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Sample records for autunite

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

    OpenAIRE

    Zheng, Zuoping; Wan, Jiamin; Tokunaga, Tetsu K.

    2004-01-01

    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 sodium meta-autunite colloids, and characterized their morphology, chemical composition, structure, ...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  5. Dissolution Kinetics of Synthetic and Natural Meta-Autunite Minerals, X3-n(n)+ [(UO2)(PO4)]2 · xH2O, Under Acidic Conditions

    International Nuclear Information System (INIS)

    Mass transport within the uranium geochemical cycle is impacted by the availability of phosphorus. In oxidizing environments, in which the uranyl ionic species is typically mobile, formation of sparingly soluble uranyl phosphate minerals exert a strong influence on uranium transport. Autunite group minerals have been identified as the long-term uranium controlling phases in many systems of geochemical interest. Anthropogenic operations related to uranium mining operations have created acidic environments, exposing uranyl phosphate minerals to low pH groundwater. Investigations regarding the dissolution behavior of autunite group minerals under acidic conditions have not been reported; consequently, knowledge of the longevity of uranium controlling solids is incomplete. The purpose of this investigation was to: (1) quantify the dissolution kinetics of natural calcium and synthetic sodium meta-autunite, under acidic conditions, (2) measure the effect of temperature and pH on meta-autunite mineral dissolution, and (3) investigate the formation of secondary uranyl phosphate phases as long-term controls on uranium migration. Single-pass flow-through (SPFT) dissolution tests were conducted over the pH range of 2 to 5 and from 5 to 70 C. Results presented here illustrate meta-autunite dissolution kinetics are strongly dependent on pH, but are relatively insensitive to temperature variations. In addition, the formation of secondary uranyl-phosphate phases such as, uranyl phosphate, (UO2)3(PO4)2 · x H2O, may serve as a secondary phase limiting the migration of uranium in the environment

  6. Effects of pH, temperature, and aqueous organic material on the dissolution kinetics of meta-autunite minerals, (Na, Ca)2-1[(UO2)(PO4)]2-3H2O

    International Nuclear Information System (INIS)

    Autunite minerals have been frequently identified in contaminated sediments as the long-term controlling phase of uranium. Under these conditions the mobility of uranium in subsurface pore waters is limited by the rate of dissolution of autunite and meta-autunite group minerals, [(UO2)(PO4)]2 - xH2O. Single-pass flow-through (SPFT) tests were conducted to quantify the dissolution kinetics of natural calcium meta-autunite, Ca[(UO2)2(PO4)2]2 - 3H2O, and synthetic sodium meta-autunite, Na2[(UO2)(PO4)]2 - 3H2O, as a function of pH (7 -10) and temperature (5 - 70 C) in the presence and absence of aqueous organic material. The data indicate that release of uranium and phosphorus are non-stoichiometric over the range of experimental conditions investigated. In a 0.1 M NH4OH buffer solution, acquisition of valid dissolution rate data was limited by uramphite solubility, NH4[(UO2)(PO4)]2 - xH2O. Dissolution rates obtained in a 0.01 M TRIS [tris (hydroxymethyl) aminomethane] buffered solution increased by a factor of ∼100X over the pH interval of 7 to 10 (? = 0.90-0.08), irrespective of temperature. At constant pH the rate data showed a minor increase with temperature. Data from experiments using a more concentrated 0.05 M TRIS buffer exhibited a ∼35-fold increase in rates compared to those in a 0.01 M TRIS buffer at constant temperature and pH. The difference in rate between interlayer cation (Na+ or Ca2+) and uranium release is ∼10,000 in neutral solutions; however, the difference diminishes to ∼10 at higher pH values. The combination of structural dissolution and ion exchange explain these trends in interlayer cation behavior. Data presented here illustrate the significance of pH and dissolved organic material on the dissolution of autunite minerals

  7. Discovery of uraninite in a pegmatite located in Benfica, Marica township, state of Rio de Janeiro

    International Nuclear Information System (INIS)

    The SPAR pegmatite is located in Benfica (Marica township, State of Rio de Janeiro). In this pegmatite, uraninite occurs within the quartz, feldspar and muscovite. It was found in four differents places, alwayw surrounded by secondary products. Localization, geology, feature, mineralogy and a study of radioactive minerals of the pegmatite are given. Uraninite, uranophane, autunite and meta-autunite are the uranium mineral species determined. (Author)

  8. Supporting soil remediation at Fernald by electron beam methods

    International Nuclear Information System (INIS)

    Electron beam techniques have been used to characterize uranium-contaminated soils at the Fernald Site, Ohio. The major uranium phases have been identified by analytical electron microscopy (AEM) as uranyl phosphate (autunite), uranium oxide (uraninite), and uranium phosphite [U(PO3)4]. Luminescence and X-ray absorption spectroscopy incorrectly identified uranium oxide hydrate (schoepite) as the major phase in Fernald soils. The solubilities of schoepite and autunite are very different, so a solubility-dependent remediation method selected for schoepite will not be effective for removing autunite. AEM is the only technique capable of precisely identifying unknown submicron phases. The uranium phosphite has been found predominantly at the incinerator site at Fernald. This phase has not been removed successfully by any of the chemical remediation technologies. We suggest that an alternative physical extraction procedure be applied to remove this phase

  9. Uranium occurrences in the pegmatite 'Las Cuevas', province of San Luis, Argentine Republic

    International Nuclear Information System (INIS)

    Mineral associations found in an uranium deposit of Sierras Pampeanas, San Luis, are considered in these papers. Damourite stands out among the uranium minerals related to uraninite and coffinite. Pyrite, marcasite and other sulphides are found together with apatite and gummite. Autunite is the uranium secondary mineral more abundant. A mineralization with epigenetic contribution by circulating solutions is suggested to the studied area. (Author)

  10. The nature of contaminant uranium phases at Fernald

    International Nuclear Information System (INIS)

    Uranium-contaminated soils at the Fernald Site in Ohio have been examined using transmission electron microscopy. The uranium-bearing phases were identified as calcium uranyl phosphate (meta-autunite), uranium oxide (uraninite), uranium metaphosphate [U(PO3)4], uranium calcium oxide, uranium silicate (boltwoodite), and uranium silicide. Uranium have been deposited on the soil through chemical spills and from the operation of an incinerator plant at the site. The uranium metaphosphate phase was found predominantly at an incinerator site at Fernald. Carbonate leaching in an oxygen environment has removed some of the U(IV) phases, however [U(PO3)4] has not been removed by any of the chemical remediation technologies. The identified phases have been included in geochemical modeling of the uranium, these studies show that meta-autunite is the solubility controlling phase for uranium in Fernald soils

  11. Weathering of mine wastes after historical silver mining in the Jachymov ore district (Czech Republic) and migration of uranium

    International Nuclear Information System (INIS)

    Weathering of 450 years old mine wastes after silver mining at Geister vein in the Jachymov ore district (Czech Republic) and migration of uranium were studied. Specific gamma-ray activity of 226Ra, measured by field gamma-ray spectrometry, varies from 38 Bq/kg (3 ppm eU) to 3816 Bq/kg (309 ppm eU) in the observed area. The most active material forms the top layer of the dump. The gamma-ray activity of the top layer is caused mainly by 226Ra. Uranium is leached from upper layer and accumulated in fossil soils beneath. U-micas were studied using X-ray powder diffraction and EDA. The following succession of supergene alteration was found: autunite → meta-autunite → bassetite →- oxidized bassetite. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  13. Dissolution Kinetics of Meta-Torbernite under Circum-neutral to Alkaline Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Wellman, Dawn M.; McNamara, Bruce K.; Bacon, Diana H.; Cordova, Elsa A.; Ermi, Ruby M.; Top, Laken M.

    2009-12-21

    Autunite group minerals have been identified in contaminated sediments as the long-term controlling phase of uranium. Meta-torbernite, has been identified in subsurface environments which were subjected to co-contaminant disposal practices from past nuclear weapons and fuel operations. Under these conditions the mobility of uranium in subsurface pore waters is limited by the rate of meta-torbernite dissolution; however, there are no known investigations which report the dissolution behavior of meta-torbernite. The purpose of this investigation was to conduct a series of single-pass flow-through (SPFT) tests to 1) quantify the effect of temperature (23 - 90oC) and pH (6 -10) on meta-torbernite dissolution, 2) compare the dissolution of meta-torbernite to other autunite-group minerals, and 3) evaluate the effect of aqueous phosphate on the dissolution kinetics of meta-torbernite. Results presented here illustrate meta-torbernite dissolution rates increase by ~100X over the pH interval of 6 to 10 (eta = 0.59 ± 0.07), irrespective of temperature. The power law coefficient for meta-torbernite, eta = 0.59 ± 0.07, is greater than that quantified for Ca-meta-autunite, eta = 0.42 ± 0.12. This suggests the stability of meta-torbernite is greater than that of meta-autunite, which is reflected in the predicted stability constants. The rate equation for the dissolution of meta-torbernite as a function of aqueous phosphate concentration is log rdissol (mol m-2 sec-1) = -4.7 x 10-13 + 4.1 x 10-10 [PO43-].

  14. Mineralogical Study of Workable Material Coming from Mina Fe Ciudad Rodrigo

    International Nuclear Information System (INIS)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  17. 300 Area Uranium Stabilization Through Polyphosphate Injection: Final Report

    Energy Technology Data Exchange (ETDEWEB)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    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

  19. Sedimentary uranium deposit of the Ipora/Amorinopolis region, state of Goias, Brazil

    International Nuclear Information System (INIS)

    The uranium mineralization is chiefly found within arkosic sandstones at the base of the Devonian Ponta Grossa Formation. The ore is tabular and concordant with the bedding, the controls being simultaneously litho-stratigraphical and biochemical. Narrow permeable horizons of arkosic sandstone lie between impermeable shale and siltstone layers. Within the permeable horizon, the fossil remains (probably brachiopods) are replaced by uranium minerals. The oxidized iron minerals may have acted as to insulate and preserve the secondary soluble uranium minerals. The mineral paragenesis is represented by renardite, meta - autunite I, fourmarierite, Koninckite, ranquilite, meta-uranocircite II, barite, apatite, calophane, wavelite, varscite, an unnamed uranium mineral, quartz, calcedony, goethite, lepidocrocite and hematite. (Author)

  20. Uranium-bearing phases in a U-mill disposal site in Northern Canada: Products of the interaction between leachate/raffinate and tailings material

    International Nuclear Information System (INIS)

