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Sample records for becquerelite

  1. Retardation of uranium and thorium by a cementitious backfill developed for radioactive waste disposal.

    Science.gov (United States)

    Felipe-Sotelo, M; Hinchliff, J; Field, L P; Milodowski, A E; Preedy, O; Read, D

    2017-07-01

    The solubility of uranium and thorium has been measured under the conditions anticipated in a cementitious, geological disposal facility for low and intermediate level radioactive waste. Similar solubilities were obtained for thorium in all media, comprising NaOH, Ca(OH) 2 and water equilibrated with a cement designed as repository backfill (NRVB, Nirex Reference Vault Backfill). In contrast, the solubility of U(VI) was one order of magnitude higher in NaOH than in the remaining solutions. The presence of cellulose degradation products (CDP) results in a comparable solubility increase for both elements. Extended X-ray Absorption Fine Structure (EXAFS) data suggest that the solubility-limiting phase for uranium corresponds to a becquerelite-type solid whereas thermodynamic modelling predicts a poorly crystalline, hydrated calcium uranate phase. The solubility-limiting phase for thorium was ThO 2 of intermediate crystallinity. No breakthrough of either uranium or thorium was observed in diffusion experiments involving NRVB after three years. Nevertheless, backscattering electron microscopy and microfocus X-ray fluorescence confirmed that uranium had penetrated about 40 μm into the cement, implying active diffusion governed by slow dissolution-precipitation kinetics. Precise identification of the uranium solid proved difficult, displaying characteristics of both calcium uranate and becquerelite. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Characterization of uranium minerals from Chihuahua using synchrotron radiation

    International Nuclear Information System (INIS)

    Burciaga V, D. C.; Reyes C, M.; Reyes R, A.; Renteria V, M.; Esparza P, H.; Fuentes C, L.; Fuentes M, L; Silva S, M.; Herrera P, E.; Munoz, A.; Montero C, M. E.

    2010-01-01

    Uranium mineral deposits in the vicinity of Chihuahua City (northern Mexico) have motivated a multidisciplinary investigation due to their tech no-environmental importance. It provides a broad scope study of representative mineral samples extracted from the San Marcos deposit, located northwest of Chihuahua City. The zone of interest is the source of the Sacramento River, which runs at Chihuahua City. The high uranium content of the San Marcos deposit, which was formed by hydrothermal mineralization, has resulted in elevated levels of uranium in surface and ground water, fish, plants and sediments in this region. Mineral identification of the uranium-bearing phases was accomplished with a suite of techniques. Among these phases are those called meta tyuyamunite (Ca(UO 2 ) 2 (VO 4 ) 2 ·3-5 H 2 O) and becquerelite [Ca(UO 2 ) 6 O 4 (OH) 6 ·8(H 2 O)]. It was decided to study an almost pure meta tyuyamunite sample extracted from Pena Blanca, Chihuahua uranium ore and to synthesize the becquerelite, using a modified procedure from a published one. In the current work the crystal structure of meta tyuyamunite is presented, resolved by the Rietveld refinement. Both samples were studied by X-ray absorption fine structure at beamline 2-3, Stanford Synchrotron Radiation Light source. In the present work both the spectra and extended X-ray absorption fine structure parameters are presented. (Author)

  3. Characterization of uranium minerals from Chihuahua using synchrotron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Burciaga V, D. C.; Reyes C, M.; Reyes R, A.; Renteria V, M.; Esparza P, H.; Fuentes C, L.; Fuentes M, L; Silva S, M.; Herrera P, E.; Munoz, A.; Montero C, M. E. [Centro de Investigacion en Materiales Avanzados, S. C., Miguel de Cervantes 120, Complejo Industrial Chihuahua, Chihuahua (Mexico)

