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Sample records for boltwoodite

  1. New data on boltwoodite

    International Nuclear Information System (INIS)

    Bayushkin, I.M.; Butler, A.S.; Gurvich, M.Yu.

    1984-01-01

    New data on boltwoodite (uranyl silicate) discovered in the oxidation zone of carbonatite massif of Pliocene-Quaternary age in Afghanistan are presented. The mineral is established by means of X-ray diffraction analysis. Parameters of the elementary cell of K-Na-boltwoodite essentially differ from those given earlier. The results of high-temperature X-ray diffraction analysis have revealed that water weakly bound and removing at t deg =130 deg and structurally bound partially removing from the mineral at t deg above 300 deg occurs in K-Na-boltwoodite. At heating up to 540 deg K-Na-boltwoodite passes the stage of amorphization and at further increase of temperature decrystallization of sodium, potassium uranates and minerals of complex composition (of vicsite type) is observed

  2. The Dissolution of Synthetic Na-Boltwoodite in Sodium Carbonate Solutions

    International Nuclear Information System (INIS)

    Ilton, Eugene S.; Liu, Chongxuan; Yantasee, Wassana; Wang, Zheming; Moore, Dean A.; Felmy, Andrew R.; Zachara, John M.

    2006-01-01

    Uranyl silicates such as uranophane and Na-boltwoodite appear to control the solubility of uranium in the contaminated sediments at the US Department of Energy Hanford site (Liu et al., 2004). Consequently, the solubility of synthetic Na-boltwoodite was determined over a wide range of bicarbonate concentrations, from circumneutral to alkaline pH, that are representative of porewater and groundwater compositions at the Hanford site. Results show that Na-boltwoodite dissolution was nearly congruent and its solubility increased with increasing bicarbonate concentration. Calculated solubility constants varied by nearly 2 log units from low bicarbonate (no added NaCO3) to 50 mmol/L bicarbonate. However, the solubility constants only vary by 0.5 log units from 0 added bicarbonate to 1.2 mmol/L bicarbonate, where logKsp = 5.39-5.92 and the average logKsp = 5.63. No systematic trend in logKsp was apparent over this range in bicarbonate concentrations. LogKsp values trended down with increasing bicarbonate concentration, where logKsp = 4.06 at 50 mmol/L bicarbonate. We conclude that the calculated solubility constants at high bicarbonate are compromised by an incomplete or inaccurate uranyl-carbonate speciation model

  3. Influence of Calcium on Microbial Reduction of Solid Phase Uranium (VI)

    International Nuclear Information System (INIS)

    Liu, Chongxuan; Jeon, Byong-Hun; Zachara, John M.; Wang, Zheming

    2007-01-01

    The effect of calcium on microbial reduction of a solid phase U(VI), sodium boltwoodite (NaUO2SiO3OH · 1.5H2O), was evaluated in a culture of a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1. Batch experiments were performed in a non-growth bicarbonate medium with lactate as electron donor at pH 7 buffered with PIPES. Calcium increased both the rate and extent of Na-boltwoodite dissolution by increasing its solubility through the formation of a ternary aqueous calcium-uranyl-carbonate species. The ternary species, however, decreased the rates of microbial reduction of aqueous U(VI). Laser-induced fluorescence spectroscopy (LIFS) and transmission electron microscopy (TEM) revealed that microbial reduction of solid phase U(VI) is a sequentially coupled process of Na-boltwoodite dissolution, U(VI) aqueous speciation, and microbial reduction of dissolved U(VI) to U(IV) that accumulated on bacterial surfaces/periplasm. The overall rates of microbial reduction of solid phase U(VI) can be described by the coupled rates of dissolution and microbial reduction that were both influenced by calcium. The results demonstrated that dissolved U(VI) concentration during microbial reduction was a complex function of solid phase U(VI) dissolution kinetics, aqueous U(VI) speciation, and microbial activity

  4. Quantum-Mechanical Methods for Quantifying Incorporation of Contaminants in Proximal Minerals

    Directory of Open Access Journals (Sweden)

