Crystalline Uranium Research Articles

Insight into γ-Irradiation-Induced Structure Evolution of Uranium(IV) Germanates as Crystalline Nuclear Waste Forms.

New kinds of crystalline waste forms with improved structural stability are desirable for actinide immobilization. In this work, using a molten salt method, two uranium(IV) germanate compounds, namely, K2UGe3O9 (1) and K2UGe2O7 (2), were synthesized, whose compositions consisted of trimeric and dimeric units of germanate, as well as tetravalent uranium, as proved by bond valence calculation and X-ray absorption spectra. Radiation stability assessment is further performed by γ-irradiation to assess the potential of as-synthesized uranium germanate compounds as nuclear waste forms. Powder X-ray diffraction and single-crystal diffraction analyses reveal that 1 remains stable within 1 MGy dosage and undergoes a significant structural change with increasing dosage at 2 MGy, leading to a transformation of 1 to 1-ir analogous to 2 in chemical structure. The underlying mechanism was further studied through a combination of different characterization techniques, including Raman, UV-vis, and electron paramagnetic resonance spectroscopies. Density functional theory calculations of 1 and 2 were also conducted to probe the coordination interaction of germanium and uranium with oxygen atoms. This work reports new crystalline uranium germanates by flux growth and, most importantly, provides insights into the irradiation stability of these materials, which will be beneficial to developing waste forms for long-term immobilization of radionuclides.

Optical properties and electronic structure of epitaxial uranium films

Uranium exhibits high chemical activity. The preparation of single crystalline uranium films via molecular beam epitaxy, followed by in situ characterization under ultrahigh vacuum condition, effectively avoids sample contamination caused by the environmental atmosphere. In this work, single crystalline uranium films were grown on the W(110) surface by a deflected electron beam evaporator. The optical constants of the W(110) substrate and the uranium films were obtained through in situ ultrahigh vacuum spectroscopic ellipsometry, while the electronic structure of uranium films was measured by angle-resolved photoemission spectroscopy (ARPES). Notably, the optical constants of uranium film differ from those previously reported measured by the ex situ experiments. The band structure and optical constants of the uranium film were calculated by the ab initio method, and theoretical calculations were compared with the experimental results. The calculated band structure of α-U is consistent with the bulk electronic structure of uranium films measured by ARPES, except for a surface-state-like feature. The parameters of the Drude oscillator derived from the ellipsometric fitting were used to revise the calculated optical constants, which obviously improves the accuracy of the calculations. Our study provides the most strictly fundamental data of the uranium up to now.

Cathodic Processes in Uranium Containing Molybdate Melts

Cathodic processes in Li2MoO4–K2MoO4–MoO3 and K2MoO4–MoO3 melts containing added UO2MoO4 were investigated at 550–800 °C using cyclic voltammetry, cathodic polarization and bulk electrolysis. Cathodic reduction of molybdate melts (not containing uranium) resulted in formation of molybdenum dioxide. Products of the cathodic reactions in the melts containing uranium molybdate predominantly consisted of crystalline uranium oxides (mostly UO2 and U4O9) and MoO2. Minor products formed included other uranium oxides (U3O8, U13O34), mixed uranium-molybdenum oxides (U1.5Mo10O32, Mo2UO8) and molybdates (provisionally attributed to K2U(MoO4)3). Effect of temperature, cathodic current density 0.05–1 A cm−2), excess MoO3 concentration (30–50 mol%) on the composition of the cathodic reaction products were analyzed. Oxygen-to-uranium atomic ratio (oxygen coefficient) for primary uranium oxide phases was determined and varied from 1.963 to 2.161 for UO2±x and from 2.209 to 2.287 for U4O9±y. The effect of the electrolysis regime on the composition of the cathodic product was also considered. Constant-current and constant-potential electrolysis, as well pulsed-current, pulsed-potential and pulsed-reversed-current electrolysis were investigated with varying the parameters of alternating pulses (duration, current density or potential). Chemical and phase composition of the products produced by bulk electrolysis was fully characterized.