    2010-02-15

    Uranium mineral deposits in the vicinity of Chihuahua City (northern Mexico) have motivated a multidisciplinary investigation due to their tech no-environmental importance. It provides a broad scope study of representative mineral samples extracted from the San Marcos deposit, located northwest of Chihuahua City. The zone of interest is the source of the Sacramento River, which runs at Chihuahua City. The high uranium content of the San Marcos deposit, which was formed by hydrothermal mineralization, has resulted in elevated levels of uranium in surface and ground water, fish, plants and sediments in this region. Mineral identification of the uranium-bearing phases was accomplished with a suite of techniques. Among these phases are those called meta tyuyamunite (Ca(UO{sub 2}){sub 2}(VO{sub 4}){sub 2{center_dot}}3-5 H{sub 2}O) and becquerelite [Ca(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6{center_dot}}8(H{sub 2}O)]. It was decided to study an almost pure meta tyuyamunite sample extracted from Pena Blanca, Chihuahua uranium ore and to synthesize the becquerelite, using a modified procedure from a published one. In the current work the crystal structure of meta tyuyamunite is presented, resolved by the Rietveld refinement. Both samples were studied by X-ray absorption fine structure at beamline 2-3, Stanford Synchrotron Radiation Light source. In the present work both the spectra and extended X-ray absorption fine structure parameters are presented. (Author)

  4. New french uranium mineral species

    International Nuclear Information System (INIS)

    Branche, G.; Chervet, J.; Guillemin, C.

    1952-01-01

    In this work, the authors study the french new uranium minerals: parsonsite and renardite, hydrated phosphates of lead and uranium; kasolite: silicate hydrated of uranium and lead uranopilite: sulphate of uranium hydrated; bayleyite: carbonate of uranium and of hydrated magnesium; β uranolite: silicate of uranium and of calcium hydrated. For all these minerals, the authors give the crystallographic, optic characters, and the quantitative chemical analyses. On the other hand, the following species, very rare in the french lodgings, didn't permit to do quantitative analyses. These are: the lanthinite: hydrated uranate oxide; the α uranotile: silicate of uranium and of calcium hydrated; the bassetite: uranium phosphate and of hydrated iron; the hosphuranylite: hydrated uranium phosphate; the becquerelite: hydrated uranium oxide; the curite: oxide of uranium and lead hydrated. Finally, the authors present at the end of this survey a primary mineral: the brannerite, complex of uranium titanate. (author) [fr

  5. New french uranium mineral species; Nouvelles especes uraniferes francaises

    Energy Technology Data Exchange (ETDEWEB)

    Branche, G; Chervet, J; Guillemin, C [Commissariat a l' Energie Atomique, Lab. du Fort de Chatillon, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1952-07-01

    In this work, the authors study the french new uranium minerals: parsonsite and renardite, hydrated phosphates of lead and uranium; kasolite: silicate hydrated of uranium and lead uranopilite: sulphate of uranium hydrated; bayleyite: carbonate of uranium and of hydrated magnesium; {beta} uranolite: silicate of uranium and of calcium hydrated. For all these minerals, the authors give the crystallographic, optic characters, and the quantitative chemical analyses. On the other hand, the following species, very rare in the french lodgings, didn't permit to do quantitative analyses. These are: the lanthinite: hydrated uranate oxide; the {alpha} uranotile: silicate of uranium and of calcium hydrated; the bassetite: uranium phosphate and of hydrated iron; the hosphuranylite: hydrated uranium phosphate; the becquerelite: hydrated uranium oxide; the curite: oxide of uranium and lead hydrated. Finally, the authors present at the end of this survey a primary mineral: the brannerite, complex of uranium titanate. (author) [French] Dans ce travail, les auteurs etudient les nouveaux mineraux uraniferes francais: parsonsite et renardite, phosphates hydrates de plomb et d'uranium; kasolite: silicate hydrate d'uranium et de plomb uranopilite: sulfate d'uranium hydrate; bayleyite: carbonate d'uranium et de magnesium hydrate; {beta} uranolite: silicate d'uranium et de calcium hydrate. Pour tous ces mineraux, les auteurs donnent les caracteres cristallographiques, optiques, et les analyses chimiques quantitatives. Par contre, les especes suivantes, tres rares dans les gites francais, n'ont pas permis d'effectuer d'analyses quantitatives. Ce sont: l'ianthinite: oxyde uraneux hydrate; l'{alpha} uranotile: silicate d'uranium et de calcium hydrate; le bassetite: phosphate d'uranium et de fer hydrate; la hosphuranylite: phosphate duranium hydrate; la becquerelite: oxyde d'uranium hydrate; la curite: oxyde d'uranium et de plomb hydrate. Enfin, les auteurs presentent a la fin de cette etude

