• Bulletin of the Korean Chemical Society
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• v.17 no.9
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• pp.814-819
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• 1996

In search of simple host molecules for uranyl ion which form 1: 1-type complexes with high formation constants that can be used either in extraction of uranium from seawater or in catalysis of biologically important organic reactions, the uranophile activities of dihydroxyazobenzene derivative 1 were studied. Uranyl ion and 1 form a 1: 1-type complex with a very large formation constant. The formation constant was measured at pH 7-11.6 by competition experiments with carbonate ion. From the resulting pH dependence, ionization constants of the two aquo ligands coordinated to the uranium of the uranyl complex of 1 were calculated. The ionization constants were also measured by potentiometric titration of the uranyl complex of 1. Based on these results, the pKa values of the two aquo ligands were estimated as 7.1 and 11.0, respectively. At pH 7.5-9.5, therefore, the complex exists mostly as monohydroxo species. Under the conditions of seawater, 1 possesses greater affinity toward uranyl ion compared with other uranophiles such as carbonate ion, calixarene derivatives, or a macrocyclic octacarboxylate. In addition, complexation of 1 with uranyl ion is much faster than that of the calixarene or octacarboxylate uranophiles.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.15 no.2
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• pp.101-116
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• 2017

The interaction of U(VI) (hexavalent uranium) species with natural organic matter (NOM) in KURT (KAERI Underground Research Tunnel) groundwater is investigated using a laser spectroscopic technique. The luminescence spectra of the NOM are observed in the ultraviolet and blue wavelength regions by irradiating a laser beam at 266 nm in groundwater. The luminescence spectra of U(VI) species in groundwater containing uranium concentrations of $0.034-0.788mg{\cdot}L^{-1}$ are measured in the green-colored wavelength region. The luminescence characteristics (peak wavelengths and lifetime) of U(VI) in the groundwater agree well with those of $Ca_2UO_2(CO_3)_3(aq)$ in a standard solution prepared in a laboratory. The luminescence intensities of U(VI) in the groundwater are weaker than those of $Ca_2UO_2(CO_3)_3(aq)$ in the standard solution at the same uranium concentrations. The luminescence intensities of $Ca_2UO_2(CO_3)_3(aq)$ in the standard solution mixed with the groundwater are also weaker than those of $Ca_2UO_2(CO_3)_3(aq)$ in the standard solution at the same uranium concentrations. These results can be ascribed to calcium-U(VI)-carbonate species interacting with NOM and forming non-radiative U(VI) complexes in groundwater.

• Analytical Science and Technology
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• v.21 no.4
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• pp.326-331
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• 2008

Distribution coefficients (Kd) of uranyl ion onto divinylbenzene amidoxime resins were measured in sodium carbonate solution and the Kd values were increased up to about 70 as the resin bead size was decreased. At a condition of 0.0044 M $Na_2CO_3$, the adsorption capacity for uranium was $3.4{\mu}mole$ U/g-resin. The Kd values in the 0.5 M $Na_2CO_3-NaHCO_3$ solution, ranging from pH 9 to pH 11, revealed that they were increased as the pH increased and revealed lower values than those in the pure sodium carbonate solution. The amidoxime resins were characterized by FTIR-ATR showing the absorption bands of the amidoxime functional groups. A species of the uranyltricarbonate complex, $UO_2(CO_3)_3^{-4}$, was confirmed by UV-Vis spectroscopy, revealing four absorption peaks between 400 and 500 nm. Uranium was separated from some fission products by a column operation. However, most of the uranium and fission products were eluted before an adsorption and only a small amount of uranium was adsorbed onto the resin due to the low capacity of the resin.

• Nuclear Engineering and Technology
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• v.41 no.6
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• pp.867-874
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• 2009

Solubility of a radionuclide is important for defining the release source term of a radioactive waste in the safety and performance assessments of a radioactive waste repository. When the pH and redox potential of the KURT groundwater were changed by an electrical method, the concentrations of uranium and thorium released from $UO_2$(cr) and $ThO_2$(cr) at alkali pH(8.1 ${\sim}$ 11.4) and reducing potential (Eh < -0.2 V) conditions were less than $10^{-7}mole/L$. Unexpectedly, the concentration of tetravalent thorium is slightly higher than that of uranium at pH = 8.1 and Eh= -0.2 V conditions, and this difference may be due to the formation of hydroxide-carbonate complex ions. When $UO_2$(s) and $UO_2$(am, hyd.), and $ThO_2$(s) and $Th(OH)_4(am)$ were assumed as solubility limiting solid phases, the concentrations of uranium and thorium in the KURT groundwater calculated by the PHREEQC code were comparable to the experimental results. The dominating aqueous species of uranium and thorium were presumed as $UO_2(CO_3)_3^{4-}$ and $Th(OH)_3CO_3^-$ at pH = 8.1 ${\sim}$ 9.8, and $UO_2(OH)_3^-$ and $Th(OH)_4(aq)$ at pH = 11.4.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.4 no.3
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• pp.235-243
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• 2006

In this study, an experimental study on the sorption properties of uranium(VI) onto a bentonite colloid generated from Gyeongju bentonite which is a potential buffer material in a high-level radioactive waste repository was performed as a function of the pH and the ionic strength. The bentonite colloid prepared by separating a colloidal fraction was mainly composed of montmorillonite. The concentration and the size fraction of the prepared bentonite colloid measured using a gravitational filtration method was about 5100 ppm and 200-450 nm in diameter, respectively. The amount of uranium removed by the sorption reaction bottle walls, by precipitation, and by ultrafiltration was analyzed by carrying out some blank tests. The removed amount of uranium was found not to be significant except the case of ultrafiltration at 0.001 M $NaClO_4$. The ultrafiltration was significant in the lower ionic strength of 0.001 M $NaClO_4$ due to the cationic sorption onto the ultrafilter by a surface charge reversion. The distribution coefficient $K_d$ (or pseudo-colloid formation constant) of uranium(VI) for the bentonite colloid was about $10^4{\sim}10^7mL/g$ depending upon pH and ionic strength of $NaClO_4$ and the $K_d$ was highest in the neutral pH around 6.5. It is noted that the sorption of uranium(VI) onto the bentonite colloid is closely related with aqueous species of uranium depending upon geochemical parameters such as pH, ionic strength, and carbonate concentration. As a consequence, the bentonite colloids generated from a bentonite buffer can mobilize the uranium(VI) as a colloidal form through geological media due to their high sorption capacity.

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

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