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 Np2O5. In this study, we investigate both of these controls on aqueous neptunium(V) concentrations. We synthesize two uranyl silicates, soddyite, (UO2)2SiO4·2H2O, and boltwoodite, (K, Na)(UO2)(SiO3OH)·1.5H2O, 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, Np2O5(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 (Ksp) 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 – Np2O5(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 Np2O5 nanoparticles, suggesting an additional potential mobility vector for Np in geologic systems. Our
Liu, Chongxuan; Zachara, John M.; Yantasee, Wassana; Majors, Paul D.; McKinley, James P.
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.
Microscopic and spectroscopic analysis of uranium-contaminated sediment cores beneath the BX waste tank farm at the US Department of Energy (DOE) Hanford site revealed that uranium (U) existed as uranyl precipitates primarily associated with the intragrain fractures of granitic clasts in the sediment (McKinley et al. 2005). The dissolution of the precipitates appeared to be controlled by intragrain ion diffusion coupled with the dissolution kinetics of the uranyl precipitates most likely as Na-boltwoodite. Here we presented a coupled microscopic reactive diffusion model by independently characterizing the intragrain diffusion and dissolution kinetics of Na-boltwoodite. Diffusion characterization with a nuclear magnetic resonance (NMR) pulse gradient spin-echo (PGSE) technique showed that the intragrain fractures of the granitic clasts in the Hanford sediment contain two domains with distinct diffusivities. The fast diffusion domain has an apparent tortuosity of about 1.5, while the slow region has a tortuosity of 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 when the sediment was contaminated by U-containing wastes at the site. Rapid precipitation of Na-boltwoodite was simulated when a U-containing, alkaline caustic, and high carbonate tank waste solution diffused into intragrain fractures originally containing Si-rich solutions. The model was also used to simulate uranyl dissolution and release from the contaminant sediment to aqueous solutions. 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, and the intragrain uranyl precipitates could serve as a long-term uranyl source for the vadose porewater and underlying groundwater at this site
The degree of radioactive nonequilibrium of ores was found to increase in the following order in accordance with the varying mineral content: relatively coarse-grained uraninite (UO2) - coffinite (USiO4), brannerite (UTi2O6) - secondary fine grained coffinite, brannerite-secondary minerals of thin veins, boltwoodite ((Ca,Na,K)(UO2)[SiO3OH]·1.5H2O), and membranous uraninite (UO2.25). This is ascribed to a different loss of radioactive recoil atoms by crystals because of real crystals dimensions and defects and features of ideal atomic structure of minerals
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
Friese, Judah I.; Douglas, Matthew; McNamara, Bruce K.; Clark, Sue B.; Hanson, Brady D.
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.
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.
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.
Geochemical information relevant to the retention of radionuclides by candidate high-level nuclear waste geologic repositories being characterized by Department of Energy (DOE) projects is being evaluated by Oak Ridge National Laboratory (ORNL) for the Nuclear Regulatory Commission (NRC). During this report period, emphasis was given to evaluation of published sorption and solubility information for key radionuclides which is relevant to the Hanford Site in the Columbia River basalts. The removal of neptunium from solution by basalt/groundwater systems under anoxic redox conditions at 600C proved to be sensitive to the basalt particle size and the test contact time. it was not possible to establish if the neptunium removal from solution was due to sorption or precipitation processes. In studies of uranium solubility, sodium boltwoodite was shown to be the U(VI)-containing phase that precipitates from synthetic groundwater at 600C. The precipitation of sodium boltwoodite, rather than schoepite which is predicted by geochemical modeling, shows the importance of identifying the solid phase in radionuclide experiments and highlights the weaknesses of the actinide thermodynamic data bases used in geochemical modeling calculations. An evaluation was made of the information developed by DOE on the native copper deposits of Michigan as a natural analog for the possible emplacement of copper canisters in a repository in basalt. The similarity in bulk chemistry of the basalts, relied upon heavily controls, particularly controls on the geochemical conditions, exist within the basalt/water systems at Michigan and the Hanford Site. Thus, the DOE analysis is insufficient to conclude, with reasonable assurance, that copper will be stable at the Hanford Site
Nagy, K. L.; Sturchio, N. C.; Klie, R. F.; Skanthakumar, S.; Soderholm, L.