    Highlights: ► Uranyl-phases in an U-tailings site. ► Raffinate–tailings interaction. ► U-bearing gypsum. ► Ammonium-bearing autunite and zippeite. - Abstract: The Above Ground Tailings Management Facility (AGTMF) is a licensed tailings receiving facility at the Key Lake mine site, Northern Saskatchewan, Canada. Tailings within the AGTMF were deposited between 1983 and 1995 and are derived from mining and milling of the Gaertner and Deilmann ore-bodies at Key Lake. The tailings are primarily composed of quartz, phyllosilicate and clay gangue minerals, minor amounts of Ni–Co–S-arsenides, iron oxide minerals and gypsum. They typically contain U concentrations on the order of between 50 and 300 ug/g U. A small area of the AGTMF receives occasional mill-process upset solutions with an initial pH-range of 2–6. The solutions contain elevated activities of U-bearing aqueous-species and are rapidly buffered to neutral and sub-alkaline pH values during interaction with surroundings tailings solids having a pH of approximately 10. This buffering and neutralization process results in the precipitation of gypsum and minor amounts of uranyl minerals. Phases of the autunite-group (chernikovite, (H3O)[(UO2)(PO4)](H2O)3 and troegerite, (H3O)[(UO2)(AsO4)] (H2O)3 with minor NH4+) occur predominantly in the gypsum matrix but can also occur as crusts on silicates. The occurrence of troegerite is due to elevated concentrations of As within the deposited tailings solids. Surface alteration on phyllosilicates within tailings affected by the mill process solutions results in elevated concentrations of K at the phyllosilicate–water interface, which are ideal nucleation sites for the formation of single crystals of zippeite, K3(H2O)3[(UO2)4(SO4)2O3(OH)]. Use of NH4-sulfates and ammonia in the extraction and yellow-cake precipitation cycles and subsequent entrainment of (NH4)+ species in the tailings results in the occurrence of (NH4)-bearing phases of the zippeite- and

  1. Contaminated water, stream sediments and soils close to the abandoned Pinhal do Souto uranium mine, central Portugal

    OpenAIRE

    Neiva, A. M. R.; Carvalho, P. C. S.; Antunes, I. M. H. R.; Silva, M. M. V. G.; Santos, A. C. T.; Pinto, M. M. S. Cabral; Cunha, P.P.

    2014-01-01

    The Pinhal do Souto mine exploited a quartz vein containing uranium minerals, mainly autunite and torbernite. This vein intersects a two-mica granite containing 10 ppm U and uraninite. The mine was exploited underground and produced 93091 kg U3O8 between 1978 and 1989 and was then closed down. Two dumps were left in the mine area and these are partially covered by natural vegetation. Groundwater and surface water have a similar slightly acid-to-alkaline pH. The 2  2 UO is a...

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

    OpenAIRE

    Yung, Mimi C.; Jiao, Yongqin

    2014-01-01

    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 ...

  3. Uranium occurence in California near Bucaramanga (Columbia)

    International Nuclear Information System (INIS)

    The mining district of California, Bucaramanga, is on the west side of the Cordillera Oriental in the Santander massif region. The oldest rocks of the area form a complex of metamorphites and migmatites of the predevonic age. Amphibolite various types of paragneiss and orthogneiss are represented. Several stages of metamorphism can be documented in some rocks, as well as double anatexis. Triassic to jurassic quarz diorites and leukogranites show wide distribution. Porphyric rocks of granodioritic to granitic composition, to which the uranium mineralization is mainly bonded, intruded into the sediments of the lower cretaceous. Atomic absorption spectral analyses were carried out for the elements Cu, Zn and Li, as well as the uranium contents of some samples using fluorimetry. Uranium is primarily bonded to pitch blende and coffinite. The latter mostly occur in fine distribution grown in quarz and belong to the most recent mineralization phase. Autunite, meta-autunite, torbernite, meta-torbernite, zeunerite, meta-zeunerite and meta uranocircite detected as secondary uranium minerals. (orig./HP)

  4. Challenges Associated with Apatite Remediation of Uranium in the 300 Area Aquifer

    Energy Technology Data Exchange (ETDEWEB)

    Wellman, Dawn M.; Fruchter, Jonathan S.; Vermeul, Vincent R.; Williams, Mark D.

    2008-05-01

    Sequestration of uranium as insoluble phosphate phases appears to be a promising alternative for treating the uranium-contaminated groundwater at the Hanford 300 Area. The proposed approach involves both the direct formation of autunite by the application of a polyphosphate mixture, as well as the formation of apatite in the aquifer as a continuing source of phosphate for long-term treatment of uranium. After a series of bench-scale tests, a field treatability test was conducted in a well at the 300 Area. 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. The results indicated that while the direct formation of autunite appears to have been successful, the outcome of the apatite formation of the test was more limited. Two separate overarching issues impact the efficacy of apatite remediation for uranium sequestration within the 300 Area: 1) the efficacy of apatite for sequestering uranium under the present geochemical and hydrodynamic conditions, and 2) the formation and emplacement of apatite via polyphosphate technology. This paper summarizes these issues.

  5. Uranium Biomineralization As a Result of Bacterial Phosphatase Activity: Insights From Bacterial Isolates From a Contaminated Subsurface

    International Nuclear Information System (INIS)

    Uranium contamination is an environmental concern at the Department of Energy's Field Research Center in Oak Ridge, Tennessee. In this study, we investigated whether phosphate biomineralization, or the aerobic precipitation of U(VI)-phosphate phases facilitated by the enzymatic activities of microorganisms, offers an alternative to the more extensively studied anaerobic U(VI) bioreduction. Three heterotrophic bacteria isolated from FRC soils were studied for their ability to grow and liberate phosphate in the presence of U(VI) and an organophosphate between pH 4.5 and 7.0. The objectives were to determine whether the strains hydrolyzed sufficient phosphate to precipitate uranium, to determine whether low pH might have an effect on U(VI) precipitation, and to identify the uranium solid phase formed during biomineralization. Two bacterial strains hydrolyzed sufficient organophosphate to precipitate 73-95% total uranium after 120 h of incubation in simulated groundwater. The highest rates of uranium precipitation and phosphatase activity were observed between pH 5.0 and 7.0. EXAFS spectra identified the uranyl phosphate precipitate as an autunite/meta-autunite group mineral. The results of this study indicate that aerobic heterotrophic bacteria within a uranium-contaminated environment that can hydrolyze organophosphate, especially in low pH conditions, may play an important role in the bioremediation of uranium

  6. Uranium Plume Treatability Demonstration at the Hanford Site 300 Area: Development of Polyphosphate Remediation Technology for In-Situ Stabilization of Uranium - 8070

    International Nuclear Information System (INIS)

    A groundwater plume containing uranium, originating from a combination of purposeful discharges of wastewater to cribs, trenches and ponds, along with some accidental leaks and spills during nuclear fuel fabrication activities, has persisted beneath the Hanford Site 300 Area for many years. Despite the cessation of uranium releases and the removal of shallow vadose zone source materials, the goal of less than 30 (micro)g/L has not been achieved within the anticipated 10-year time period. Polyphosphate technology has been demonstrated to delay the precipitation of phosphate phases for controlled in situ precipitation of stable phosphate phases to control the long-term fate of uranium. Precipitation occurs when polyphosphate compounds hydrolyze to yield the orthophosphate molecule. Based on the hydrolysis kinetics of the polyphosphate polymer, the amendment can be tailored to act as a time-released source of phosphate for lateral plume treatment, immediate and sustained remediation of dissolved uranium, and to preclude rapid precipitation which could result in a drastic change in hydraulic conductivity of the target aquifer. Critical to successful implementation of polyphosphate remediation technology is a site specific evaluation and optimization of multi-length polyphosphate amendment formulations. A multi-faceted approach has been taken to provide key fundamental science knowledge regarding optimization of the polyphosphate remedy through: (1) phosphorus-31 nuclear magnetic resonance to quantify the effects of Hanford groundwater and sediment on the degradation of inorganic phosphates, (2) static tests to quantify the kinetics, loading, and stability of apatite as a long-term sorbent for uranium, and (3) single-pass flow through testing to quantify the stability of autunite and apatite under relevant site conditions. Dynamic column tests were utilized to (1) optimize the composition of the polyphosphate formulation for the formation and emplacement of apatite and

  7. Potentialities of in-situ leaching of uranium and copper ore material in west central Sinai, Egypt

    International Nuclear Information System (INIS)

    A low grade uranium-copper ore material is recently recorded in the Paleozoic sedimentary sequence in west central Sinai, Egypt. The host rocks composed mainly of siltstone, clay, sand and gravel. A number of secondary uranium and copper minerals have been reported including mainly uranophane, carnotite, meta-tyuyamunite and meta-autunite beside atacamite, para-atacamite and langite. Series of lab percolation leaching experiments in both vertical and horizontal columns have been performed using acid and alkaline leaching reagents. Due to the fact that the ore material is situated above the water table, the in-situ leaching technique is doubtful. However, other natural leaching methods especially heap and in place leaching could be proposed. (author). 23 refs, 12 figs, 4 tabs

  8. Sedimentary and tectonic environments for uranium mineralization on the Parana Basin, Brazil

    International Nuclear Information System (INIS)

    The Parana Basin is an isolated intracratonic basin in Southeastern South America and is characterized by Paleozoic and Mesozoic clastic sediments and by the location of one of the world's largest lava flows. Uranium mineralization occurs mainly in lower Devonian epineritic feldsphatic sandstones and in fluvio-deltaic channels developed in middle Permian mudstones and sandstones. Stratigraphic and sedimentologic conditions plus tectonic barriers in association with underground water controlled the mineralization. Two uranium deposits with 4250 and 6800 tonnes U of RAR plus EAR were found containing primary (pitchblende and coffinite) and secondary (autunite, sabugalite, uranocircite) minerals. A paleochannel model for the Permo-carboniferous mineralization is quite well established whereas many questions are still open for the confirmation of a model for the Devonian occurrences. Host rock sedimentary environment, ore-forming conditions and source rocks are discussed. (author)

  9. Minerals from Morvan; Les mineraux du Morvan

    Energy Technology Data Exchange (ETDEWEB)

    Bayle, L.D

    2007-07-01

    Morvan is a mountainous and wooded region of Bourgogne (Burgundy, France) which represents the NE end of the French Massif central. The geologic history of this area has been propitious to the setting up of numerous ore deposits: iron, fluor, manganese, lead, barium and uranium. Morvan is the cradle of the French uranium industry. This book presents, first, the geology, geodynamics and ore deposits of Morvan, the history of the discovery of autunite and the exploitation of uranium. The three uranium mining districts are reviewed with the list of uranium minerals. The uranium exploitation activity was abandoned in 1990. An overview of a dozen of fluorine, barytine, lead and silver-bearing ore deposits is presented as well. A summary of all other mineral species associated to the granitic, metamorphic and volcanic areas of the region is proposed. (J.S.)

