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Sample records for autunite

  1. Sodium meta-autunite colloids: Synthesis, characterization,stability

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    zzuoping@lbl.gov

    2004-04-10

    Waste forms of U such as those in the United States Department of Energy's Hanford Site often contain high concentrations of Na and P. Low solubility sodium uranyl phosphates such as sodium meta-autunite have the potential to form mobile colloids that can facilitate transport of this radionuclide. In order to understand the geochemical behavior of uranyl phosphate colloids, we synthesized sodiummeta-autunite colloids, and characterized their morphology, chemical composition, structure, dehydration, and surface charge. The stability of these synthetic plate-shaped colloids was tested with respect to time and pH. The highest aggregation rate was observed at pH 3, and the rate decreases as pH increases, indicating that higher stability of colloid dispersion under neutral and alkaline pH conditions. The synthetic colloids are all negatively charged and no isoelectric points were found over a pH range of 3 to 9. The zeta-potentials of the colloids in the phosphate solution show a strong pH-dependence in the more acidic range over time, but are relatively constant in the neutral and alkaline pH range. The geochemical behavior of the synthetic colloids can be interpreted using DLVO theory. The results suggest that formation of mobile sodium meta-autunite colloids can enhance the transport of U in some contaminated sediments.

  2. Investigation on Microbial Dissolution of Uranium (VI) from Autunite Mineral - 13421

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    Sepulveda, Paola; Katsenovich, Yelena; Lagos, Leonel [Applied Research Center, Florida International University. 10555 West Flagler St. Suite 2100, Miami Fl 33175 (United States)

    2013-07-01

    Precipitating autunite minerals by polyphosphate injection was identified as a feasible remediation strategy for sequestering uranium in contaminated groundwater and soil in situ at the Hanford Site. Autunite stability under vadose and saturated zone environmental conditions can help to determine the long-term effectiveness of this remediation strategy. The Arthrobacter bacteria are one of the most common groups in soils and are found in large numbers in Hanford soil as well as other subsurface environments contaminated with radionuclides. Ubiquitous in subsurface microbial communities, these bacteria can play a significant role in the dissolution of minerals and the formation of secondary minerals. The main objective of this investigation was to study the bacterial interactions under oxidizing conditions with uranium (VI); study the potential role of bicarbonate, which is an integral complexing ligand for U(VI) and a major ion in groundwater compositions; and present data from autunite dissolution experiments using Arthrobacter strain G968, a less U(VI)-tolerant strain. Sterile 100 mL glass mixed reactors served as the major bioreactor for initial experimentation. These autunite-containing bioreactors were injected with bacterial cells after the autunite equilibrated with the media solution amended with 0 mM, 3 mM 5 mM and 10 mM concentrations of bicarbonate. G968 Arthrobacter cells in the amount of 10{sup 6} cells/mL were injected into the reactors after 27 days, giving time for the autunite to reach steady state. Abiotic non-carbonate controls were kept without bacterial inoculation to provide a control for the biotic samples. Samples of the solution were analyzed for dissolved U(VI) by means of kinetic phosphorescence analyzer KPA-11 (Chemcheck Instruments, Richland, WA). Analysis showed that as [HCO{sub 3}{sup -}] increases, a diminishing trend on the effect of bacteria on autunite leaching is observed. Viability of cells was conducted after 24 hours of cell

  3. Solubility of triuranyl diphosphate tetrahydrate (TDT) and Na autunite at 23 and 50 degrees C

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    Armstrong, Christopher R.; Felmy, Andrew R.; Clark, Sue B.

    2010-11-01

    In this report we present experimental solubility data for well-characterized triuranyl diphosphate tetrahydrate (TDT: (UO2)(3)(PO4)(2)center dot 4H(2)O) and Na autunite (Na[UO2PO4]center dot xH(2)O) at 23 and 50 degrees C in NaClO4-HClO4 solutions at pC(H+) = 2. Duplicate samples of TDT in 0.1, 0.5, 1.0, 2.0 and 5.0 in solutions were equilibrated at 23 and 50 degrees C. TDT solid was synthesized and characterized with ICP-OES, ATR-IR and powder XRD before and after solubility experiments. The pH of the suspensions were monitored throughout the experiments. Equilibrium was achieved from undersaturation with respect to TDT and oversaturation for Na autunite. Steady-state conditions were achieved in all cases within 82 d. TDT was unstable at ionic strengths above 0.1 m, where its complete conversion to Na autunite was observed. The ion-interaction model was used to interpret the experimental solubility data. The solubility product, log K-sp, for TDT was determined to be -49.7 and -51.3 at 23 and 50 degrees C respectively. log K for Na autunite was determined to be -24.4 (23 degrees C) and -24.1 +/- 0.2 (50 degrees C).

  4. Solubility of triuranyl diphosphate tetrahydrate (TDT) and Na autunite at 23 and 50 C

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    Armstrong, C.R.; Clark, S.B. [Washington State Univ., Pullman, WA (United States); Felmy, A.R. [Pacific Northwest National Lab., Richland, WA (United States)

    2010-07-01

    In this report we present experimental solubility data for well-characterized triuranyl diphosphate tetrahydrate (TDT: (UO{sub 2}){sub 3}(PO{sub 4}){sub 2} . 4H{sub 2}O) and Na autunite (Na[UO{sub 2}PO{sub 4}] . xH{sub 2}O) at 23 and 50 C in NaClO{sub 4}-HClO{sub 4} solutions at pC{sub H1} = 2. Duplicate samples of TDT in 0.1, 0.5, 1.0, 2.0 and 5.0 m solutions were equilibrated at 23 and 50 C. TDT solid was synthesized and characterized with ICP-OES, ATR-IR and powder XRD before and after solubility experiments. The pH of the suspensions were monitored throughout the experiments. Equilibrium was achieved from undersaturation with respect to TDT and oversaturation for Na autunite. Steady-state conditions were achieved in all cases within 82 d. TDT was unstable at ionic strengths above 0.1 m, where its complete conversion to Na autunite was observed. The ion-interaction model was used to interpret the experimental solubility data. The solubility product, log K{sub sp}, for TDT was determined to be -49.7 and -51.3 at 23 and 50 C respectively. log K{sub sp} for Na autunite was determined to be -24.4 (23 C) and -24.1 {+-} 0.2 (50 C). (orig.)

  5. Enhanced U(VI) release from autunite mineral by aerobic Arthrobacter sp. in the presence of aqueous bicarbonate

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    Katsenovich, Yelena; Carvajal, Denny A.; Wellman, Dawn M.; Lagos, Leonel

    2012-04-20

    The bacterial effect on U(VI) leaching from the autunite mineral (Ca[(UO{sub 2})(PO{sub 4})]{sub 2} {center_dot} 3H{sub 2}O) was investigated to provide a more comprehensive understanding into important microbiological processes affecting autunite stability within subsurface bicarbonate-bearing environments. Experiments were performed in a culture of G975 Arthrobacter oxydans strain, herein referred to as G975, a soil bacterium previously isolated from Hanford Site soil. 91 mg of autunite powder and 50 mL of phosphorus-limiting sterile media were amended with bicarbonate ranging between 1-10 mM in glass reactor bottles and inoculated with G975 strain after the dissolution of autunite was at steady state. SEM observations indicated G975 formed a biofilm on the autunite surface and penetrated the mineral cleavages. The mineral surface colonization by bacteria tended to increase concomitantly with bicarbonate concentrations. Additionally, a sterile cultureware with inserts was used in non-contact bioleaching experiments where autunite and bacteria cells were kept separately. The data suggest the G975 bacteria is able to enhance U(VI) leaching from autunite without the direct contact with the mineral. In the presence of bicarbonate, the damage to bacterial cells caused by U(VI) toxicity was reduced, yielding similar values for total organic carbon (TOC) degradation and cell density compared to U(VI)-free controls. The presence of active bacterial cells greatly enhanced the U(VI) bioleaching from autunite in bicarbonate-amended media.

  6. Enhanced U(VI) release from autunite mineral by aerobic Arthrobacter sp. in the presence of aqueous bicarbonate

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    Katsenovich, Yelena P.; Carvajal, Denny A.; Wellman, Dawn M.; Lagos, Leonel E.

    2012-05-01

    The bacterial effect on U(VI) release from the autunite mineral (Ca[(UO2)(PO4)]2•3H2O) was investigated to provide a more comprehensive understanding of the important microbiological processes affecting autunite stability within subsurface bicarbonate-bearing environments. Experiments were performed in a culture of the Arthrobacter oxydans G975 strain, herein referred to as G975, a soil bacterium previously isolated from Hanford Site soil. 91 mg of autunite powder and 50 mL of phosphorous-limiting sterile media were amended with bicarbonate (ranging between 1 and 10 mM) in glass reactor bottles and inoculated with the G975 strain after the dissolution of autunite was at steady state. SEM observations indicated that G975 formed a biofilm on the autunite surface and penetrated the mineral cleavages. The mineral surface colonization by bacteria tended to increase concomitantly with bicarbonate concentrations. Additionally, a sterile culture-ware with inserts was used in non-contact dissolution experiments where autunite and bacteria cells were kept separately. The data suggest that G975 bacteria is able to enhance the release of U(VI) from autunite without direct contact with the mineral. In the presence of bicarbonate, the damage to bacterial cells caused by U(VI) toxicity was reduced, yielding similar values for total organic carbon (TOC) degradation and cell density compared to U(VI)-free controls. The presence of active bacterial cells greatly enhanced the release of U(VI) from autunite in bicarbonate-amended media.

