WorldWideScience

Sample records for schoepite

  1. Alternate source term models for Yucca Mountain performance assessment based on natural analog data and secondary mineral solubility

    Energy Technology Data Exchange (ETDEWEB)

    Murphy, W.M.; Codell, R.B.

    1999-07-01

    Performance assessment calculations for the proposed high level radioactive waste repository at Yucca Mountain, Nevada, were conducted using the Nuclear Regulatory Commission Total-System Performance Assessment (TPA 3.2) code to test conceptual models and parameter values for the source term based on data from the Pena Blanca, Mexico, natural analog site and based on a model for coprecipitation and solubility of secondary schoepite. In previous studies the value for the maximum constant oxidative alteration rate of uraninite at the Nopal I uranium body at Pena Blanca was estimated. Scaling this rate to the mass of uranium for the proposed Yucca Mountain repository yields an oxidative alteration rate of 22 kg/y, which was assumed to be an upper limit on the release rate from the proposed repository. A second model was developed assuming releases of radionuclides are based on the solubility of secondary schoepite as a function of temperature and solution chemistry. Releases of uranium are given by the product of uranium concentrations at equilibrium with schoepite and the flow of water through the waste packages. For both models, radionuclides other than uranium and those in the cladding and gap fraction were modeled to be released at a rate proportional to the uranium release rate, with additional elemental solubility limits applied. Performance assessment results using the Pena Blanca oxidation rate and schoepite solubility models for Yucca Mountain were compared to the TPA 3.2 base case model, in which release was based on laboratory studies of spent fuel dissolution, cladding and gap release, and solubility limits. Doses calculated using the release rate based on natural analog data and the schoepite solubility models were smaller than doses generated using the base case model. These results provide a degree of confidence in safety predictions using the base case model and an indication of how conservatism in the base case model may be reduced in future analyses.

  2. 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.

  3. Unsaturated zone waters from the Nopal I natural analog, Chihuahua, Mexico -- Implications for radionuclide mobility at Yucca Mountain

    Energy Technology Data Exchange (ETDEWEB)

    Pickett, D.A.; Murphy, W.M.

    1999-07-01

    Chemical and U-Th isotopic data on unsaturated zone waters from the Nopal I natural analog reveal effects of water-rock interaction and help constrain models of radionuclide release and transport at the site and, by analogy, at the proposed nuclear waste repository at Yucca Mountain. Geochemical reaction-path modeling indicates that, under oxidizing conditions, dissolution of uraninite (spent fuel analog) by these waters will lead to eventual schoepite precipitation regardless of initial silica concentration provided that groundwater is not continuously replenished. Thus, less soluble uranyl silicates may not dominate the initial alteration assemblage and keep dissolved U concentrations low. Uranium-series activity ratios are consistent with models of U transport at the site and display varying degrees of leaching versus recoil mobilization. Thorium concentrations may reflect the importance of colloidal transport of low-solubility radionuclides in the unsaturated zone.

  4. Np Behavior in Synthesized Uranyl Phases: Results of Initial Tests

    Energy Technology Data Exchange (ETDEWEB)

    Friese, Judah I.; Douglas, Matthew; McNamara, Bruce K.; Clark, Sue B.; Hanson, Brady D.

    2004-09-28

    Initial tests were completed at Pacific Northwest National Laboratory for developing a potential mechanism to retard the mobility of neptunium at the Yucca Mountain repository. Neptunium is of concern because of its mobility in the environment and long half life, contributing a large percentage of the potential dose over extended times at the perimeter of the site. The mobility of neptunium could be retarded by associating with uranium mineral phases. The following four uranium mineral phases were examined and are potential secondary phases expected to form as a result of interactions of spent nuclear fuel with the local environment: meta-schoepite, studtite, uranophane, and sodium boltwoodite. The fate of the neptunium was examined in these synthetic experiments.