The electrosorption of uranium (VI) onto the modified porous biocarbon with ammonia low-temperature plasma: Kinetics and mechanism

Constructing the excellent rich-mesoporous carbon and exploring its electrosorption process are keys to promote the electrosorption industrialization of uranium. In this work, we develop a rich-mesoporous biocarbon by using alkali-thermal-pyrolysis and ammonia low-temperature plasma, and then systematically investigate its electrosorption kinetics and mechanism of U(VI) considering a series of Faradaic side reactions. After the above treatment, the electrosorption efficiency of U(VI) onto biocarbon improves from 49.75% to 94.45%, and the ultra-high U-selectivity coefficient (SU/M) is higher than 120 from the mixed solution. The kinetic diffusion process of U(VI) into the pores is crucial, even in different water systems. Importantly, Faradaic side reactions are proved to be non-negligible factors in the electrosorption of uranium. Especially, the oxygen reduction at the cathode can convert dissolved oxygen into H2O2, which oxides the amorphous electro-reduced U(V, IV) to U(VI), and finally forms crystalline uranium peroxide species. To sum up, this work not only offers an excellent uranium-selectivity electroadsorbent, but firstly confirms the influence of Faradaic side reactions that has been ignored in the current electrosorption of uranium.

U-Fe-Al metallic glasses with superior glass forming ability and corrosion resistance

U-Fe-based ternary alloys have showed weaker glass forming ability (GFA) than U-Co-based ones, although U-Fe is a better base glass system than U-Co. To solve this puzzling point, the present work was aimed to study the formation of U-Fe-Al metallic glasses (MGs) together with their crystallization and corrosive properties. Through melt-spinning, the U-Fe-Al alloys designed by introducing Al to U-Fe alloys in the eutectic zone formed fully glassy phase in a large composition range. Among them, U60Fe27.5Al12.5 is the best glass former having the maximum Tg, Tg/Tm and supercooled liquid region of 635K, 0.612 and 48K, respectively. Its GFA exceeds other known U-based MGs including the U-Co-based ones. Moreover, compared with some U-Co-based MGs and crystalline uranium materials, U60Fe27.5Al12.5 MG also displayed more excellent anti-corrosive performance in neutral solution, indicating alluring application prospect in nuclear-related fields. However, these U-Fe-Al MGs exhibited very low Tg/TL values, which is essentially owing to that their compositions may be hypoeutectic and lie on the side of the Fe2U-typed eutectic phase with melting point much higher than the eutectic temperature.

Study on Uranium Minerals and Metallogenic Material Sources of Huayang Chuan Uranium Polymetallic Deposit

Huayangchuan uranium polymetallic deposit is located in Huaxian County, Huayin City, Shaanxi Province.The geotectonic location belongs to the Xiaoqinling intracontinental orogenic belt on the southern margin of the North China block.Uranium ore bodies are layered, vein-like and thick reticulated veins.The average content of uranium is 2×10−4 in the deposit.Through microscopic identification and electron probe analysis, we believe that uranium minerals are mainly betafite, crystalline uranium and uranothorite.According to the characteristics of rare earth elements in uranium ores, we believe that the ore-forming materials mainly come from the mantle.

The Impact of Coordination Environment on the Thermodynamic Stability of Uranium Oxides

Amorphous uranium oxides are known to arise via industrial processes relevant to the nuclear fuel cycle yet evade rigorous structural characterization. A promising approach is to develop statistical relationships between uranium–oxygen coordination environments and thermodynamic stability from which general statements about the likelihood of observing particular U–O arrangements can be made. The number of known crystalline uranium oxides is insufficient to build statistical relationships. We have developed a database of theoretical compounds using genetic algorithms with the density functional theory as a foundation to analyze coordination geometries in the uranium–oxygen phase space. We draw fundamental insights into the nature of uranium–oxygen interactions by correlating total energy with the coordination environment. The most stable configuration of U cations with O anions is in an environment with coordination numbers 5–8 in a cubic configuration. Higher and lower coordination numbers are observed only in metastable phases. General trends are observable in the relationships between the coordination number, density, and uranium fraction in each structure. The new insight into uranium coordination enabled by these analyses is foundational for further studies into the characteristic properties of individual uranium oxide materials and for elucidation of potential oxidation pathways for uranium metal.

Uranium Release from Acidic Weathered Hanford Sediments: Single-Pass Flow-Through and Column Experiments.