  7. The Effect of Bicarbonate on the Microbial Dissolution of Autunite Mineral in the Presence of Gram-Positive Bacteria

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    Sepulveda-Medina, Paola; Katsenovich, Yelena; Wellman, Dawn M.; Lagos, Leonel

    2015-06-01

    Bacteria are key players in the processes that govern fate and transport of contaminants. The uranium release from Na and Ca-autunite by Arthrobacter oxydans strain G968 was evaluated in the presence of bicarbonate ions. This bacterium was previously isolated from Hanford Site soil and in earlier prescreening tests demonstrated low tolerance to U(VI) toxicity compared to other A.oxydans isolates. Experiments were conducted using glass serum bottles as mixed bioreactors and sterile 6-well cell culture plates with inserts separating bacteria cells from mineral solids. Reactors containing phosphorus-limiting media were amended with bicarbonate ranging between 0-10 mM and metaautunite solids to provide a U(VI) concentration of 4.4 mmol/L. Results showed that in the presence of bicarbonate, A.oxydans G968 was able to enhance the release of U(VI) from Na and Ca autunite at the same capacity as other A.oxydans isolates with relatively high tolerance to U(VI). The effect of bacterial strains on autunite dissolution decreases as the concentration of bicarbonate increases. The results illustrate that direct interaction between the bacteria and the mineral is not necessary to result in U (VI) biorelease from autunite. The formation of secondary calcium-phosphate mineral phases on the surface of the mineral during the dissolution can ultimately reduce the natural autunite mineral contact area, which bacterial cells can access. This thereby reduces the concentration of uranium released into the solution. This study provides a better understanding of the interactions between meta-autunite and microbes in conditions mimicking arid and semiarid subsurface environments of western U.S.

  8. Quantification of Kinetic Rate Law Parameters of Uranium Release from Sodium Autunite as a Function of Aqueous Bicarbonate Concentrations

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    Gudavalli, Ravi; Katsenovich, Yelena; Wellman, Dawn M.; Lagos, Leonel; Tansel, Berrin

    2013-09-05

    ABSTRACT: Hydrogen carbonate is one of the most significant components within the uranium geochemical cycle. In aqueous solutions, hydrogen carbonate forms strong complexes with uranium. As such, aqueous bicarbonate may significantly increase the rate of uranium release from uranium minerals. Quantifying the relationship of aqueous hydrogen carbonate solutions to the rate of uranium release during dissolution is critical to understanding the long-term fate of uranium within the environment. Single-pass flow-through (SPTF) experiments were conducted to estimate the rate of uranium release from Na meta-autunite as a function of bicarbonate solutions (0.0005-0.003 M) under the pH range of 6-11 and temperatures of 5-60oC. Consistent with the results of previous investigation, the rate of uranium release from sodium autunite exhibited minimal dependency on temperature; but were strongly dependent on pH and increasing concentrations of bicarbonate solutions. Most notably at pH 7, the rate of uranium release exhibited 370 fold increases relative to the rate of uranium release in the absence of bicarbonate. However, the effect of increasing concentrations of bicarbonate solutions on the release of uranium was significantly less under higher pH conditions. It is postulated that at high pH values, surface sites are saturated with carbonate, thus the addition of more bicarbonate would have less effect on uranium release. Results indicate the activation energies were unaffected by temperature and bicarbonate concentration variations, but were strongly dependent on pH conditions. As pH increased from 6 to 11, activation energy values were observed to decrease from 29.94 kJ mol-1 to 13.07 kJ mol-1. The calculated activation energies suggest a surface controlled dissolution mechanism.

  9. Comparison of the Kinetic Rate Law Parameters for the Dissolution of Natural and Synthetic Autunite in the Presence of Aqueous Bicarbonate Ions

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    Gudavalli, Ravi; Katsenovich, Yelena; Wellman, Dawn M.; Idarraga, Melina; Lagos, Leonel; Tansel, Berrin

    2013-08-02

    Bicarbonate is one of the most significant components within the uranium geochemical cycle. In aqueous solutions, bicarbonate forms strong complexes with uranium. As such, aqueous bicarbonate may significantly increase the rate of uranium release from uranium minerals. Quantifying the relationship of aqueous bicarbonate concentration to the rate of uranium release during dissolution is critical to understanding the long-term fate of uranium within the environment. Single-pass flow-through (SPTF) experiments were conducted to estimate the rate of uranium release from Na meta-autunite as a function of bicarbonate (0.0005-0.003 M) under the pH range of 6-11 and a temperature range of 5-60oC. Consistent with the results of previous investigation, the rate of uranium release exhibited minimal dependency on temperature; but were strongly dependent on pH. Increasing aqueous bicarbonate concentrations afforded comparable increases in the rate of release of uranium. Most notably under low pH conditions the aqueous bicarbonate resulted in up to 370 fold increases in the rate of uranium release in relative to the rate of uranium release in the absence of bicarbonate. However, the effect of aqueous bicarbonate on the release of uranium was significantly less under higher pH conditions. It is postulated that at high pH values, surface sites are saturated with carbonate, thus the addition of more bicarbonate would have less effect on uranium release.

  10. Treatability Test Plan for 300 Area Uranium Stabilization through Polyphosphate Injection

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    Vermeul, Vincent R.; Williams, Mark D.; Fritz, Brad G.; Mackley, Rob D.; Mendoza, Donaldo P.; Newcomer, Darrell R.; Rockhold, Mark L.; Williams, Bruce A.; Wellman, Dawn M.

    2007-06-01

    The U.S. Department of Energy has initiated a study into possible options for stabilizing uranium at the 300 Area using polyphosphate injection. As part of this effort, PNNL will perform bench- and field-scale treatability testing designed to evaluate the efficacy of using polyphosphate injections to reduced uranium concentrations in the groundwater to meet drinking water standards (30 ug/L) in situ. This technology works by forming phosphate minerals (autunite and apatite) in the aquifer that directly sequester the existing aqueous uranium in autunite minerals and precipitates apatite minerals for sorption and long term treatment of uranium migrating into the treatment zone, thus reducing current and future aqueous uranium concentrations. Polyphosphate injection was selected for testing based on technology screening as part of the 300-FF-5 Phase III Feasibility Study for treatment of uranium in the 300-Area.

  11. Mineralogical Study of Workable Material Coming from Mina Fe Ciudad Rodrigo; Estudio mineralogico del material beneficiable procedente de la Mina Fe. Ciudad Rodrigo (Salamanca)

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    Mingarro Martin, E.

    1962-07-01

    A mineralogical analysis is made to ascertain the effects of acid bleaching on normalized conditions. Uranium is mainly found under uranotile, pitchblende and autunite form with an average assay of 0.4 p. ct. The loss of uranium in tailings under current conditions of attach, mainly is due to pitchblende resistance, being practically no leachable, and to uranium absorption by hydrated iron oxides and colloidal ores. This last problem will be discussed in a next paper. (Author) 5 refs.

  12. Interim Report: Uranium Stabilization Through Polyphosphate Injection - 300 Area Uranium Plume Treatability Demonstration Project

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    Wellman, Dawn M.; Pierce, Eric M.; Richards, Emily L.; Butler, Bart C.; Parker, Kent E.; Glovack, Julia N.; Burton, Sarah D.; Baum, Steven R.; Clayton, Eric T.; Rodriguez, Elsa A.

    2007-07-31

    This report presents results from bench-scale treatability studies conducted under site-specific conditions to optimize the polyphosphate amendment for implementation of a field-scale technology demonstration to treat aqueous uranium within the 300 Area aquifer of the Hanford site. The general treatability testing approach consists of conducting studies with site sediment and under site conditions, in order to develop an effective chemical formulation for the polyphosphate amendments and evaluate the transport properties of these amendments under site conditions. Phosphorus-31 (31P) NMR was utilized to determine the effects of Hanford groundwater and sediment on the degradation of inorganic phosphates. Static batch tests were conducted to optimize the composition of the polyphosphate formulation for the precipitation of apatite and autunite, as well as to quantify the kinetics, loading and stability of apatite as a long-term sorbent for uranium. Dynamic column tests were used to further optimize the polyphosphate formulation for emplacement within the subsurface and the formation of autunite and apatite. In addition, dynamic testing quantified the stability of autunite and apatite under relevant site conditions. Results of this investigation provide valuable information for designing a full-scale remediation of uranium in the 300 aquifer.

  13. 300 Area Uranium Stabilization Through Polyphosphate Injection: Final Report

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    Vermeul, Vincent R.; Bjornstad, Bruce N.; Fritz, Brad G.; Fruchter, Jonathan S.; Mackley, Rob D.; Newcomer, Darrell R.; Mendoza, Donaldo P.; Rockhold, Mark L.; Wellman, Dawn M.; Williams, Mark D.

    2009-06-30

    The objective of the treatability test was to evaluate the efficacy of using polyphosphate injections to treat uranium-contaminated groundwater in situ. A test site consisting of an injection well and 15 monitoring wells was installed in the 300 Area near the process trenches that had previously received uranium-bearing effluents. This report summarizes the work on the polyphosphate injection project, including bench-scale laboratory studies, a field injection test, and the subsequent analysis and interpretation of the results. Previous laboratory tests have demonstrated that when a soluble form of polyphosphate is injected into uranium-bearing saturated porous media, immobilization of uranium occurs due to formation of an insoluble uranyl phosphate, autunite [Ca(UO2)2(PO4)2•nH2O]. These tests were conducted at conditions expected for the aquifer and used Hanford soils and groundwater containing very low concentrations of uranium (10-6 M). Because autunite sequesters uranium in the oxidized form U(VI) rather than forcing reduction to U(IV), the possibility of re-oxidation and subsequent re-mobilization is negated. Extensive testing demonstrated the very low solubility and slow dissolution kinetics of autunite. In addition to autunite, excess phosphorous may result in apatite mineral formation, which provides a long-term source of treatment capacity. Phosphate arrival response data indicate that, under site conditions, the polyphosphate amendment could be effectively distributed over a relatively large lateral extent, with wells located at a radial distance of 23 m (75 ft) reaching from between 40% and 60% of the injection concentration. Given these phosphate transport characteristics, direct treatment of uranium through the formation of uranyl-phosphate mineral phases (i.e., autunite) could likely be effectively implemented at full field scale. However, formation of calcium-phosphate mineral phases using the selected three-phase approach was problematic. Although

  14. Experimental Plan: 300 Area Treatability Test: In Situ Treatment of the Vadose Zone and Smear Zone Uranium Contamination by Polyphosphate Infiltration

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    Wellman, Dawn M.; Pierce, Eric M.; Oostrom, Mart; Fruchter, Jonathan S.