  5. Identification of Uranium Minerals in Natural U-Bearing Rocks Using Infrared Reflectance Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Beiswenger, Toya N. [Pacific Northwest National Laboratory, Richland, WA, USA; Gallagher, Neal B. [Eigenvector Research, Inc., Manson, WA, USA; Myers, Tanya L. [Pacific Northwest National Laboratory, Richland, WA, USA; Szecsody, James E. [Pacific Northwest National Laboratory, Richland, WA, USA; Tonkyn, Russell G. [Pacific Northwest National Laboratory, Richland, WA, USA; Su, Yin-Fong [Pacific Northwest National Laboratory, Richland, WA, USA; Sweet, Lucas E. [Pacific Northwest National Laboratory, Richland, WA, USA; Lewallen, Tricia A. [Pacific Northwest National Laboratory, Richland, WA, USA; Johnson, Timothy J. [Pacific Northwest National Laboratory, Richland, WA, USA

    2017-10-24

    The identification of minerals, including uranium-bearing minerals, is traditionally a labor-intensive-process using x-ray diffraction (XRD), fluorescence, or other solid-phase and wet chemical techniques. While handheld XRD and fluorescence instruments can aid in field identification, handheld infrared reflectance spectrometers can also be used in industrial or field environments, with rapid, non-destructive identification possible via spectral analysis of the solid’s reflectance spectrum. We have recently developed standard laboratory measurement methods for the infrared (IR) reflectance of solids and have investigated using these techniques for the identification of uranium-bearing minerals, using XRD methods for ground-truth. Due to the rich colors of such species, including distinctive spectroscopic signatures in the infrared, identification is facile and specific, both for samples that are pure or are partially composed of uranium (e.g. boltwoodite, schoepite, tyuyamunite, carnotite, etc.) or non-uranium minerals. The method can be used to detect not only pure and partial minerals, but is quite sensitive to chemical change such as hydration (e.g. schoepite). We have further applied statistical methods, in particular classical least squares (CLS) and multivariate curve resolution (MCR) for discrimination of such uranium minerals and two uranium pure chemicals (U3O8 and UO2) against common background materials (e.g. silica sand, asphalt, calcite, K-feldspar) with good success. Each mineral contains unique infrared spectral features; some of the IR features are similar or common to entire classes of minerals, typically arising from similar chemical moieties or functional groups in the minerals: phosphates, sulfates, carbonates, etc. These characteristic 2 infrared bands generate the unique (or class-specific) bands that distinguish the mineral from the interferents or backgrounds. We have observed several cases where the chemical moieties that provide the

  6. Solid state speciation and potential bioavailability of depleted uranium particles from Kosovo and Kuwait

    Energy Technology Data Exchange (ETDEWEB)

    Lind, O.C. [Isotope Laboratory, Department of Plant and Environmental Sciences, Norwegian University of Life Sciences, P.O. Box 5003, N-1432 As (Norway)], E-mail: ole-christian.lind@umb.no; Salbu, B.; Skipperud, L. [Isotope Laboratory, Department of Plant and Environmental Sciences, Norwegian University of Life Sciences, P.O. Box 5003, N-1432 As (Norway); Janssens, K.; Jaroszewicz, J.; De Nolf, W. [Department of Chemistry, University of Antwerp, Universiteitsplein 1, Antwerp (Belgium)

    2009-04-15

    A combination of synchrotron radiation based X-ray microscopic techniques ({mu}-XRF, {mu}-XANES, {mu}-XRD) applied on single depleted uranium (DU) particles and semi-bulk leaching experiments has been employed to link the potential bioavailability of DU particles to site-specific particle characteristics. The oxidation states and crystallographic forms of U in DU particles have been determined for individual particles isolated from selected samples collected at different sites in Kosovo and Kuwait that were contaminated by DU ammunition during the 1999 Balkan conflict and the 1991 Gulf war. Furthermore, small soil or sand samples heavily contaminated with DU particles were subjected to simulated gastrointestinal fluid (0.16 M HCl) extractions. Characteristics of DU particles in Kosovo soils collected in 2000 and in Kuwait soils collected in 2002 varied significantly depending on the release scenario and to some extent on weathering conditions. Oxidized U (+6) was determined in large, fragile and bright yellow DU particles released during fire at a DU ammunition storage facility and crystalline phases such as schoepite (UO{sub 3}.2.25H{sub 2}O), dehydrated schoepite (UO{sub 3}.0.75H{sub 2}O) and metaschoepite (UO{sub 3}.2.0H{sub 2}O) were identified. As expected, these DU particles were rapidly dissolved in 0.16 M HCl (84 {+-} 3% extracted after 2 h) indicating a high degree of potential mobility and bioavailability. In contrast, the 2 h extraction of samples contaminated with DU particles originating either from corrosion of unspent DU penetrators or from impacted DU ammunition appeared to be much slower (20-30%) as uranium was less oxidized (+4 to +6). Crystalline phases such as UO{sub 2}, UC and metallic U or U-Ti alloy were determined in impacted DU particles from Kosovo and Kuwait, while the UO{sub 2,34} phase, only determined in particles from Kosovo, could reflect a more corrosive environment. Although the results are based on a limited number of DU particles