Uranium(VI)-silicates are the dominant crystalline form of U(VI) at and near Earth's surface, but are difficult to form as pure phases under ambient conditions because of slow reaction kinetics aided by similar thermodynamic stabilities of the many possible minerals. We have investigated the effects of pH (2 to 11) and time (1 to 10 days) on the formation of U(VI)-silicates from initial solutions with U = 0.05 M and a fixed molar ratio of U:Si = 2:1, 1:1, 1:2, and 1:5 using high-energy X-ray scattering (HEXS), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), powder X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM) and solution thermodynamic modeling. Previously, we used HEXS to identify from solutions with U:Si = 1:2 at pH 5 to 9, aged for one day, a trimeric U-silicate structural unit, or synthon, approximately one nanometer in dimension with U-U correlation lengths of about 0.4 nm. This synthon is a structural building block in uranyl silicate minerals such as soddyite, boltwoodite, and weeksite. ATR-FTIR results on the full set of samples show systematic changes in peak positions along with appearance and disappearance of vibrational modes that occurred with reaction time, pH and/or U:Si ratio; whereas, XRD indicated only a crystalline Na-boltwoodite-like phase at pH 11 and without the correlation length-scale resolution of HEXS. HRTEM results show few particles in a matrix of material containing areas having the lower correlation length visible in HEXS data. The data show clearly different mixtures of solids, including silica, and precipitate sizes under all conditions that transform over the 1 to 10 day aging period. The experimental reactions simulate conditions in the subsurface at sites contaminated with uranium, and the results are relevant to processes of uranium adsorption and colloid formation. [This work is supported by DOE's Environmental Remediation Science Program].
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)
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
Experiments are being conducted that examine the reaction of UO2 with dripping oxygenated ground water at 90 degrees C. The experiments are designed to identify secondary phases formed during UO2 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 UO2 under unsaturated conditions expected to exist at the proposed Yucca Mountain repository site. Results suggest the UO2 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 UO2 surface, characterizes the reaction between one to two years. Rapid dissolution of intergrain boundaries and spallation of UO2 granules appears to be responsible for much of the U released. Differential release of the UO2 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
Kanematsu, Masakazu; Perdrial, Nicolas; Um, Wooyong; Chorover, Jon; O'Day, Peggy A
Uranium speciation and physical-chemical characteristics were studied in solids precipitated from synthetic acidic to circumneutral wastewaters in the presence and absence of dissolved silica and phosphate to examine thermodynamic and kinetic controls on phase formation. Composition of synthetic wastewater was based on disposal sites 216-U-8 and 216-U-12 Cribs at the Hanford site (WA, USA). In the absence of dissolved silica or phosphate, crystalline or amorphous uranyl oxide hydrates, either compreignacite or meta-schoepite, precipitated at pH 5 or 7 after 30 d of reaction, in agreement with thermodynamic calculations. In the presence of 1 mM dissolved silica representative of groundwater concentrations, amorphous phases dominated by compreignacite precipitated rapidly at pH 5 or 7 as a metastable phase and formation of poorly crystalline boltwoodite, the thermodynamically stable uranyl silicate phase, was slow. In the presence of phosphate (3 mM), meta-ankoleite initially precipitated as the primary phase at pH 3, 5, or 7 regardless of the presence of 1 mM dissolved silica. Analysis of precipitates by U LIII-edge extended X-ray absorption fine structure (EXAFS) indicated that "autunite-type" sheets of meta-ankoleite transformed to "phosphuranylite-type" sheets after 30 d of reaction, probably due to Ca substitution in the structure. Low solubility of uranyl phosphate phases limits dissolved U(VI) concentrations but differences in particle size, crystallinity, and precipitate composition vary with pH and base cation concentration, which will influence the thermodynamic and kinetic stability of these phases. PMID:24754743