    2007-08-31

    The overall objectives of the treatability test is to evaluate and optimize polyphosphate remediation technology for infiltration either from ground surface, or some depth of excavation, providing direct stabilization of uranium within the deep vadose and capillary fringe above the 300 Area aquifer. Expected result from this experimental plan is a data package that includes: 1) quantification of the retardation of polyphosphate, 2) the rate of degradation and the retardation of degradation products as a function of water content, 3) an understanding of the mechanism of autunite formation via the reaction of solid phase calcite-bound uranium and aqueous polyphosphate remediation technology, 4) an understanding of the transformation mechanism, identity of secondary phases, and the kinetics of the reaction between uranyl-carbonate and –silicate minerals with the polyphosphate remedy under solubility-limiting conditions, 5) quantification of the extent and rate of uranium released and immobilized based on the infiltration rate of the polyphosphate remedy and the effect of and periodic wet-dry cycling on the efficacy of polyphosphate remediation for uranium in the vadose zone and capillary fringe, and 6) quantification of reliable equilibrium solubility values for autunite under hydraulically unsaturated conditions allowing accurate prediction of the long-term stability of autunite. Moreover, results of intermediate scale testing will quantify the transport of polyphosphate and degradation products, and yield degradation rates, at a scale that is bridging the gap between the small-scale UFA studies and the field scale. These results will be used to test and verify a site-specific, variable saturation, reactive transport model and to aid in the design of a pilot-scale field test of this technology. In particular, the infiltration approach and monitoring strategy of the pilot test would be primarily based on results from intermediate-scale testing. Results from this

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

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    Mehta, Vrajesh S.; Maillot, Fabien; Wang, Zheming; Catalano, Jeffrey G.; Giammar, Daniel E.

    2016-03-15

    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 was 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.

  16. Evaluation of Reagent Emplacement Techniques for Phosphate-based Treatment of the Uranium Contamination Source in the 300 Area White Paper

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    Nimmons, Michael J.

    2010-06-04

    Persistent uranium contamination of groundwater under the 300 Area of the Hanford Site has been observed. The source of the uranium contamination resides in uranium deposits on sediments at the groundwater interface, and the contamination is mobilized when periodically wetted by fluctuations of Columbia River levels. Treatability work is ongoing to develop and apply phosphate-containing reagents to promote the formation of stable and insoluble uranium phosphate minerals (i.e., autunite) and other phosphate precipitates (di-calcium phosphate, apatite) to stabilize the uranium source. Technologies for applying phosphate-containing reagents by vertical percolation and lateral injection into sediments of the periodically wetted groundwater interface are being investigated. This report is a preliminary evaluation of technologies for lateral injection.

  17. Use of combined microscopic and spectroscopic techniques to reveal interactions between uranium and Microbacterium sp. A9, a strain isolated from the Chernobyl exclusion zone

    Energy Technology Data Exchange (ETDEWEB)

    Theodorakopoulos, Nicolas [CEA, DSV, IBEB, SBVME, LIPM, F-13108 Saint-Paul-lez-Durance (France); CNRS, UMR 7265, F-13108 Saint-Paul-lez-Durance (France); Université d' Aix-Marseille, F-13108 Saint-Paul-lez-Durance (France); IRSN/PRP-ENV/SERIS/L2BT, bat 183, B.P. 3, F-13115 Saint Paul-lez-Durance (France); Chapon, Virginie [CEA, DSV, IBEB, SBVME, LIPM, F-13108 Saint-Paul-lez-Durance (France); CNRS, UMR 7265, F-13108 Saint-Paul-lez-Durance (France); Université d' Aix-Marseille, F-13108 Saint-Paul-lez-Durance (France); Coppin, Fréderic; Floriani, Magali [IRSN/PRP-ENV/SERIS/L2BT, bat 183, B.P. 3, F-13115 Saint Paul-lez-Durance (France); Vercouter, Thomas [CEA, DEN, DANS, DPC SEARS, LANIE, F-91191 Gif-Sur-Yvette Cedex (France); Sergeant, Claire [Univ Bordeaux, CENBG, UMR5797, F-33170 Gradignan (France); CNRS, IN2P3, CENBG, UMR5797, F-33170 Gradignan (France); Camilleri, Virginie [IRSN/PRP-ENV/SERIS/L2BT, bat 183, B.P. 3, F-13115 Saint Paul-lez-Durance (France); Berthomieu, Catherine [CEA, DSV, IBEB, SBVME, LIPM, F-13108 Saint-Paul-lez-Durance (France); CNRS, UMR 7265, F-13108 Saint-Paul-lez-Durance (France); Université d' Aix-Marseille, F-13108 Saint-Paul-lez-Durance (France); Février, Laureline, E-mail: laureline.fevrier@irsn.fr [IRSN/PRP-ENV/SERIS/L2BT, bat 183, B.P. 3, F-13115 Saint Paul-lez-Durance (France)

    2015-03-21

    Highlights: • Microbacterium sp. A9 develops various detoxification mechanisms. • Microbacterium sp. A9 promotes metal efflux from the cells. • Microbacterium sp. A9 releases phosphate to prevent uranium entrance in the cells. • Microbacterium sp. A9 stores U intracellularly as autunite. - Abstract: Although uranium (U) is naturally found in the environment, soil remediation programs will become increasingly important in light of certain human activities. This work aimed to identify U(VI) detoxification mechanisms employed by a bacteria strain isolated from a Chernobyl soil sample, and to distinguish its active from passive mechanisms of interaction. The ability of the Microbacterium sp. A9 strain to remove U(VI) from aqueous solutions at 4 °C and 25 °C was evaluated, as well as its survival capacity upon U(VI) exposure. The subcellular localisation of U was determined by TEM/EDX microscopy, while functional groups involved in the interaction with U were further evaluated by FTIR; finally, the speciation of U was analysed by TRLFS. We have revealed, for the first time, an active mechanism promoting metal efflux from the cells, during the early steps following U(VI) exposure at 25 °C. The Microbacterium sp. A9 strain also stores U intracellularly, as needle-like structures that have been identified as an autunite group mineral. Taken together, our results demonstrate that this strain exhibits a high U(VI) tolerance based on multiple detoxification mechanisms. These findings support the potential role of the genus Microbacterium in the remediation of aqueous environments contaminated with U(VI) under aerobic conditions.

  18. Structural setting and UPb dating of Uranium mineralizations from the Northeastern part of Nigeria (Upper Benue Region)

    Science.gov (United States)

    Maurin, J. C.; Lancelot, J. R.

    In the Northeastern part of Nigeria (Upper Benue region) uranium mineralizations occur widespread along major fracture zones within the Precambrian crystalline basement bounding the Cretaceous deposits of the Benue trough. In two mineralized areas (Mika and Ghumchi) structural analysis and UPb dating of these mineralizations have been performed. Isotopic data indicate an age of 148 ± 12 M.a. for the crystallization of Mika primary pitchblende, followed by a simple UPb evolution (without leakage of intermediate decay products) and a strong recent mobilization of the uranium (autunite and coffinite formation). The pitchblende crystallized in "en echelon" array megatension gashes due to regional dextral wrench mechanism along a N140E trend. On a regional scale, this fracturing episode and the uranium concentration phase are contemporaneous with the emplacement of a bimodal volcanism dated at 147 ± 7 M.a. which is related to the early stages of opening of the Benue trough (Popoff et al., 1982). Isotopic data of Ghumchi mineralization provide an age of 14 ± 3 m.y. for the crystallization of cryptocrystalline coffinite and like in Mika, actual- and strong mobilization of uranium affect the mineralizations (autunite formation). The mineralizations crystallized along passive preexisting structures (mylonites, faults and lamprophyric dykes) which acted as favorable traps for uranium concentration. Pb/Pb data on galena microcubes, associated with the coffinite, provide an isotopic composition comparable to those of recent alkali basalt series which intrude the African plate (e.g. Mandara-Cameroon, Kenya, Ahaggar, Canary Islands). Then, such a noticeable Pb isotopic composition together with the post-tectonic character and the Neogene age of the Ghumchi mineralization suggest that their crystallization is linked with the emplacement of Neogene alkali basalt lava flows and trachytic plugs which occur in the vicinity of Ghumchi area.

  19. Potential remediation approach for uranium-contaminated groundwaters through potassium uranyl vanadate precipitation

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    Tokunaga, T.K.; Kim, Y.; Wan, J.

    2009-06-01

    Methods for remediating groundwaters contaminated with uranium (U) through precipitation under oxidizing conditions are needed because bioreduction-based approaches require indefinite supply of electron donor. Although strategies based on precipitation of some phosphate minerals within the (meta)autunite group have been considered for this purpose, thermodynamic calculations for K- and Ca-uranyl phopsphates, meta-ankoleite and autunite, predict that U concentrations will exceed the Maximum Contaminant Level (MCL = 0.13 {micro}M for U) at any pH and pCO{sub 2}, unless phosphate is maintained at much higher concentrations than the sub-{micro}M levels typically found in groundwaters. We hypothesized that potassium uranyl vanadate will control U(VI) concentrations below regulatory levels in slightly acidic to neutral solutions based on thermodynamic data available for carnotite, K{sub 2}(UO{sub 2}){sub 2}V{sub 2}O8. The calculations indicate that maintaining U concentrations below the MCL through precipitation of carnotite will be sustainable in some oxidizing waters having pH in the range of 5.5 to 7, even when dissolution of this solid phase becomes the sole supply of sub-{micro}M levels of V. Batch experiments were conducted in solutions at pH 6.0 and 7.8, chosen because of their very different predicted extents of U(VI) removal. Conditions were identified where U concentrations dropped below its MCL within 1 to 5 days of contact with oxidizing solutions containing 0.2 to 10 mM K, and 0.1 to 20 {micro}M V(V). This method may also have application in extracting (mining) U and V from groundwaters where they both occur at elevated concentrations.

