a previous report has been subjected to further validationmore » study using new sets of experimental data generated from a rolling mill at PNNL. Simulation results of both hot rolling and cold rolling of uranium-10% molybdenum coupons have been compared with experimental results. The model was used to predict roll-separating forces at different temperatures and reductions for five rolling mills within the National Nuclear Security Administration Fuel Fabrication Capability project. This report also presents initial results of a finite-element model microstructure-based approach to study the surface roughness at the interface between zirconium and uranium-10% molybdenum.« less

Transgenerational Adaptation to Pollution Changes Energy Allocation in Populations of Nematodes.

PubMed

Goussen, Benoit; Péry, Alexandre R R; Bonzom, Jean-Marc; Beaudouin, Rémy

2015-10-20

Assessing the evolutionary responses of long-term exposed populations requires multigeneration ecotoxicity tests. However, the analysis of the data from these tests is not straightforward. Mechanistic models allow the in-depth analysis of the variation of physiological traits over many generations, by quantifying the trend of the physiological and toxicological parameters of the model. In the present study, a bioenergetic mechanistic model has been used to assess the evolution of two populations of the nematode Caenorhabditis elegans in control conditions or exposed to uranium. This evolutionary pressure resulted in a brood size reduction of 60%. We showed an adaptation of individuals of both populations to experimental conditions (increase of maximal length, decrease of growth rate, decrease of brood size, and decrease of the elimination rate). In addition, differential evolution was also highlighted between the two populations once the maternal effects had been diminished after several generations. Thus, individuals that were greater in maximal length, but with apparently a greater sensitivity to uranium were selected in the uranium population. In this study, we showed that this bioenergetics mechanistic modeling approach provided a precise, certain, and powerful analysis of the life strategy of C. elegans populations exposed to heavy metals resulting in an evolutionary pressure across successive generations.

Air Shipment of Highly Enriched Uranium Spent Nuclear Fuel from Romania

DOE Office of Scientific and Technical Information (OSTI.GOV)

K. J. Allen; I. Bolshinsky; L. L. Biro

2010-07-01

Romania safely air shipped 23.7 kilograms of Russian origin highly enriched uranium (HEU) spent nuclear fuel from the VVR S research reactor at Magurele, Romania, to the Russian Federation in June 2009. This was the world’s first air shipment of spent nuclear fuel transported in a Type B(U) cask under existing international laws without special exceptions for the air transport licenses. This shipment was coordinated by the Russian Research Reactor Fuel Return Program (RRRFR), part of the U.S. Department of Energy Global Threat Reduction Initiative (GTRI), in cooperation with the Romania National Commission for Nuclear Activities Control (CNCAN), the Horiamore » Hulubei National Institute of Physics and Nuclear Engineering (IFIN-HH), and the Russian Federation State Corporation Rosatom. The shipment was transported by truck to and from the respective commercial airports in Romania and the Russian Federation and stored at a secure nuclear facility in Russia where it will be converted into low enriched uranium. With this shipment, Romania became the 3rd country under the RRRFR program and the 14th country under the GTRI program to remove all HEU. This paper describes the work, equipment, and approvals that were required to complete this spent fuel air shipment.« less

Extrusion-formed uranium-2. 4 wt % article with decreased linear thermal expansion and method for making the same. [Patent application

DOEpatents

Anderson, R.C.; Jones, J.M.; Kollie, T.G.

1982-05-24

The present invention is directed to the fabrication of an article of uranium-2.4 wt % niobium alloy in which the linear thermal expansion in the direction transverse to the extrusion direction is less than about 0.98% between 22 and 600/sup 0/C which corresponds to a value greater than the 1.04% provided by previous extrusion operations over the same temperature range. The article with the improved thermal expansion possesses a yield strength at 0.2% offset of at least 400 MPa, an ultimate tensile strength of 1050 MPa, a compressive yield strength of at least 0.2% offset of at least 675 MPa, and an elongation of at least 25% over 25.4 mm/s. To provide this article with the improved thermal expansion, the uranium alloy billet is heated to 630/sup 0/C and extruded in the alpha phase through a die with a reduction ratio of at least 8.4:1 at a ram speed no greater than 6.8 mm/s. These critical extrusion parameters provide the article with a desired decrease in the linear thermal expansion while maintaining the selected mechanical properties without encountering crystal disruption in the article.