    Lindsay C. Shuller-Nickles

    2014-07-01

    Full Text Available Incorporation reactions play an important role in dictating immobilization and release pathways for chemical species in low-temperature geologic environments. Quantum-mechanical investigations of incorporation seek to characterize the stability and geometry of incorporated structures, as well as the thermodynamics and kinetics of the reactions themselves. For a thermodynamic treatment of incorporation reactions, a source of the incorporated ion and a sink for the released ion is necessary. These sources/sinks in a real geochemical system can be solids, but more commonly, they are charged aqueous species. In this contribution, we review the current methods for ab initio calculations of incorporation reactions, many of which do not consider incorporation from aqueous species. We detail a recently-developed approach for the calculation of incorporation reactions and expand on the part that is modeling the interaction of periodic solids with aqueous source and sink phases and present new research using this approach. To model these interactions, a systematic series of calculations must be done to transform periodic solid source and sink phases to aqueous-phase clusters. Examples of this process are provided for three case studies: (1 neptunyl incorporation into studtite and boltwoodite: for the layered boltwoodite, the incorporation energies are smaller (more favorable for reactions using environmentally relevant source and sink phases (i.e., ΔErxn(oxides > ΔErxn(silicates > ΔErxn(aqueous. Estimates of the solid-solution behavior of Np5+/P5+- and U6+/Si4+-boltwoodite and Np5+/Ca2+- and U6+/K+-boltwoodite solid solutions are used to predict the limit of Np-incorporation into boltwoodite (172 and 768 ppm at 300 °C, respectively; (2 uranyl and neptunyl incorporation into carbonates and sulfates: for both carbonates and sulfates, it was found that actinyl incorporation into a defect site is more favorable than incorporation into defect-free periodic

  5. A study on mineralization U,REE and related processes in anomaly No.6 Khoshomy area central Iran

    International Nuclear Information System (INIS)

    Heidaryan, F.

    2005-01-01

    Uranium mineralization in Khoshomy prospect, located in central. part of Iran, with 303-15000 (cps) and 14 to 4000 (ppm) released, The main rock types include: gneiss, granite, pegmatite and migmatite, that influenced by pegmatite-albitic vines (quartz-heldespatic). Acidic and basic dykes, granodioritic, units and dolomite and marble have been seen. The alteration associated with the mineralization is potassic, argillic, propylitic, carbonization, silisificaition and hematitizaition. Uranium mineralization occurred in a hydrothermal phase with Cu, Mo, Ni and Au elements. Uranium primary minerals include pitchblende, coffinite, uraninite; and uranium secondary minerals include uranophane and . boltwoodite. REE mineralization occurred by the potassic phase in peginatitization process

  6. Advective Removal of Intraparticle Uranium from Contaminated Vadose Zone Sediments, Hanford, USA

    International Nuclear Information System (INIS)

    Ilton, Eugene S.; Qafoku, Nikolla; Liu, Chongxuan; Moore, D. A.; Zachara, John M.

    2008-01-01

    A column study on U contaminated vadose zone sediments from the Hanford Site, WA, was performed in order to aid the development of a model for predicting U(VI) release rates under a dynamic flow regime and for variable geochemical conditions. The sediments of interest are adjacent to and below tank BX-102, part of the BX tank farm that contained high level liquid radioactive waste. Two sediments, with different U(VI) loadings and intraparticle large fracture vs. smaller fracture ratios, were reacted with three different solutions. The primary reservoir for U(VI) appears to be a micron-sized nanocrystalline Na-U-Si phase, possibly Na-boltwoodite, that nucleated and grew on plagioclase grains that line fractures within sand-sized granitic clasts. The solutions were all calcite saturated and in equilibrium with atmospheric CO2, where one solution was simply DI-water, the second was a synthetic ground water (SGW) with elevated Na, and the third was the same SGW but with both elevated Na and Si. The latter two solutions were employed, in part, to test the effect of saturation state on U(VI) release. For both sediments and all three electrolytes, there was an initial rapid release of U(VI) to the advecting solution followed by a plateau of low U(VI) concentration. U(VI) effluent concentration increased during subsequent stop flow (SF) events. The electrolytes with elevated Na and Si appreciably depressed U(VI) concentrations relative to DI water. The effluent data for both sediments and all three electrolytes was simulated reasonably well by a three domain model (the advecting fluid, fractures, and matrix) that coupled U(VI) dissolution rates, intraparticle U(VI) diffusion, and interparticle advective transport of U(VI); where key transport and dissolution processes had been parameterized in previous batch studies. For the calcite-saturated DI-water, U(VI) concentrations in the effluent remained far below saturation with respect to Na-boltwoodite and release of U(VI) to

  7. Corrosion mechanisms of spent fuel under oxidizing conditions

    International Nuclear Information System (INIS)

    Finn, P.A.; Finch, R.; Buck, E.; Bates, J.