  6. Kinetic and thermodynamic studies of uranium minerals. Assessment of the long-term evolution of spent nuclear fuel

    Energy Technology Data Exchange (ETDEWEB)

    Casas, I; Bruno, J; Cera, E [MBT Tecnologia Ambiental, Cerdanyola (Spain); Finch, R J; Ewing, R C [Department of Earth and Planetary Sciences, University of New Mexico, Albuquerque, NM (United States)

    1994-10-01

    We have studied the dissolution behavior of uraninite, becquerelite, schoepite and uranophane. The information obtained under a variety of experimental conditions has been combined with extensive solid phase characterizations, performed in both leached and unleached samples. The overall objective is to construct a thermodynamic and kinetic model for the long-term oxidation alteration of UO{sub 2}(s), as an analogy of the spent nuclear fuel matrix. We have determined the solubility product for becquerelite (logK{sub s0} 32.7{+-}1.3) and uranophane (logK{sub s0} = 7.8{+-}0.8). In some experiments, the reaction progress has shown initial dissolution of uranophane followed by precipitation of a secondary solid phase, characterized as soddyite. The solubility production for this phase has been determined (logK{sub s0} = 3.0{+-}2.9). We have studied the kinetics of dissolution of uraninite, uranophane and schoepite under oxidizing conditions in synthetic granitic groundwater. BET measurements have been performed for uraninite and uranophane. For schoepite, the measurement has not been performed due to lack of sufficient amount of sample. The normalized rates of dissolution of uraninite and uranophane have been calculated referred to the uranium release, as 1.97x10{sup -8} moles h{sup -1} m{sup -2} and 4.0x 10{sup -9} moles h{sup -1} m{sup -2}, respectively. For schoepite, the dissolution process has shown two different rates, with a relatively fast initial dissolution rate of 1.97x10{sup -8} moles h{sup -1} followed, after approximately 1000 hours, by a slower one of 1.4x10{sup -9} moles h{sup -1}. No formation of secondary phases has been observed in those experiments, although final uranium concentrations have in all cases exceeded the solubility of uranophane, the thermodynamically more stable phase under the experimental conditions. 24 refs, 45 figs.

  7. Kinetic and thermodynamic studies of uranium minerals. Assessment of the long-term evolution of spent nuclear fuel

    International Nuclear Information System (INIS)

    Casas, I.; Bruno, J.; Cera, E.; Finch, R.J.; Ewing, R.C.

    1994-10-01

    We have studied the dissolution behavior of uraninite, becquerelite, schoepite and uranophane. The information obtained under a variety of experimental conditions has been combined with extensive solid phase characterizations, performed in both leached and unleached samples. The overall objective is to construct a thermodynamic and kinetic model for the long-term oxidation alteration of UO 2 (s), as an analogy of the spent nuclear fuel matrix. We have determined the solubility product for becquerelite (logK s0 32.7±1.3) and uranophane (logK s0 = 7.8±0.8). In some experiments, the reaction progress has shown initial dissolution of uranophane followed by precipitation of a secondary solid phase, characterized as soddyite. The solubility production for this phase has been determined (logK s0 = 3.0±2.9). We have studied the kinetics of dissolution of uraninite, uranophane and schoepite under oxidizing conditions in synthetic granitic groundwater. BET measurements have been performed for uraninite and uranophane. For schoepite, the measurement has not been performed due to lack of sufficient amount of sample. The normalized rates of dissolution of uraninite and uranophane have been calculated referred to the uranium release, as 1.97x10 -8 moles h -1 m -2 and 4.0x 10 -9 moles h -1 m -2 , respectively. For schoepite, the dissolution process has shown two different rates, with a relatively fast initial dissolution rate of 1.97x10 -8 moles h -1 followed, after approximately 1000 hours, by a slower one of 1.4x10 -9 moles h -1 . No formation of secondary phases has been observed in those experiments, although final uranium concentrations have in all cases exceeded the solubility of uranophane, the thermodynamically more stable phase under the experimental conditions. 24 refs, 45 figs

