• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.19 no.3
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• pp.353-366
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• 2021

The solubilities of different multicomponent lanthanide oxide (Ln₂O₃) solid solutions including binary (Ln₁ and Ln₂ = La, Nd, Eu, or Tm), ternary (Ln₁, Ln₂, and Ln₃ = La, Nd, Eu, or Tm), and higher systems (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) were studied after aging for four weeks at 60℃. Our recent study revealed that the phase transformations in binary ((La, Nd) and (La, Eu)) and ternary (La, Nd, Eu) systems are responsible for the formation of (La, Nd)(OH)₃, (La, Eu)(OH)₃, and (La, Nd, Eu)(OH)₃ solid solutions, respectively. The variations in the mole fractions of La³⁺, Nd³⁺, and Eu³⁺ in the sample solutions of these hydroxide solid solutions indicated that a thermodynamic equilibrium might account for the apparent La, Nd, and Eu solubilities. Conversely, the binary and ternary systems containing Tm₂O₃ as the heavy lanthanide oxide retained the oxide-based solid solutions, and their solubility behaviors were dominated by their congruent dissolutions. In the higher multicomponent system, the X-ray diffraction patterns of the solid phases, before and after contact with the aqueous phase indicated the formation of a stable oxide solid solution and their solubility behavior was explained by its congruent dissolution.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.20 no.4
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• pp.399-410
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• 2022

The solubility and species distribution of radionuclides in groundwater are essential data for the safety assessment of deep underground spent nuclear fuel (SNF) disposal systems. Americium is a major radionuclide responsible for the long-term radiotoxicity of SNF. In this study, the solubility of americium compounds was evaluated in synthetic groundwater (SynDB3), simulating groundwater from the DB3 site of the KAERI Underground Research Tunnel. Geochemical modeling was performed using the ThermoChimie_11a thermochemical database. Concentration of dissolved Am(III) in Syn-DB3 in the pH range of 6.4-10.5 was experimentally measured under over-saturation conditions by liquid scintillation counting over 70 d. The absorption spectra recorded for the same period suggest that Am(III) colloidal particles formed initially followed by rapid precipitation within 2 d. In the pH range of 7.5-10.5, the concentration of dissolved Am(III) converged to approximately 2×10^-7 M over 70 d, which is comparable to that of the amorphous AmCO₃OH(am) according to the modeling results. As the samples were aged for 70 d, a slow equilibrium process occurred between the solid and solution phases. There was no indication of transformation of the amorphous phase into the crystalline phase during the observation period.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.22 no.3
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• pp.237-249
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• 2024

The initial radionuclide migration quantity depends on the total amount of solubilized species. Geochemical modeling based on a thermodynamic database (TDB) has been employed to assess the solubility of radionuclides. It is necessary to evaluate whether the TDB describes the domestic repository conditions appropriately. An effective way to validate the TDB-based modeling results is through direct comparisons with experimentally measured values under the conditions of interest. Here, the solubilities of trivalent Sm, Eu, and Am were measured in synthetic KURT-DB3 groundwater (SynDB3) and compared with modeling results based on ThermoChimie TDB. Ln₂(CO₃)₃·xH₂O(cr) (Ln = Sm, Eu) solids were introduced into the Syn-DB3 and dissolved Sm and Eu concentrations were monitored over 223 days. X-ray diffraction analysis confirmed that the crystallinity of the solid compounds was maintained throughout the experiments. The dissolved Sm and Eu concentrations at equilibrium were close to the predicted solubilities of Sm₂(CO₃)₃(s) and Eu₂(CO₃)₃(s) based on the ThermoChimie TDB. The Am solubility measured under oversaturated conditions was comparable to the measured Eu concentrations, although they were measured under different experimental settings. More experimental data are needed for Am-carbonate solid systems with careful characterization of the solid phases to better evaluate Am solubility in domestic groundwater conditions.

• Proceedings of the Korean Radioactive Waste Society Conference
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• 2004.06a
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• pp.257-258
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• 2004