  20. Promoting Uranium Immobilization by the Activities of Microbial Phosphatases

    Energy Technology Data Exchange (ETDEWEB)

    Robert J. Martinez; Melanie J. Beazley; Samuel M. Webb; Martial Taillefert (co-PI); and Patricia A. Sobecky

    2007-04-19

    precipitation of U(VI) must be mediated by biological activity as less than 3% soluble U(VI) was removed either from the abiotic or the heat-killed cell controls. Interestingly, the pH has a strong effect on growth and U(VI) biomineralization rates by Rahnella. Thermodynamic modeling identifies autunite-type minerals [Ca(UO2)2(PO4)2] as the precipitate likely formed in the synthetic FRC groundwater conditions at all pH investigated. Extended X-ray absorption fine structure measurements have recently confirmed that the precipitate found in these incubations is an autunite and meta-autunite-type mineral. A kinetic model of U biomineralization at the different pH indicates that hydrolysis of organophosphate can be described using simple Monod kinetics and that uranium precipitation is accelerated when monohydrogen phosphate is the main orthophosphate species in solution. Overall, these experiments and ongoing soil slurry incubations demonstrate that the biomineralization of U(VI) through the activity of phosphatase enzymes can be expressed in a wide range of geochemical conditions pertaining to the FRC site.

  1. Influence of uranium on bacterial communities: a comparison of natural uranium-rich soils with controls.

    Directory of Open Access Journals (Sweden)

    Laure Mondani

    Full Text Available This study investigated the influence of uranium on the indigenous bacterial community structure in natural soils with high uranium content. Radioactive soil samples exhibiting 0.26% - 25.5% U in mass were analyzed and compared with nearby control soils containing trace uranium. EXAFS and XRD analyses of soils revealed the presence of U(VI and uranium-phosphate mineral phases, identified as sabugalite and meta-autunite. A comparative analysis of bacterial community fingerprints using denaturing gradient gel electrophoresis (DGGE revealed the presence of a complex population in both control and uranium-rich samples. However, bacterial communities inhabiting uraniferous soils exhibited specific fingerprints that were remarkably stable over time, in contrast to populations from nearby control samples. Representatives of Acidobacteria, Proteobacteria, and seven others phyla were detected in DGGE bands specific to uraniferous samples. In particular, sequences related to iron-reducing bacteria such as Geobacter and Geothrix were identified concomitantly with iron-oxidizing species such as Gallionella and Sideroxydans. All together, our results demonstrate that uranium exerts a permanent high pressure on soil bacterial communities and suggest the existence of a uranium redox cycle mediated by bacteria in the soil.

  2. Uranium Biominerals Precipitated by an Environmental Isolate of Serratia under Anaerobic Conditions.

    Directory of Open Access Journals (Sweden)

    Laura Newsome

    Full Text Available Stimulating the microbially-mediated precipitation of uranium biominerals may be used to treat groundwater contamination at nuclear sites. The majority of studies to date have focussed on the reductive precipitation of uranium as U(IV by U(VI- and Fe(III-reducing bacteria such as Geobacter and Shewanella species, although other mechanisms of uranium removal from solution can occur, including the precipitation of uranyl phosphates via bacterial phosphatase activity. Here we present the results of uranium biomineralisation experiments using an isolate of Serratia obtained from a sediment sample representative of the Sellafield nuclear site, UK. When supplied with glycerol phosphate, this Serratia strain was able to precipitate 1 mM of soluble U(VI as uranyl phosphate minerals from the autunite group, under anaerobic and fermentative conditions. Under phosphate-limited anaerobic conditions and with glycerol as the electron donor, non-growing Serratia cells could precipitate 0.5 mM of uranium supplied as soluble U(VI, via reduction to nano-crystalline U(IV uraninite. Some evidence for the reduction of solid phase uranyl(VI phosphate was also observed. This study highlights the potential for Serratia and related species to play a role in the bioremediation of uranium contamination, via a range of different metabolic pathways, dependent on culturing or in situ conditions.

  3. 300 Area Treatability Test: Laboratory Development of Polyphosphate Remediation Technology for In Situ Treatment of Uranium Contamination in the Vadose Zone and Capillary Fringe

    Energy Technology Data Exchange (ETDEWEB)

    Wellman, Dawn M.; Pierce, Eric M.; Bacon, Diana H.; Oostrom, Martinus; Gunderson, Katie M.; Webb, Samuel M.; Bovaird, Chase C.; Cordova, Elsa A.; Clayton, Eric T.; Parker, Kent E.; Ermi, Ruby M.; Baum, Steven R.; Vermeul, Vincent R.; Fruchter, Jonathan S.

    2008-09-30

    This report presents results from bench-scale treatability studies conducted under site-specific conditions to optimize the polyphosphate amendment for implementation of a field-scale technology demonstration to stabilize uranium within the 300 Area vadose and smear zones of the Hanford Site. The general treatability testing approach consisted of conducting studies with site sediment and under site conditions, to develop an effective chemical formulation and infiltration approach for the polyphosphate amendment under site conditions. Laboratory-scale dynamic column tests were used to 1) quantify the retardation of polyphosphate and its degradation products as a function of water content, 2) determine the rate of polyphosphate degradation under unsaturated conditions, 3) develop an understanding of the mechanism of autunite formation via the reaction of solid phase calcite-bound uranium and aqueous polyphosphate remediation technology, 4) develop an understanding of the transformation mechanism, the identity of secondary phases, and the kinetics of the reaction between uranyl-carbonate and -silicate minerals with the polyphosphate remedy under solubility-limiting conditions, and 5) quantify the extent and rate of uranium released and immobilized based on the infiltration rate of the polyphosphate remedy and the effect of and periodic wet-dry cycling on the efficacy of polyphosphate remediation for uranium in the vadose zone and smear zone.

  4. Biomineralization of Uranium by PhoY Phosphatase Activity Aids Cell Survival in Caulobacter crescentus

    Energy Technology Data Exchange (ETDEWEB)

    Yung, M C [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Jiao, Y [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2014-07-22

    Caulobacter crescentus is known to tolerate high levels of uranium [U(VI)], but its detoxification mechanism is poorly understood. Here we show that C. crescentus is able to facilitate U(VI) biomineralization through the formation of U-Pi precipitates via its native alkaline phosphatase activity. The U-Pi precipitates, deposited on the cell surface in the form of meta-autunite structures, have a lower U/Pi ratio than do chemically produced precipitates. The enzyme that is responsible for the phosphatase activity and thus the biomineralization process is identified as PhoY, a periplasmic alkaline phosphatase with broad substrate specificity. Furthermore, PhoY is shown to confer a survival advantage on C. crescentus toward U(VI) under both growth and nongrowth conditions. Results obtained in this study thus highlight U(VI) biomineralization as a resistance mechanism in microbes, which not only improves our understanding of bacterium-mineral interactions but also aids in defining potential ecological niches for metal-resistant bacteria.

  5. A cryogenic fluorescence spectroscopic study of uranyl carbonate, phosphate and oxyhydroxide minerals

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Z.; Zachara, J.M.; Liu, C.; Gassman, P.L.; Felmy, A.R. [Pacific Northwest National Lab., Richland, WA (United States); Clark, S.B. [Washington State Univ., Pullman, WA (United States)

    2008-07-01

    In this work we applied time-resolved laser-induced fluorescence spectroscopy (TRLIF) at both room temperature (RT) and near liquid-helium temperature (6 K) to characterize a series of natural and synthetic minerals of uranium carbonate, phosphate and oxyhydroxides including rutherfordine, zellerite, liebigite, phosphuranylite, meta-autunite, meta-torbernite, uranyl phosphate, sodium-uranyl-phosphate, becquerelite, schoepite, meta-schoepite, dehydrated schoepite and compreignacite, and have compared the spectral characteristics among these minerals as well as our previously published data on uranyl silicates. For the carbonate minerals, the fluorescence spectra of rutherfordine showed significant difference from those of zellerite and liebigite. The fluorescence spectra of the phosphate minerals closely resemble each other despite the differences in their composition and structure. For all uranium oxyhydroxides, the fluorescence spectra are largely red-shifted as compared to those of the uranium carbonates and phosphates and their vibronic bands are broad and less resolved at RT. The enhanced spectra resolution at 6 K allows more accurate determination of the fluorescence band origin and offers a complemental method to measure the O=U=O symmetrical stretch frequency, {nu}{sub 1}, from the spacings of the vibronic bands of the fluorescence spectra. The average {nu}{sub 1} values appear to be inversely correlated with the average pK{sub a} values of the anions. (orig.)

  6. A cryogenic fluorescence spectroscopic study of uranyl carbonate, phosphate, and oxyhydroxide minerals

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zheming; Zachara, John M.; Liu, Chongxuan; Gassman, Paul L.; Felmy, Andrew R.; Clark, Sue B.

    2008-11-03

    In this work we have applied liquid-helium temperature (LHeT) time-resolved laser-induced fluorescence spectroscopy (TRLIF) to characterize a series of natural and synthetic minerals of uranium carbonate, phosphate and oxyhydroxides including rutherfordine, zellerite, liebigite, phosphuranylite, meta-autunite, meta-torbernite, uranyl phosphate, sodium-uranyl-phosphate, bequerelite, clarkeite, curite, schoepite and compregnacite, and compared their spectral characteristics among these minerals as well as our previously published data on uranyl silicates. For the carbonate minerals, the fluorescence spectra depend on the stoichiometry of the mineral. For the phosphate minerals the fluorescence spectra closely resemble each other despite the differences in their composition and structure. For all uranium oxyhydroxides, the fluorescence spectra are largely red-shifted as compared with those of the uranium carbonates and phosphates and their vibronic bands are broadened and less resolved. The much enhanced spectra resolution at LHeT allows more accurate calculation of the O=U=O symmetrical stretch frequency, ν1, corresponding to the average spacing of the vibronic peaks of the fluorescence spectra and the spectral origin as reflected by the position of the first vibronic band. It was found that both the average ν1 and λ1 values correlate well with the average basicity of the inorganic anion.