Extrusion-formed uranium-2.4 wt. % article with decreased linear thermal expansion and method for making the same

DOEpatents

Anderson, Robert C.; Jones, Jack M.; Kollie, Thomas G.

1982-01-01

The present invention is directed to the fabrication of an article of uranium-2.4 wt. % niobium alloy in which the linear thermal expansion in the direction transverse to the extrusion direction is less than about 0.98% between 22.degree. C. and 600.degree. C. which corresponds to a value greater than the 1.04% provided by previous extrusion operations over the same temperature range. The article with the improved thermal expansion possesses a yield strength at 0.2% offset of at least 400 MPa, an ultimate tensile strength of 1050 MPa, a compressive yield strength of at least 0.2% offset of at least 675 MPa, and an elongation of at least 25% over 25.4 mm/sec. To provide this article with the improved thermal expansion, the uranium alloy billet is heated to 630.degree. C. and extruded in the alpha phase through a die with a reduction ratio of at least 8.4:1 at a ram speed no greater than 6.8 mm/sec. These critical extrusion parameters provide the article with the desired decrease in the linear thermal expansion while maintaining the selected mechanical properties without encountering crystal disruption in the article.

PUREX/UO{sub 3} deactivation project management plan

DOE Office of Scientific and Technical Information (OSTI.GOV)

Washenfelder, D.J.

1993-12-01

From 1955 through 1990, the Plutonium-Uranium Extraction Plant (PUREX) provided the United States Department of Energy Hanford Site with nuclear fuel reprocessing capability. It operated in sequence with the Uranium Trioxide (UO{sub 3}) Plant, which converted the PUREX liquid uranium nitrate product to solid UO{sub 3} powder. Final UO{sub 3} Plant operation ended in 1993. In December 1992, planning was initiated for the deactivation of PUREX and UO{sub 3} Plant. The objective of deactivation planning was to identify the activities needed to establish a passively safe, environmentally secure configuration at both plants, and ensure that the configuration could be retainedmore » during the post-deactivation period. The PUREX/UO{sub 3} Deactivation Project management plan represents completion of the planning efforts. It presents the deactivation approach to be used for the two plants, and the supporting technical, cost, and schedule baselines. Deactivation activities concentrate on removal, reduction, and stabilization of the radioactive and chemical materials remaining at the plants, and the shutdown of the utilities and effluents. When deactivation is completed, the two plants will be left unoccupied and locked, pending eventual decontamination and decommissioning. Deactivation is expected to cost $233.8 million, require 5 years to complete, and yield $36 million in annual surveillance and maintenance cost savings.« less

Vanishing Act: Experiments on Fission Track Annealing in Monazite

NASA Astrophysics Data System (ADS)

Shipley, N. K.; Fayon, A. K.

2006-12-01

To determine the viability of monazite as a low temperature thermochronometer, we conducted fission track annealing experiments under isothermal conditions. These experiments evaluated the effects of uranium concentration and zoning on annealing rates. Fission track annealing rates in monazite were also compared to those in Durango apatite. Preliminary results indicate that monazite grains with higher initial track densities anneal at faster rates than those with low initial densities and that fission tracks in monazite anneal at a faster rate than those in apatite. Monazite sand grains were selected from a placer sand deposit, mounted in teflon, and polished. Grains were imaged with electron backscattering to characterize zoning patterns and variations in uranium concentration. Monazite grain mounts were etched in boiling 37% HCl for 50 minutes and fission track densities were determined using standard fission track counting techniques. Durango apatite was etched in 5N HNO3 at room temperature for 20 seconds. After the initial track densities were determined, mounts in one group were annealed at 150 ° C for 1to 6 h. The mounts in a second group were annealed at 200 ° C for 2 hour periods along with mounts of Durango apatite grains. All grains were re-polished prior to each anneal. Upon completion of the experiment, backscatter images were taken of grains from which fission track counts were obtained to verify continuance of concentric zoning. Results of these experiments indicate that annealing rates of fission tracks in monazite vary as a function of uranium concentration. Uranium concentration was constrained on the basis of zoning patterns obtained from electron backscatter images. Fission track densities in grains with initial track densities of approximately 2.4 × 106 tracks/cm2 were reduced at average rate of 16% every two hours. In contrast, track densities in grains with initial track densities of approximately 1.6 × 106 tracks/cm2 average 4.6% density reduction every two hours. In both cases, track density reduction in monazite was faster than the rate of 0.1 % every two hours obtained for apatite. This would indicate that fission track annealing occurs at a lower temperature in monazite than in apatite. Thus monazite would be useful as a low temperature chronometer for determining cooling histories in recently exhumed rocks.