The reaction of acidic radioactive waste with sediments can induce mineral transformation reactions that, in turn, control contaminant fate. Here, sediment weathering by synthetic uranium-containing acid solutions was investigated using bench-scale experiments to simulate waste disposal conditions at Hanford's cribs (Hanford, WA). During acid weathering, the presence of phosphate exerted a strong influence over uranium mineralogy and a rapidly precipitated, crystalline uranium phosphate phase (meta-ankoleite [K(UO2)(PO4)·3H2O]) was identified using spectroscopic and diffraction-based techniques. In phosphate-free system, uranium oxyhydroxide minerals such as K-compreignacite [K2(UO2)6O4(OH)6·7H2O] were formed. Single-pass flow-through (SPFT) and column leaching experiments using synthetic Hanford pore water showed that uranium precipitated as meta-ankoleite during acid weathering was strongly retained in the sediments, with an average release rate of 2.67 × 10-12 mol g-1 s-1. In the absence of phosphate, uranium release was controlled by dissolution of uranium oxyhydroxide (compreignacite-type) mineral with a release rate of 1.05-2.42 × 10-10 mol g-1 s-1. The uranium mineralogy and release rates determined for both systems in this study support the development of accurate U-release models for the prediction of contaminant transport. These results suggest that phosphate minerals may be a good candidate for uranium remediation approaches at contaminated sites.

Research progress in U-based amorphous alloys

Uranium-based amorphous alloys are a unique family of amorphous materials, which have so far been less studied due to the high chemical activity and radioactivity of uranium metal. In this paper, we review the compositions, preparations and thermal stability characteristics of U-based amorphous alloys obtained in the early experimental studies, and summarizes our recent results of the preparations and material properties of stable U-based amorphous alloys. The latest progress in our study of U-based amorphous alloys is presented in the three aspects. Firstly, the preparation methods, alloy systems and compositions, formation and crystallization behaviors of the new U-based amorphous alloys, along with the preliminary mechanisms for their formation and structure stabilization are reviewed. A number of new uranium-based amorphous alloy systems have been established based on eutectic law and structural packing model. These alloys show high ability to form glass, and the reduction of glass transition temperatures of some alloys to those of conventional amorphous alloys. The formation rules of binary (U-Fe/U-Co/U-Cr), ternary (U-Co-Al/U-Fe-Sn) and multicomponent alloy system have been investigated. It was found that the ability to form glass is strongly related to some physical parameters such as the local cluster structure, the electron concentration, the enthalpy of mixing, the electronegativity of the alloy component as well as the atomic size. The fragilities of U-based amorphous alloys indicate that they belong to a class of strong glass forming system, which means that the critical dimensions of such amorphous alloys can be further enhanced, and bulk amorphous samples are expected to be prepared. The crystallization activation of this kind of amorphous alloy is higher, and the crystallization process is dominated by nucleation. Then, the microstructures especially the first high-resolution electron microscopic results of the unique amorphous materials are reviewed. Finally, the micro-mechanical and anti-corrosion properties are reported in great detail. It is found that U-based amorphous materials show excellent mechanical properties and corrosion resistance, and the strength and hardness are much higher than those of conventional crystalline uranium alloys, and the corrosion resistance is also superior to the latter, which may be caused by its disorderly amorphous structural characteristics. Amorphous alloys have been the subject of intense fundamental and application research in recent years. Stable U-based amorphous alloys appear to cover all physical phenomena displayed by amorphous alloys. The discovery of outstanding properties in these new alloys therefore would stimulate both the fundamental studies including structure, electronic, glass transition, crystallization, etc., and the application-orientated studies of the thermal stability, mechanical and corrosion properties.

Stable U-based metallic glasses

A series of U-based U-Co-Al metallic glasses with greatly improved glass-forming ability and thermal stability were obtained by the alloying addition of Al into U-Co alloys. The fragility of these glasses approached 28, indicating strong liquid behavior. The corrosion resistance and mechanical hardness of the glasses were substantially enhanced in comparison with crystalline uranium materials. The roles of delocalization of 5f electrons and their bonding states are stressed in the discussion of the glass formation, thermal stability and the deviation of elastic modulus from the rule of mixtures. The finding not only adds a new member to the family of metallic glasses, but also provides a category of potentially useful uranium materials.

