• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
• /
• v.2 no.2
• /
• pp.135-143
• /
• 2004

An experimental study on the sorption of U(VI) onto a Korean granite was performed as a function of the geochemical parameters such as contact time, pH, ionic strength, and carbonate concentration using a batch procedure. The distribution coefficient,$K_d$, was about 1-200 mL/g depending on the experimental conditions. The sorption of U(VI) onto granite particles was greatly dependent upon the contact time, pH, and carbonate concentration, but insignificantly dependent on the ionic strength. It was noticed that the sorption of U(VI) onto granite particles was highly correlated with the uranium speciation in the solution, which was dependent on the pH and carbonate concentrations. It was deduced from the kinetic sorption experiment that a two-step first-order kinetic behavior could dominate the kinetic sorption of U(VI) onto granite particles. In the alkaline range of a pH above 7, U(VI) sorption was greatly decreased and this might be due to the formation of anionic U(VI)-carbonate aqueous complexes as predicted by the speciation calculations.

• Journal of Powder Materials
• /
• v.4 no.3
• /
• pp.214-221
• /
• 1997

The densification and grain growth mechanisms of $UO_{2+x}$ in $H_2$ and in $CO_2$ have been investigated. Uranium dioxide powder compacts were sintered at 1$700^{\circ}C$ in $H_2$ or at 110$0^{\circ}C$ in $CO_2$ for various times from 0.5 h to 16 h. The grain size and density of the specimens were measured. From the measured data, the mechanisms of the densification and grain growth were determined by use of available kinetic equations which express the relations between densification and grain growth. In both atmospheres, it has been found that the densification was controlled by the lattice diffusion and the grain growth by the surface diffusion of atoms around pores. It appears that the surface diffusivity as well as the lattice diffusivity increase considerably with the increase in O/U ratio in the specimen.

• Membrane and Water Treatment
• /
• v.11 no.3
• /
• pp.207-215
• /
• 2020

Vivianite (Fe₃²⁺(PO₄)2·8H₂O) and green rust ([Fe₄²⁺Fe₂³⁺(OH)^-₁₂][SO₄^2-·2H₂O]^2-), ferrous containing minerals, could remove aqueous U(VI) in 5 min. and the efficiencies of green rust were roughly 2 times higher than that of vivianite. The zeta potential measurement results implies that the better performance of green rust might be attributed to the favorable surface charge toward uranyl phosphate species. The removal behaviors of the minerals were well fitted by pseudo-second order kinetic model (R² > 0.990) indicating the dominant removal process was chemical adsorption. Effects of Ca²⁺ and CO₃^2- at pH 7 were examined in terms of removal kinetic and capacity. The kinetic constants of aqueous U(VI) were 8 and 13 times lower (0.492 × 10^-3 g/(mg·min); 0.305 × 10^-3 g/(mg·min)) compared to the value in the absence of the ions. The thermodynamic equilibrium calculation showed that the stable uranyl species (uranyl tri-carbonate) were newly formed at the condition. Surface investigation on the reacted mineral with uranyl phosphates species were carried out by XPS. Ferrous iron and U(VI) on the green rust surface were completely oxidized and reduced into Fe(III) and U(IV) after 7 d. It suggests that the ferrous minerals can retard U(VI) migration in phosphate-rich groundwater through the adsorption and subsequent reduction processes.

• Nuclear Engineering and Technology
• /
• v.50 no.7
• /
• pp.1112-1119
• /
• 2018

Dicalcium phosphate nanoparticles (DCP-NPs) was synthesized chemically and used for adsorptive removal of uranyl ions from aqueous solutions in a batch system. A commercial grade of DCP (monetite) was also employed for comparison. The synthesized and commercial adsorbents (S-DCP and C-DCP) were characterized by FT-IR, SEM and XRD techniques. The investigation of adsorption isotherms indicated that the maximum adsorption capacities ($q_m$) for C-DCP and S-DCP were 714.3 and $666.7mg\;g^{-1}$ (at 293 K), respectively. The experimental kinetics were well-described by the pseudo-second-order kinetic and the equilibrium data were fitted with both Langmuir and Freundlich adsorption models. Thermodynamic studies indicated that the adsorption of uranyl ions on the monetite surface was a spontaneous exothermic process. The exhausted adsorbents could be regenerated by washing with $0.10mol\;L^{-1}$ NaOH.

• Journal of the Korean Chemical Society
• /
• v.32 no.4
• /
• pp.351-357
• /
• 1988

The electrochemical reduction of uranyl ion at the dropping mercury electrode and/or mercury microelectrode has been studied in propanediol-1,2-carbonate (PDC) by voltammetric techniques. The position of peak potentials, the nature of limiting currents, their dependency on temperature and on concentrations, reversibility of electrode reactions, and influence of addition of phenol are described. The influence of PDC in aqueous solution of uranyl ion was also described. The values of kinetic parameters, viz., transfer coefficient, formal constant for the electrode reactions bave been determined by Koutecky's method as extended by Meites and Israel. The values of ${\Delta}H,\;{\Delta}G\;and\;{\Delta}S$ have also been calculated.