40 CFR 421.322 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2010 CFR

2010-07-01

... refinery Chromium 32.270 13.200 Copper 139.300 73.340 Nickel 140.800 93.140 Fluoride 2,567.000 1,459.000... processed in the refinery Chromium (total) 2.009 0.822 Copper 8.675 4.566 Nickel 8.767 5.799 Fluoride 159... pounds) of uranium processed in the refinery Chromium (total) 2.802 1.146 Copper 12.100 6.369 Nickel 12...

40 CFR 421.323 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... Chromium (total) 27.14 11.00 Copper 93.88 44.74 Nickel 40.34 27.14 Fluoride 2,567.00 1,459.00 (b) Slag... in the refinery Chromium (total) 1.689 0.685 Copper 5.844 2.785 Nickel 2.511 1.689 Fluoride 159.800... per million pounds) of uranium processed in the refinery Chromium (total) 2.357 0.955 Copper 8.152 3...

40 CFR 421.323 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2010 CFR

2010-07-01

... Chromium (total) 27.14 11.00 Copper 93.88 44.74 Nickel 40.34 27.14 Fluoride 2,567.00 1,459.00 (b) Slag... in the refinery Chromium (total) 1.689 0.685 Copper 5.844 2.785 Nickel 2.511 1.689 Fluoride 159.800... per million pounds) of uranium processed in the refinery Chromium (total) 2.357 0.955 Copper 8.152 3...

40 CFR 421.322 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... refinery Chromium 32.270 13.200 Copper 139.300 73.340 Nickel 140.800 93.140 Fluoride 2,567.000 1,459.000... processed in the refinery Chromium (total) 2.009 0.822 Copper 8.675 4.566 Nickel 8.767 5.799 Fluoride 159... pounds) of uranium processed in the refinery Chromium (total) 2.802 1.146 Copper 12.100 6.369 Nickel 12...

Method for photochemical reduction of uranyl nitrate by tri-N-butyl phosphate and application of this method to nuclear fuel reprocessing

DOEpatents

De Poorter, Gerald L.; Rofer-De Poorter, Cheryl K.

1978-01-01

Uranyl ion in solution in tri-n-butyl phosphate is readily photochemically reduced to U(IV). The product U(IV) may effectively be used in the Purex process for treating spent nuclear fuels to reduce Pu(IV) to Pu(III). The Pu(III) is readily separated from uranium in solution in the tri-n-butyl phosphate by an aqueous strip.

Fast track pathway reduces sight loss in giant cell arteritis: results of a longitudinal observational cohort study.

PubMed

Patil, P; Williams, M; Maw, W W; Achilleos, K; Elsideeg, S; Dejaco, C; Borg, F; Gupta, S; Dasgupta, B

2015-01-01

To investigate the effectiveness of a fast track pathway (FTP) on sight loss in patients with suspected giant cell arteritis (GCA). A longitudinal observational cohort study was conducted in the secondary care rheumatology department. One hundred and thirty-five newly referred suspected GCA patients seen via the FTP (Jan. 2012-Dec. 2013) were compared to 81 patients seen through the conventional referral and review system (Jan. 2009-Dec. 2011). The FTP resulted in significant reduction in irreversible sight loss from 37.0% (as seen in the historical cohort 2009-2011) to 9.0 % (2012-2013, OR 0.17, p=0.001). Adjustment for clinical and demographic parameters including known risk factors for GCA associated blindness did not significantly change the primary result (OR 0.08, p=0.001). FTP resulted in a reduction of time from symptom onset to diagnosis, particularly by reduction of time from general practitioner's (GP) referral to the rheumatology review (79% of FTP patients were seen within one working day compared to 64.6 % in the conventional pathway, p=0.023). The FTP has seen a reduction in number of GP appointments. There was a significant reduction of permanent sight loss with a fast track GCA pathway. The effect may be due to multiple factors including better GP education and reduction in delayed diagnosis. These results need verification at other sites.