  10. Uranium mineralization in the Mesoproterozoic Banganapalle formation near Nagayapalle, Cuddapah Basin, Andhra Pradesh

    International Nuclear Information System (INIS)

    Cuddapah Basin is the hub of uranium exploration for years together in India. Initial efforts were for quartz-pebble-conglomerate type mineralization. However, the emphasis later shifted towards dolostone-hosted mineralization and finally to unconformity-associated uranium mineralization. The recent finding of uranium mineralization associated with the Banganapalle Formation near Nagayapalle is the outcome of continuous exploration input in the Cuddapah Basin over years. Uranium mineralization (up to 0.278% U3O8) associated with the Mesoproterozoic Banganapalle Formation near Nagayapalle is represented by pitchblende and autunite. Pitchblende occurs as tiny grains in the intergranular spaces and along grain boundaries; and also at places replaces pyrite and covellite grains. The geological set-up indicates that the geodomain is favourable for uranium mineralization. (author)

  11. Dating methods based on the radioactive disequilibrium (1961)

    International Nuclear Information System (INIS)

    The existence in the uranium families of two long-life descendants: ionium (half-life 80000 years) and protactinium (half-life 32000 years), together with the differences in geochemical behaviour of the various natural radio-elements, particularly thorium, make it possible to envisage several models of geological time-scales covering-periods from 0 to 500000 years The theory of two of the most important models i s developed and methods are described for making radiochemical measurements on the various nuclides which are essential for resolving these models (U238, Th234, Th230, Ra226, Pa231, Th232, Th228, Po210) An example of dating is given in the case of a secondary mineralisation on a weathered portion of a deposit in the Limouzat (Forez). Samples of autunite and chalcolite taken at different levels of the mine were calculated to be between 30000 and 240000 years old. (authors)

  12. Contaminant uranium phases and leaching at the Fernald site in Ohio

    International Nuclear Information System (INIS)

    Electron beam techniques were used to characterize uranium-contaminated soils at the Fernald site in Ohio. Uranium particulates had been deposited on the soil through chemical spills and from the operation of an incinerator plant on the site. The major uranium phases were identified using analytical electron microscopy (AEM) combined with electron diffraction as uranyl phosphate (meta-autunite), uranium oxide (uraninite), and uranium metaphosphate [U(PO3)4]. The U(PO3)4 was found predominantly at an incinerator site at Fernald. Carbonate leaching in an oxygen environment has removed some of the U(IV) phases; however, U(PO3)4 has not been removed by any of the chemical remediation technologies tried to date. These observations suggest that an additional physical extraction procedure is needed to remove this phase. Some evidence suggests that the uranium has undergone weathering, resulting in its redistribution within the soil. 21 refs., 5 figs., 3 tabs

  13. Mineralogical Investigations and Physical Upgrading of Abu Rusheid cataclastic rocks, South Eastern Desert, Egypt

    International Nuclear Information System (INIS)

    An economically important rare-metal mineralization is recorded in the cataclastic rocks at Wadi Abu Rusheid area, South Eastern Desert of Egypt. Radiometric measurements of the main varieties of cataclastic rocks (protomylonites, mylonites, ultramylonites) show that their equivalent thorium (eTh) content is 7560, 8660 and 6210 ppm, whereas the equivalent uranium (eU) is 2544,4170 and 790 ppm respectively. Microscopic examination, X-ray diffraction (XRD) and grain counting techniques revealed that thorite, zircon and columbite are the predominant radioactive minerals in all rock varieties , together with minor amounts of xenotime, cassiterite and sulphides. Beside these minerals, uranophane, kasolite and meta- autunite occur as inclusions in other minerals. Physical upgrading of these minerals was carried out using gravitative separation technique. Applying the proposed flowsheet, it is possible to attain a good concentrate for these minerals with an acceptable recovery. It is recommended to subject the final concentrates to hydrometallurgical treatments to extract the important metals.

  14. Geochemical and Mineralogical Characterization of Natash Volcanics, South Eastern Desert, Egypt

    International Nuclear Information System (INIS)

    The two ring structures of Western Ghurfa and Gaziret Khashm Natash as well as the ring dyke, G. El Ghurfa have extruded through the volcanic flows. The three rings range in composition from volcanic flows, represented by trachybasalt, trachyandesite, normal trachyte and alkaline trachyte and pyroclastic rocks (agglomerates, tuffs, pumice and scoria). The rings are semicircular to circular in outline range from 1 km to 0.6 km. The high contents of uranium in the studied rocks are due to the presence of secondary uranium minerals such as meta-autunite and kasolite as well as the accessory minerals bearing uranium such as monazite, xenotime, zircon and allanite. The geochemical studies of the volcanic rocks revealed that the rock samples fall in the trachyte, trachyandesite , trachybasalt and basalt fields. These rocks were originated from alkaline magma, and developed in continental basalt environment. The enrichment of the LREEs (182-391 ppm) is most due to the presences of garnet in the source.

  15. NUEXCO reports on uranium operations

    International Nuclear Information System (INIS)

    Uranium prospecting has been commonplace in northeastern Washington since the early 1950's. Discovery of the Midnight deposit on the Spokane Indian Reservation in early 1954 stimulated prospecting throughout the entire eastern part of the state. The three important deposits in the Spokane Mountain area are the Midnight deposit, the Togo formation, and the Sherwood deposit. The Spokane Mountain uranium deposit was discovered by geological, geophysical and geochemical methods. Uranium activities in the Mt. Spokane area have had little economic impact on the district, but the nature of the uranium occurrence is important to future exploration. The only uranium mineral present is meta-autunite. Unoxidized minerals have not been noted in the area

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

    Energy Technology Data Exchange (ETDEWEB)

    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. Phurcalite and others secondary uranium minerals from Perus, Sao Paulo, Brazil

    International Nuclear Information System (INIS)

    Phurcalite has been found filling fractures in the tourmaline-bearing granitic pegmatite of Perus, in the north-west part of Sao Paulo city, Brazil. It forms aggregates of radiating euhedral crystals up to 5 mm in length. The crystals are bright yellow, transparent and display vitreous to adamantine lustre. Its streak is pale yellow. Phurcalite is brittle, with a conchoidal fracture, and non-fluorescent. The crystal structure of phurcalite has been solves by single-crystal x-ray diffraction methods and refined to R = 3.8% using 2065 observed [I > 3σ(I)] reflections. The structure consists of [(U O2)3 O2 (P O4)24n-]n layers, parallel to (010), connected by Ca2+ ions and H2 O. The coordination polyhedra are: for U(1) hexagonal bi pyramid; for U(2) and U(3) pentagonal bi pyramids; for Ca(4) and Ca(5) capped trigonal prism and triangulated dodecahedron, respectively; and for P(6) and P(7) tetrahedra. As a consequence of this work, the molecular formula of phurcalite previously reported as Ca2 (U O2)3 (P O4)2 (OH)4.4 H2 O must be changed to Ca2 (U O2)3 O2 (P O4)2.7 H2 O. Other secondary uranium minerals associated with Perus phurcalite are autunite, torbernite, meta-autunite, meta-torbernite, chernikovite, meta-uranocircite I, phosphuranylite, uranophane-alpha, uranophane-beta, haiweeite, barian week site and perhaps also bassetite, meta-tyuyamunite and meta-haiweeite. Opal, tridymite, cristobalite, secondary quartz, saponite and rhodochrosite occur associated to the uranium minerals. (author)

  19. Radiometric geological exploration method used in the central part of the State of Sonora

    International Nuclear Information System (INIS)

    The purpose of this study is to make known the importance of the radiometric data, the physical principles on which they are based and the geological interpretation which will permit in an indirect way to select important radioactive areas in order to carry out verification studies on the ground to see if there are sufficient reasons to show any interest in these areas. Till now this work has been realized in the State of Sonora (Mexico) in an area of 51,000 Km2 subdivided in 14 zones, numbered from 201 to 214, and for the present work the zone 208 has been selected. This Zone is located at the north-west of the City of Hermosillo, and has a total area of 3400 Km2 which has been the object of the study by plane through systematic flights in an east-west direction, in order to obtain the configuration and interpret it from a radiometrical point of view. The obtained isorads configuration plans of 4 channels of detection are the following: total counting, potassium, bismuth and thallium as well as their relations. From the 14 verified anomalies the anomaly Noche Buena was selected in order to carry out reconnaissance surveys and preliminary and detailed geological studies. The geology of the area is represented by extrusive and intrusive igneous rocks as well as sedimentary. The uraniferous mineralization is secondary and is represented by autunite, meta-autunite and torbenite which represent an average of 200 g to 3.08 Kg. of U3O8 per ton. (author)

  20. Promoting Uranium Immobilization by the Activities of Microbial Phosphatases

    International Nuclear Information System (INIS)

    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. 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.

  2. Dynamic interplay between uranyl phosphate precipitation, sorption, and phase evolution

    International Nuclear Information System (INIS)

    Highlights: • In all experiments, final concentrations of uranium were lower than U.S. EPA standards. • U–P minerals more stable than chernikovite were slow to develop without sorption. • Heterogeneous nucleation was not observed. • U sorbs much more readily to the goethite than mica in the absence of phosphate. • Nucleation-growth-sorption cycles occur over weeks, not hours, at room temperature. - Abstract: Natural examples demonstrate uranyl-phosphate minerals can maintain extremely low levels of aqueous uranium in groundwaters due to their low solubility. Therefore, greater understanding of the geochemical factors leading to uranyl phosphate precipitation may lead to successful application of phosphate-based remediation methods. However, the solubility of uranyl phosphate phases varies over >3 orders of magnitude, with the most soluble phases typically observed in lab experiments. To understand the role of common soil/sediment mineral surfaces in the nucleation and transformation of uranyl phosphate minerals under environmentally relevant conditions, batch experiments were carried out with goethite and mica at pH 6 in mixed electrolyte solutions ranging from 1–800 μM U and 1–800 μM P. All experiments ended with uranium concentrations below the USEPA MCL for U, but with 2–3 orders of magnitude difference in uranium concentrations. Despite the presence of many cations that are well known to incorporate into less soluble autunite-group minerals, chernikovite rapidly precipitated in all experiments containing U and P, except for solutions with 1 μM U and 1 μM P that were calculated to be undersaturated. Textures of uranyl phosphates observed by AFM and TEM indicate that nucleation was homogenous and independent of the initial mineral content. Comparison of time-course U and P concentrations from the experiments with thermodynamic modeling of solution equilibria demonstrated that aqueous uranium concentrations in the experimental systems evolved

  3. The natural radioactivity in the Serido Pegmatite Province - Rio Grande do Norte State (Brazil): assessment and monitoring of water's source

    International Nuclear Information System (INIS)