Preparation of UO2, ThO2 and (Th,U)O2 pellets from photochemically-prepared nano-powders

Photochemically-induced preparation of nano-powders of crystalline uranium and/or thorium oxides and their subsequent pelletizing has been investigated. The preparative method was based on the photochemically induced formation of amorphous solid precursors in aqueous solution containing uranyl and/or thorium nitrate and ammonium formate. The EXAFS analyses of the precursors shown that photon irradiation of thorium containing solutions yields a compound with little long-range order but likely “ThO2 like” and the irradiation of uranium containing solutions yields the mixture of U(IV) and U(VI) compounds. The U-containing precursors were carbon free, thus allowing direct heat treatment in reducing atmosphere without pre-treatment in the air. Subsequent heat treatment of amorphous solid precursors at 300–550 °C yielded nano-crystalline UO2, ThO2 or solid (Th,U)O2 solutions with high purity, well-developed crystals with linear crystallite size <15 nm. The prepared nano-powders of crystalline oxides were pelletized without any binder (pressure 500 MPa), the green pellets were subsequently sintered at 1300 °C under an Ar:H2 (20:1) mixture (UO2 and (Th,U)O2 pellets) or at 1600 °C in ambient air (ThO2 pellets). The theoretical density of the sintered pellets varied from 91 to 97%.

Sonochemical precipitation of amorphous uranium phosphates from trialkyl phosphate solutions and their thermal conversion to UP2O7

Insoluble amorphous precipitates containing uranyl and phosphate ions are obtained by sonication of solutions of three uranyl precursors, UO2(X)2, X=NO3, CH3COO, CH3C(O)CHC(O)CH3 (acetylacetonate, acac), in triesters of phosphoric acid, OP(OR)3, R=Me (trimethyl phosphate, TMP), Et (triethyl phosphate, TEP). TMP and TEP are used as high-boiling solvents and they serve also as a source of phosphate anions. Sonolysis experiments were carried out under flow of Ar at 40°C on a Sonics and Materials VXC 500W system (f=20kHz, Pac=0.49Wcm−3). Powder X-ray diffraction (PXRD) reveals amorphous character of all obtained precipitates. The presence of uranyl and phosphate is evidenced by IR spectroscopy and ICP-OES analysis reveals the content of both U (38.6–43.4wt%) and P (11.0–13.6wt%). The thermal behavior of the substances was studied by TG/DSC analysis, which shows weight losses in the range of 19.21–24.08%. On heating the amorphous precipitates to 1000°C, crystalline uranium diphosphate UP2O7 is obtained in all cases as the only crystalline phase. Uranyl(VI) is reduced during thermolysis to U(IV) as there is no characteristic vibration of UO22+ in the IR spectra of solid UP2O7 products. The ICP-OES analysis of U and P content in precipitates allowed us to calculate the efficiency of precipitation of uranium from mother liquor and to compare it with the efficiency calculated from the data received by the PXRD and TG/DSC analyses. The efficiency of the uranium removal attained by our sonoprecipitation procedure was typically 30–35%. These sonochemical precipitation reactions providing insoluble uranium phosphates may be potentially interesting models for the description of behavior of uranium-containing waste or reprocessing streams.

Structure and properties of uranium oxide thin films deposited by pulsed dc magnetron sputtering

Crystalline uranium oxide thin films were deposited in an unbalanced magnetron sputtering system by sputtering from a depleted uranium target in an Ar+O2 mixture using middle frequency pulsed dc magnetron sputtering. The substrate temperature was constantly maintained at 500°C. Different uranium oxide phases (including UO2−x, UO2, U3O7 and U3O8) were obtained by controlling the percentage of the O2 flow rate to the total gas flow rate (fO2) in the chamber. The crystal structure of the films was characterized using X-ray diffraction and the microstructure of the films was studied using transmission electron microscopy and atom probe tomography. When the fO2 was below 10%, the film contains a mixture of metallic uranium and UO2−x phases. As the fO2 was controlled in the range of 10–13%, UO2 films with a (220) preferential orientation were obtained. The oxide phase rapidly changed to a mixture of U3O7 and U3O8 as the fO2 was increased to the range of 15–18%. Further increasing the fO2 to 20% and above, polycrystalline U3O8 thin films with a (001) preferential orientation were formed. The hardness and Young's modulus of the uranium oxide films were evaluated using nanoindentation. The film containing a single UO2 phase exhibited the maximum hardness of 14.3GPa and a Young's modulus of 195GPa. The UO2 thin film also exhibited good thermal stability in that no phase change was observed after annealing at 600°C in vacuum for 104h.