40 CFR 421.320 - Applicability: Description of the secondary uranium subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... secondary uranium subcategory. 421.320 Section 421.320 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Secondary Uranium Subcategory § 421.320 Applicability: Description of the secondary uranium... uranium (including depleted uranium) by secondary uranium facilities. ...

40 CFR 421.320 - Applicability: Description of the secondary uranium subcategory.

Code of Federal Regulations, 2011 CFR

2011-07-01

... secondary uranium subcategory. 421.320 Section 421.320 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Secondary Uranium Subcategory § 421.320 Applicability: Description of the secondary uranium... uranium (including depleted uranium) by secondary uranium facilities. ...

40 CFR 421.320 - Applicability: Description of the secondary uranium subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... secondary uranium subcategory. 421.320 Section 421.320 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Secondary Uranium Subcategory § 421.320 Applicability: Description of the secondary uranium... uranium (including depleted uranium) by secondary uranium facilities. ...

40 CFR 421.320 - Applicability: Description of the secondary uranium subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... secondary uranium subcategory. 421.320 Section 421.320 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Secondary Uranium Subcategory § 421.320 Applicability: Description of the secondary uranium... uranium (including depleted uranium) by secondary uranium facilities. ...

40 CFR 421.320 - Applicability: Description of the secondary uranium subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... secondary uranium subcategory. 421.320 Section 421.320 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Secondary Uranium Subcategory § 421.320 Applicability: Description of the secondary uranium... uranium (including depleted uranium) by secondary uranium facilities. ...

Release behavior of uranium in uranium mill tailings under environmental conditions.

PubMed

Liu, Bo; Peng, Tongjiang; Sun, Hongjuan; Yue, Huanjuan

2017-05-01

Uranium contamination is observed in sedimentary geochemical environments, but the geochemical and mineralogical processes that control uranium release from sediment are not fully appreciated. Identification of how sediments and water influence the release and migration of uranium is critical to improve the prevention of uranium contamination in soil and groundwater. To understand the process of uranium release and migration from uranium mill tailings under water chemistry conditions, uranium mill tailing samples from northwest China were investigated with batch leaching experiments. Results showed that water played an important role in uranium release from the tailing minerals. The uranium release was clearly influenced by contact time, liquid-solid ratio, particle size, and pH under water chemistry conditions. Longer contact time, higher liquid content, and extreme pH were all not conducive to the stabilization of uranium and accelerated the uranium release from the tailing mineral to the solution. The values of pH were found to significantly influence the extent and mechanisms of uranium release from minerals to water. Uranium release was monitored by a number of interactive processes, including dissolution of uranium-bearing minerals, uranium desorption from mineral surfaces, and formation of aqueous uranium complexes. Considering the impact of contact time, liquid-solid ratio, particle size, and pH on uranium release from uranium mill tailings, reducing the water content, decreasing the porosity of tailing dumps and controlling the pH of tailings were the key factors for prevention and management of environmental pollution in areas near uranium mines. Copyright © 2017 Elsevier Ltd. All rights reserved.

A reverse KREBS cycle in photosynthesis: consensus at last

NASA Technical Reports Server (NTRS)

Buchanan, B. B.; Arnon, D. I.