    Full text: This abstract show the preliminary considerations of a study accomplished on the radioactive minerals, primary and secondary uranium minerals that occur in the pegmatites of the Serido Region, State of Rio Grande do Norte, Brazil and their influence on the several sources of water provision and on population nuclei of the area from the municipal district of Parelhas and Ecuador. In general, the pegmatite from the area of Ecuador-Parelhas present high environmental radioactivity so much due to the dispersed uranium in the crystalline structure of minerals (columbite-tantalite, albite, microcline, quartz, phosphate minerals, tourmaline, lepidolite and apatite), as primary and secondary uranium minerals (uraninite, pitchblende, gummite, autunite, torbernite, and uranium-bearing opal, etc.). These uranium minerals appear associates to the fracture and voids in the pegmatite and in the tourmaline-bearing granite. These minerals were identified by petrography, X-Rays diffraction, ultraviolet fluorescence analysis, infrared spectroscopy, radioactivity (HPGe gamma spectrometry), thermal behavior and chemical analysis (ICP-MS and AAS, Microprobe). Geochemistry and hydrochemistry preliminary environmental studies on the pegmatites bodies from Serido Region show gamma radiation level which between 150 to 30.000 cps; uranium (U3O8) and thorium (ThO2) content in Columbite-Tantalite (and/or polycrase) varying between 0,3% - 3,0% and 0,1% - 0,5% respectively, and the coating existent in these minerals show uranium contents varying between 20% to 60%. While the soil samples gathered in Ecuador/Parelhas districts show an average activity of 226Ra, 232Th, and 40K of 27.1/39.1; 33.74/48.5; 260.1/234.8 (Bq.kg-1, dry-weight), respectively, and the corresponding kerma rate (l) in air are 50 and 67 nGyh-1], suggesting that the acid underground waters and others oxidizers attack and dissolve the radioactive minerals from pegmatite, generating solutions rich in U6+ ions (UO22

  4. Technological studies on the Manisa-Koprubasi uranium ores of Turkey

    International Nuclear Information System (INIS)

    At the end of the laboratory and pilot plant scale technological experiments, three main types of ore have been classified: (i) Kasar type: The ores consist of secondary uranium mineralization (autunite, meta-autunite and torbenite) in loosely consolidated sands, gravels and clays of Neogene Age. Heap leaching has been carried out on 100 and 1000 t ore samples (0.05% U3O8) under economical conditions, such as 20 to 40 kg of H2SO4 per tonne of ore at ambient temperature; original size -20 cm, solid/liquid ratio of 10, 20 days, and 90% recovery of uranium has been reached. The uraniferous solutions (1 to 2 g of U3O8 per litre) obtained from the heap leaching operations were purified in a solvent extraction unit with a capacity of 100 ltr/h by using an Alamine 336-kerosene-decanol solution. The uranium in the purified and concentrated solutions (15 g of U3O8 per litre) was then precipitated as a yellow cake with 65 to 75% U3O8 content by means of magnesia milk. (ii) Tasharman type: No specific uranium mineral has been detected in the mineralogical determination, although uranium is disseminated in phosphate minerals as dahllite and apatite. Uranium in the ore has been leached under rather uneconomical conditions; 100 kg of H2SO4 per tonne of ore, particle size -1 cm, 250C, 30 days. In the SX-treatment of pregnant solutions phosphate ions, higher acidity than pH 1, and compounds formed as a chemical precipitation, hindered the SX-recoveries. In such cases, the addition of acid, dilution of pregnant solutions, membrane filtration, or 400C temperature have been applied to decrease the uranium loss in the raffinate. (iii) Carbonate type: Even if alkaline leaching at 650C, or leaching with 400 kg of H2SO4 per tonne of ore, was carried out on -200 mesh ore samples, no acceptable uranium recoveries were obtained

  5. Uranium prospecting; La prospection de l'uranium

    Energy Technology Data Exchange (ETDEWEB)

    Roubault, M. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1955-07-01

    This report is an instruction book for uranium prospecting. It appeals to private prospecting. As prospecting is now a scientific and technical research, it cannot be done without preliminary studies. First of all, general prospecting methods are given with a recall of fundamental geologic data and some general principles which are common with all type of prospecting. The peculiarities of uranium prospecting are also presented and in particular the radioactivity property of uranium as well as the special aspect of uranium ores and the aspect of neighbouring ores. In a third part, a description of the different uranium ores is given and separated in two different categories: primary and secondary ores, according to the place of transformation, deep or near the crust surface respectively. In the first category, the primary ores include pitchblende, thorianite and rare uranium oxides as euxenite and fergusonite for example. In the second category, the secondary ores contain autunite and chalcolite for example. An exhaustive presentation of the geiger-Mueller counter is given with the presentation of its different components, its functioning and utilization and its maintenance. The radioactivity interpretation method is showed as well as the elaboration of a topographic map of the measured radioactivity. A brief presentation of other detection methods than geiger-Mueller counters is given: the measurement of fluorescence and a chemical test using the fluorescence properties of uranium salts. Finally, the main characteristics of uranium deposits are discussed. (M.P.)

  6. Geology of the uranium occurrence in the Bungua area, Siavonga District, Zambia

    International Nuclear Information System (INIS)

    Uranium mineralization related to the fluviatile continental sandstone of the Escarpment Grit Formation of Upper Karroo System has been studied in detail in the Bungua area. Airborne and ground gamma-radiation surveys resulted in the discovery of mineralized bodies containing secondary minerals such as meta-autunite, phosphuranylite, uranocircite, abernythite, boltwoodite, etc. disseminated in various ways. Geological, radiometric, stratigraphic, sedimentological and petrological studies coupled with exploration pitting, trenching and drilling were employed to assess the nature, distribution and sub-surface continuation of mineralized bodies. Drilling, logging and XRF analysis revealed that the uranium mineralized bodies are mainly lenses at different levels, which may be concordant or discordant with bedding. The thickness and grade of ore horizons differ considerably. Mineral distribution and controls are complex and that the main deposit is controlled by reducing lithologies, organic matter, clay traps, micas, iron cementing and permeable channels. Although no definite mode of origin can be attributed to the presently seen uranium mineralized bodies, they appear to be from a pre-existing ore deposit which is mobilized and redistributed during oxidation by supergene processes. It is suggested that the original uranium was in solution as uranylion and came from the same source area as the host rocks and the uranium-bearing groundwater and streams moved in the same direction as the associated Escarpment Grit sediments. Uranium was precipitated wherever favourable conditions prevailed in the Escarpment Grit Formation. (author)

  7. Geology and uranium mineralization, Nyaan Sector, Upper Mahakam, East Kalimantan

    International Nuclear Information System (INIS)

    Nyaan Sector covered 0.5 km2 area. The aim of research is to understand the geological setting, mineralization and potency of uranium in Nyaan Sector. The research activities involved topography measurement, soil radioactivity measurement by grid of 20 x 20 m2, stratigraphic and detailed geological structure observation, the making of peels at any anomaly area and radioactivity anomaly area. There are 3 (three) significant radiometric anomaly locations at Nyaan Sector. They are anomaly Sungai Marta, Marta Hulu and Aloha with radiometric value ranges from 8000 c/s to > 15000 c/s with background value of 100 c/s. In these areas, the making of peels, trench and test pit were conducted by sampling mineralization using systematic channel sampling system by the sum of 15 channels sampling and 8 chips sampling. The petrography and mineralogy analysis exhibited that mineralization of pitchblende, monazite, autunite were associated with bornite, chalcocite, chalcopyrite, lolingite, pyrite, sphalerite, ilmenite, limonite, magnetite, marchasite, rutile, malnicovite, hematite and iron oxide. Results of geochemical analysis for total uranium content in the rocks ranged between 345 to 11.425 ppm of uranium. (author)

  8. Geology and uranium occurrences in Paluq Sector, Upper Mahakam, East Kalimantan

    International Nuclear Information System (INIS)

    Systematic prospecting stage was conducted with area covered Paluq Sector (0.8 km2). The aims of activities are to get geological setting, mineralization and potency of uranium in Nyaan and Paluq Sector. The activities in this stage involved topographic measurement, soil radioactivity measurement, stratigraphic and detailed geological structure observation, making of peels at anomaly area and radioactivity anomaly area. At Paluq Sector there are 5 (five) significant radiometric anomaly locations which are Putra River, Roos, Upper Paluq, Mahakam and Siweg with radiometric value 500 - 10.000 c/s, with a background value of 100 c/s furthermore making peels, trance and test pit were conducted by sampling mineralization using systematic channel sampling method. The petrography and mineralogy analysis exhibited that mineralization of pitchblende, monazite, autunite were associated with bornite, chalcocite, chalcopyrite, lolingite, pyrite, sfalerite, ilmenite, limonite, magnetite, marcasite, rutile, malnicovite, hematite and iron oxide. Result of geochemical analysis for total uranium content in the rocks ranged between 35 to 4.600 ppm of uranium. (author)

  9. 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. PMID:24878600

  10. Uraniferous calcretes of Thar Desert from Kanji Ki Sird and Jodhsingh Ki Sird Areas, Jodhpur District, Rajasthan

    International Nuclear Information System (INIS)

    Secondary uranium mineral-bearing calcrete formations have been located for the first time in India at Kanji Ki Sird (27°29 min 30 secN, 72°28min 06 secE) and Jodhsingh Ki Sird (27°29 min17 sec N, 72°29 min 04 secE) areas in Thar Desert environs of the Jodhpur district of Rajasthan. Seven zones of uraniferous calcretes in varying dimensions from 25 m x 25 m to 500 m x 200 m have been delineated by pitting and trenching over an area of 2 sq. km. The thickness of the uraniferous (assayed up to 0.047% U3O8 and chemical up to 0.024% U3O8) calcrete horizon varies from 30 cm to about a meter. These zones fall within a half-kilometer wide WNW-ESE trending low gradient drainage channel. Greenish to yellowish coloured secondary uranium minerals occur along cavities, vugs and fractures in calcretes and along rock fragment boundaries. Uranium minerals identified by X-ray diffraction technique are tyuyamunite (Ca(UO2)2(VO4)2.5-8H2O), wyartite (Ca3U (UO2)6(CO3)2(OH)163-5 H2O) and meta-autunite (Ca(UO2)2(PO4)2.10-12H2O). The Bap Boulder Bed and Badhaura sandstone exposed in the catchment area are the provenance rocks for uranium. (author)

  11. Uranium mineralization along the northeastern margin of proterozoic Chhattisgarh Basin around Chitakhol, Central India: a petromineralogical study

    International Nuclear Information System (INIS)

    Uranium mineralization occurs along the unconformity contact between the basement granites and the overlying Chandrapur sediments of the Chhattisgarh Supergroup along the northeastern margin of the Chhattisgarh Basin around Chitakhol area, Korba and Janjgir - Champa districts, Chhattisgarh. A number of uranium occurrences, spread over an area of 20 km2, have been delineated with surface samples analyzing up to 0.39% U3O8 in sediments, 2.72% U3O8 in basement granites and up to 0.21% U3O8 in basic dykes. The uranium mineralization is confined to the basement granites and the overlying sediments proximal to the unconformity contact. The basic dykes traversing the basement granites are also mineralized. Uranium mineralization at the depth is associated with carbonaceous black shale and is represented by coffinite and pitchblende. Uraninite, brannerite with 'U-Fe-Ti' complex, meta-autunite and uranophane also contribute to the mineralization. However, in surface and near surface samples uranium occurs in adsorbed state on to goethite and also as filling the criss-cross fractures. Fracture filled, epigenetic, hydrothermal type of uranium mineralization related to the Proterozoic unconformity is manifested

  12. 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.