  7. Biomineralization of uranium by PhoY phosphatase activity aids cell survival in Caulobacter crescentus.

    Science.gov (United States)

    Yung, Mimi C; Jiao, Yongqin

    2014-08-01

    Caulobacter crescentus is known to tolerate high levels of uranium [U(VI)], but its detoxification mechanism is poorly understood. Here we show that C. crescentus is able to facilitate U(VI) biomineralization through the formation of U-Pi precipitates via its native alkaline phosphatase activity. The U-Pi precipitates, deposited on the cell surface in the form of meta-autunite structures, have a lower U/Pi ratio than do chemically produced precipitates. The enzyme that is responsible for the phosphatase activity and thus the biomineralization process is identified as PhoY, a periplasmic alkaline phosphatase with broad substrate specificity. Furthermore, PhoY is shown to confer a survival advantage on C. crescentus toward U(VI) under both growth and nongrowth conditions. Results obtained in this study thus highlight U(VI) biomineralization as a resistance mechanism in microbes, which not only improves our understanding of bacterium-mineral interactions but also aids in defining potential ecological niches for metal-resistant bacteria.

  8. Uranium Biomineralization by Caulobacter crescentus

    Science.gov (United States)

    Jiao, Y.; Yung, M.; Park, D.

    2014-12-01

    It is well known that microorganisms are able to mediate removal of U(VI) from solution through reduction to insoluble U(IV) oxides under anaerobic conditions, but microbial transformation of U(VI) under aerobic conditions are less well understood. Here, we describe two processes of U(VI) transformation by the aerobic bacterium Caulobacter crescentus, known for its ubiquitous presence in aquatic systems and high U(VI) tolerance. U(VI) causes a temporary growth arrest in Caulobacter and growth recovery is not due to a decrease in U solubility, a common detoxification strategy employed by other microorganisms. Through functional reporter assays, we discovered that Caulobacter is able to reduce U(VI) bioavailability through a metabolism-dependent increase of medium pH, representing a novel U detoxification strategy. Upon recovery from growth arrest, Caulobacter proliferates with normal growth kinetics, accompanied by active U(VI) biomineralization. We found that phosphate metabolism is actively involved in the formation of U-P precipitates that are similar to autunite-group minerals. Comparisons of growth and U(VI) precipitation by wild type versus a phosphatase mutant indicates that extra-cytoplasmic phosphatase activity is not only responsible for the formation of cell-surface-bound U-P precipitates, but also plays an important role in cell survival under U stress. Our results highlight the importance of aerobic bacterial metabolism for U biogeochemistry.

  9. The Sorption Processes of U(VI) onto SiO2 in the Presence of Phosphate: from Binary Surface Species to Precipitation.

    Science.gov (United States)

    Comarmond, M Josick; Steudtner, Robin; Stockmann, Madlen; Heim, Karsten; Müller, Katharina; Brendler, Vinzenz; Payne, Timothy E; Foerstendorf, Harald

    2016-11-01

    The ternary system containing aqueous U(VI), aqueous phosphate and solid SiO2 was comprehensively investigated using a batch sorption technique, in situ attenuated total reflection Fourier-transform infrared (ATR FT-IR) spectroscopy, time-resolved luminescence spectroscopy (TRLS), and surface complexation modeling (SCM). The batch sorption studies on silica gel (10 g/L) in the pH range 2.5 to 5 showed no significant increase in U(VI) uptake in the presence of phosphate at equimolar concentration of 20 μM, but significant increase in U(VI) uptake was observed for higher phosphate concentrations. In situ infrared and luminescence spectroscopic studies evidence the formation of two binary U(VI) surface species in the absence of phosphate, whereas after prolonged sorption in the presence of phosphate, the formation of a surface precipitate, most likely an autunite-like phase, is strongly suggested. From SCM, excellent fitting results were obtained exclusively considering two binary uranyl surface species and the formation of a solid uranyl phosphate phase. Ternary surface complexes were not needed to explain the data. The results of this study indicate that the sorption of U(VI) on SiO2 in the presence of inorganic phosphate initially involves binary surface-sorption species and evolves toward surface precipitation.

  10. Bio-precipitation of uranium by two bacterial isolates recovered from extreme environments as estimated by potentiometric titration, TEM and X-ray absorption spectroscopic analyses

    Energy Technology Data Exchange (ETDEWEB)

    Merroun, Mohamed L., E-mail: merroun@ugr.es [Institute of Radiochemistry, Helmholtz Centre Dresden-Rossendorf, Dresden (Germany); Departamento de Microbiologia, Universidad de Granada, Campus Fuentenueva s/n 18071, Granada (Spain); Nedelkova, Marta [Institute of Radiochemistry, Helmholtz Centre Dresden-Rossendorf, Dresden (Germany); Ojeda, Jesus J. [Cell-Mineral Interface Research Programme, Kroto Research Institute, University of Sheffield, Broad Lane, Sheffield S3 7HQ (United Kingdom); Experimental Techniques Centre, Brunel University, Uxbridge, Middlesex UB8 3PH (United Kingdom); Reitz, Thomas [Institute of Radiochemistry, Helmholtz Centre Dresden-Rossendorf, Dresden (Germany); Fernandez, Margarita Lopez; Arias, Jose M. [Departamento de Microbiologia, Universidad de Granada, Campus Fuentenueva s/n 18071, Granada (Spain); Romero-Gonzalez, Maria [Cell-Mineral Interface Research Programme, Kroto Research Institute, University of Sheffield, Broad Lane, Sheffield S3 7HQ (United Kingdom); Selenska-Pobell, Sonja [Institute of Radiochemistry, Helmholtz Centre Dresden-Rossendorf, Dresden (Germany)

    2011-12-15

    Highlights: Black-Right-Pointing-Pointer Precipitation of uranium as U phosphates by natural bacterial isolates. Black-Right-Pointing-Pointer The uranium biomineralization involves the activity of acidic phosphatase. Black-Right-Pointing-Pointer Uranium bioremediation could be achieved via the biomineralization of U(VI) in phosphate minerals. - Abstract: This work describes the mechanisms of uranium biomineralization at acidic conditions by Bacillus sphaericus JG-7B and Sphingomonas sp. S15-S1 both recovered from extreme environments. The U-bacterial interaction experiments were performed at low pH values (2.0-4.5) where the uranium aqueous speciation is dominated by highly mobile uranyl ions. X-ray absorption spectroscopy (XAS) showed that the cells of the studied strains precipitated uranium at pH 3.0 and 4.5 as a uranium phosphate mineral phase belonging to the meta-autunite group. Transmission electron microscopic (TEM) analyses showed strain-specific localization of the uranium precipitates. In the case of B. sphaericus JG-7B, the U(VI) precipitate was bound to the cell wall. Whereas for Sphingomonas sp. S15-S1, the U(VI) precipitates were observed both on the cell surface and intracellularly. The observed U(VI) biomineralization was associated with the activity of indigenous acid phosphatase detected at these pH values in the absence of an organic phosphate substrate. The biomineralization of uranium was not observed at pH 2.0, and U(VI) formed complexes with organophosphate ligands from the cells. This study increases the number of bacterial strains that have been demonstrated to precipitate uranium phosphates at acidic conditions via the activity of acid phosphatase.

  11. Persistent U(IV) and U(VI) following in-situ recovery (ISR) mining of a sandstone uranium deposit, Wyoming, USA

    Science.gov (United States)

    Gallegos, Tanya J.; Campbell, Kate M.; Zielinski, Robert A.; Reimus, P.W.; J.T. Clay,; N. Janot,; J. J. Bargar,; Benzel, William M.

    2015-01-01

    Drill-core samples from a sandstone-hosted uranium (U) deposit in Wyoming were characterized to determine the abundance and distribution of uranium following in-situ recovery (ISR) mining with oxygen- and carbon dioxide-enriched water. Concentrations of uranium, collected from ten depth intervals, ranged from 5 to 1920 ppm. A composite sample contained 750 ppm uranium with an average oxidation state of 54% U(VI) and 46% U(IV). Scanning electron microscopy (SEM) indicated rare high uranium (∼1000 ppm U) in spatial association with P/Ca and Si/O attributed to relict uranium minerals, possibly coffinite, uraninite, and autunite, trapped within low permeability layers bypassed during ISR mining. Fission track analysis revealed lower but still elevated concentrations of U in the clay/silica matrix and organic matter (several 10 s ppm) and yet higher concentrations associated with Fe-rich/S-poor sites, likely iron oxides, on altered chlorite or euhedral pyrite surfaces (but not on framboidal pyrite). Organic C (<1.62%), total S (<0.31%), and P (<0.03%) were in low abundance relative to the overall bulk composition. Microbial community analysis showed a diverse group of bacteria present with a wide range of putative metabolisms, and provides evidence for a variety of redox microenvironments co-existing in core samples. Although the uranium minerals persisting in low permeability areas in association with organic carbon were less affected by oxidizing solutions during mining, the likely sequestration of uranium within labile iron oxides following mining and sensitivity to changes in redox conditions requires careful attention during groundwater restoration.

  12. Decrease of U(VI immobilization capability of the facultative anaerobic strain Paenibacillus sp. JG-TB8 under anoxic conditions due to strongly reduced phosphatase activity.

    Directory of Open Access Journals (Sweden)

    Thomas Reitz

    Full Text Available Interactions of a facultative anaerobic bacterial isolate named Paenibacillus sp. JG-TB8 with U(VI were studied under oxic and anoxic conditions in order to assess the influence of the oxygen-dependent cell metabolism on microbial uranium mobilization and immobilization. We demonstrated that aerobically and anaerobically grown cells of Paenibacillus sp. JG-TB8 accumulate uranium from aqueous solutions under acidic conditions (pH 2 to 6, under oxic and anoxic conditions. A combination of spectroscopic and microscopic methods revealed that the speciation of U(VI associated with the cells of the strain depend on the pH as well as on the aeration conditions. At pH 2 and pH 3, uranium was exclusively bound by organic phosphate groups provided by cellular components, independently on the aeration conditions. At higher pH values, a part (pH 4.5 or the total amount (pH 6 of the dissolved uranium was precipitated under oxic conditions in a meta-autunite-like uranyl phosphate mineral phase without supplying an additional organic phosphate substrate. In contrast to that, under anoxic conditions no mineral formation was observed at pH 4.5 and pH 6, which was clearly assigned to decreased orthophosphate release by the cells. This in turn was caused by a suppression of the indigenous phosphatase activity of the strain. The results demonstrate that changes in the metabolism of facultative anaerobic microorganisms caused by the presence or absence of oxygen can decisively influence U(VI biomineralization.