1990-01-01

The Krebs cycle (citric acid or tricarboxylic acid cycle), the final common pathway in aerobic metabolism for the oxidation of carbohydrates, fatty acids and amino acids, is known to be irreversible. It liberates CO2 and generates NADH whose aerobic oxidation yields ATP but it does not operate in reverse as a biosynthetic pathway for CO2 assimilation. In 1966, our laboratory described a cyclic pathway for CO2 assimilation (Evans, Buchanan and Arnon 1966) that was unusual in two respects: (i) it provided the first instance of an obligate photoautotroph that assimilated CO2 by a pathway different from Calvin's reductive pentose phosphate cycle (Calvin 1962) and (ii) in its overall effect the new cycle was a reversal of the Krebs cycle. Named the 'reductive carboxylic acid cycle' (sometimes also called the reductive tricarboxylic acid cycle) the new cycle appeared to be the sole CO2 assimilation pathway in Chlorobium thiosulfatophilum (Evans et al. 1966) (now known as Chlorobium limicola forma thiosulfatophilum). Chlorobium is a photosynthetic green sulfur bacterium that grows anaerobically in an inorganic medium with sulfide and thiosulfate as electron donors and CO2 as an obligatory carbon source. In the ensuing years, the new cycle was viewed with skepticism. Not only was it in conflict with the prevailing doctrine that the 'one important property ... shared by all (our emphasis) autotrophic species is the assimilation of CO2 via the Calvin cycle' (McFadden 1973) but also some of its experimental underpinnings were challenged. It is only now that in the words of one of its early skeptics (Tabita 1988) 'a long and tortuous controversy' has ended with general acceptance of the reductive carboxylic acid cycle as a photosynthetic CO2 assimilation pathway distinct from the pentose cycle. (Henceforth, to minimize repetitiveness, the reductive pentose phosphate cycle will often be referred to as the pentose cycle and the reductive carboxylic acid cycle as the carboxylic acid cycle.) Aside from photosynthetic pathways which are the focus of this article, CO2 assimilation is also known to sustain autotrophic growth via the acetyl-CoA pathway (Wood et al. 1986). Our aim here is to discuss (i) the findings that led our group to the discovery of the reductive carboxylic acid cycle, (ii) the nature and resolution of the controversy that followed, and (iii) the possible evolutionary implications of the cycle as an ancient mechanism for photosynthetic CO2 assimilation that preceded the pentose cycle and served as a precursor of the Krebs cycle in aerobic metabolism.

A reverse KREBS cycle in photosynthesis: consensus at last.

PubMed

Buchanan, B B; Arnon, D I

1990-01-01

The Krebs cycle (citric acid or tricarboxylic acid cycle), the final common pathway in aerobic metabolism for the oxidation of carbohydrates, fatty acids and amino acids, is known to be irreversible. It liberates CO2 and generates NADH whose aerobic oxidation yields ATP but it does not operate in reverse as a biosynthetic pathway for CO2 assimilation. In 1966, our laboratory described a cyclic pathway for CO2 assimilation (Evans, Buchanan and Arnon 1966) that was unusual in two respects: (i) it provided the first instance of an obligate photoautotroph that assimilated CO2 by a pathway different from Calvin's reductive pentose phosphate cycle (Calvin 1962) and (ii) in its overall effect the new cycle was a reversal of the Krebs cycle. Named the 'reductive carboxylic acid cycle' (sometimes also called the reductive tricarboxylic acid cycle) the new cycle appeared to be the sole CO2 assimilation pathway in Chlorobium thiosulfatophilum (Evans et al. 1966) (now known as Chlorobium limicola forma thiosulfatophilum). Chlorobium is a photosynthetic green sulfur bacterium that grows anaerobically in an inorganic medium with sulfide and thiosulfate as electron donors and CO2 as an obligatory carbon source. In the ensuing years, the new cycle was viewed with skepticism. Not only was it in conflict with the prevailing doctrine that the 'one important property ... shared by all (our emphasis) autotrophic species is the assimilation of CO2 via the Calvin cycle' (McFadden 1973) but also some of its experimental underpinnings were challenged. It is only now that in the words of one of its early skeptics (Tabita 1988) 'a long and tortuous controversy' has ended with general acceptance of the reductive carboxylic acid cycle as a photosynthetic CO2 assimilation pathway distinct from the pentose cycle. (Henceforth, to minimize repetitiveness, the reductive pentose phosphate cycle will often be referred to as the pentose cycle and the reductive carboxylic acid cycle as the carboxylic acid cycle.) Aside from photosynthetic pathways which are the focus of this article, CO2 assimilation is also known to sustain autotrophic growth via the acetyl-CoA pathway (Wood et al. 1986). Our aim here is to discuss (i) the findings that led our group to the discovery of the reductive carboxylic acid cycle, (ii) the nature and resolution of the controversy that followed, and (iii) the possible evolutionary implications of the cycle as an ancient mechanism for photosynthetic CO2 assimilation that preceded the pentose cycle and served as a precursor of the Krebs cycle in aerobic metabolism.