  8. Corrosion of Uranium in Desert Soil, with Application to GCD Source Term Models

    International Nuclear Information System (INIS)

    ANDERSON, HOWARD L.; BACA, JULIANNE; KRUMHANSL, JAMES L.; STOCKMAN, HARLAN W.; THOMPSON, MOLLIE E.

    1999-01-01

    Uranium fragments from the Sandia Sled Track were studied as analogues for weapons components and depleted uranium buried at the Greater Confinement Disposal (GCD) site in Nevada. The Sled Track uranium fragments originated as weapons mockups and counterweights impacted on concrete and soil barriers, and experienced heating and fragmentation similar to processes thought to affect the Nuclear Weapons Accident Residues (NWAR) at GCD. Furthermore, the Sandia uranium was buried in unsaturated desert soils for 10 to 40 years, and has undergone weathering processes expected to affect the GCD wastes. Scanning electron microscopy, X-ray diffraction and microprobe analyses of the fragments show rapid alteration from metals to dominantly VI-valent oxy-hydroxides. Leaching studies of the samples give results consistent with published U-oxide dissolution rates, and suggest longer experimental periods (ca. 1 year) would be required to reach equilibrium solution concentrations. Thermochemical modeling with the EQ3/6 code indicates that the uranium concentrations in solutions saturated with becquerelite could increase as the pore waters evaporate, due to changes in carbonate equilibria and increased ionic strength

  9. Corrosion of Uranium in Desert Soil, with Application to GCD Source Term M

    Energy Technology Data Exchange (ETDEWEB)

    ANDERSON, HOWARD L.; BACA, JULIANNE; KRUMHANSL, JAMES L.; STOCKMAN, HARLAN W.; THOMPSON, MOLLIE E.

    1999-09-01

    Uranium fragments from the Sandia Sled Track were studied as analogues for weapons components and depleted uranium buried at the Greater Confinement Disposal (GCD) site in Nevada. The Sled Track uranium fragments originated as weapons mockups and counterweights impacted on concrete and soil barriers, and experienced heating and fragmentation similar to processes thought to affect the Nuclear Weapons Accident Residues (NWAR) at GCD. Furthermore, the Sandia uranium was buried in unsaturated desert soils for 10 to 40 years, and has undergone weathering processes expected to affect the GCD wastes. Scanning electron microscopy, X-ray diffraction and microprobe analyses of the fragments show rapid alteration from metals to dominantly VI-valent oxy-hydroxides. Leaching studies of the samples give results consistent with published U-oxide dissolution rates, and suggest longer experimental periods (ca. 1 year) would be required to reach equilibrium solution concentrations. Thermochemical modeling with the EQ3/6 code indicates that the uranium concentrations in solutions saturated with becquerelite could increase as the pore waters evaporate, due to changes in carbonate equilibria and increased ionic strength.

  10. Thermodynamics of Uranyl Minerals: Enthalpies of Formation of Uranyl Oxide Hydrates

    International Nuclear Information System (INIS)

    Kubatko, K.; Helean, K.; Navrotsky, A.; Burns, P.C.