  13. The chemical evolution and paragenesis of uranium minerals from the ruggles and palermo granitic pegmatites, New Hampshire

    Science.gov (United States)

    Korzeb, S.L.; Foord, E.E.; Lichte, F.E.

    1997-01-01

    A study of the chemical evolution and paragenesis of the uranium minerals at the Palermo No. 1 and Ruggles granitic pegmatites, Grafton County, New Hampshire, revealed four stages of secondary mineralization. A total of eight uranium minerals were identified in the four stages. The first stage is a mixture of uranyl oxide hydroxide-hydrates represented by mineral "A", which surrounds and replaces a uraninite core. The second stage is a carbonate stage found only at the Palermo No. 1 pegmatite, and is represented by rutherfordine. The third stage is represented by uranyl silicates. At the Palermo No. 1 pegmatite, this stage consists of ??-uranophane, and at the Ruggles pegmatite, it consists of soddyite and ??-uranophane. A final fourth stage is a phosphate stage represented by phosphuranylite and meta-autunite I. The first three stages of mineralization developed from hydrothermal and meteoric processes. With dropping temperatures, hydrothermal fluids reached meteoric temperatures and acquired the characteristics of meteoric water. The pH shifted from acidic (pH less than about 6 at 100??C) to alkaline (pH > 7 at 25??C). Since mineral "A" contains hydroxyl and a low amount of molecular water, it probably formed at a temperature greater than 100??C in the acidic environment. After the first stage, the hydrothermal fluids likely reached the temperatures of meteoric water. The initial pH of the meteoric water was acidic (pH less than about 6 at 25??C) and then slowly shifted to alkaline. The mineralizing fluids became oversaturated in CO3, Ca, K, and Si. Uraninite and mineral "A" became unstable and were replaced by rutherfordine and uranyl silicates. The fourth or phosphate stage developed from the introduction of groundwater. The uranyl phosphate minerals precipitated from an acidic fluid (pH < 7 at 25??C) that was oversaturated with Ca, K, U, and P.

  14. Microbial diversity in opalinus clay and interaction of dominant microbial strains with actinides

    Energy Technology Data Exchange (ETDEWEB)

    Moll, Henry; Luetke, Laura; Bachvarova, Velina; Steudtner, Robin; Geissler, Andrea; Krawczyk-Baersch, Evelyn; Selenska-Pobell, Sonja; Bernhardt, Gert

    2013-07-01

    For the first time microbial tDNA could be isolated from 50 g unperturbed Mont Terri Opalinus Clay. Based on the analysis of the tDNA the bacterial diversity of the unperturbed clay is dominated by representatives of Firmicutes, Betaproteobacteria, and Bacteriodetes. Firmicutes also dominate after treatment of the clay with R2A medium. Bacteria isolated from Mont Terri Opalinus Clay on R2A medium were related to Sporomusa spp., Paenibacillus spp., and Clostridium spp. All further investigations are concentrated on the unique isolates Sporomusa sp. MT-2 and Paenibacillus sp. MT-2. Cells of the type Sporomusa sp. MT-2 and Paenibacillus sp. MT-2 were comprehensively analyzed in terms of growing, morphology, functional groups of the cell envelope, and cell membrane structure. Strong actinide(An)/lanthanide(Ln)-interactions with the Opalinus Clay isolates and the Aespoe-strain Pseudomonas fluorescens (CCUG 32456) could be determined within a broad pH range (2-8). The metals bind as a function of pH on protonated phosphoryl, carboxyl and deprotonated phosphoryl sites of the respective cell membrane. The thermodynamic surface complexation constants of bacterial An/Ln-species were determined and can be used in modeling programs. Depending on the used An different interaction mechanisms were found (U(VI): biosorption, partly biomineralisation; Cm(III): biosorption, indications for embedded Cm(III); Pu: biosorption, bioreduction and indications for embedded Pu). Different strategies of coping with U(VI) were observed comparing P. fluorescens planktonic cells and biofilms under the chosen experimental conditions. An enhanced capability of the biofilm to form meta-autunite in comparison to the planktonic cells was proven. Conclusively, the P. fluorescens biofilm is more efficient in U(VI) detoxification. In conclusion, Mont Terri Opalinus Clay contains bacterial communities, that may influence the speciation and hence the migration behavior of selected An/Ln under

  15. Uranium Occurrences and Its Mineral Combination Characteristics in Uranium Deposit No.302%302铀矿床矿石中铀的存在形式及矿物组合特征

    Institute of Scientific and Technical Information of China (English)

    赵奇峰; 夏菲; 潘家永; 陈黎明; 林坤

    2015-01-01

    Electronic probe analysis indicated that uranium in uranium deposit No.302 mainly existed as independent uranium minerals and minors occurred as isomorphism of thorium in zircon and rutile and other accessory minerals.The independent uranium ore minearal mainly as pitchblende,some as coffinG ite,uranothorite, brannerite and the second uranium minerals of uranophane, autunite, chalcolite. The ore consist of five kind mineral combination,the diversity of uranium ore mineral combination reG flects the long term and complex activity of hydrothermal fluid in the deposit,which also indicate the multiphases and variety of fluid composition and forming environment in hydrothermal activity. Alteration related with uranium mineralization are siliconization,hematization,purple black fluoritizaG tion,pyritization,calcitization,sericitization and chloritization,etc.%电子探针分析显示,302铀矿床矿石中铀的存在形式以独立铀矿物为主,少量呈类质同像赋存于钍石、锆石及金红石等副矿物之中。独立铀矿物以沥青铀矿为主,其次有铀石、铀钍石、钛铀矿等原生铀矿物和硅钙铀矿、钙铀云母、铜铀云母等次生铀矿物。铀矿石具有5种不同的矿物组合,这种矿物组合的多样性,反映了该矿床热液流体活动的长期性和复杂性,即成矿热液流体作用具有多阶段性,以及热液流体组成和成矿环境的多变性。与铀矿化相关的蚀变有硅化、赤铁矿化、紫黑色萤石化、黄铁矿化、方解石化、绢云母化及绿泥石化等。

  16. Biosorption and Biomineralization of U(VI by the marine bacterium Idiomarina loihiensis MAH1: effect of background electrolyte and pH.

    Directory of Open Access Journals (Sweden)

    Fernando Morcillo

    Full Text Available The main goal of this study is to compare the effects of pH, uranium concentration, and background electrolyte (seawater and NaClO4 solution on the speciation of uranium(VI associated with the marine bacterium Idiomarina loihiensis MAH1. This was done at the molecular level using a multidisciplinary approach combining X-ray Absorption Spectroscopy (XAS, Time-Resolved Laser-Induced Fluorescence Spectroscopy (TRLFS, and High Resolution Transmission Electron Microscopy (HRTEM. We showed that the U(VI/bacterium interaction mechanism is highly dependent upon pH but also the nature of the used background electrolyte played a role. At neutral conditions and a U concentration ranging from 5·10(-4 to 10(-5 M (environmentally relevant concentrations, XAS analysis revealed that uranyl phosphate mineral phases, structurally resembling meta-autunite [Ca(UO22(PO42 2-6H2O] are precipitated at the cell surfaces of the strain MAH1. The formation of this mineral phase is independent of the background solution but U(VI luminescence lifetime analyses demonstrated that the U(VI speciation in seawater samples is more intricate, i.e., different complexes were formed under natural conditions. At acidic conditions, pH 2, 3 and 4.3 ([U] = 5·10(-4 M, background electrolyte  = 0.1 M NaClO4, the removal of U from solution was due to biosorption to Extracellular Polysaccharides (EPS and cell wall components as evident from TEM analysis. The LIII-edge XAS and TRLFS studies showed that the biosorption process observed is dependent of pH. The bacterial cell forms a complex with U through organic phosphate groups at pH 2 and via phosphate and carboxyl groups at pH 3 and 4.3, respectively. The differences in the complexes formed between uranium and bacteria on seawater compared to NaClO4 solution demonstrates that the actinide/microbe interactions are influenced by the three studied factors, i.e., the pH, the uranium concentration and the chemical composition of the

  17. Geochemical modelling of the weathering zone of the 'Mina Fe' U deposit (Spain): A natural analogue for nuclear spent fuel alteration and stability processes in radwaste disposal

    Energy Technology Data Exchange (ETDEWEB)

    Arcos, D. [AMPHOS XXI Consulting S.L., Passeig de Rubi, 29-31, 08197 Valldoreix, Barcelona (Spain)], E-mail: david.arcos@amphos21.com; Perez del Villar, L. [CIEMAT, Dpto.de Medio Ambiente, Avda, Complutense 22, 28040 Madrid (Spain); Bruno, J.; Domenech, C. [AMPHOS XXI Consulting S.L., Passeig de Rubi, 29-31, 08197 Valldoreix, Barcelona (Spain)

    2008-04-15

    The 'Mina Fe' U deposit (Salamanca, Spain) has been studied in the context of Enresa's programme for U-mine sites restoration and also as a natural analogue for processes in high-level nuclear waste (HLNW) geological disposal. The investigations encompassed an array of geoscience disciplines, such as structural geology, mineralogy, hydrogeology and elemental and isotopic geochemistry and hydrogeochemistry of the site. Based on the obtained results, a conceptual mineralogical and geochemical model was performed integrating the main geochemical processes occurring at the site: the interaction between oxidised and slightly acidic water with pyrite, pitchblende, calcite and dolomite, as essential minerals of the U fracture-filling mineralisation, and hydroxyapatite from the host rock, as the main source of P. This conceptual model has been tested in a systematic numerical model, which includes the main kinetic (pyrite and pitchblende dissolution) and equilibrium processes (carbonate mineral dissolution, and goethite, schoepite and autunite secondary precipitation). The results obtained from the reactive-transport model satisfactorily agree with the conceptual model previously established. The assumption of the precipitation of coffinite as a secondary mineral in the system cannot be correctly evaluated due to the lack of hydrochemical data from the reducing zone of the site and valid thermodynamic and kinetic data for this hydrated U(IV)-silicate. This precipitation can also be hampered by the probable existence of dissolved U(IV)-organic matter and/or uranyl carbonate complexes, which are thermodynamically stable under the alkaline and reducing conditions that prevail in the reducing zone of the system. Finally, the intense downwards oxic and acidic alteration in the upper part of the system is of no relevance for the performance assessment of a HLNW disposal. However, the acidic and oxidised conditions are quickly buffered to neutral-alkaline and