Investigation of the effects of radiolytic-gas bubbles on the long-term operation of solution reactors for medical-isotope production

NASA Astrophysics Data System (ADS)

Souto Mantecon, Francisco Javier

One of the most common and important medical radioisotopes is 99Mo, which is currently produced using the target irradiation technology in heterogeneous nuclear reactors. The medical isotope 99Mo can also be produced from uranium fission using aqueous homogeneous solution reactors. In solution reactors, 99Mo is generated directly in the fuel solution, resulting in potential advantages when compared with the target irradiation process in heterogeneous reactors, such as lower reactor power, less waste heat, and reduction by a factor of about 100 in the generation of spent fuel. The commercial production of medical isotopes in solution reactors requires steady-state operation at about 200 kW. At this power regime, the formation of radiolytic-gas bubbles creates a void volume in the fuel solution that introduces a negative coefficient of reactivity, resulting in power reduction and instabilities that may impede reactor operation for medical-isotope production. A model has been developed considering that reactivity effects are due to the increase in the fuel-solution temperature and the formation of radiolytic-gas bubbles. The model has been validated against experimental results from the Los Alamos National Laboratory uranyl fluoride Solution High-Energy Burst Assembly (SHEBA), and the SILENE uranyl nitrate solution reactor, commissioned at the Commissariat a l'Energie Atomique, in Valduc, France. The model shows the feasibility of solution reactors for the commercial production of medical isotopes and reveals some of the important parameters to consider in their design, including the fuel-solution type, 235U enrichment, uranium concentration, reactor vessel geometry, and neutron reflectors surrounding the reactor vessel. The work presented herein indicates that steady-state operation at 200 kW can be achieved with a solution reactor consisting of 120 L of uranyl nitrate solution enriched up to 20% with 235U and a uranium concentration of 145 kg/m3 in a graphite-reflected cylindrical geometry.

In vivo assimilation of one-carbon via a synthetic reductive glycine pathway in Escherichia coli.

PubMed

Yishai, Oren; Bouzon, Madeleine; Döring, Volker; Bar-Even, Arren

2018-05-15

Assimilation of one-carbon compounds presents a key biochemical challenge, which limits their use as sustainable feedstocks for microbial growth and production. The reductive glycine pathway is a synthetic metabolic route that could provide an optimal way for the aerobic assimilation of reduced C1 compounds. Here, we show that a rational integration of native and foreign enzymes enables the tetrahydrofolate and glycine cleavage/synthase systems to operate in the reductive direction, such that Escherichia coli satisfies all of its glycine and serine requirements from the assimilation of formate and CO2. Importantly, the biosynthesis of serine from formate and CO2 does not lower the growth rate, indicating high flux that is able to provide 10% of cellular carbon. Our findings assert that the reductive glycine pathway could support highly efficient aerobic assimilation of C1-feedstocks.

A first principles investigation of electron transfer between Fe(II) and U(VI) on insulating Al- vs. semiconducting Fe-oxide surfaces via the proximity effect

NASA Astrophysics Data System (ADS)

Taylor, S. D.; Marcano, M. C.; Becker, U.