    1997-01-01

    The release of 99 Tc can be used as a reliable marker for the extent of spent oxide fuel reaction under unsaturated high-drip-rate conditions at 90 degrees C. Evidence from leachate data and from scanning and transmission electron microscopy (SEM and TEM) examination of reacted fuel samples is presented for radionuclide release, potential reaction pathways, and the formation of alteration products. In the ATM-103 fuel, 0.03 of the total inventory of 99 Tc is released in 3.7 years under unsaturated and oxidizing conditions. Two reaction pathways that have been identified from SEM are (1) through-grain dissolution with subsequent formation of uranyl alteration products, and (2) grain-boundary dissolution. The major alteration product identified by x-ray diffraction (XRD) and SEM, is Na-boltwoodite, Na[(UO 2 )(SiO 3 OH)]lg-bullet H 2 O, which is formed from sodium and silicon in the water leachant

  8. Remediation of Uranium in the Hanford Vadose Zone Using Ammonia Gas: FY 2010 Laboratory-Scale Experiments

    International Nuclear Information System (INIS)

    Szecsody, James E.; Truex, Michael J.; Zhong, Lirong; Qafoku, Nikolla; Williams, Mark D.; McKinley, James P.; Wang, Zheming; Bargar, John; Faurie, Danielle K.; Resch, Charles T.; Phillips, Jerry L.

    2010-01-01

    This investigation is focused on refining an in situ technology for vadose zone remediation of uranium by the addition of ammonia (NH3) gas. Objectives are to: (a) refine the technique of ammonia gas treatment of low water content sediments to minimize uranium mobility by changing uranium surface phases (or coat surface phases), (b) identify the geochemical changes in uranium surface phases during ammonia gas treatment, (c) identify broader geochemical changes that occur in sediment during ammonia gas treatment, and (d) predict and test injection of ammonia gas for intermediate-scale systems to identify process interactions that occur at a larger scale and could impact field scale implementation. Overall, NH3 gas treatment of low-water content sediments appears quite effective at decreasing aqueous, adsorbed uranium concentrations. The NH3 gas treatment is also fairly effective for decreasing the mobility of U-carbonate coprecipitates, but shows mixed success for U present in Na-boltwoodite. There are some changes in U-carbonate surface phases that were identified by surface phase analysis, but no changes observed for Na-boltwoodite. It is likely that dissolution of sediment minerals (predominantly montmorillonite, muscovite, kaolinite) under the alkaline conditions created and subsequent precipitation as the pH returns to natural conditions coat some of the uranium surface phases, although a greater understanding of these processes is needed to predict the long term impact on uranium mobility. Injection of NH3 gas into sediments at low water content (1% to 16% water content) can effectively treat a large area without water addition, so there is little uranium mobilization (i.e., transport over cm or larger scale) during the injection phase.

  9. Remediation of Uranium in the Hanford Vadose Zone Using Ammonia Gas: FY 2010 Laboratory-Scale Experiments

    Energy Technology Data Exchange (ETDEWEB)

    Szecsody, James E.; Truex, Michael J.; Zhong, Lirong; Qafoku, Nikolla; Williams, Mark D.; McKinley, James P.; Wang, Zheming; Bargar, John; Faurie, Danielle K.; Resch, Charles T.; Phillips, Jerry L.

    2010-12-01

    This investigation is focused on refining an in situ technology for vadose zone remediation of uranium by the addition of ammonia (NH3) gas. Objectives are to: a) refine the technique of ammonia gas treatment of low water content sediments to minimize uranium mobility by changing uranium surface phases (or coat surface phases), b) identify the geochemical changes in uranium surface phases during ammonia gas treatment, c) identify broader geochemical changes that occur in sediment during ammonia gas treatment, and d) predict and test injection of ammonia gas for intermediate-scale systems to identify process interactions that occur at a larger scale and could impact field scale implementation.Overall, NH3 gas treatment of low-water content sediments appears quite effective at decreasing aqueous, adsorbed uranium concentrations. The NH3 gas treatment is also fairly effective for decreasing the mobility of U-carbonate coprecipitates, but shows mixed success for U present in Na-boltwoodite. There are some changes in U-carbonate surface phases that were identified by surface phase analysis, but no changes observed for Na-boltwoodite. It is likely that dissolution of sediment minerals (predominantly montmorillonite, muscovite, kaolinite) under the alkaline conditions created and subsequent precipitation as the pH returns to natural conditions coat some of the uranium surface phases, although a greater understanding of these processes is needed to predict the long term impact on uranium mobility. Injection of NH3 gas into sediments at low water content (1% to 16% water content) can effectively treat a large area without water addition, so there is little uranium mobilization (i.e., transport over cm or larger scale) during the injection phase.