  18. Mineralogy and radioactivity of pegmatites from South Wadi Khuda area, Eastern Desert, Egypt

    Institute of Scientific and Technical Information of China (English)

    Mohamed F.Raslan; Mohamed A.Ali; Mohamed G.El-Feky

    2010-01-01

    Radioactive minerals in pegmatites associated with granitic rocks are commonly encountered in the south of the Wadi Khuda area and found as dyke-like and small bodies. They are observed within garnet-muscovite granites near the contact with older granitoids. Field surveys indicated that the studied pegmatites vary in dimensions ranging from 2 to 10 m in width and from 10 to 500 m in length. They are composed mainly of intergrowth of milky quartz, reddish-pink K-feldspar and plagioclase together with small pockets of muscovite. Field radiometric measurements indicated that radioactivity in pegmatites is more than twice that of their enclosing country rocks. Radionuclide measurements revealed that the average contents of U and Th increase gradually from rocks of dioritic to granodioritic composition (1.5×10-6 U and 4.3×10-6 Th) and increase significantly in biotite granites (5.8×10-6 U and 15.2×10-6 Th) but drastically decrease in muscovite granites (2.2×10-6 U and 5.6×10-6 Th). The average contents of U and Th of anomalous pegmatites are 95.3×10-6 and 116.9×10-6, respectively, indicating their uraniferous nature. In the south of the Wadi Khuda area, pegmatites are low in average Th/U (1.4) and high in average U/K (35.6), which suggests that uranium concentrating processes did not affect the pegmatites, indicating poor source-rocks. Mineralogical investigations of the studied pegmatites revealed the presence of secondary uranium minerals (kasolite and autunite), in addition to zircon, thorite, apatite, garnet and biotite. Primary and secondary radioactive mineralizations indicated that the mineralization is not only magmatic, but also post-magmatic. Electron microprobe analyses showed distinct cryptic chemical zoning within thorite where UO2 decreases from core to rim. This feature in thorite is sporadic, suggesting non-uniform redistributions of UO2 within thorite during magmatic processes.

  19. An investigation of the interactions of Eu³⁺ and Am³⁺ with uranyl minerals: implications for the storage of spent nuclear fuel.

    Science.gov (United States)

    Biswas, Saptarshi; Steudtner, Robin; Schmidt, Moritz; McKenna, Cora; León Vintró, Luis; Twamley, Brendan; Baker, Robert J

    2016-04-21

    The reaction of a number of uranyl minerals of the (oxy)hydroxide, phosphate and carbonate types with Eu(iii), as a surrogate for Am(iii), have been investigated. A photoluminescence study shows that Eu(iii) can interact with the uranyl minerals Ca[(UO2)6(O)4(OH)6]·8H2O (becquerelite) and A[UO2(CO3)3]·xH2O (A/x = K3Na/1, grimselite; CaNa2/6, andersonite; and Ca2/11, liebigite). For the minerals [(UO2)8(O)2(OH)12]·12H2O (schoepite), K2[(UO2)6(O)4(OH)6]·7H2O (compreignacite), A[(UO2)2(PO4)2]·8H2O (A = Ca, meta-autunite; Cu, meta-torbernite) and Cu[(UO2)2(SiO3OH)2]·6H2O (cuprosklodowskite) no Eu(iii) emission was observed, indicating no incorporation into, or sorption onto the structure. In the examples with Eu(3+) incorporation, sensitized emission is seen and the lifetimes, hydration numbers and quantum yields have been determined. Time Resolved Laser Induced Fluroescence Spectroscpoy (TRLFS) at 10 K have also been measured and the resolution enhancements at these temperatures allow further information to be derived on the sites of Eu(iii) incorporation. Infrared and Raman spectra are recorded, and SEM analysis show significant morphology changes and the substitution of particularly Ca(2+) by Eu(3+) ions. Therefore, Eu(3+) can substitute Ca(2+) in the interlayers of becquerelite and liebigite and in the structure of andersonite, whilst in grimselite only sodium is exchanged. These results have guided an investigation into the reactions with (241)Am on a tracer scale and results from gamma-spectrometry show that becquerelite, andersonite, grimselite, liebigite and compreignacite can include americium in the structure. Shifts in the U[double bond, length as m-dash]O and C-O Raman active bands are similar to that observed in the Eu(iii) analogues and Am(iii) photoluminescence measurements are also reported on these phases; the Am(3+) ion quenches the emission from the uranyl ion.

  20. Effect of Phosphate on U(VI) Sorption to Montmorillonite: Ternary Complexation and Precipitation Barriers

    Energy Technology Data Exchange (ETDEWEB)

    Troyer, Lyndsay D.; Maillot, Fabien; Wang, Zheming; Wang, Zimeng; Mehta, Vrajesh; Giammar, Daniel; Catalano, Jeffrey G.

    2016-02-15

    Phosphate addition is a potential treatment method to lower the solubility of U(VI) in soil and groundwater systems by causing U(VI) phosphate precipitation as well as enhancing adsorption. Previous work has shown that iron oxide surfaces may facilitate the nucleation of U(VI) phosphate minerals and, that under weakly acidic conditions, phosphate also enhances U(VI) adsorption to such phases. Like iron oxides, clays are important reactive phases in the subsurface but little is known about the interaction of U(VI) and phosphate with these minerals. The effect of aqueous phosphate on U(VI) binding to Wyoming montmorillonite (SWy-2) in air-equilibrated systems was investigated. Equilibrium U(VI) uptake to montmorillonite was determined at pH 4, 6 and 8 at discrete initial phosphate concentrations between 0 and 100 μM. The observed behavior of U(VI) indicates a transition from adsorption to precipitation with increasing total uranium and phosphate concentrations at all pH values. At the highest phosphate concentration examined at each pH value, a barrier to U(VI) phosphate nucleation is observed. At lower concentrations, phosphate has no effect on macroscopic U(VI) adsorption. To assess the mechanisms of U(VI)-phosphate interactions on smectite surfaces, U(VI) speciation was investigated under selected conditions using laser-induced fluorescence spectroscopy (LIFS) and extended X-ray absorption fine-structure (EXAFS) spectroscopy. Samples above the precipitation threshold display EXAFS and LIFS spectral signatures consistent with the autunite family of U(VI) phosphate minerals. However, at lower U(VI) concentrations, changes in LIFS spectra upon phosphate addition suggest that U(VI)-phosphate ternary surface complexes form on the montmorillonite surface at pH 4 and 6 despite the lack of a macroscopic effect on adsorption. The speciation of solid-associated U(VI) below the precipitation threshold at pH 8 is dominated by U(VI)-carbonate surface complexes. This work

  1. Effect of phosphate on U(VI) sorption to montmorillonite: Ternary complexation and precipitation barriers

    Science.gov (United States)

    Troyer, Lyndsay D.; Maillot, Fabien; Wang, Zheming; Wang, Zimeng; Mehta, Vrajesh S.; Giammar, Daniel E.; Catalano, Jeffrey G.

    2016-02-01

    Phosphate addition is a potential treatment method to lower the solubility of U(VI) in soil and groundwater systems by causing U(VI) phosphate precipitation as well as enhancing adsorption. Previous work has shown that iron oxide surfaces may facilitate the nucleation of U(VI) phosphate minerals and, that under weakly acidic conditions, phosphate also enhances U(VI) adsorption to such phases. Like iron oxides, clays are important reactive phases in the subsurface but little is known about the interaction of U(VI) and phosphate with these minerals. The effect of aqueous phosphate on U(VI) binding to Wyoming montmorillonite (SWy-2) in air-equilibrated systems was investigated. Equilibrium U(VI) uptake to montmorillonite was determined at pH 4, 6 and 8 at discrete initial phosphate concentrations between 0 and 100 μM. The observed behavior of U(VI) indicates a transition from adsorption to precipitation with increasing total uranium and phosphate concentrations at all pH values. At the highest phosphate concentration examined at each pH value, a barrier to U(VI) phosphate nucleation is observed. At lower concentrations, phosphate has no effect on macroscopic U(VI) adsorption. To assess the mechanisms of U(VI)-phosphate interactions on smectite surfaces, U(VI) speciation was investigated under selected conditions using laser-induced fluorescence spectroscopy (LIFS) and extended X-ray absorption fine-structure (EXAFS) spectroscopy. Samples above the precipitation threshold display EXAFS and LIFS spectral signatures consistent with the autunite family of U(VI) phosphate minerals. However, at lower U(VI) concentrations, changes in LIFS spectra upon phosphate addition suggest that U(VI)-phosphate ternary surface complexes form on the montmorillonite surface at pH 4 and 6 despite the lack of a macroscopic effect on adsorption. The speciation of solid-associated U(VI) below the precipitation threshold at pH 8 is dominated by U(VI)-carbonate surface complexes. This work

  2. Long-term performance of elemental iron and hydroxyapatite for uranium retention in permeable reactive barriers used for groundwater remediation; Langzeitverhalten von elementarem Eisen und Hydroxylapatit zur Uranrueckhaltung in permeablen reaktiven Waenden bei der Grundwassersanierung

    Energy Technology Data Exchange (ETDEWEB)

    Biermann, V.

    2007-11-21

    from HAP surfaces. The uranium phases chernikovite and meta-ankoleite of the autunite group were identified by x-ray diffraction. The existence of these mineral phases proves that surface precipitation also occurs under favourable conditions. No uranium mineral phases could be identified in spent Fe{sup 0} column material. But image analysis (ESEM / EDX) indicates formation of a mixed U(IV)/U(VI) oxide. While HAP long-term performance depends mainly on sorption capacity, maintaining hydraulic conductivity is crucial for Fe{sup 0}. In both cases water compositon has a great influence as well. (orig.)