  7. Analysis of a Uranium Oxide Sample Interdicted in Slovakia (FSC 12-3-1)

    Energy Technology Data Exchange (ETDEWEB)

    Borg, Lars E. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Dai, Zurong [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Eppich, Gary R. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Gaffney, Amy M. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Genetti, Victoria G. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Grant, Patrick M. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Gray, Leonard W. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Holiday, Kiel S. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Hutcheon, Ian D. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Kayzar, Theresa M. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Klunder, Gregory L. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Knight, Kimberly B. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Kristo, Michael J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Lindvall, Rachel E. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Marks, Naomi E. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Ramon, Christina E. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Ramon, Erick C. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Robel, Martin [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Roberts, Sarah K. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Schorzman, Kerri C. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Sharp, Michael A. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Singleton, Michael J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Williams, Ross W. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2014-01-17

    We provide a concise summary of analyses of a natural uranium sample seized in Slovakia in November 2007. Results are presented for compound identification, water content, U assay, trace element abundances, trace organic compounds, isotope compositions for U, Pb, Sr and O, and age determination using the 234U – 230Th and 235U – 231Pa chronometers. The sample is a mixture of two common uranium compounds - schoepite and uraninite. The uranium isotope composition is indistinguishable from natural; 236U was not detected. The O, Sr and Pb isotope compositions and trace element abundances are unremarkable. The 234U – 230Th chronometer gives an age of 15.5 years relative to the date of analysis, indicating the sample was produced in January 1997. A comparison of the data for this sample with data in the Uranium Sourcing database failed to find a match, indicating the sample was not produced at a facility represented in the database.

  8. Validation of the WATEQ4 geochemical model for uranium

    Energy Technology Data Exchange (ETDEWEB)

    Krupka, K.M.; Jenne, E.A.; Deutsch, W.J.

    1983-09-01

    As part of the Geochemical Modeling and Nuclide/Rock/Groundwater Interactions Studies Program, a study was conducted to partially validate the WATEQ4 aqueous speciation-solubility geochemical model for uranium. The solubility controls determined with the WATEQ4 geochemical model were in excellent agreement with those laboratory studies in which the solids schoepite (UO/sub 2/(OH)/sub 2/ . H/sub 2/O), UO/sub 2/(OH)/sub 2/, and rutherfordine ((UO/sub 2/CO/sub 3/) were identified as actual solubility controls for uranium. The results of modeling solution analyses from laboratory studies of uranyl phosphate solids, however, identified possible errors in the characterization of solids in the original solubility experiments. As part of this study, significant deficiencies in the WATEQ4 thermodynamic data base for uranium solutes and solids were corrected. Revisions included recalculation of selected uranium reactions. Additionally, thermodynamic data for the hydroxyl complexes of U(VI), including anionic (VI) species, were evaluated (to the extent permitted by the available data). Vanadium reactions were also added to the thermodynamic data base because uranium-vanadium solids can exist in natural ground-water systems. This study is only a partial validation of the WATEQ4 geochemical model because the available laboratory solubility studies do not cover the range of solid phases, alkaline pH values, and concentrations of inorganic complexing ligands needed to evaluate the potential solubility of uranium in ground waters associated with various proposed nuclear waste repositories. Further validation of this or other geochemical models for uranium will require careful determinations of uraninite solubility over the pH range of 7 to 10 under highly reducing conditions and of uranyl hydroxide and phosphate solubilities over the pH range of 7 to 10 under oxygenated conditions.

