bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Effect of Cs On The Structural Properties Of Barium Titanate Hollandites
Authors: Whittle K.R. , Lumpkin G.R. , Ashbrook S.E. 
Published: April 2011

AbstractHollandite, based on Ba and Ti, has been shown to be an ideal medium by which active 135Cs and 137Cs can be immobilised. Diffraction measurements have shown that Cs modifies the symmetry of the material, from monoclinic to tetragonal. Experiments carried out here show the effects of Cs on two hollandite systems based on Ba-Al-Ti and Ba-Mg-Ti. Structural measurements are reported for neutron diffraction, and MAS NMR. The results show that Cs modifies the overall crystal symmetry while having little effect on the order/disorder of Al-Ti and Mg-Ti octahedra.
Mn Oxidation States in Bax CsyMnzTi8-zO16
Authors: Carter M.L. , Vance E.R. , Mitchell D. R. G. , Zhang Z. 
Published: April 2011

AbstractTwo Bax CsyMnzTi8-zO16 hollandite samples, containing excess rutile, have been prepared, targeting the Mn valence as 3+ by sintering at 1300oC in air (z = 2x +y) and as 2+ (z = x + y/2) in argon. SEM showed the sample sintered in air to contain major hollandite and minor Mn titanate and rutile. The sample sintered in argon contain major hollandite, and minor Ba titanate and rutile. X-ray absorption near edge spectroscopy (XANES), electron energy loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS) were used to determine the oxidation state of the Mn in the samples. Transmission manganese K-edge X-ray absorption spectra of the samples were similar but the precise ratio of oxidation states could not be calculated from these spectra.
Compositional Effects on the Long-Term Durability of Nuclear Waste Glasses: A Statistical Approach
Authors: Ribet Solange , Muller Isabelle S. , Pegg Ian L. , Gin Stéphane , Frugier Pierre 
Published: April 2011

AbstractAs a result of the development of a reference glass formulation for the immobilization of West-Valley nuclear waste, a large number of glass compositions have been tested under a variety of leaching conditions for extended durations. In this work, data from the standard PCT leaching procedure (deionized water, 90°C, S/V = 2000 m-1) are evaluated for a subset of 98 of these glasses, for which the alteration times extend up to fifteen years. Analysis of the leachate data over this extended period has led to a classification of the glass compositions according to their PCT behavior, as characterized by the boron release in solution, the decrease in the rate of alteration, or the occurrence of a resumption of alteration. Three types of behavior are associated with a normalized mass loss of boron after 100 days of around 1, 2, or 5 g m-2 respectively, and a ratio of the rate of alteration at 7 days to the rate at 1000 days of about 30. A fourth type is characterized by a much larger decrease between the rates at 7 and 1000 days with a ratio exceeding 120. Four further categories are associated with late-stage resumption of glass alteration. A statistical analysis of the data has been used to model the leachate data as a function of glass composition. The effects of seven major elements (Si, B, Al, Li, Na, K, Fe) on the long-term glass durability have been studied. As a result of this analysis, the different types of leaching behaviors can be predicted with a good reliability from the composition of the pristine glass.
Comparison of a Non Electrostatic Surface Complexation Model and Surface Phase Theories for Prediction of Future Sorption Properties.
Authors: Emrén Allan T. , Jacobsson Anna-Maria 
Published: April 2011

AbstractIn performance assessments, sorption of radionuclides dissolved in groundwater is mostly handled by the use of fixed Kd values. It has been well known that this approach is unsatisfying. Only during the last few years, however, tools have become available that make it possible to predict the actual Kd value in an aqueous solution that differs from the one in which the sorption properties were measured.One such approach is surface complexation (SC) that gives a detailed knowledge of the sorption properties. In SC, one tries to find what kinds of sorbed species are available on the surface and the thermodynamics for their formation from species in the bulk aqueous solution. Recently, a different approach, surface phase method (SP), has been developed. In SP, a thin layer including the surface is treated as a separate phase. In the bulk aqueous solution, the surface phase is treated as a virtual component, and from the chemical potential of this component, the sorption properties can be found.In the paper, we compare advantages and disadvantages of the two kinds of models. We also investigate the differences in predicted sorption properties of a number of radionuclides (Co, Np, Th and U). Furthermore, we discuss under which circumstances, one approach or the other is preferable.
Diffusion of Iodine and Technetium-99 Through Waste Encasement Concrete and Unsaturated Soil Fill Material
Authors: Mattigod Shas V. , Whyatt Greg A. , Serne J. R. , Wood Marcus I. 
Published: April 2011