Molecular-dynamic simulation of the thermophysical properties of liquid uranium

The procedure for the calculation of the embedded atom model (EAM) potential, which involves the use of data on the structure of liquid metal in the vicinity of the melting temperature and of the results of impact tests, is applied to uranium. The use of the method of molecular dynamics and of the EAM potential produces good agreement with experiment as regards the structure, density, and potential energy of liquid metal at temperatures up to 5000 K, as well as along the shock adiabat up to pressures of ≈360 GPa. The thermodynamic properties of solid (bcc) and liquid uranium are determined at pressures up to 470 GPa and temperatures up to 12 000 K. The predicted value of bulk modulus of liquid at 1406 K is close to the actual value. The self-diffusion coefficient under isobaric heating increases with temperature by the power law with exponent of ≈2.103. The Stokes—Einstein relation is used to determine the dynamic viscosity at temperatures up to 6000 K. The obtained potential is not quite adequate for describing crystalline uranium under normal conditions. The melting temperature of uranium with EAM potential is equal to 1455 ± 2 K and somewhat higher than real. The melting temperature monotonically increases with pressure and reaches the value of 7342 K at 444 GPa. For obtaining agreement with experimental data for energy of uranium along the p = 0 isobar, it is assumed that an additional contribution to energy emerges at elevated temperatures, which is due to excitation of atomic electrons and leads to a high heat capacity: it may be as high as almost 100 kJ/mol at 5000 K. This contribution further causes a high heat capacity of highly compressed states of uranium.

Uranium and thorium sequestration by a Pseudomonas sp.: Mechanism and chemical characterization

The mechanism and chemical nature of uranium and thorium sequestration by a Pseudomonas strain was investigated by transmission electron microscopy, energy dispersive X-ray (EDX) analysis, FTIR spectroscopy and X-ray diffractometry. Atomic force microscopy (AFM) used in the tapping mode elucidated the morphological changes in bacterial cells following uranium and thorium binding. Transmission electron microscopy revealed intracellular sequestration of uranium and thorium throughout the cell cytoplasm with electron dense microprecipitations of accumulated metals. Energy dispersive X-ray analysis confirmed the cellular deposition of uranium and thorium. EDX and elemental analysis of sorption solution indicated the binding of uranium and thorium by the bacterial biomass via displacement of cellular potassium and calcium. The strong involvement of cellular phosphate, carboxyl and amide groups in radionuclide binding was ascertained by FTIR spectroscopy. X-ray powder diffraction (XRD) analyses confirmed cellular sequestration of crystalline uranium and thorium phosphates. Overall results indicate that a combined ion-exchange–complexation–microprecipitation mechanism could be involved in uranium and thorium sequestration by this bacterium. Atomic force microscopy and topography analysis revealed an undamaged cell surface with an increase in cell length, width and height following radionuclide accumulation. The arithmetic average roughness ( R a) and root mean square (RMS) roughness ( R q) values indicated an increase in surface roughness following uranium and thorium sequestration.

Electronic structure of crystalline uranium nitrides UN, U2N3 and UN2: LCAO calculations with the basis set optimization

The results of LCAO DFT calculations of lattice parameters, cohesive energy and bulk modulus of the crystalline uranium nitrides UN, U2N3 and UN2 are presented and discussed. The LCAO computer codes Gaussian03 and Crystal06 are applied. The calculations are made with the uranium atom relativistic effective small core potential by Stuttgart-Cologne group (60 electrons in the core). The calculations include the U atom basis set optimization. Powell, Hooke-Jeeves, conjugated gradient and Box methods are implemented in the author's optimization package, being external to the codes for molecular and periodic calculations. The basis set optimization in LCAO calculations improves the agreement of the lattice parameter and bulk modulus of UN crystal with the experimental data, the change of the cohesive energy due to the optimization is small. The mixed metallic-covalent chemical bonding is found both in LCAO calculations of UN and U2N3 crystals; UN2 crystal has the semiconducting nature.

Study of the solubility of amorphous and crystalline uranium dioxide by combined spectroscopic methods

Colloid formation and solubility of U(IV) in acidic HClO4/NaClO4solutions are investigated by coulometric titration. Quantification of traces of U(VI) by laser fluorescence spectroscopy proves that the tetravalent state of uranium had been maintained. Laser-induced breakdown detection (LIBD) is applied for the detection of traces of uranium colloids as the pH is increased. The pH values at the onset of colloid formation are used for thermodynamic calculations aimed at determining the solubility productsK°spof crystalline and amorphous uranium dioxides. The particle size of the colloids determined by means of LIBD is taken into account since it influences the solubility product. The results indicate the formation of crystalline UO2(cr) at low pH∼1 (logK°sp= -59.6±1.0) whereas the amorphous hydrous oxide UO2·xH2O(am) is formed at pH ∼ 3 (logK°sp= -54.1 ± 1.0). Measurements by EXAFS, XRD and REM confirm the occurrence of these different phases. The obtained solubility products fit well in the known series of solubility products of the other tetravalent actinides.