  3. Final Report: Dominant Mechanisms of Uranium-Phosphate Reactions in Subsurface Sediments

    Energy Technology Data Exchange (ETDEWEB)

    Catalano, Jeffrey G. [Washington Univ., St. Louis, MO (United States); Giammar, Daniel E. [Washington Univ., St. Louis, MO (United States); Wang, Zheming [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2016-03-08

    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 of 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

  4. Uranium-bearing lignite and its relation to the White River and Arikaree formations in northwestern South Dakota and adjacent states

    Science.gov (United States)

    Denson, N.M.; Bachman, G.O.; Zeller, H.D.

    1954-01-01

    In northwestern South Dakota and adjacent areas uranium-bearing lignite beds occur at many horizons in the Hell Creek formation of late Cretaceous age and the overlying Ludlow, Tongue River, and Sentinel Butte members of the Fort Union formation of Paleocene age. Uranium analyses of 275 surface and auger samples and about 1,000 core samples show that many of the lignite beds contain 0. 005 to 0. 02 percent uranium with concentrations of 0. 05 to 0.10 percent uranium in the lignite ash. Analytical data indicate that the region contains an aggregate of at least 47,500, 000 tons of lignite with an average grade of slightly more than .0. 008 percent containing 3, 900 tons of uranium. Almost a fifth of the estimated reserves are adapted to strip mining and are in beds averaging about 4 feet in thickness. Uranium concentrations of this magnitude in lignite indicate that these deposits upon the development of proper utilization techniques and processes may be an important future source of uranium. Recent discoveries of ore-grade deposits of autunite-bearing lignite and secondary uranium minerals in carbonaceous sandstone at Cave Hills and Slim Buttes indicate that northwestern South Dakota and adjacent areas may containimportant reserves of uranium-ore. The stratigraphic units containing the uraniferous lignite beds have a combined thickness of about 1, 500 feet and are unconformably overlapped by 300 feet or more of tuffaceous sandstone and bentonitic claystone of the White River and Arikaree formations of Oligocene and Miocene age. The stratigraphically highest lignite beds in the local sequence have the greatest concentration of uranium,, and the uranium content is greatest at the top of thick lignite beds, diminishing progressively downward to a vanishing point in their lower parts. Variations in permeability of the rock overlying the mineralized lignite beds seem to be reflected in the intensity of uranium mineralization. Most of the known uranium-bearing lignite

  5. Spatial distribution of environmental risk associated to a uranium abandoned mine (Central Portugal)

    Science.gov (United States)

    Antunes, I. M.; Ribeiro, A. F.

    2012-04-01

    The abandoned uranium mine of Canto do Lagar is located at Arcozelo da Serra, central Portugal. The mine was exploited in an open pit and produced about 12430Kg of uranium oxide (U3O8), between 1987 and 1988. The dominant geological unit is the porphyritic coarse-grained two-mica granite, with biotite>muscovite. The uranium deposit consists of two gaps crushing, parallel to the coarse-grained porphyritic granite, with average direction N30°E, silicified, sericitized and reddish jasperized, with a width of approximately 10 meters. These gaps are accompanied by two thin veins of white quartz, 70°-80° WNW, ferruginous and jasperized with chalcedony, red jasper and opal. These veins are about 6 meters away from each other. They contain secondary U-phosphates phases such as autunite and torbernite. Rejected materials (1000000ton) were deposited on two dumps and a lake was formed in the open pit. To assess the environmental risk of the abandoned uranium mine of Canto do Lagar, were collected and analysed 70 samples on stream sediments, soils and mine tailings materials. The relation between samples composition were tested using the Principal Components Analysis (PCA) (multivariate analysis) and spatial distribution using Kriging Indicator. The spatial distribution of stream sediments shows that the probability of expression for principal component 1 (explaining Y, Zr, Nb, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Hf, Th and U contents), decreases along SE-NW direction. This component is explained by the samples located inside mine influence. The probability of expression for principal component 2 (explaining Be, Na, Al, Si, P, K, Ca, Ti, Mn, Fe, Co, Ni, Cu, As, Rb, Sr, Mo, Cs, Ba, Tl and Bi contents), increases to middle stream line. This component is explained by the samples located outside mine influence. The spatial distribution of soils, shows that the probability of expression for principal component 1 (explaining Mg, P, Ca, Ge, Sr, Y, Zr, La, Ce, Pr

  6. Sorption/desorption processes of uranium in clayey samples of the Bangombe natural reactor zone, Gabon

    Energy Technology Data Exchange (ETDEWEB)

    Nero, M. del [Inst. de Recherches Subatomiques, CNRS/IN2P3, Strasbourg (France); Salah, S.; Clement, A.; Gauthier-Lafaye, F. [Centre de Geochimie de la Surface, CNRS, Strasbourg (France); Miura, T. [National Lab. for High Energy Physics, Tsukuba-Shi Ibaraki-Ken (Japan)

    1999-07-01

    Experimental studies have been undertaken in order to provide new insights into the relative efficiency of the different mineral phases and sorption processes for the control of U retention in the weathered zones surrounding the natural nuclear reactor at Bangombe (Oklo, Gabon). Clayey and Fe-oxihydroxides rich samples from the oxidizing weathered zones located above the reactor were examined. An experimental study of uranium adsorption/desorption processes in these samples was carried out using a uranium isotope exchange technique in order to estimate the proportion of uranium adsorbed on mineral surfaces. A sequential extraction technique was used to identify the major U-containing minerals in the samples. In the U-rich iron crust rocks close to the reactor, the fraction of total uranium adsorbed at mineral surfaces is small. Extraction experiments reveal that a large part of uranium is associated to Fe-oxihydroxides, to minor P-rich phases, and presumably to Mn-oxihydroxides. A possible mechanism for U retention is an incorporation into the structure of iron oxihydroxides and/or of ferric phosphates occurring as surface precipitates on Fe-oxihydroxides. Traces of autunite-like mineral are also present in the zone. For the clayey samples in the weathering profile, it may be inferred that several processes and minerals contribute significantly to U retention: adsorption processes occurring mainly at clay surfaces, association with traces of Mn-containing carboantes and iron oxihydroxides. A significant proportion of total U is adsorbed at mineral surfaces and is thereby easily accessible to weathering solutions. In a second part of this work, {sup 233}U sorption data obtained on a Fe- and Mn-poor illitic Bangombe sample were modeled using a surface complexation modeling approach. As a first approximation, it was assumed in modeling that uranyl binding occurs at aluminol edge sites of the illite component. The binding constant required for modeling was firstly

  7. Alteration of coffinite under reducing and oxidizing conditions

    Science.gov (United States)

    Deditius, Artur P.; Utsunomiya, Satoshi; Pointeau, Veronique; Ewing, Rodney C.

    2010-05-01

    Coffinite, USiO4, is a one of the two naturally occurring actinide silicates (second is thorite, ThSiO4) studied to elucidate the alteration of spent nuclear fuel (SNF) under reducing conditions in a Si-rich environment. In order to understand the stability of coffinite under different redox condition in natural systems, we have investigated coffinite the Grants Uranium Belt, New Mexico, USA (reducing and oxidizing conditions) utilizing a variety of electron microbeam techniques. Fine-grained coffinite (≤10 μm) from Woodrow Mine coexists with carbonate-fluorapatite (CFAp) and (Ca,Sr)-(meta)autunite (M-Aut). It precipitated under reducing conditions replacing CFAp, pyrite and aluminosilicates. Electron-microprobe analyses (EMPA) of coffinite indicate limited incorporation of P2O5 and CaO, below 2.7 and 3.0 wt.%, respectively, into the coffinite structure during replacement of CFAp. The chemical formula of coffinite is (U0.95±0.09Ca0.15±0.02)Σ1.10±0.1(Si0.84±0.08P0.06±0.02)Σ0.90±0.08. Analysis by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) revealed that coffinite initially formed as crystals as large as 100 nm at the edges of altered CFAp. Subsequently, infiltration of (Na,Ba,Sr)-rich oxidizing fluids into fractures resulted in precipitation of Sr-rich M-Aut (up to 4 wt.% of SrO) at the expense of coffinite and CFAp. High-resolution TEM reveals that Na-rich fluids caused a distortion of the ideal coffinite structure and stabilized amorphous domains that formed due to alpha-decay event radiation damage. Subsequently, the Na-enriched amorphous areas of coffinite were preferentially altered, and secondary porosity formed at the scale of ~1 μm. Porosity also was formed during alteration of CFAp to M-Aut, which facilitated the migration of oxidizing fluids over distances of ~150 μm into CFAp, as evidenced by precipitation of M-Aut. These results show that micro-scale dissolution of apatite can create conditions

  8. Huréaulita, Mn+2(5(H2O4[PO3(OH]2[PO4]2, de diferentes yacimientos del distrito pegmatítico Totoral, San Luis Hureaulite, Mn+2(5(H2O4[PO3(OH]2[PO4]2, from different deposits of the Totoral pegmatitic field, San Luis

    Directory of Open Access Journals (Sweden)

    J. Oyarzábal

    2007-06-01

    associated with ferrisicklerite, purpurite, phosphosiderite, strengite, reddingite, meta-autunite, eosphorite, vivianite and hydroxil-apatite and has been formed by hydrothermal reworking of triphylite; the crystals are 5 mm in length and show typical monoclinic forms. In San Luis II, a lithium-bearing pegmatite located in the Paso del Rey group, huréaulite has been found as short prismatic crystals or thin coating layers intergrowed between fibrous dufrénite, in association with ferrisicklerite, bermanite and carbonate-fluorapatite and formed by extreme hydrothermal alteration of primary lithiophilite. The huréaulite from these different occurrences shows similar physical and optical properties, but different degrees of Fe-Mg-Ca octahedrical substitutions, according with the secondary phosphate minerals that form the assemblages.