2017-01-01

This study investigates how the intrinsic chemical and electronic properties of mineral surfaces and their associated electron transfer (ET) pathways influence the reduction of U(VI) by surface-associated Fe(II). Density functional theory (DFT), including the Hubbard U correction to the exchange-correlation functional, was used to investigate sorption/redox reactions and ET mechanisms between Fe(II) and U(VI) coadsorbed on isostructural, periodic (0 0 1) surfaces of the insulator corundum (α-Al2O3) vs. the semiconductor hematite (α-Fe2O3). Furthermore, the coadsorbed Fe(II) and U(VI) ions are spatially separated from one another on the surfaces (⩾5.9 Å) to observe whether electronic-coupling through the semiconducting hematite surface facilitates ET between the adsorbates, a phenomenon known as the proximity effect. The calculations show that the different chemical and electronic properties between the isostructural corundum and hematite (0 0 1) surfaces lead to considerably different ET mechanisms between Fe(II) and U(VI). ET on the insulating corundum (0 0 1) surface is limited by the adsorbates' structural configuration. When Fe(II) and U(VI) are spatially separated and do not directly interact with one another (e.g. via an inner-sphere complex), U(VI) reduction by Fe(II) cannot occur as there is no physical pathway enabling ET between the adsorbates. In contrast to the insulating corundum (0 0 1) surface, the hematite (0 0 1) surface can potentially participate in ET reactions due to the high number of electron acceptor sites from the Fe d-states near the Fermi level at the hematite surface. The adsorption of Fe(II) also introduces d-states near the Fermi level as well as shifts unoccupied d-states of the Fe cations at the hematite surface to lower energies, making the surface more conductive. In turn, electronic coupling through the surface can link the spatially separated adsorbates to one another and provide distinct ET pathways for an electron from Fe(II) to travel through the hematite surface and reach U(VI). The progression and extent of ET occurring on the semiconducting hematite (0 0 1) surface via the proximity effect depends on the electronic properties of the surface. ET between the spatially separated U(VI) and Fe(II) occurs most readily when orbitals between the Fe and U adsorbates overlap with those of neighboring O and Fe ions at the hematite surface, as shown by calculations without the Hubbard U correction. Analyses of the spins densities confirm that the U and Fe adsorbates were reduced and oxidized, respectively, (acquiring 0.33 μB and 0.11-0.20 μB, respectively), while Fe cations at the hematite surface were reduced (losing ⩽0.6 μB). If electrons are highly localized, the amount of orbital mixing and electronic coupling through the hematite surface decreases and in turn leads to a lower degree of spin transfer, as predicted by calculations with the Hubbard U correction. Thus, the proximity effect is a potential mechanism on semiconducting surfaces facilitating surface-mediated redox reactions, although its significance varies depending on the electronic properties and subsequent charge-carrying ability of the surface. These results provide insight into ET pathways and mechanisms on insulating Al- and semiconducting Fe oxide surfaces influencing the reduction U(VI) by Fe(II) that may subsequently limit uranium's transport in the subsurface.

Comparison of life cycle greenhouse gases from natural gas pathways for medium and heavy-duty vehicles.

PubMed

Tong, Fan; Jaramillo, Paulina; Azevedo, Inês M L

2015-06-16

The low-cost and abundant supply of shale gas in the United States has increased the interest in using natural gas for transportation. We compare the life cycle greenhouse gas (GHG) emissions from different natural gas pathways for medium and heavy-duty vehicles (MHDVs). For Class 8 tractor-trailers and refuse trucks, none of the natural gas pathways provide emissions reductions per unit of freight-distance moved compared to diesel trucks. When compared to the petroleum-based fuels currently used in these vehicles, CNG and centrally produced LNG increase emissions by 0-3% and 2-13%, respectively, for Class 8 trucks. Battery electric vehicles (BEVs) powered with natural gas-produced electricity are the only fuel-technology combination that achieves emission reductions for Class 8 transit buses (31% reduction compared to the petroleum-fueled vehicles). For non-Class 8 trucks (pick-up trucks, parcel delivery trucks, and box trucks), BEVs reduce emissions significantly (31-40%) compared to their diesel or gasoline counterparts. CNG and propane achieve relatively smaller emissions reductions (0-6% and 19%, respectively, compared to the petroleum-based fuels), while other natural gas pathways increase emissions for non-Class 8 MHDVs. While using natural gas to fuel electric vehicles could achieve large emission reductions for medium-duty trucks, the results suggest there are no great opportunities to achieve large emission reductions for Class 8 trucks through natural gas pathways with current technologies. There are strategies to reduce the carbon footprint of using natural gas for MHDVs, ranging from increasing vehicle fuel efficiency, reducing life cycle methane leakage rate, to achieving the same payloads and cargo volumes as conventional diesel trucks.