  9. Behaviour of high purity UO{sub 2}/H{sub 2}O interfaces under helium beam irradiation in deaerated conditions; Comportement des interfaces UO{sub 2}/H{sub 2}O de haute purete sous faisceau d'ions He{sup 2+} en milieu desaere

    Energy Technology Data Exchange (ETDEWEB)

    Mendes, E

    2005-11-15

    A question put within the framework of the nuclear fuel storage worn in geological site is what become to them in the presence of water. The aim of a fundamental program, of PRECCI project (ECA), is to highlight the behaviour of interfaces which can be used as models for the interfaces nuclear spent fuel/water if the fuel is uranium UO{sub 2} dioxide. This doctorate is interested in the effect of the alpha activity which is the only one that exist in the spent fuel after long periods. The aim is to identify the mechanisms of alteration and of leaching of surfaces under alpha irradiation. A method is developed to irradiate UO{sub 2}/H{sub 2}O interfaces in deaerated conditions with the beam of He{sup 2+} produced by a cyclotron. The He{sup 2+} ions cross an UO{sub 2} disc and emerge in water with an energy of 5 MeV. Leachings under irradiation are carried with a large range of particles flux. The post-irradiation characterization of the surface of the discs realised by micro-Raman spectroscopy allowed to identify the alteration layer. It is made up of studtite UO{sub 2}(O{sub 2}),4H{sub 2}O, and of schoepite UO{sub 3},xH{sub 2}O. The analysis of the solutions shows that the uranium release strongly increases. The electrochemical properties of the interfaces under irradiation strongly differ from those before irradiation. This work allows to propose that the radiolytic species seen by the interface are it during the heterogeneous phase of evolution of the traces and are species of short lives. Modeling show that the radiolytic radicals species can migrate toward the interface and react with the UO{sub 2} surface. (author)

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

    Science.gov (United States)

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

    2016-04-21

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

  11. Hydrothermal interactions of cesium and strontium phases from spent unreprocessed fuel with basalt phases and basalts

    Energy Technology Data Exchange (ETDEWEB)

    Komarneni, S.; Scheetz, B.E.; McCarthy, G.J.; Coons, W.E.

    1980-03-01

    This investigation is a segment of an extensive research program aimed at investigating the feasibility of long-term, subsurface storage of commercial nuclear waste. Specifically, it is anticipated that the waste will be housed in a repository mined from the basalt formations which lie beneath the Hanford Site. The elements monitored during the present experiments were Cs and Sr. These two elements represent significant biohazards if released from a repository and are the major heat producing radionuclides present in commercial radioactive waste. Several Cs phases and/or solutions were reacted with either isolated basalt phases or bulk-rock basalt, and the resulting solids and solutions were analyzed. The hydrothermal reactivity of SrZrO/sub 3/, which is believed to be a probable host for Sr in SFE was investigated. While so far no evidence exists which indicates that Sr is present in a water soluble phase in spent fuel elements (SFE), detailed investigation of a potential hazard is warranted. This investigation has determined that some Cs compounds likely to be stable components of spent fuel (i.e., CsOH, Cs/sub 2/MoO/sub 4/, Cs/sub 2/U/sub 2/O/sub 7/) have significant hydrothermal solubilities. These solubilities are greatly decreased in the presence of basalt and/or basalt minerals. The decrease in the amount of Cs in solution results from reactions which form pollucite and/or CsAlSiO/sub 4/, with the production of pollucite exceeding that of CsAlSiO/sub 4/. Dissolution of ..beta..-Cs/sub 2/U/sub 2/O/sub 7/ implies solubilizing a uranium species to an undetermined extent. The production of schoepite (UO/sub 3/.3H/sub 2/O) during some experiments containing basalt phases, indicates a tendency to oxidize U/sup 4 +/ to U/sup 6 +/. When diopside (nominally CaMgSi/sub 2/O/sub 6/) and ..beta..-Cs/sub 2/U/sub 2/O/sub 7/ were hydrothermally reacted, at 300/sup 0/C both UO/sub 2/ and UO/sub 3/.3H/sub 2/O were produced. Results of experiments on SrZrO/sub 3/ show it to be