  13. 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.

  14. Atomic mineral speciation in Cuddapah Basin and its environs (India): genetic implications for uranium mineralisation

    International Nuclear Information System (INIS)

    The X-ray diffraction (XRD) studies reveal that in syngenetically-mineralised (widespread) Neoarchaean to Palaeoproterozoic basement granitoids, the primary uranium minerals (PUMs) are uranium oxide (uraninite), uranium-silicate (coffinite), and uranium titanium oxide (brannerite), whereas, the (remobilised) secondary uranium minerals (SUMs) have only three species: (i) hydrous oxide hydrate (ianthinite and masuyite), (ii) silicate (uranophane, beta-uranophane, and kasolite), and (iii) phosphate (hydrogen-autunite, metaautunite, and meta-uranocircite), besides a solitary occurrence of arsenate hydrate (metazeunerite) in a fracture zone. Interestingly, thorium and rare-earth element (REE) mineral occurrences are also widespread though with limited speciations. Syngenetic thorium and REE mineral species are phosphate (monazite and xenotime) and silicate (thorite and chevkinite). Furthermore, niobium-tantalum mineral phases, with occasional occurrences in pegmatitic phases within the basement granitoids, are exemplified by columbite-tantalite, samarskite, microlite, and euxenite. In the Nellore schist belt, restricted species of uranium minerals have been noted: oxide (uraninite) and silicate (uranophane and beta-uranophane), whereas, the REE phase is chevkinite. Considerable speciations of rare-metal, rare-earth, and thorium minerals are noted in the younger granite

  15. Uranium in the Carnmenellis granite, Cornwall, England

    International Nuclear Information System (INIS)

    Samples from a 30 meter core from the Rosemanowas quarry in the Carnmenellis granite in Cornwall, England were analyzed by induced fission track detection, delayed neutron detection, backscattered electron imaging in a SEM, and energy dispersive x-ray spectrometry. Uranium occurs mainly in: (1) primary accessory minerals; (2) alteration and replacement phases, and (3) microcrack-sealing phases. Zircon, monazite, and apatite are common uraniferous primary accessory minerals. Uraniferous alteration phases include hematite, rutile and pyrolusite. Hematite is a common uraniferous replacement phase. Most sealed microcracks contain uranium. Hematite and pyrolusite are ubiquitous uraniferous crack-sealing phases. Autunite and churchite are occasional uraniferous crack-sealing phases. Whole rock uranium concentrations are extremely variable. High uranium contents result from high percentages of uraniferous primary accessory phases and/or rutile. Hydrothermal activity, such as hematization, can result in depleted whole rock uranium concentrations. Results of this study indicate that uranium and light rare earth elements have been mobilized and redistributed in this section of the Carnmenellis granite by postmagmatic processes. 28 refs., 13 figs. 2 tabs

  16. Geologic and radiometric study in the Picacho, Arizpe's Municipality, Sorora (Mexico) area

    International Nuclear Information System (INIS)

    This research work was aimed chiefly at studying the geology and radiometry of the El Picacho area in order to establish its uranium mineralization potential. Another purpose was to ascertain the factors favouring deposition of radioactive material in areas bordering on the Sierra del Manzanal, where the work was carried out. Detailed geological-radiometric surveys were made, both inside the El Picacho mine and at the surface. The geological surveys were carried out by means of compass bearings and stadia, while scintillometers and spectrometers were used for the radiometric studies. The work was supported by a general geological exploration of the central part of the Serra del Manzanal. To ascertain the radiometric anomalies, the distribution of the population of values was determined by statistical methods, the frequency, cumulative frequency and frequency percentage being evaluated for that purpose. The geological survey at the El Picacho mine revealed a group of fractures enclosing the following minerals: torbernite, iriginite and autunite. These fractures are no thicker than 5 cm and tend to wedge out after 3 meters. Primary uraniferous ore is likely to be found in this zone, so surveys based on (a) radon gas emanometry and (b) sediment geochemistry in the Siera del Manzanal are recommended. The basic data relating to this area could be supplemented by mineragraphic and X-ray studies, which would provide a fuller picture of the class of mineralogical species and of the paragenesis of radioactive material presnent in the zone. (author)

  17. Mineralogy of The Radioactive Occurrence at The Northern Periphery of Gabal Gattar Granites, North Eastern Desert, Egypt

    International Nuclear Information System (INIS)

    The northern periphery of G. Gattar granites is mineralogically studied. The study area exhibits significant potential for radioactive occurrences especially in the strongly altered granites at the intersection between the basic dykes striking N30°E and a sinestral strike-slip fault trending N-S. These occurrences are mostly of epigenetic origin. They are closely associated with the hydrothermal alterations; hematitization, kaolinitization and episyenitization causing marked enrichment of some elements notably, Zr, Y, Zn, Ba and REEs. The uranium occurrences vary considerably in their contents from 68 ppm to 4800 ppm, whereas the thorium contents reach up to 600 ppm especially in the desilicified granites. These radioactive occurrences may be due to the existence of some primary and secondary radioactive minerals. The primary minerals comprising uraninite and thorianite whereas the secondary ones including altered aggregated fragments of coffinite, becquerelitewid gummite which were probably formed in the early stages due to uraninite dissolution. Furthermore, uranophane, kasolite, weeksite and autunite are the most conspicuous supergene uranium minerals which are mostly formed as a result of the extensive alterations of the pre-existing primary ones. The latter four minerals display mutual genetic association, hence, it is suggested that the heterogeneous hydrothermal solutions may play a crucial role in formation of the observed secondary U- minerals association in the northern part of Gattar granites pluton.

  18. Uranium distribution in mineral phases or rocks by a five phase sequential extraction procedure

    International Nuclear Information System (INIS)

    Sequential extraction techniques are used to measure the fractionation of uranium and thorium series nuclides in iron/clay/quartz phases etc. as part of the uranium/thorium desequilibria database preparation and understand how the two (or more) separated phases are related to the ore minerals and their accessibility to groundwater. Samples have been characterized for elemental associations and mineralogical distributions. Special attention was given to those elements which have particular significance for the geochemical modelling including species such as phosphate. In the secondary ore body, crystalline iron minerals such as limonite and pyrite appear as the significant mineral phase associated with uranium accumulation. The Morgan's and Tamm's solution extractable minerals (adsorbed and carbonate, and amorphous iron minerals respectively) are accessible to groundwater and so their 234U/238U activity ratios, less than unity, are equal to that of the groundwater. The remaining resistant minerals (mainly quartz) are the significant mineral phase found to be enrich with 234U by the alpha recoil effect. However, in the shallow region of the primary ore body, the Tamm's solution extractable minerals (secondary uranium minerals such as autunite and torbernite - uranyl phosphates) are the significant mineral phase associated with the uranium accumulation. In the deeper region of the primary ore body, the 6 M HCl extractable minerals (clay and some refactory minerals) seems to be predominant. 5 refs., 1 tab., 3 figs

  19. 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.

  20. Phosphate-induced metal stabilization: Use of apatite and bone char for the removal of soluble radionuclides in authentic and simulated DOE groundwater

    International Nuclear Information System (INIS)

    The apatite group of minerals is a family of calcium phosphate phases. Apatite is the principal component of bone tissue, and it also occurs naturally as mineral deposits in the geosphere. Bone char is calcined (coked) animal bone, containing activated carbon as well as calcium phosphate mineral phases. Apatite IItrademark is a more reactive form of apatite, supplied by UFA Ventures, Inc., at a cost of approximately 1/4 that of commercial bone char. Apatite is shown to be effective for the removal of select heavy metal impurities in groundwater. Previous investigations have demonstrated that apatite is an effective medium for the stabilization of soluble lead, cadmium, and zinc from mine waste leachate by the formation of highly insoluble precipitate phases. The performance of bone char and apatite II are compared with other candidate sorption media (including granular activated carbon and anion exchange resin) for the removal of soluble uranyl ion in synthetic DOE Site groundwater supplemented with varying levels of interfering nitrate ion. Apatite II has a greater affinity for U(VI), especially in the presence of nitrate ion, as evidenced by a larger value for the conditional distribution coefficient (Kd) in batch test experiments. Contact of uranyl nitrate solution with apatite II is shown to produce highly insoluble mineral phases of the autunite group (calcium uranyl phosphate hydrates). Apatite II is also demonstrated to be moderately effective for the removal of soluble radioactive isotopes of strontium, but not cesium, when these ions are supplemented into authentic DOE Site groundwater

  1. Effects of calcium and phosphate on uranium(IV) oxidation. Comparison between nanoparticulate uraninite and amorphous UIV–phosphate

    Energy Technology Data Exchange (ETDEWEB)

    Latta, Drew E. [Argonne National Lab. (ANL), Argonne, IL (United States); Kemner, Kenneth M. [Argonne National Lab. (ANL), Argonne, IL (United States); Mishra, Bhoopesh [Argonne National Lab. (ANL), Argonne, IL (United States); Illinois Inst. of Technology, Chicago, IL (United States); Boyanov, Maxim I. [Argonne National Lab. (ANL), Argonne, IL (United States); Bulgarian Academy of Sciences, Sofia (Bulgaria)

    2016-02-01

    The mobility of uranium in subsurface environments depends strongly on its redox state, with UIV phases being significantly less soluble than UVI minerals. This study compares the oxidation kinetics and mechanisms of two potential products of UVI reduction in natural systems, a nanoparticulate UO2 phase and an amorphous UIV–Ca–PO4 analog to ningyoite (CaUIV(PO4)2·1–2H2O). The valence of U was tracked by X-ray absorption near-edge spectroscopy (XANES), showing similar oxidation rate constants for UIVO2 and UIV–phosphate in solutions equilibrated with atmospheric O2 and CO2 at pH 7.0 (kobs,UO2 = 0.17 ± 0.075 h-1 vs. kobs,UIVPO4 = 0.30 ± 0.25 h-1). Addition of up to 400 μM Ca and PO4 decreased the oxidation rate constant by an order of magnitude for both UO2 and UIV–phosphate. The intermediates and products of oxidation were tracked by electron microscopy, powder X-ray diffraction (pXRD), and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the absence of Ca or PO4, the product of UO2 oxidation is Na–uranyl oxyhydroxide (under environmentally relevant concentrations of sodium, 15 mM NaClO4 and low carbonate concentration), resulting in low concentrations of dissolved UVI (<2.5 × 10-7 M). Oxidation of UIV–phosphate produced a Na-autunite phase (Na2(UO2)PO4·xH2O), resulting in similarly low dissolved U concentrations (<7.3 × 10-8 M). When Ca and PO4 are present in the solution, the EXAFS data and the solubility of the UVI phase resulting from oxidation of UO2 and UIV–phosphate are consistent with the precipitation of Na-autunite. Bicarbonate extractions and Ca K-edge X-ray absorption spectroscopy of oxidized solids indicate the formation of a Ca–UVI–PO4 layer on the UO2 surface and suggest a passivation layer mechanism for the decreased rate of UO2 oxidation in the presence of Ca and PO4. Interestingly, the extractions were unable to remove all of the oxidized U from partially oxidized UO2 solids, suggesting that oxidized U is

  2. Effects of calcium and phosphate on uranium(IV) oxidation: Comparison between nanoparticulate uraninite and amorphous UIV-phosphate

    Science.gov (United States)

    Latta, Drew E.; Kemner, Kenneth M.; Mishra, Bhoopesh; Boyanov, Maxim I.