Microfluidic Experiments Studying Pore Scale Interactions of Microbes and Geochemistry

NASA Astrophysics Data System (ADS)

Chen, M.; Kocar, B. D.

2016-12-01

Understanding how physical phenomena, chemical reactions, and microbial behavior interact at the pore-scale is crucial to understanding larger scale trends in groundwater chemistry. Recent studies illustrate the utility of microfluidic devices for illuminating pore-scale physical-biogeochemical processes and their control(s) on the cycling of iron, uranium, and other important elements 1-3. These experimental systems are ideal for examining geochemical reactions mediated by microbes, which include processes governed by complex biological phenomenon (e.g. biofilm formation, etc.)4. We present results of microfluidic experiments using a model metal reducing bacteria and varying pore geometries, exploring the limitations of the microorganisms' ability to access tight pore spaces, and examining coupled biogeochemical-physical controls on the cycling of redox sensitive metals. Experimental results will provide an enhanced understanding of coupled physical-biogeochemical processes transpiring at the pore-scale, and will constrain and compliment continuum models used to predict and describe the subsurface cycling of redox-sensitive elements5. 1. Vrionis, H. A. et al. Microbiological and geochemical heterogeneity in an in situ uranium bioremediation field site. Appl. Environ. Microbiol. 71, 6308-6318 (2005). 2. Pearce, C. I. et al. Pore-scale characterization of biogeochemical controls on iron and uranium speciation under flow conditions. Environ. Sci. Technol. 46, 7992-8000 (2012). 3. Zhang, C., Liu, C. & Shi, Z. Micromodel investigation of transport effect on the kinetics of reductive dissolution of hematite. Environ. Sci. Technol. 47, 4131-4139 (2013). 4. Ginn, T. R. et al. Processes in microbial transport in the natural subsurface. Adv. Water Resour. 25, 1017-1042 (2002). 5. Scheibe, T. D. et al. Coupling a genome-scale metabolic model with a reactive transport model to describe in situ uranium bioremediation. Microb. Biotechnol. 2, 274-286 (2009).

A Uranium Bioremediation Reactive Transport Benchmark

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yabusaki, Steven B.; Sengor, Sevinc; Fang, Yilin

A reactive transport benchmark problem set has been developed based on in situ uranium bio-immobilization experiments that have been performed at a former uranium mill tailings site in Rifle, Colorado, USA. Acetate-amended groundwater stimulates indigenous microorganisms to catalyze the reduction of U(VI) to a sparingly soluble U(IV) mineral. The interplay between the flow, acetate loading periods and rates, microbially-mediated and geochemical reactions leads to dynamic behavior in metal- and sulfate-reducing bacteria, pH, alkalinity, and reactive mineral surfaces. The benchmark is based on an 8.5 m long one-dimensional model domain with constant saturated flow and uniform porosity. The 159-day simulation introducesmore » acetate and bromide through the upgradient boundary in 14-day and 85-day pulses separated by a 10 day interruption. Acetate loading is tripled during the second pulse, which is followed by a 50 day recovery period. Terminal electron accepting processes for goethite, phyllosilicate Fe(III), U(VI), and sulfate are modeled using Monod-type rate laws. Major ion geochemistry modeled includes mineral reactions, as well as aqueous and surface complexation reactions for UO2++, Fe++, and H+. In addition to the dynamics imparted by the transport of the acetate pulses, U(VI) behavior involves the interplay between bioreduction, which is dependent on acetate availability, and speciation-controlled surface complexation, which is dependent on pH, alkalinity and available surface complexation sites. The general difficulty of this benchmark is the large number of reactions (74), multiple rate law formulations, a multisite uranium surface complexation model, and the strong interdependency and sensitivity of the reaction processes. Results are presented for three simulators: HYDROGEOCHEM, PHT3D, and PHREEQC.« less