    2005-01-01

    The enthalpies of formation of seven uranyl oxide hydrate phases and one uranate have been determined using high-temperature oxide melt solution calorimetry: [(UO 2 ) 4 O(OH) 6 ](H 2 O) 5 , metaschoepite; β-UO 2 (OH) 2 ; CaUO 4 ; Ca(UO 2 ) 6 O 4 (OH) 6 (H 2 O) 8 , becquerelite; Ca(UO 2 ) 4 O 3 (OH) 4 (H 2 O) 2 ; Na(UO 2 )O(OH), clarkeite; Na 2 (UO 2 ) 6 O 4 (OH) 6 (H 2 O) 7 , the sodium analogue of compreignacite and Pb 3 (UO 2 ) 8 O 8 (OH) 6 (H 2 O) 2 , curite. The enthalpy of formation from the binary oxides, ΔH f-ox , at 298 K was calculated for each compound from the respective drop solution enthalpy, ΔH ds . The standard enthalpies of formation from the elements, ΔH f o , at 298 K are -1791.0 ± 3.2, -1536.2 ± 2.8, -2002.0 ± 3.2, -11389.2 ± 13.5, -6653.1 ± 13.8, -1724.7 ± 5.1, -10936.4 ± 14.5 and -13163.2 ± 34.4 kJ mol -1 , respectively. These values are useful in exploring the stability of uranyl oxide hydrates in auxiliary chemical systems, such as those expected in U-contaminated environments

  11. Sensitivity analysis of uranium solubility under strongly oxidizing conditions

    International Nuclear Information System (INIS)

    Liu, L.; Neretnieks, I.

    1999-01-01

    To evaluate the effect of geochemical conditions in the repository on the solubility of uranium under strongly oxidizing conditions, a mathematical model has been developed to determine the solubility, by utilizing a set of nonlinear algebraic equations to describe the chemical equilibria in the groundwater environment. The model takes into account the predominant precipitation-dissolution reactions, hydrolysis reactions and complexation reactions that may occur under strongly oxidizing conditions. The model also includes the solubility-limiting solids induced by the presence of carbonate, phosphate, silicate, calcium, and sodium in the groundwater. The thermodynamic equilibrium constants used in the solubility calculations are essentially taken from the NEA Thermochemical Data Base of Uranium, with some modification and some uranium minerals added, such as soddyite, rutherfordite, uranophane, uranyl orthophosphate, and becquerelite. By applying this model, the sensitivities of uranium solubility to variations in the concentrations of various groundwater component species are systematically investigated. The results show that the total analytical concentrations of carbonate, phosphate, silicate, and calcium in deep groundwater play the most important role in determining the solubility of uranium under strongly oxidizing conditions

  12. Thermodynamics of Uranyl Minerals: Enthalpies of Formation of Uranyl Oxide Hydrates

    Energy Technology Data Exchange (ETDEWEB)

    K. Kubatko; K. Helean; A. Navrotsky; P.C. Burns

    2005-05-11

    The enthalpies of formation of seven uranyl oxide hydrate phases and one uranate have been determined using high-temperature oxide melt solution calorimetry: [(UO{sub 2}){sub 4}O(OH){sub 6}](H{sub 2}O){sub 5}, metaschoepite; {beta}-UO{sub 2}(OH){sub 2}; CaUO{sub 4}; Ca(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 8}, becquerelite; Ca(UO{sub 2}){sub 4}O{sub 3}(OH){sub 4}(H{sub 2}O){sub 2}; Na(UO{sub 2})O(OH), clarkeite; Na{sub 2}(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 7}, the sodium analogue of compreignacite and Pb{sub 3}(UO{sub 2}){sub 8}O{sub 8}(OH){sub 6}(H{sub 2}O){sub 2}, curite. The enthalpy of formation from the binary oxides, {Delta}H{sub f-ox}, at 298 K was calculated for each compound from the respective drop solution enthalpy, {Delta}H{sub ds}. The standard enthalpies of formation from the elements, {Delta}H{sub f}{sup o}, at 298 K are -1791.0 {+-} 3.2, -1536.2 {+-} 2.8, -2002.0 {+-} 3.2, -11389.2 {+-} 13.5, -6653.1 {+-} 13.8, -1724.7 {+-} 5.1, -10936.4 {+-} 14.5 and -13163.2 {+-} 34.4 kJ mol{sup -1}, respectively. These values are useful in exploring the stability of uranyl oxide hydrates in auxiliary chemical systems, such as those expected in U-contaminated environments.