AbstractAn assessment of long-term performance of low level waste-enclosing cement grouts requires diffusivity data for radionuclide species such as, 129I and 99Tc. The diffusivity of radionuclides in soil and concrete media was collected by conducting soil-soil and concrete-soil half-cell experiments. The soil diffusivity coefficients for iodide were 7.03 × 10−8 cm2/s and 2.42 × 10−7cm2/s for soils at 4% and 7% moisture contents, respectively. Iodide diffusivity in soil is a function of moisture content and is about an order of magnitude slower at lower moisture content. The soil diffusivity coefficients for 99Tc were 5.89±0.80 × 10−8 cm2/s (4% moisture content) and 2.04±0.57 × 10−7 cm2/s (7% moisture content), respectively. The soil diffusivity of iodide and 99Tc were similar in magnitude at both water contents, indicating that these ions have similar diffusion mechanisms in unsaturated coarse-textured Hanford soil. The diffusivity of iodide in concrete ranged from 2.07 × 10−14 cm2/s (4% soil moisture content) to 1.31 × 10−12 cm2/s (7% soil moisture content), indicating that under unsaturated soil moisture conditions, iodide diffusivity is highly sensitive to changing soil moisture conditions. Depending on the soil moisture content, the diffusivity of 99Tc in concrete ranged from 4.54 × 10−13 cm2/s to 8.02 × 10−12 cm2/s. At 4% soil moisture content, iodide diffused about 20 times more slowly than 99Tc, and at 7% soil moisture content, iodide in concrete diffused about 6 times slower than 99Tc.
Using Linear Free Energy Relationship to Predict the Stability Constants of Aqueous Complexes of Metal-Organic Ligands
Authors: Xu Huifang , Wang Yifeng 
Published: April 2011

AbstractThe Sverjensky-Molling linear free energy relationship was originally developed to correlate the Gibbs free energies of formation of an isostrutural family of solid phases to the thermodynamic properties of aqueous cations. In this paper, we demonstrate that the similar relationship also exists between metal complexes and simple metal cations in aqueous solutions. We extend the Sverjensky-Molling relationship to predict the Gibbs free energies of formation or dissociation constants for a family of metal complexes with a given complexing ligand. The discrepancies between the predicted and experimental data are generally less than 1.5 kcal/mol (or one log unit for stability constants). The use of this linear free energy correlation can significantly enhance our ability to predict the speciation, mobility, and toxicity of heavy metals in natural environments. According the obtained results, Gibbs free energies of formation of cations (δG0f, Mn+) can be used as an indicator for the hardness/softness of a metal cation (acid). The higher negative value of a metal cation, the harder acid it will be. It is logical to postulate that the coefficienta*MLcharacterizes the softness of a complexing ligand (base).
Uranium Redox States in Borosilicate Compositions
Authors: Aloy A.S. , Trofimenko A.V. , Iskhakova O.A. , Jardine L.J. 
Published: April 2011

AbstractThe results of the studies of uranium valent states in the borosilicate glasses incorporating the components of uranium-containing sludge of Mining and Chemical Combine (MCC, Zheleznogorsks.) is presented in this work. The glasses were made under oxidative and reducing conditions.The optical spectrophotometry, nuclear gamma-resonance (NGR) and X-ray diffraction (XRD) showed that glasses produced under oxidative conditions are characterized by the presence of only U(6+), while U(4+) in the reducing conditions is present along with U(6+). The ratio U(6+)/to U(4+) varies in depending on the synthesis conditions.The glass samples synthesized under oxidative conditions were researched at initial solid state. The others synthesized under reducing conditions was dissolved preliminary without distort of uranium valency.The effect of U(4+)/U(6+) ratio on the uranium leach rates from the glasses has been studied at 90° using MCC-1 test.
The Dissolution of Uranophane in CaCl2-SiO2(aq) Test Solutions
Authors: Prikryl James D. , Murphy William M. 
Published: April 2011