  10. Np Incorporation into Uranyl Alteration Phases: A Quantum Mechanical Approach

    International Nuclear Information System (INIS)

    L.C. Huller; R.C. Win; U.Ecker

    2006-01-01

    Neptunium is a major contributor to the long-term radioactivity in a geologic repository for spent nuclear fuel (SNF) due to its long half-life (2.1 million years). The mobility of Np may be decreased by incorporation into the U 6+ phases that form during the corrosion of SNF. The ionic radii of Np (0.089nm) and U (0.087nm) are similar, as is their chemistry. Experimental studies have shown Np can be incorporated into uranyl phases at concentrations of ∼ 100 ppm. The low concentration of Np in the uranyl phases complicates experimental detection and presents a significant challenge for determining the incorporation mechanism. Therefore, we have used quantum mechanical calculations to investigate incorporation mechanisms and evaluate the energetics of Np substituting for U. CASTEP, a density functional theory based code that uses plane waves and pseudo-potentials, was used to calculate optimal H positions, relaxed geometry, and energy of different uranyl phases. The incorporation energy for Np in uranyl alteration phases was calculated for studtite, [(UO 2 )O 2 (H 2 O) 2 ](H 2 ) 2 , and boltwoodite, HK(UO 2 )(SiO 4 )* 1.5(H 2 O). Studtite is the rare case of a stable uranyl hydroxyl-peroxide mineral that forms in the presence of H 2 O 2 from the radiolysis of H 2 O. For studtite, two incorporation mechanisms were evaluated: (1) charge-balanced substitution of Np 5+ and H + for one U 6+ , and (2) direct substitution of Np 6+ for U 6+ . For boltwoodite, the H atomic positions prior to Np incorporation were determined, as well as the Np incorporation mechanisms and the corresponding substitution energies. The preferential incorporation of Np into different structure types of U 6+ minerals was also investigated. Quantum mechanical substitution energies have to be derived at Np concentrations higher than the ones found in experiments or expected in a repository. However, the quantum mechanical results are crucial for subsequent empirical force-field and Monte

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

    International Nuclear Information System (INIS)

    Prasad, R.S.; Money, N.J.; Thieme, J.G.

    1979-01-01

    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)

  12. Uranium Phases in Contaminated Sediments Below Hanford's U Tank Farm

    International Nuclear Information System (INIS)

    Um, Wooyong; Wang, Zheming; Serne, R. Jeffrey; Williams, Benjamin D.; Brown, Christopher F.; Dodge, Cleveland J.; Francis, Arokiasamy J.

    2009-01-01

    Macroscopic and spectroscopic investigations (XAFS, XRF and TRLIF) on Hanford contaminated vadose zone sediments from the U-tank farm showed that U(VI) exists as different surface phases as a function of depth below ground surface (bgs). Dominant U(VI) silicate precipitates (boltwoodite and uranophane) were present in shallow-depth sediments (15-16 m bgs). In the intermediate depth sediments (20-25 m bgs), adsorbed U(VI) phases dominated but small amounts of surface precipitates consisting of polynuclear U(VI) surface complex were also identified. The deep depth sediments (> 28 m bgs) showed no signs of contact with tank wastes containing Hanford-derived U(VI), but natural uranium solid phases were observed. Most of the U(VI) was preferentially associated with the silt and clay size fractions and showed strong correlation with Ca, especially for the precipitated U(VI) silicate phase in the shallow depth sediments. Because U(VI) silicate precipitates dominate the U(VI) phases in the shallow depth sediments, macroscopic (bi)carbonate leaching should result in U(VI) releases from both desorption and dissolution processes. Having several different U(VI) surface phases in the Hanford contaminated sediments indicates that the U(VI) release mechanism could be complicated and that detailed characterization of the sediments would be needed to estimate U(VI) fate and transport in vadose zone

  13. Leaching action of EJ-13 water on unirradiated UO2 surfaces under unsaturated conditions at 90 degree C: Interim report

    International Nuclear Information System (INIS)

    Wronkiewicz, D.J.; Bates, J.K.; Gerding, T.J.; Veleckis, E.; Tani, B.S.