• Korean Journal of Mineralogy and Petrology
• /
• v.36 no.4
• /
• pp.289-302
• /
• 2023

The study area was Gangnim-myeon, Hoengseong-gun, Gangwon-do, composed of the Chiaksan gneiss complex, and it was revealed that the concentrations of uranium (U) and thorium (Th) within the groundwater of the study area exceeded their water quality standards. Hence, artificial weathering experiments were conducted to elucidate mineralogically the mechanisms of their leaching using drilling cores obtained from the corresponding groundwater aquifers. First of all, the mineralogical compositions of core samples were observed, and the results indicated that the content of clinochlore, a member of the chlorite group of minerals that can form through low- and intermediate-temperature metamorphisms, was relatively higher. In addition, the Th concentration was measured ten times higher than that of U. The results of artificial weathering experiments suggested that the Th concentrations gradually increased through the dissolution of radioactive-element-bearing minerals up to the first day, and then they tended to decrease. It could be attributed to the fact that Th was leached with the dissolution of thorite, which might be a secondary mineral, and then dissolved Th was re-precipitated as the various forms of salt, such as sulfate. Even though the U content was lower than that of Th in the core samples, the U concentration was one hundred times higher than that of Th after the weathering experiments. It is likely caused by the gradual dissolution and desorption of U included in intensively weathered thorite or adsorbed as a form of UO₂²⁺ on the mineral surface. In addition, the leaching tendency of U and Th was positively correlated with the bicarbonate concentration. However, the concentrations between U and Th in groundwater exhibited a relatively lower correlation, which might result from the fact that they occurred from different sources, as aforementioned. Among various kinetic models, the parabolic diffusion and pseudo-second-order kinetic models were confirmed to best fit the dissolution kinetics of both elements. The period that would be taken for the U concentration to exceed its drinking-water standard was inferred using the regressed parameters of the best-fitted models, and the duration of 29.4 years was predicted in the neutral-pH aquifers with relatively higher concentrations of HCO₃, indicating that U could be relatively quickly leached out into groundwater.

• Economic and Environmental Geology
• /
• v.56 no.5
• /
• pp.603-618
• /
• 2023

This study focused on evaluating the suitability of the WRK (waste repository Korea) bentonite as a buffer material in the SNF (spent nuclear fuel) repository. The U (uranium) adsorption/desorption characteristics and the adsorption mechanisms of the WRK bentonite were presented through various analyses, adsorption/desorption experiments, and kinetic adsorption modeling at various pH conditions. Mineralogical and structural analyses supported that the major mineral of the WRK bentonite is the Ca-montmorillonite having the great possibility for the U adsorption. From results of the U adsorption/desorption experiments (intial U concentration: 1 mg/L) for the WRK bentonite, despite the low ratio of the WRK bentonite/U (2 g/L), high U adsorption efficiency (>74%) and low U desorption rate (<14%) were acquired at pH 5, 6, 10, and 11 in solution, supporting that the WRK bentonite can be used as the buffer material preventing the U migration in the SNF repository. Relatively low U adsorption efficiency (<45%) for the WRK bentonite was acquired at pH 3 and 7 because the U exists as various species in solution depending on pH and thus its U adsorption mechanisms are different due to the U speciation. Based on experimental results and previous studies, the main U adsorption mechanisms of the WRK bentonite were understood in viewpoint of the chemical adsorption. At the acid conditions (＜pH 3), the U is apt to adsorb as forms of UO₂²⁺, mainly due to the ionic bond with Si-O or Al-O(OH) present on the WRK bentonite rather than the ion exchange with Ca²⁺ among layers of the WRK bentonite, showing the relatively low U adsorption efficiency. At the alkaline conditions (>pH 7), the U could be adsorbed in the form of anionic U-hydroxy complexes (UO₂(OH)₃^-, UO₂(OH)₄^2-, (UO₂)₃(OH)₇^-, etc.), mainly by bonding with oxygen (O^-) from Si-O or Al-O(OH) on the WRK bentonite or by co-precipitation in the form of hydroxide, showing the high U adsorption. At pH 7, the relatively low U adsorption efficiency (42%) was acquired in this study and it was due to the existence of the U-carbonates in solution, having relatively high solubility than other U species. The U adsorption efficiency of the WRK bentonite can be increased by maintaining a neutral or highly alkaline condition because of the formation of U-hydroxyl complexes rather than the uranyl ion (UO₂²⁺) in solution,and by restraining the formation of U-carbonate complexes in solution.

• Nuclear Engineering and Technology
• /
• v.26 no.3
• /
• pp.425-432
• /
• 1994

Voltammogram analysis of U(VI) reduction at electrochemically non-pretreated/pretreated Ti electrodes in nitric acid and hydrazine($N_2$H$_4$)/protonated hydrazine($N_2$H$_{5}$$^{＋}$) media was done in order to determine the effect of hydrazine form and Ti electrode condition on the reduction of U(VI) in nitric acid. In the case of non-pretreated Ti electrode, the reduction in nitric acid and hydrazine mono-hydrate solution needed a high activation overpotential and was affected by the ratio of hydrazine to nitric acid rather than by only absolute amount of hydrazine because of the decrease of solution conductivity and increase of iR drop, which were caused by proton consumption in the solution by the hydrazine. In the case of pretreated Ti electrode in nitric acid and protonated hydrazine solution, the reduction current peaks of U(VI) were clearer and higher enough to perform a kinetic analysis, compared with the case with the non-pretreated Ti electrode at the same potential, and the behavior was strongly affected by nitric acid. The presence of hydrazine was important in the reduction of U(VI) at the pretreated Ti electrode for preventing the reoxidation of U(IV), but the concentration of protonated hydrazine was not.t.