AbstractUranophane [Ca(UO2)2(SiO3OH)2 · 5H2O] is a corrosion product of long-term leaching of spent fuel under oxidizing conditions and is a weathering product of uraninite in uranium ore deposits hosted by siliceous rocks. Incorporation of radionuclides into uranophane by coprecipitation may occur as a result of spent fuel alteration. Dissolution of uranophane leading to release of these radionuclides may therefore influence the longterm dissolved concentration and mobility of radionuclides at the proposed nuclear waste repository at Yucca Mountain, Nevada. In this study, the dissolution of uranophane in Ca- and Si-rich test solutions was investigated. Batch dissolution experiments were designed to approach uranophane equilibrium from undersaturated solutions at nearneutral pH (~6.0). Test solutions had initial U concentrations of 0.0 and 10-7 mol/L in matrices of ~10-2 mol/L CaCl2 and ~10-3 mol/L SiO2(aq). The test solutions were reacted with synthetic uranophane (confirmed by XRD and chemical analyses) and analyzed periodically over 10 weeks. Reaction quotients (Log Qs) derived from aqueous speciations of experimental solutions considered to be near equilibrium with uranophane ranged from 10.54 to 11.06 for the dissolution reaction: Ca(UO2)2(SiO3OH)2 · 5H2O + 6H+ ⇔ Ca2+ + 2UO22+ + 2SiO2(aq) + 9H2O.
Ab-initio Based Diffusive Studies of Plutonium with Relevance to Nuclear Waste Management
Authors: Setty A. K. 
Published: April 2011

AbstractAn approach to study the diffusion of plutonium (Pu) waste into the material of the storage containers is presented. The delta phase of Pu has been examined, in this article, using a spin and orbitally polarized ab-initio (full potential LMTO) approach [1, 2]. These computations are relatively inexpensive, and it is the intention to see if the results obtained would be satisfactory (compared to the accurate SIC-LDA computations [1-2]) for diffusive studies of Pu into the material of storage containers (for example, into FCC iron as a surrogate for steel [2]). The combination of LDA and spin and orbitally polarized LMTO calculations that we use successfully predict a delocalized 5f, (i.e. bonding) monoclinic ground state and a localized FCC excited state with a density about 8% greater than experiment (compared to the 30% error from pure LDA calculations by various groups [3-6]). The density of states is computed and compared to experimental photoemission studies; there is qualitative agreement. The spin, orbital and total magnetic moment for the FCC phase is computed; the results are qualitatively in agreement with those of other studies. An analytical method for studying the time-dependent diffusion of Pu across an interface with another atomic species is presented.
Geopolymers for the Immobilization of Radioactive Waste
Authors: Perera D S , Blackford M G , Vance E R , Hanna J V , Finnie K S , Nicholson C L 
Published: April 2011

AbstractGeopolymers are made by adding aluminosilicates to concentrated alkali solutions for dissolution and subsequent polymerization to form a solid. They are amorphous to semicrystalline three dimensional aluminosilicate networks. Although they have been used in several applications their widespread use is restricted due to lack of long term durability studies and detailed scientific understanding. Three important tools for the study of geopolymers are transmission electron microscopy (TEM), solid state magic angle spinning nuclear magnetic resonance (MAS NMR) and infra red (IR) spectroscopy.Cs and Sr are two of the most difficult radionuclides to immobilize and are therefore suitable elements to study in assessing geopolymers as matrices for immobilization of radioactive wastes. In this study Cs or Sr was added to geopolymer samples prepared using fly ash precursors. A commercial metakaolinite geopolymer was studied for comparison.The geopolymers were mainly amorphous as shown by TEM, whether they were made from fly ash or metakaolinite. In the fly ash geopolymer, Cs preferentially inhabited the amorphous phase over the minor crystalline phases, whereas Sr was shared in both. The MAS NMR showed that Cs is held mostly in the geopolymer structure for both fly ash and metakaolinite geopolymers. The IR spectra showed a slight shift in antisymmetric Si-O-Al stretch band to a lower wavenumber for the fly ash geopolymer, which implies that more Al is incorporated in this geopolymer structure than in the metakaolinite geopolymer.
Enrichment of Uranium inside Wood: a Natural Analog from a Sandstone-hosted Roll-type Uranium Ore Deposit
Authors: X Huifang , Min Maozhong , Zhen Jia , Peng Xinjian , Wang Jinping , Barton Larry , Wang Yifeng 
Published: April 2011