  13. Dissolution of unirradiated UO{sub 2} fuel in synthetic groundwater. Final report (1996-1998)

    Energy Technology Data Exchange (ETDEWEB)

    Ollila, K. [VTT Chemical Technology, Espoo (Finland)

    1999-05-01

    This study was a part of the EU R and D programme 1994-1998: Nuclear Fission Safety, entitled `Source term for performance assessment of spent fuel as a waste form`. The research carried out at VTT Chemical Technology was focused on the effects of granitic groundwater composition and redox conditions on UO{sub 2} solubility and dissolution mechanisms. The synthetic groundwater compositions simulated deep granitic fresh and saline groundwaters, and the effects of the near-field material, bentonite, on very saline groundwater. Additionally, the Spanish granite/bentonite water was used. The redox conditions (Eh), which are obviously the most important factors that influence on UO{sub 2} solubility under the disposal conditions of spent fuel, varied from strongly oxidising (air-saturated), anaerobic (N{sub 2}, O{sub 2} < l ppm) to reducing (N{sub 2}, low Eh). The objective of the air-saturated dissolution experiments was to yield the maximum solution concentrations of U, and information on the formation of secondary phases that control the concentrations, with different groundwater compositions. The static batch solubility experiments of long duration (up to 1-2 years) were performed using unirradiated UO{sub 2} pellets and powder. Under anaerobic and reducing conditions, the solubilities were also approached from oversaturation. The results of the oxic, air-saturated dissolution experiments with UO{sub 2} powder showed that the increase in the salinity (< 1.7 M) had a minor effect on the measured steady-state concentrations of U. The concentrations, (1.2 ...2.5) x 10{sup -5} M, were at the level of the theoretical solubility of schoepite or another uranyl oxide hydrate, e.g. becquerelite (possibly Na-polyuranate). The higher alkalinity of the fresh (Allard) composition increased the aqueous U concentration. Only some kind of oxidised U-phase (U{sub 3}O{sub 8}-UO{sub 3}) was identified with XRD when studying possible secondary phases after the contact time of one year

  14. Dissolution of unirradiated UO2 fuel in synthetic groundwater. Final report (1996-1998)

    International Nuclear Information System (INIS)

    Ollila, K.

    1999-05-01

    This study was a part of the EU R and D programme 1994-1998: Nuclear Fission Safety, entitled 'Source term for performance assessment of spent fuel as a waste form'. The research carried out at VTT Chemical Technology was focused on the effects of granitic groundwater composition and redox conditions on UO 2 solubility and dissolution mechanisms. The synthetic groundwater compositions simulated deep granitic fresh and saline groundwaters, and the effects of the near-field material, bentonite, on very saline groundwater. Additionally, the Spanish granite/bentonite water was used. The redox conditions (Eh), which are obviously the most important factors that influence on UO 2 solubility under the disposal conditions of spent fuel, varied from strongly oxidising (air-saturated), anaerobic (N 2 , O 2 2 , low Eh). The objective of the air-saturated dissolution experiments was to yield the maximum solution concentrations of U, and information on the formation of secondary phases that control the concentrations, with different groundwater compositions. The static batch solubility experiments of long duration (up to 1-2 years) were performed using unirradiated UO 2 pellets and powder. Under anaerobic and reducing conditions, the solubilities were also approached from oversaturation. The results of the oxic, air-saturated dissolution experiments with UO 2 powder showed that the increase in the salinity ( -5 M, were at the level of the theoretical solubility of schoepite or another uranyl oxide hydrate, e.g. becquerelite (possibly Na-polyuranate). The higher alkalinity of the fresh (Allard) composition increased the aqueous U concentration. Only some kind of oxidised U-phase (U 3 O 8 -UO 3 ) was identified with XRD when studying possible secondary phases after the contact time of one year with all groundwater compositions. Longer contact times are needed to identify secondary phases predicted by modelling (EQ3/6). In the anoxic dissolution experiments with UO 2 pellets, the