    2016-02-01

    The mobility of uranium in subsurface environments depends strongly on its redox state, with UIV phases being significantly less soluble than UVI minerals. This study compares the oxidation kinetics and mechanisms of two potential products of UVI reduction in natural systems, a nanoparticulate UO2 phase and an amorphous UIV-Ca-PO4 analog to ningyoite (CaUIV(PO4)2·1-2H2O). The valence of U was tracked by X-ray absorption near-edge spectroscopy (XANES), showing similar oxidation rate constants for UIVO2 and UIV-phosphate in solutions equilibrated with atmospheric O2 and CO2 at pH 7.0 (kobs,UO2 = 0.17 ± 0.075 h-1 vs. kobs,UIVPO4 = 0.30 ± 0.25 h-1). Addition of up to 400 μM Ca and PO4 decreased the oxidation rate constant by an order of magnitude for both UO2 and UIV-phosphate. The intermediates and products of oxidation were tracked by electron microscopy, powder X-ray diffraction (pXRD), and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the absence of Ca or PO4, the product of UO2 oxidation is Na-uranyl oxyhydroxide (under environmentally relevant concentrations of sodium, 15 mM NaClO4 and low carbonate concentration), resulting in low concentrations of dissolved UVI (<2.5 × 10-7 M). Oxidation of UIV-phosphate produced a Na-autunite phase (Na2(UO2)PO4·xH2O), resulting in similarly low dissolved U concentrations (<7.3 × 10-8 M). When Ca and PO4 are present in the solution, the EXAFS data and the solubility of the UVI phase resulting from oxidation of UO2 and UIV-phosphate are consistent with the precipitation of Na-autunite. Bicarbonate extractions and Ca K-edge X-ray absorption spectroscopy of oxidized solids indicate the formation of a Ca-UVI-PO4 layer on the UO2 surface and suggest a passivation layer mechanism for the decreased rate of UO2 oxidation in the presence of Ca and PO4. Interestingly, the extractions were unable to remove all of the oxidized U from partially oxidized UO2 solids, suggesting that oxidized U is distributed between

  3. Solubility and dissolution kinetics study of uranium phosphates and vanadates: implications for the front end of the electronuclear cycle

    International Nuclear Information System (INIS)

    In the current context of restart of the nuclear energy, the needs in uranium are expected to increase significantly. Moreover, in a perspective of sustainable development, the exploitation, the treatment and the purification of uranium ores need to be optimized. It is thus necessary to determine reliable thermodynamic data (and especially solubility constants) for the systems of interest, especially uranium(VI) phosphates and vanadates. In this aim, a multi parametric study of the dissolution of meta-torbernite Cu0.8(H3O)0.2(UO2)2(PO4)2.8H2O, meta-autunite Ca(UO2)2(PO4)2.6H2O, meta-ankoleite K2(UO2)2(PO4)2.6H2O and carnotite K2(UO2)2(VO4)2.3H2O was undertaken. First, analogues of these four minerals were synthesized, based only on dry chemistry process for carnotite or on wet chemistry methods for the phosphate phases. They were then extensively characterized (in terms of structure, microstructure and chemical composition). It particularly highlighted the similar structures of such compounds. The anionic groups (PO43- or V2O86-) and uranyl form parallel layers between which counter cations (Cu2+, Ca2+ or K+) and water molecules are inserted. However, the counter cations present in the interlayer space of the three phosphate phases present different lability. The synthetic phases were also compared to their natural analogues, except for meta-ankoleite, which allowed us to point out significant differences in the composition (presence of impurities in natural samples) and the morphology (grain size). The dissolution of these phases was then studied from a kinetic and thermodynamic point of view, through leaching tests in static and dynamic conditions, in various acid media (sulfuric, nitric and hydrochloric) and at different temperatures. In these conditions, the dissolution of meta-autunite was found to be un-congruent due to the precipitation of uranyl phosphate then avoiding the determination of solubility constants. Similarly, the dissolution of meta

  4. 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.

  5. 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

  6. Microorganisms of radionuclides-contaminated soils of Chernobyl: in depth analysis of diversity and study of uranium-bacteria interactions

    International Nuclear Information System (INIS)

    In this study, we explored the microbial diversity of Bacteria and Archaea evolving since 25 years in a radioactive-waste repository trench located in the Chernobyl exclusion zone. To assess the effect of long-term RNs exposure on diversity, microbial assemblages of soil samples highly contaminated with radionuclides (RNs) such as 137Cs and uranium were compared with nearby controls using high throughput pyro-sequencing of 16S rRNA genes. The analysis of 690,023 sequences evidenced high diversity in all samples with 34 bacterial and 2 archaeal phylum represented. Chloroflexi, Acidobacteria, Proteobacteria and Verrucomicrobia were the most consistently detected phyla, representing 90% of all sequences.This result demonstrates that a long term exposure did not lead to the decrease of microbial diversity. Furthermore, principal component analysis of pyro-sequencing data showed that microbial communities of RNs contaminated samples differed significantly from that of controls, suggesting the presence of RNs adapted species in the contaminated samples. Several heterotrophic aerobic bacteria have been cultured from the contaminated samples. Among them, the strain Microbacterium sp. A9 exhibited high uranium tolerance. The interaction between this strain and uranium was investigated by a combination of spectroscopic (FTIR and TRLFS) and microscopic (TEM/EDX) approaches. Comparison of data obtained at 4 and 25 deg. C evidenced active and passive mechanisms of uranium uptake and release. We demonstrated that after a first step of uranium and phosphate release via an active efflux mechanism, Microbacterium sp. A9 accumulates U(VI) as intracellular needle-like structures composed of autunite. The functional groups involved in the interactions with uranium were identified. Document available in abstract form only. (authors)

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

    International Nuclear Information System (INIS)

    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

  8. Petrogenesis and Mineralogical Characterization of Pegmatites from K hour Aba lea, South Eastern Desert, Egypt

    International Nuclear Information System (INIS)

    Khour Abalea in Abu Rusheid area is located at the midst part of the cataclastic rocks having U-shaped It was formed as a result of deep strike-slip faults, some forming shear zone in some trends. Two forms of pegmatites have been distinguished (pockets and veins) occurring within the cataclastic rocks as hosted rocks. Petrographically, they consist of quartz, orthoclase, microcline and micas. The identified minerals in the studied pegmatites can be grouped into primary uranium minerals (uraninite), secondary uranium minerals (kasolite, uranophane and meta-autunite), thorium minerals (thorite and uranothorite), the niobium-tantalum minerals (columbite, ferro-columbite, samarskite, euxenite and fergusonite), the accessories (zircon, monazite, cassiterite, pyrite and fluorite) and mica (muscovite, phlogopite and fluor-phlogopite) as well as the opaques (hematite and goethite). Geochemically, the studied pegmatite (S-type) are calc-alkaline and peraluminous in nature. It is highly fractionated possibly due to hydrothermal alterations. The REEs display clear tetrad effect of M-type accompanied with relative enrichment of the HREE over the LREE and marked negative Eu anomaly (Eu/Eu* =0.03 to 0.36). The calculated tetrad effect in the pegmatite demonstrates clear tendency towards the ratios of the common isovalents such as Zr/Hf, Nb/Ta and Y/Ho. However, the tetrad effect seems not to be mutual with the content of Na20 and Rb/Sr. The absence of coherence between tetrad effect and soda or potassic contents may indicate insignificant role of the Na- or K-metasomatism in developing the tetrad effect. Detailed spectrometric survey of the study pegmatite revealed their enrichment of eU (49-306 ppm) and eTh (76-634 ppm) and the potential anomalous radioactivity is attributed to both magmatic and hydrothermal processes.

  9. The chemical evolution and paragenesis of uranium minerals from the Ruggles and Palermo granitic pegmatites, New Hampshire

    International Nuclear Information System (INIS)

    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. pegmatite, and is represented by rutherfordine. The third stage is represented by uranyl silicates. At the Palermo No. 1 pegmatite, this stage consists of β-uranophane, and at the Ruggles pegmatite, it consists of soddyite and β-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 100oC) to alkaline (pH > 7 at 25oC). Since mineral A contains hydroxyl and a low amount of molecular water, it probably formed at a temperature greater than 100oC 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 25oC) 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 oC) that was oversaturated with Ca, K, U, and P. (author). 22 refs., 1 tab., 2 figs

  10. International Uranium Resources Evaluation Project (IUREP) national favourability studies: Belgium

    International Nuclear Information System (INIS)

    Uranium occurrences and resources - To date the uranium identified in Belgium is limited to a number of occurrences and none of these have as yet proved significant from a reserve or resource viewpoint. The main uranium occurrences ares (1) In the Upper Cambrian graphite schists corresponding to the culm of Sweden small zones are found (30 - 50 cm thick) with an average of 20 ppm uranium. (2) Near Vise at the base of the Carboniferous the Visean formation is discordantly superimposed on the Permian (Frasnian) and overlain by shales and phyllites. Solution pockets at the boundary contain phosphatic lenses that contain uranium values of up to 200 ppm. Autunite and Torbernite are the main uranium minerals associated with a number of complex phosphatic minerals. Within the Chalk (Maestrichtien) of the Mons basin, that is mainly in the Ciply - St. Symphorien and Baudow district. Here is found enrichment of uranium up to 140 ppm over large areas related to phosphatic chalk. The thickness of the zone varies from a few to 20 metres. However, as the P2O5 content is not high enough for the deposits to be exploited at present for phosphate there is little possibility of the uranium being concentrated at high enough levels to be exploited for itself alone. (4) Near to Vielsalm (in the Stavelot Massif) are some thin quartz veins containing small amounts of copper and uranium minerals (Torbornite). Values of up to 70 ppm are recorded. (5) A number of low uranium values are recorded associated with phosphatic nodules and zones in the Lower Pleistocene and Tertiary

  11. Influence of phosphate and silica on U(VI) precipitation from acidic and neutralized wastewaters.

    Science.gov (United States)

    Kanematsu, Masakazu; Perdrial, Nicolas; Um, Wooyong; Chorover, Jon; O'Day, Peggy A

    2014-06-01

    Uranium speciation and physical-chemical characteristics were studied in solids precipitated from synthetic acidic to circumneutral wastewaters in the presence and absence of dissolved silica and phosphate to examine thermodynamic and kinetic controls on phase formation. Composition of synthetic wastewater was based on disposal sites 216-U-8 and 216-U-12 Cribs at the Hanford site (WA, USA). In the absence of dissolved silica or phosphate, crystalline or amorphous uranyl oxide hydrates, either compreignacite or meta-schoepite, precipitated at pH 5 or 7 after 30 d of reaction, in agreement with thermodynamic calculations. In the presence of 1 mM dissolved silica representative of groundwater concentrations, amorphous phases dominated by compreignacite precipitated rapidly at pH 5 or 7 as a metastable phase and formation of poorly crystalline boltwoodite, the thermodynamically stable uranyl silicate phase, was slow. In the presence of phosphate (3 mM), meta-ankoleite initially precipitated as the primary phase at pH 3, 5, or 7 regardless of the presence of 1 mM dissolved silica. Analysis of precipitates by U LIII-edge extended X-ray absorption fine structure (EXAFS) indicated that "autunite-type" sheets of meta-ankoleite transformed to "phosphuranylite-type" sheets after 30 d of reaction, probably due to Ca substitution in the structure. Low solubility of uranyl phosphate phases limits dissolved U(VI) concentrations but differences in particle size, crystallinity, and precipitate composition vary with pH and base cation concentration, which will influence the thermodynamic and kinetic stability of these phases. PMID:24754743

  12. 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.