  12. The influence of citric acid, EDTA, and fulvic acid on U(VI) sorption onto kaolinite

    Energy Technology Data Exchange (ETDEWEB)

    Barger, Michelle, E-mail: Michelle.l.barger@wmich.edu [Department of Geosciences, Western Michigan University, Kalamazoo, MI (United States); Koretsky, Carla M. [Department of Geosciences, Western Michigan University, Kalamazoo, MI (United States)

    2011-06-15

    Uranium(VI) sorption onto kaolinite was investigated as a function of pH (3-12), sorbate/sorbent ratio (1 x 10{sup -6}-1 x 10{sup -4} M U(VI) with 2 g/L kaolinite), ionic strength (0.001-0.1 M NaNO{sub 3}), and pCO{sub 2} (0-5%) in the presence or absence of 1 x 10{sup -2}-1 x 10{sup -4} M citric acid, 1 x 10{sup -2}-1 x 10{sup -4} M EDTA, and 10 or 20 mg/L fulvic acid. Control experiments without-solids, containing 1 x 10{sup -6}-1 x 10{sup -4} M U(VI) in 0.01 M NaNO{sub 3} were used to evaluate sorption to the container wall and precipitation of U phases as a function of pH. Control experiments demonstrate significant loss (up to 100%) of U from solution. Although some loss, particularly in 1 x 10{sup -5} and 1 x 10{sup -4} M U experiments, is expected due to precipitation of schoepite, adsorption on the container walls is significant, particularly in 1 x 10{sup -6} M U experiments. In the absence of ligands, U(VI) sorption on kaolinite increases from pH {approx}3 to 7 and decreases from pH {approx}7.5 to 12. Increasing ionic strength from 0.001 to 0.1 M produces only a slight decrease in U(VI) sorption at pH < 7, whereas 10% pCO{sub 2} greatly diminishes U(VI) sorption between pH {approx}5.5 and 11. Addition of fulvic acid produces a small increase in U(VI) sorption at pH < 5; in contrast, between pH 5 and 10 fulvic acid, citric acid, and EDTA all decrease U(VI) sorption. This suggests that fulvic acid enhances U(VI) sorption slightly via formation of ternary ligand bridges at low pH, whereas EDTA and citric acid do not form ternary surface complexes with the U(VI), and that all three ligands, as well as carbonate, form aqueous uranyl complexes that keep U(VI) in solution at higher pH.

  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. Production and characterization of monodisperse uranium particles for nuclear safeguards applications

    Energy Technology Data Exchange (ETDEWEB)

    Knott, Alexander

    2016-07-01

    demonstrated that the particle size can be controlled primarily by the aerosol precursor solution and the production parameters during the aerosol generation - in particular the liquid feed rate and the frequency of the orifice. The final particle morphology is controlled by the precipitation conditions during the conversion from aerosol droplets to solid entities. Small changes to these parameters have a significant influence on the final geometry, size and morphology. The second part of this thesis deals with the characterization of microparticles. A selection of particles was chosen to present the developments over a period of 12 months. Scanning Electron Microscopy coupled with Energy Dispersive X-Ray Spectroscopy (SEM-EDX) was used for various applications, e.g. to verify the elemental content and to assess the size and geometry of the particles. Combined Focused Ion Beam (FIB-SEM) studies revealed the presence of a porous inner structure for all solid particles. Hence, the resulting overall density was less than expected. Time of Flight Secondary Ionization Mass Spectrometry (TOF-SIMS) studies evaluated the elemental content and demonstrated the need for cleanliness since minute quantities of contaminations could be found in single particles. Micro Raman investigations were used to determine the crystallinity, crystal orientation and uranium species. The measurements showed that particles primarily consist of U{sub 3}O{sub 8}. Parts consist of Meta-schoepite and U(IV)-hydroxide which indicates residual water inside the crystal lattice. Micro Raman investigations were performed at CEA (Ile de France) and at the TU-Vienna. SIMS measurements were performed at Safeguards Analytical Services - Environmental Sample Laboratory (SGAS-ESL) on the Large Geometry-SIMS (LG-SIMS) with the scope to assess their performance as a QC material. Particles produced at Juelich were also compared directly against existing QC- and reference materials. Investigations and characterization assays