AbstractFurniture contaminated with uranium will be disposed of, together with U-bearing waste, in ageological repository such as the WIPP site in New Mexico. It is important to understand the effect of the wooden furniture on the migration of uranium in order to predict long-term behavior of uranium in a geological repository environment. In this paper, we present natural uraninite-bearing carbonized wood pieces from a sandstone-hosted roll-type uranium ore deposit in NW China. Results from SEM and TEM observations show that there are nanometer sized, and micron-sized, uraninite crystals that have accumulated on cell walls of the carbonized wood. Some uranitite crystrals display oval and round shapes that may be the result of microbial-induced reduction of uranium from groundwater. The wood carbonized fragments are the most uranium-rich “phase.” In some areas, aggregates of pyrite crystals occur withthe uraninite. It is proposed that organic components from the decay of the wood cells provide nutrientsfor the anaerobic bacteria to grow. The wood pieces with the bacteria inside may serve as scavengers of uranium because of the local reducing chemical environment.
Effects of the Orientation of Clay Particles and Ionic Strength on Diffusion and Activation Enthalpies of I−and Cs+ Ions in Compacted Bentonite
Authors: Sato Haruo 
Published: April 2011

AbstractApparent diffusivities (Da) for I− and Cs+ in compacted Na-smectite were studied as a function of smectite's dry density (0.9–1.4 Mg/m3, ionic strength (IS: [NaCl]=0.01, 0.51 M), temperature (22–60 °C) and diffusion directionto the orientated direction of smectite particles. The Da-values for both ions in parallel direction to the orientated direction showed a tendency to be higher than those in the perpendicular direction at lowIS. The Da-values for I− showed different trends depending on diffusion direction and dry density at high IS, but Da-values for Cs+ increased with increasing IS in both diffusion directions. The activation enthalpies (ΔEa) for I−, slightly higher than that of diffusivity in free water (Do) at low IS, similar level to that of Do at high IS, increased with increasing dry density. While, ΔEa-values for Cs+, clearly higher than that of Do for all conditions, increased with increasing dry density. Since it is known that interlayer distance depends on both dry density and IS, diffusive pathway is considered to differ depending on the charge of diffusion species.
Migration Behavior of Ferrous Ions in Compacted Bentonite Under Reducing Conditions Using Electromigration
Authors: Idemitsu Kazuya , Xia Xiaobin , Kikuchi Yoshiro , Inagaki Yaohiro , Arima Tatsumi 
Published: April 2011

AbstractCarbon steel is one of the candidate overpack materials for high-level waste disposal and is expected to assure complete containment of vitrified waste glass during an initial period of 1000 years in Japan. The lifetime of the carbon steel overpack will depend on its corrosion rate. The corrosion rate of carbon steel is reduced by the presence of buffer material such as bentonite. Buffer material will delay the supply of corrosive materials and discharge of corrosion products through it. Carbon steeloverpack will be corroded by consuming oxygen introduced by repository construction after closure of repository and then will keep the reducing environment in the vicinity of repository. Therefore, it is important to study the migration of iron corrosion products through the buffer material because it may affect the corrosion rate of overpack, migration of redox-sensitive radionuclides, and the properties of the buffer material. Electromigration experiments have been carried out with source of iron ions supplied byanode corrosion of iron coupon in compacted bentonite. The carbon steel coupon was connected as the working electrode to the potentiostat and was held at a constant applied potential between - 200 to 1000 mV vs. Ag/AgCl electrode for 48 hours. Corrosion currents were 0.5 to 2mA initially and depended on the supplied electrical potential, then decreased to approximately 0.1 mA in a few hours. The final corrosion current was independent of supplied electrical potential. It is expected that iron ion could migrate as ferrous ion through interlayer of montmorillonite replacing exchangeable sodium ions in the interlayer. The rate-determining process of this experimental configuration could be infiltration rate of ferrousioninto bentonite. Infiltration rate of ferrous ion into bentonite was increasing with dry density of bentonite.
Evaporative Evolution of Carbonate-Rich Brines from Synthetic Topopah Spring Tuff Pore Water, YuccaMountain, NV
Authors: Sutton Mark , Alai Maureen , Carroll Susan 
Published: April 2011