  13. Geology of the Brysch uranium mine, Karnes County, Texas

    International Nuclear Information System (INIS)

    Approximately 13,700 tons (12,400 tonnes) of oxidized uranium ore, averaging about 0.1 percent U3O8, was mined during 1966 and 1967 from the lower unit of the Deweesville Sandstone Member of the upper Eocene Whitsett Formation, from depths of 75 to 90 feet (23-27 m). The mine is in the Karnes County uranium area, 3 miles (5 km) east of Falls City, Tex. Meta-autunite, Ca(UO2)2(PO4)2.2-6H2O, and meta-tyuyamunite, Ca(UO2)2(PO4)2.3-5H2O, were identified in samples of the ore. The host rock is light-colored, medium-grained, well-sorted feldspathic sandstone that contains fossil wood and Ophiomorpha. It also contains clinoptilolite, cristobalite, and montmorillonite that probably formed as alteration products of volcanic grains in the original sediment. The host rock was deposited in a beach environment near or on a delta formed at the mouth of a stream channel oriented roughly normal to the beach. The Deweesville can be traced for many miles on the surface and represents in general the point of maximum transgression in a transgressive-regressive cycle. The upper unit of the Deweesville, which overlies the host rock, is now exposed in the mine and contains, in ascending order, storm-beach, shoreface, beach, and tidal-flat facies. The shape of the ore body suggests that it originated as an unoxidized ore roll. The ore-bearing fluids may have entered through porous fluvial rock extending updip. Plant material, abundant in the original host sediment, probably supplied reductant necessary for the roll formation

  14. Trend areas and exploration techniques. South-Texas uranium: geologic controls, exploration techniques, and potential

    International Nuclear Information System (INIS)

    Host rocks for uranium in the South-Texas Coastal Plain are Tertiary sedimentary rocks that dip gently to the southeast toward the Gulf of Mexico and into the Gulf Coast geosyncline. The uranium host rocks are mainly porous sandstone units found in the upper Eocene Whitsett Formation, the Oligocene Frio clay, and the Miocene Catahoula Tuff and Oakville Sandstone. The primary source of uranium in the South Texas deposits was probably the Catahoula Tuff. The uranium was dissolved under mildly alkaline, oxidizing conditions accompanying the semi-arid climate that was apparently predominant throughout the late Tertiary in the South Texas area. The dissolved uranium was transported in streams or underground conduits to an area of strong chemical reduction, where it was precipitated. Uranium deposits in South Texas have been found in three principal areas, each characterized by a different host rock. The principal host rocks are the Whitsett Formation in the Karnes County area, the Oakville Sandstone in the Live Oak County area, and the Catahoula Tuff in the Duval County area. The ore bodies are generally in the form of rolls that are elongate perpendicular to the direction of groundwater movement and that are crescent-shaped in cross-section. The wings of the crescent point in the direction from which the uranium-bearing groundwater came, which is generally updip to the northwest in the general area under review. The ore minerals in most of the deposits are coffinite and uraninite, except in the ore bodies at or near the surface in the oxidized zone where autunite and tyuyamunite predominate.Exploration techniques have generally consisted of surface mapping, drilling and logging, and airborne and surface radiometric studies

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

    International Nuclear Information System (INIS)

    Highlights: ► Precipitation of uranium as U phosphates by natural bacterial isolates. ► The uranium biomineralization involves the activity of acidic phosphatase. ► 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.

  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. Geochemistry and mineralogy of the radioactive minerals associated with some pegmatite veins of the Ukma-Nawahatu Hursi sector, Purulia district, W.B., in the Precambrian Chhotanagpur Gneissic complex

    International Nuclear Information System (INIS)

    Some barite-bearing pegmatites in the Ukma-Nawahatu-Hursi sector (23° 25 min - 26 sec N, 86° 02 min - 04 sec E) in Purulia dist., West Bengal, have association of radioactive minerals in the form of coarse-grained pitchblack lumps and irregular patches. The present author and his associates first reported the occurrence of this radioactive belt along a ENE-WSW shearzone during their fieldwork in November, 1978. Groundborne radiometric survey and isorad mapping has established a radioactive high zone of about 15 km length running through Ukma, Nawahatu and Hursi areas. Mineralogical studies of the radioactive minerals have revealed the occurrence of Chevkinite, Aeschynite, Brannerite, Allanite, Uraninite, Tyuyamunite, Davidite, Euxenite, Samarskite, Thorutite, Autunite, Cerianite, in association with quartz, barite, microcline as the principal minerals and various minor minerals like biotite, vermiculite, hornblende, augite, orthoclase, celsian, muscovite, calcite, epidote, zoisite, ilmenite, sphene, rutile, hematite, magnetite, anatase, galena and sodic plagioclase. The barite-bearing pegmatites occur as lenses or lenticular veins hosted by garnetiferous sillimanite-biotite-quartz-schist or occasionally by migmatite. Near Nawahatu the radioactive barite-pegmatite vein occurs at or near the junction between the footwall amphibolite and hangingwall garnetiferous schist. The pegmatite veins have followed mainly schistosity of the host rock and dip at 70°-80° towards south. Chemical analyses of individual radioactive minerals by SEM-EDX and also of the bulk radioactive lumps by ICP-MS have shown significant concentration of U, Tb and Rare earths. Minor and trace element analyses also record notable contents of Zr, Ga, Sc, Pb, Zn, Nb, Cu, Ni, V, Cr, As, W, Pd, Ag and TI. Details of chemical analytical data are presented here. Chemically active fluids generated during metamorphism, metasomatism and granitic activity appear to have played a significant role in the

  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 Eu(3+) and Am(3+) 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

    2016-04-12

    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. PMID:27028717

  20. Bacterial biodiversity analysis of a contaminated soil from the Chernobyl exclusion zone and characterization of the committed interaction of a Microbacterium strain with uranium

    International Nuclear Information System (INIS)

    characterization of the interactions between the selected bacteria isolate (Microbacterium) and U(VI) highlighted an active mechanism of detoxification which involves an efflux of the U(VI) entering the cell and an intracellular precipitation of U(VI) in form of autunite. (author)

  1. 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

  2. Long-term performance of elemental iron and hydroxyapatite for uranium retention in permeable reactive barriers used for groundwater remediation

    International Nuclear Information System (INIS)

    Elemental iron (Fe0) and hydroxyapatite (HAP) were evaluated as reactive mate-rials for use in permeable reactive barriers (PRBs) to remove uranium from conta-minated groundwater. Special attention was given to the long-term performance of the materials, which was investigated by means of column tests with a duration of up to 30 months using two different artificial groundwaters (AGW) with varying composition and uranium concentration. The interaction of the materials with AGW was studied in column tests using 237U as a radiotracer to monitor the movement of the contamination front through the columns. The tested materials were shredded cast iron (granulated grey cast iron, 0.3 - 1.3 mm) supplied by Gotthard Mayer, Rheinfelden, Germany, and food quality grade hydroxyapatite (Ca5(PO4)3OH, 99 % 0 (AGW with 9.6 mg U/L and low bicarbonate content of 120 mg/L). No breakthrough was observed for the Fe0 columns with effluent uranium con-centrations being below the detection limit of 10 μg/L after treating more than 2,000 pore volumes (PV) and no uranium could be leached from loaded Fe0 columns with 200 PV of uranium free AGW. However, columns with high Fe0 content (≥ 50%) suffered from severe loss of permeability when AGW with ≥ 320 mg/L bicarbonate was used. In the HAP columns a breakthrough occurred with effluent uranium concentrations > 15 μg/l after treating 1,240 PV (10% and 50% breakthrough after 1,460 PV and 2,140 PV respectively). 12.2% of the accu-mulated uranium could be desorbed again with 840 PV of uranium free AGW. Adsorption was found to be the dominant reaction mechanism for uranium and HAP. Image analysis of high uranium content samples showed uranium and phosphate bearing crystals growing 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

  3. 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

  4. Uranium in Brazil

    International Nuclear Information System (INIS)

    The results obtained by the uranium exploration programme which has been under way for the last few years are summarized. So far NUCLEBRAS has identified eight areas with uranium resources: (1) Pocos de Caldas (Minas Gerais): It has three main types of uranium mineralization identified as (a) primary, related to hydrothermal, deuteric activities, or both, (b) primary, related to volcanic breccia chimneys, and (c) secondary, related to weathering phenomena. The total resources in this area have been calculated at 26,800 t of U2O8. (2) Figueira (Parana): In this area 8000 t of U3O8 were found. The mineralization consists mainly of uraninite and uranocircite. (3) Quadrilatero Ferrifero (Minas Gerais): Both in the Gandarela area and in Serra das Gaivotas uranium occurs chiefly in the form of uraninite (and some pitchblende). The resources at the Quadrilatero Ferrifero are estimated at 15,000 t of U3O8. (4) Amorinopolis (Goias): The main minerals are pitchblende (or uraninite or both) and coffinite with associated autunite and sabugalite. The resources have so far been calculated for only six ore bodies and amount to 5000 t of U3O8. (5) Campos Belos (Goias): Almost the entire mineralization is related to quartz veins in fractures in cataclastic 'schists' of the Araxa group. So far the resources in this area have been estimated at 1000 t of U3O8. (6) Itataia (Ceara): Uranium is associated with a phosphatic material called 'collophanite' filling fractures or cavities, or both, in rocks of the region. To date, the resources in this region are estimated at 71,000 t of U3O8. (7) Lagoa Real (Bahia): The uranium mineralization occurs in the form of uraninite and pitchblende and, secondarily, uranophane and gummite. The resources so far amount to 5500 t of U3O8. (8) Espinharas (Paraiba): The uranium mineralization occurs in dykes of feldspathic rocks within gneisses. The operations of NUCLAM at this site have so far identified resources of the order of 10,000 t of U3O8