    1991-07-01

    A set of experiments, based on the application of the Unsaturated Test method to the reaction of UO 2 with EJ-13 water, has been conducted over a period of 182.5 weeks. One half of the experiments have been terminated, while one half are still ongoing. Solutions that have dripped from UO 2 specimens have been analyzed for all experiments, while the reacted UO 2 surfaces have been examined for only the terminated experiments. A pulse of uranium release from the UO 2 solid, in conjunction with the formation of dehydrated schoepite on the surface of the UO 2 , was observed during the 39- to 96-week period. Thereafter, the uranium release decreased and a second set of secondary phases was observed. The latter phases incorporate cations from the EJ-13 water and include boltwoodite, uranophane, sklodowskite, compreignacite, and schoepite. The experiments are being continued to monitor for additional changes in solution composition and secondary phase formation, and have now reached the 319-week period. 9 refs., 17 figs., 25 tabs

  14. Identification of secondary phases formed during unsaturated reaction of UO2 with EJ-13 water

    International Nuclear Information System (INIS)

    Bates, J.K.; Tani, B.S.; Veleckis, E.

    1989-01-01

    A set of experiments, wherein UO 2 has been contacted by dripping water, has been conducted over a period of 182.5 weeks. The experiments are being conducted to develop procedures to study spent fuel reaction under unsaturated conditions that are expected to exist over the lifetime of the proposed Yucca Mountain repository site. One half of the experiments have been terminated, while one half are ongoing. Analyses of solutions that have dripped from the reacted UO 2 have been performed for all experiments, while the reacted UO 2 surfaces have been examined for the terminated experiments. A pulse of uranium release from the UO 2 solid, combined with the formation of schoepite on the surface of the UO 2 , was observed between 39 and 96 weeks of reaction. Thereafter, the uranium release decreased and a second set of secondary phases was observed. The latter phases incorporated cations from the EJ-13 water and included boltwoodite, uranophane, sklodowskite, compreignacite, and schoepite. The experiments are continuing to monitor whether additional changes in solution chemistry or secondary phase formation occurs. 6 refs., 2 figs., 2 tabs

  15. Atomistic modeling of the solid-state chemistry of actinide materials

    Science.gov (United States)

    Shuller, Lindsay C.

    Materials that incorporate actinides are critical to the nuclear fuel cycle, either as nuclear fuels or nuclear waste forms. In this thesis, I examine four materials: i) ThO2-UO2 solid solutions, ii) binary ThO2-CeO2-ZrO2 solid solutions, iii) Np-doped studtite, iv) Np-doped boltwoodite. Computational methods, particularly density functional theory (DFT) calculations and Monte-Carlo (MC) simulations, are used to determine the energetics and structures of these actinide-bearing materials. The solid-solution behavior of nuclear fuels and nuclear waste forms indicate the thermodynamic stability of the material, which is important for understanding the in-reactor fuel properties and long-term stability of used fuel. The ThxU1-xO2 and ThxCe 1-xO2 binaries are almost completely miscible; however, DeltaGmix reveals a small tendency for the systems to exsolve (e.g., DeltaEexsoln(Th xU1-xO2) = 0.13 kJ/(mol cations) at 750 K). Kinetic hindrances (e.g., interfacial energy) may inhibit exsolution, especially at the low temperatures necessary to stabilize the nanoscale exsolution lamellae observed in the ThxU1-xO2 and Ce xZr1-xO2 binaries. Miscibility in the Zr-bearing binaries is limited. At 1400 °C, only 3.6 and 0.09 mol% ZrO2 is miscible in CeO2 and ThO2, respectively. The incorporation of minor amounts of Np5+,6+ into uranium alteration phases, e.g., studtite [UO2O2 (H2O)4] or boltwoodite [K(UO2)(SiO 3OH)(H2O)1.5] , may limit the mobility of aqueous neptunyl complexes released from oxidized nuclear fuels. Np6+-incorporation into studtite requires less energy than Np5+-incorporation (e.g., with source/sink = Np2O5/UO 3 DeltaEincorp(Np6+) = 0.42 eV and DeltaEincorp(Np5+) = 1.12 eV). In addition, Np6+ is completely miscible in studtite at room temperature with respect to a hypothetical Np6+-studtite. Electronic structure calculations provide insight into Np-bonding in studtite. The Np 5f orbitals are within the band gap of studtite, resulting in the narrowing of the band gap