AbstractThe evaporation of a range of synthetic pore water solutions representative of the potential high-level-nuclear-waste repository at Yucca Mountain, NV is being investigated. The motivation of this work is to understand and predict the range of brine compositions that may contact the wastecontainers from evaporation of pore waters, because these brines could form corrosive thin films on the containers and impact their long-term integrity. A relatively complex synthetic Topopah Spring Tuff pore water was progressively concentrated by evaporation in a closed vessel, heated to 95°C in a series of sequential experiments. Periodic samples of the evaporating solution were taken to determine the evolving water chemistry. According to chemical divide theory at 25°C and 95°C our starting solution should evolve towards a high pH carbonate brine. Results at 95°C show that this solution evolves towardsa complex brinethat contains about 99 mol% Na+for the cations, and 71 mol% Cl-, 18 mol% ΣCO2(aq), 9 mol% SO42- for the anions. Initial modeling ofthe evaporating solution indicates precipitation of aragonite, halite, silica, sulfate and fluoride phases. The experiments have been used to benchmark the use of the EQ3/6 geochemical code in predicting the evolution of carbonate-rich brines during evaporation.
Thermal diffusion of Helium and volatil fission products in UO2 and zirconolite nuclear ceramics
Authors: Roudil Danièle , Deschanels Xavier , Trocellier Patrick , Jomard Fran ç ois , Boutry Annick , Jègou Christophe , Peuget Sylvain , Gosset Dominique , Nivet Pierre 
Published: April 2011

AbstractThe behaviour and diffusion mechanisms of helium in nuclear ceramics, such as uranium dioxide spent fuel matrix and zirconolite for the specific conditioning of minor actinides, significantly impact the possible evolution of those matrices in interim storage or disposal conditions. In the framework of spent fuel storage studies, the additional diffusion of gas and fission products in uranium dioxidematrix is also an essential aspect of the R&D. Specific experimental studies have been conducted, devoted to thermal diffusion under 1000 C. Data processing methods, lead to helium diffusion coefficient and associated activation energy of 1.05 eV in the zirconolite and 2 eV in UO2. Comparativelywith the uranium dioxide matrix, the helium diffusion coefficient in zirconolite is 1 to 100 million times higher; this parameter will have to be taken into account to dimension the waste form. Diffusion coefficients measurements between 800 C and 1000 C, investigated by SIMS, showed a very slow diffusion of volatile fission products Xe, I, Te and Cs, with coefficients two or three order of magnitude lower than for helium.
Effect of Gadolinium Doping on the Air Oxidation of Uranium Dioxide
Authors: Scheele Randall D. , Hanson Brady D. , Cumblidge Stephen E. , Jenson Evan D. , Kozelisky Anne E. , Sell Rachel L. , MacFarlan Paul J. , Snow Lanee A. 
Published: April 2011

AbstractResearchers at the Pacific Northwest National Laboratory (PNNL) investigated the effects of gadolinium oxide concentration on the air oxidization of gadolinium oxide-doped uranium dioxide using thermogravimetry and differential scanning calorimetry to determine if such doping could improve uraniumdioxide's stability as a nuclear fuel during potential accident scenarios in a nuclear reactor or during long-term disposal. We undertook this study to determine whether the resistance of the uranium dioxide to oxidation to the orthorhombic U3O8 with its attendant crystal expansion could be prevented by addition of gadolinium oxide. Our studies found that gadolinium has little effect on the thermal initiation of the first step of the reported two-step air oxidation of UO2; however, increasing gadolinium oxide content does stabilize the initial tetragonal or cubic product allowing significant oxidation before the second expansive step to U3O8 begins.