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

    Science.gov (United States)

    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

  6. A review of uranium minerals exploration in Ethiopia

    International Nuclear Information System (INIS)

    Full text: Radioactive minerals such as uraninite, UO2, thorianite, ThO2, thorite, ThSiO4, and the like have been valuable for their uranium and thorium contents which are becoming important energy resources today in many countries where atomic reactors are used. They are also essential ingredients in modern weapon industries for the manufacture of devastating weapons. Uraninite is the chief source of uranium although other minerals are important sources of the element such as carnotite, K2(UO2)2(VO4).3H2O, Tyuyamunite, Ca(UO2)2(VO4).5-8 1/2 H2O, torbernite, Cu(UO2)2(PO4)2.8-12H2O,and autunite (Hurlbut et.al, 1977). Th can substitute for U and a complete series between uraninite and thorianite occurs. Analyses usually show the presence of small amounts of Pb, Ra, Ce, Y, N, He and A. Lead occurs as one of two stable isotopes (Pb206 and Pb207) which result from the radioactive decay of uranium (Hurlbut et.al. 1977). According to Bill Morton, a pioneer in the study of Ethiopian Minerals and Rocks, there are a number of radioactive minerals in Ethiopia, with varying physical properties. The presence of the radioactive minerals can easily be detected using a geiger counter or scintillation counter.These radioactive minerals are mainly found in small amounts in pegmatites and in some sandstones reported from the Hararghe area, south-eastern Ethiopia. Uraninite occurs in a form of pitchblende, which is massive with a banded structure. To date no extensive radioactive mineral deposits have been discovered in Ethiopia. Besides the Uranium and thorium minerals observed in pegmatite veins belonging to gneisses of Hararge, Precambrian granite as well as Cretaceous and Jurassic sediments in the same region, i.e., south eastern Ethiopia, particularly in the Dire-Dawa - Harar area, seem to be favorable host rocks for radioactive minerals (Getaneh Assefa, 1992). There are also reports of occurrences of radioactive minerals in Sidamo (Wadera, Zenbaba and Genale localities), Kaffa

  7. 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

  8. Immobilization of uranium and neptunium by microorganisms in subsurface crystalline rock environments

    Energy Technology Data Exchange (ETDEWEB)

    Krawczyk-Baersch, Evelyn; Schmeide, Katja; Bok, Frank [Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology, P.O. Box 51 01 19, D-01314 Dresden (Germany); Pedersen, Karsten [Department of Civil and Environmental Engineering, Chalmers University of Technology, SE-412 96 Goeteborg (Sweden)

    2014-07-01

    In crystalline rock, the dominant transport medium for radionuclides is groundwater flowing through subsurface fractures. Since groundwater is containing microorganisms, fracture surfaces support biological growth of microbial communities, the so-called bio-films. The microbial diversity of these bio-films depends on the microbial consortia and the chemical composition of the fracture water. Subsurface bio-films have a significant effect on the adsorption capacity of host rock formations by forming a barrier between the rock surface and the groundwater. They can significantly affect subsurface biogeochemical interactions, leading to the immobilization and adsorption of radionuclides. Microbial studies were performed to evaluate the relevance of microbial processes for the immobilization of radionuclides in a deep crystalline repository for high-level radioactive waste. Studies were performed in Olkiluoto, in the rock characterization facility ONKALO in Finland, and in the Aespoe Hard Rock Laboratory (HRL) in Sweden. Massive 5-10-mm thick bio-films were observed in both sites attached to tunnel walls where groundwater was seeping from bedrock fractures. In experiments the effect of uranium on bio-films was studied on site in the ONKALO tunnel by adding UO{sub 2}(ClO{sub 4}){sub 2} with a final U-concentration of 1.0x10{sup -5} M to the fracture water in a self-constructed flow cell by using detached bio-film samples. bio-film specimens collected for transmission electron microscopy studies indicated that uranium in the bio-film was immobilized intracellularly in microorganisms as needle-shaped uranyl phosphate minerals, similar to meta-Autunite (Ca[UO{sub 2}]{sub 2}[PO{sub 4}]{sub 2}.10-12H{sub 2}O). In contrast, thermodynamic calculation of the theoretical predominant fields of uranium species and time-resolved laser fluorescence spectroscopy showed that the formation of aqueous uranium carbonate species Ca{sub 2}UO{sub 2}(CO{sub 3}){sub 3} and Mg{sub 2}UO{sub 2

  9. 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.

  10. 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

  11. U6+ phases in the weathering zone of the Bangombe U-deposit: observed and predicted mineralogy

    International Nuclear Information System (INIS)

    The mineralogy of the supergene-weathered Bangombe natural fission reactor (RZB) and surrounding uranium deposit has been analyzed and compared with the thermodynamically predicted minerals based on groundwater compositions. The primary U-minerals are uraninite UO2+x and minor coffinite (U[SiO4].nH2O); sometimes with phosphorous. The U6+ minerals include fourmarierite Pb1-x[(UO2)4O3-2x(OH)4+2x].4(H2O), bassetite (Fe1-x2+Fex3+[(UO2)(PO4)]2(OH)x.8-xH2O); possibly associated with U(HPO4)2.2H2O and/or chernikovite ((H3O)2[(UO2)(PO4)]2.6H2O); torbernite (Cu[(UO2)(PO4)]2.8-12H2O), Ce-francoisite-(Nd) (REE(UO2)3O(OH)(PO4)2.6H2O), and uranopilite ((UO2)6(SO4)O2(OH)6(H2O)6.8H2O). Autunite (Ca[(UO2)(PO4)]2.10-12H2O) has also been reported. Thermodynamic equilibrium modeling was completed using Geochemist's Workbench trademark with an expanded data base and the groundwater composition (-112 mV ≤ Eh ≤ 143 mV; pH = 5.96) at the base of RZB in drill-hole BAX03. The new ΔGf,298.150 data were obtained from the literature or estimated using the polyhedral contribution method. Based on the updated database, Eh-pH diagrams predict that coffinite, U(HPO4)2.H2O and UOF2.H2O are the only stable U4+ phases and that uranopilite, torbernite and bassetite will become stable during oxidative alteration. Except from UOF2.H2O, this is in accord with mineralogical observations. The role of Cu was predicted from log aCu-pH diagrams, which predicts that torbernite is stable at log aCu = 3.98 x 10-14 and pH ≥ 2.2 at Eh = 143 mV in BAX03 groundwaters. At Eh = -112 mV, torbernite is stable at pH > 5.5. Soddyite ((UO2)2SiO4.2H2O) was predicted to form at the expense of coffinite, but soddyite has not been identified at Bangombe. Previous blind prediction modeling, often omitting P and S, had only predicted soddyite and haiweeite (Ca(UO2)2[Si5O12(OH)2].4-5H2O) and hence, failed to predict the U6+ minerals observed at Bangombe. The results stress the importance of SO42- and PO43- resulting from

  12. Immobilization of uranium and neptunium by microorganisms in subsurface crystalline rock environments

    International Nuclear Information System (INIS)

    In crystalline rock, the dominant transport medium for radionuclides is groundwater flowing through subsurface fractures. Since groundwater is containing microorganisms, fracture surfaces support biological growth of microbial communities, the so-called bio-films. The microbial diversity of these bio-films depends on the microbial consortia and the chemical composition of the fracture water. Subsurface bio-films have a significant effect on the adsorption capacity of host rock formations by forming a barrier between the rock surface and the groundwater. They can significantly affect subsurface biogeochemical interactions, leading to the immobilization and adsorption of radionuclides. Microbial studies were performed to evaluate the relevance of microbial processes for the immobilization of radionuclides in a deep crystalline repository for high-level radioactive waste. Studies were performed in Olkiluoto, in the rock characterization facility ONKALO in Finland, and in the Aespoe Hard Rock Laboratory (HRL) in Sweden. Massive 5-10-mm thick bio-films were observed in both sites attached to tunnel walls where groundwater was seeping from bedrock fractures. In experiments the effect of uranium on bio-films was studied on site in the ONKALO tunnel by adding UO2(ClO4)2 with a final U-concentration of 1.0x10-5 M to the fracture water in a self-constructed flow cell by using detached bio-film samples. bio-film specimens collected for transmission electron microscopy studies indicated that uranium in the bio-film was immobilized intracellularly in microorganisms as needle-shaped uranyl phosphate minerals, similar to meta-Autunite (Ca[UO2]2[PO4]2.10-12H2O). In contrast, thermodynamic calculation of the theoretical predominant fields of uranium species and time-resolved laser fluorescence spectroscopy showed that the formation of aqueous uranium carbonate species Ca2UO2(CO3)3 and Mg2UO2(CO3)3 was predicted due to the high concentration of carbonate in the groundwater. At the

  13. 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.)

  14. The effect of remediation on water from a former Portuguese uranium mine area

    Science.gov (United States)

    Neiva, Ana; Carvalho, Paula; Antunes, Isabel; Santos, António; Cabral-Pinto, Marina

    2016-04-01

    The old Senhora das Fontes uranium mine consists of quartz veins containing autunite down to a depth of 40 m. But below, uraninite, Fe-saleeite and black uranium oxides occur in small veinlets or forming elongated nodules. The mine was exploited underground and was closed down in 1971. However, the ores from this mine and two others were treated by the heap-leach process in this area until 1982. Seven dumps containing 33,800 m3 of material were left in the area. The remediation process was carried out from May 2010 to January 2011. During this process, the relocation of the material deposited in dumps took place and was covered with erosion resisting covers. Groundwater and surface water were collected just before the remediation at November of 2009 and February 2010, in the wet season, at the beginning of the remediation, at May and June of 2010, and also after the remediation, at May and June of 2011, in the dry season. Ten wells, four springs and seven streams were chosen to collect water samples. However, some points were occasionally dry and a total of 113 water samples were obtained. The pH of groundwater and surface water was acid-to-alkaline, before, at the beginning and after the remediation, but decreased with the remediation, whereas Eh increased. In general, the uranium concentration was up to 116 μg/L in groundwater and up to 83 μg/L in surface water, before the remediation, in the wet season. The uranium water concentration increased up to 272 μg/L and 183 μg/L in the former and the latter, respectively, at the beginning of the remediation, in the dry season of 2010, due to remobilization of mine dumps and pyrite and chalcopyrite exposures, which caused the pH decrease. However, the uranium concentration decreased in groundwater and surface water at the north part of the mine area, after the remediation, in the dry season of 2011, but increased in both, particularly in groundwater up to 774 μg/L in the south and southwest parts of the area, due