Electronic structure of crystalline uranium nitride: LCAO DFT calculations

The results of electronic structure calculations performed for the first time for crystalline uranium nitride and using a LCAO basis are discussed. For calculations we used the density functional method with the PW91 exchange correlation potential and a variety of relativistic core potentials for the uranium atom. The calculated atomization energy of the crystal agrees well with the experimental data and with the results of calculations with the plane wave basis. It is shown that a chemical bond in crystalline uranium nitride is a metal covalent bond. The metal component of the bond is due to the 5f electrons localized on the uranium atom and having energies near the Fermi level and the bottom of the conduction band. The covalent component of the chemical bond results from an overlap between the uranium 6d and 7s valence orbitals and the nitrogen 2p atomic orbitals. Inclusion of the 5f electrons in the core of the uranium atom introduces relatively minor changes in the calculated binding energy and electron density distribution.

Physico-chemical study of heterogeneous equilibria in salt-aqueous systems of inorganic compounds of uranium(VI)

The report presents results obtained in systematic investigation of the physico-chemical state of heterogeneous equilibrium systems of „aqueous solution — precipitate” in the case of the crystalline mineral-like uranium (VI) compounds with the general formula Mk(AnUO2)k·nH2O, where positions denoted as „ An” are occupied by VO4 3−, PO4 3−, AsO4 3−, HSiO4 3−, or BO3 3− anions, and Mk are alkaline, alkaline earth, and the 3d-transition elements. Chemical stabilities and solubilities of uraniumvanadates, uraniumphosphates, uraniumarsenates, uraniumsilicates, and uraniumborates have been experimentally determined. Detailed quantitative description of the physico-chemical processes and reactions involved in heterogeneous equilibrium in aqueous solutions of the salts by means of equilibrium thermodynamics is presented. The description gives us the possibility to predict the behaviour of the uranium compounds under different conditions and to calculate Gibbs functions of the formation of the compounds studied.

Experimental determination of UO2(cr) dissolution kinetics: Effects of solution saturation state and pH

To evaluate the release of uranium from natural ore deposits, spent nuclear fuel repositories, and REDOX permeable reactive barriers (PRB), knowledge of the fundamental reaction kinetics associated with the dissolution of uranium dioxide is necessary. Dissolution of crystalline uranium (IV) dioxide under environmental conditions has been studied for four decades but a cardinal gap in the published literature is the effect of pH and solution saturation state on UO2(cr) dissolution. To resolve inconsistencies, UO2 dissolution experiments have been conducted under oxic conditions using the single-pass flow-through system. Experiments were conducted as a function of total dissolved carbonate ([CO3-3]T) from 0.001 to 0.1M; pH from 7.5 to 11.1; ratio of flow-through rate (q) to specific surface area (S), constant ionic strength (I)=0.1M, and temperatures (T) from 23 to 60°C utilizing both powder and monolithic specimens. The results show that UO2 dissolution varies as a function of the ratio q/S and temperature. At values of log10q/S>−7.0, UO2 dissolution becomes invariant with respect to q/S, which can be interpreted as evidence for dissolution at the forward rate of reaction. The data collected in these experiments show the rate of UO2 dissolution increased by an order of magnitude with a 30°C increase in temperature. The results also show the overall dissolution rate increases with an increase in pH and decreases as the dissolved uranium concentration approaches saturation with respect to secondary reaction products. Thus, as the value of the reaction quotient, Q, approaches equilibrium, K, (with respect to a potential secondary phase) the dissolution rate decreases. This decrease in dissolution rate (r) was also observed when comparing measured UO2 dissolution rates from static tests where r=1.7±0.14×10−8molm−2s−1 to the rate for flow-through reactors where r=3.1±1.2×10−7molm−2s−1. Thus, using traditional static test methods can result in an underestimation of the true forward rate of UO2(cr) dissolution. These results illustrate the importance of pH, solution saturation state, and the concentration of dissolved carbonate on the release of uranium from UO2 in the natural environment.