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Sample records for boltwoodite

  1. Microscopic reactive diffusion of uranium in the contaminated sediments at Hanford, United States

    Science.gov (United States)

    Liu, Chongxuan; Zachara, John M.; Yantasee, Wassana; Majors, Paul D.; McKinley, James P.

    2006-12-01

    Microscopic and spectroscopic analyses of uranium-contaminated sediments from select locations at the U.S. Department of Energy (DOE) Hanford site have revealed that sorbed uranium (U) often exists as uranyl precipitates associated with intragrain fractures of granitic clasts. The release of U to contacting fluids appears to be controlled by intragrain ion diffusion coupled with the dissolution kinetics of the precipitates that exist in the form of Na-boltwoodite. Here we present a coupled microscopic reactive diffusion model for the contaminated sediment on the basis of experimental measurements of intragrain diffusivity in the granitic lithic fragments and the dissolution kinetics of synthetic Na-boltwoodite. Nuclear magnetic resonance, pulse gradient spin echo measurements showed that the intragrain fractures of the granitic clasts isolated from the sediment contained two domains with distinct diffusivities. The fast diffusion domain had an apparent tortuosity of 1.5, while that of the slow region was two orders of magnitude larger. A two-domain diffusion model was assembled and used to infer the geochemical conditions that led to intragrain uranyl precipitation during waste-sediment interaction. Rapid precipitation of Na-boltwoodite was simulated with an alkaline U-containing, high-carbonate tank waste solution that diffused into intragrain fractures, which originally contained Si-rich pore water in equilibrium with feldspar grains in the lithic fragments. The model was also used to simulate uranyl dissolution and release from contaminated sediment to recharge waters. With independently characterized parameters for Na-boltwoodite dissolution, the model simulations demonstrated that diffusion could significantly decrease the rates of intragrain uranyl mineral dissolution due to diffusion-induced local solubility limitation with respect to Na-boltwoodite.

  2. Mineralogic controls on aqueous neptunium(V) concentrations in silicate systems

    Energy Technology Data Exchange (ETDEWEB)

    Alessi, Daniel S., E-mail: daniel.alessi@epfl.ch [Department of Civil Engineering and Geological Sciences, University of Notre Dame, 156 Fitzpatrick Hall, Notre Dame, IN 46556 (United States); Szymanowski, Jennifer E.S. [Department of Civil Engineering and Geological Sciences, University of Notre Dame, 156 Fitzpatrick Hall, Notre Dame, IN 46556 (United States); Forbes, Tori Z. [Department of Civil Engineering and Geological Sciences, University of Notre Dame, 156 Fitzpatrick Hall, Notre Dame, IN 46556 (United States); Department of Chemistry, University of Iowa, Room E331 CB, Iowa City, IA 52242 (United States); Quicksall, Andrew N. [Department of Civil Engineering and Geological Sciences, University of Notre Dame, 156 Fitzpatrick Hall, Notre Dame, IN 46556 (United States); Department of Civil and Environmental Engineering, Southern Methodist University, P.O. Box 750340, Dallas, TX 75275 (United States); Sigmon, Ginger E.; Burns, Peter C.; Fein, Jeremy B. [Department of Civil Engineering and Geological Sciences, University of Notre Dame, 156 Fitzpatrick Hall, Notre Dame, IN 46556 (United States)

    2013-02-15

    The presence of radioactive neptunium in commercially spent nuclear fuel is problematic due to its mobility in environmental systems upon oxidation to the pentavalent state. As uranium is the major component of spent fuel, incorporation of neptunium into resulting U(VI) mineral phases would potentially influence its release into environmental systems. Alternatively, aqueous neptunium concentrations may be buffered by solid phase Np{sub 2}O{sub 5}. In this study, we investigate both of these controls on aqueous neptunium(V) concentrations. We synthesize two uranyl silicates, soddyite, (UO{sub 2}){sub 2}SiO{sub 4}·2H{sub 2}O, and boltwoodite, (K, Na)(UO{sub 2})(SiO{sub 3}OH)·1.5H{sub 2}O, each in the presence of two concentrations of aqueous Np(V). Electron microscopy and electron diffraction analyses of the synthesized phases show that while significant neptunyl incorporation occurred into soddyite, the Np(V) in the boltwoodite systems largely precipitated as a secondary phase, Np{sub 2}O{sub 5(s)}. The release of Np(V) from each system into aqueous solution was measured for several days, until steady-state concentrations were achieved. Using existing solubility constants (K{sub sp}) for pure soddyite and boltwoodite, we compared predicted equilibrium aqueous U(VI) concentrations with the U(VI) concentrations released in the solubility experiments. Our experiments reveal that Np(V) incorporation into soddyite increases the concentration of aqueous U in equilibrium with the solid phase, perhaps via the formation of a metastable phase. In the mixed boltwoodite – Np{sub 2}O{sub 5(s)} system, the measured aqueous U(VI) activities are consistent with those predicted to be in equilibrium with boltwoodite under the experimental conditions, a result that is consistent with our conclusion that little Np(V) incorporation occurred into the boltwoodite. In the boltwoodite systems, the measured Np concentrations are likely controlled by the presence of Np{sub 2}O{sub 5

  3. 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

  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. 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.

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

    International Nuclear Information System (INIS)

    A set of experiments, wherein UO2 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 UO2 have been performed for all experiments, while the reacted UO2 surfaces have been examined for the terminated experiments. A pulse of uranium release from the UO2 solid, combined with the formation of schoepite on the surface of the UO2, 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