  16. 79Se: geochemical and crystallo-chemical retardation mechanisms

    International Nuclear Information System (INIS)

    Chen, F.; Ewing, R.C.

    1999-01-01

    79 Se is a long-lived (1.1 x 10 6 yrs) fission product which is chemically and radiologically toxic. Under Eh-pH conditions typical of oxidative alteration of spent nuclear fuel, selenite, SeO 3 2- or HSeO 3 - or selenate, SeO 4 2- , are the dominant aqueous species of selenium. Because of the high solubility of metal-selenites and metal-selenates and the low adsorption of selenite and selenate aqueous species by geological materials under alkaline conditions, selenium may be highly mobile. However, 79 Se released from altered fuel may become immobilized by incorporation into secondary uranyl phases as low concentration impurities, and this may significantly reduce the mobility of selenium. Analysis and comparison of the known structures of uranyl phases indicate that (SeO 3 ) may substitute for (SiO 3 OH) in structures of α-uranophane and boltwoodite that are expected to be the dominant alteration products of UO 2 in Si-rich groundwater. The substitutions (SeO 3 ) (SiO 3 OH) in sklodowskite, Mg[(UO 2 )(SiO 3 OH)] 2 (H 2 O) 6 and (SeO 3 ) (PO 4 ) in phurcalite, Ca 2 [(UO 2 ) 3 (PO 4 ) 2 O 2 ](H 2 O) 7 , may occur with the eliminated apical anion being substituted for by an H 2 O group, but experimental investigation is required. The close similarity between the sheets in the structures of rutherfordine, [(UO 2 )(CO 3 )] and [(UO 2 )(SeO 3 )] implies that the substitution (SeO 3 ) (CO 3 ) can occur in rutherfordine, and possibly other uranyl carbonates. However, the substitutions: (SeO 3 ) (SiO 4 ) in soddyite and (SeO 3 ) (PO 4 ) in phosphuranylite may disrupt their structural connectivity and are, therefore, unlikely. (orig.)

  17. Leaching patterns and secondary phase formation during unsaturated leaching of UO2 at 90 degrees C

    International Nuclear Information System (INIS)

    Wronkiewicz, D.J.; Bates, J.K.; Gerding, T.J.; Veleckis, E.; Tani, B.S.

    1991-11-01

    Experiments are being conducted that examine the reaction of UO 2 with dripping oxygenated ground water at 90 degrees C. The experiments are designed to identify secondary phases formed during UO 2 alteration, evaluate parameters controlling U release, and act as scoping tests for studies with spent fuel. This study is the first of its kind that examines the alteration of UO 2 under unsaturated conditions expected to exist at the proposed Yucca Mountain repository site. Results suggest the UO 2 matrix will readily react within a few months after being exposed to simulated Yucca Mountain conditions. A pulse of rapid U release, combined with the formation of dehydrated schoepite on the UO 2 surface, characterizes the reaction between one to two years. Rapid dissolution of intergrain boundaries and spallation of UO 2 granules appears to be responsible for much of the U released. Differential release of the UO 2 granules may be responsible for much of the variation observed between duplicate experiments. Less than 5 wt % of the released U remains in solution or in a suspended form, while the remaining settles out of solution as fine particles or is reprecipitated as secondary phases. Subsequent to the pulse period, U release rates decline and a more stable assemblage of uranyl silicate phases are formed by incorporating cations from the ground water leachant. Uranophane, boltwoodite, and sklodowskite appear as the final solubility limiting phases that form in these tests. This observed paragenetic sequence (from uraninite to schoepite-type phases to uranyl silicates) is identical to those observed in weathered zones of natural uraninite occurrences. The combined results indicate that the release of radionuclides from spent fuel may not be limited by U solubility constraints, but that spallation of particulate matter may be an important, if not the dominant release mechanism affecting release

  18. 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