The dose from radionuclides released from high-level radioactive waste (HLW) glasses as they corrode must be taken into account when assessing the performance of a disposal system. In the performance assessment (PA) calculations conducted for the proposed Yucca Mountain, Nevada, disposal system, the release of radionuclides is conservatively assumed to occur at the same rate the glass matrix dissolves. A simple model was developed to calculate the glass dissolution rate of HLW glasses in these PA calculations [1]. For the PA calculations that were conducted for Site Recommendation, it was necessary to identify ranges of parameter values that bounded the dissolution rates of the wide range of HLW glass compositions that will be disposed. The values and ranges of the model parameters for the pH and temperature dependencies were extracted from the results of SPFT, static leach tests, and Soxhlet tests available in the literature. Static leach tests were conducted with a range of glass compositions to measure values for the glass composition parameter. The glass dissolution rate depends on temperature, pH, and the compositions of the glass and solution, The dissolution rate is calculated using Eq. 1: $rate{\;}={\;}k_{o}10^{(ph){\eta})}{\cdot}e^{(-Ea/RT)}{\cdot}(1-Q/K){\;}+{\;}k_{long}$ where $k_{0},\;{\eta}$ and Eaare the parameters for glass composition, pH, $\eta$ and temperature dependence, respectively, and R is the gas constant. The term (1-Q/K) is the affinity term, where Q is the ion activity product of the solution and K is the pseudo-equilibrium constant for the glass. Values of the parameters $k_{0},\;{\eta}\;and\;E_{a}$ are the parameters for glass composition, pH, and temperature dependence, respectively, and R is the gas constant. The term (1-Q/C) is the affinity term, where Q is the ion activity product of the solution and K is the pseudo-equilibrium constant for the glass. Values of the parameters $k_0$, and Ea are determined under test conditions where the value of Q is maintained near zero, so that the value of the affinity term remains near 1. The dissolution rate under conditions in which the value of the affinity term is near 1 is referred to as the forward rate. This is the highest dissolution rate that can occur at a particular pH and temperature. The value of the parameter K is determined from experiments in which the value of the ion activity product approaches the value of K. This results in a decrease in the value of the affinity term and the dissolution rate. The highly dilute solutions required to measure the forward rate and extract values for $k_0$, $\eta$, and Ea can be maintained by conducting dynamic tests in which the test solution is removed from the reaction cell and replaced with fresh solution. In the single-pass flow-through (PFT) test method, this is done by continuously pumping the test solution through the reaction cell. Alternatively, static tests can be conducted with sufficient solution volume that the solution concentrations of dissolved glass components do not increase significantly during the test. Both the SPFT and static tests can ve conducted for a wide range of pH values and temperatures. Both static and SPFt tests have short-comings. the SPFT test requires analysis of several solutions (typically 6-10) at each of several flow rates to determine the glass dissolution rate at each pH and temperature. As will be shown, the rate measured in an SPFt test depends on the solution flow rate. The solutions in static tests will eventually become concentrated enough to affect the dissolution rate. In both the SPFt and static test methods. a compromise is required between the need to minimize the effects of dissolved components on the dissolution rate and the need to attain solution concentrations that are high enough to analyze. In the paper, we compare the results of static leach tests and SPFT tests conducted with simple 5-component glass to confirm the equivalence of SPFT tests and static tests conducted with pH buffer solutions. Tests were conducted over the range pH values that are most relevant for waste glass disssolution in a disposal system. The glass and temperature used in the tests were selected to allow direct comparison with SPFT tests conducted previously. The ability to measure parameter values with more than one test method and an understanding of how the rate measured in each test is affected by various test parameters provides added confidence to the measured values. The dissolution rate of a simple 5-component glass was measured at pH values of 6.2, 8.3, and 9.6 and $70^{\circ}C$ using static tests and single-pass flow-through (SPFT) tests. Similar rates were measured with the two methods. However, the measured rates are about 10X higher than the rates measured previously for a glass having the same composition using an SPFT test method. Differences are attributed to effects of the solution flow rate on the glass dissolution reate and how the specific surface area of crushed glass is estimated. This comparison indicates the need to standardize the SPFT test procedure.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.14 no.2
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• pp.101-112
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• 2016

This study investigated the removal of Sr, which was one of the high radioactive nuclides, by adsorption with Barium (Ba) impregnated 4A zeolite (BaA) from high-radioactive seawater waste (HSW). Adsorption of Sr by BaA (BaA-Sr), in the impregnated Ba concentration of above 20.2wt%, was decreased by increasing the impregnated Ba concentration, and the impregnated Ba concentration was suitable at 20.2wt%. The BaA-Sr adsorption was added to the co-precipitation of Sr with $BaSO_4$ precipitation in the adsorption of Sr by 4A (4A-Sr) within BaA. Thus, it was possible to remove Sr more than 99% at m/V (adsorbent weight/solution volume)=5 g/L for BaA and m/V >20 g/L for 4A, respectively, in the Sr concentration of less than 0.2 mg/L (actual concentration level of Sr in HSW). It shows that BaA-Sr adsorption is better than 4A-Sr adsorption in for the removal capacity of Sr per unit gram of adsorbent, and the reduction of the secondary solid waste generation (spent adsorbent etc.). Also, BaA-Sr adsorption was more excellent removal capacity of Sr in the seawater waste than distilled water. Therefore, it seems to be effective for the direct removal of Sr from HSW. On the other hand, the adsorption of Cs by BaA (BaA-Cs) was mainly performed by 4A within BaA. Accordingly, it seems to be little effect of impregnated Ba into BaA. Meanwhile, BaA-Sr adsorption kinetics could be expressed the pseudo-second order rate equation. By increasing the initial Sr concentrations and the ratios of V/m, the adsorption rate constants ($k_2$) were decreased, but the equilibrium adsorption capacities ($q_e$) were increasing. However, with increasing the temperature of solution, $k_2$ was conversely increased, and $q_e$ was decreased. The activation energy of BaA-Sr adsorption was 38 kJ/mol. Thus, the chemical adsorption seems to be dominant rather than physical adsorption, although it is not a chemisorption with strong bonding form.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.12 no.3
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• pp.179-189
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• 2014

Pyroprocessing has been developed for the purpose of resolving the current spent nuclear fuel management issue and enhancing the recycle of valuable resources. An electrolytic reduction of the pyroprocessing is a process to reduce oxides into metals using LiCl as an electrolyte and requires a post-treatment process due to the inclusion of residual salt in porous metal products. A vacuum distillation has been adopted for various molten salt systems and could be applied to the post-treatment process of the electrolytic reduction. The residual salt in the metal products includes LiCl, alkali chlorides, and alkaline earth chlorides. In this paper, vapor pressures of chlorides have been estimated and the composition changes on the residual liquid during the vacuum distillation process have been calculated. A model combining a material balance and vapor-liquid equilibrium relations has been proposed under a constant vapor discharging flow rate and liquid composition changes have been calculated using the vapor pressures with respect to a dimensionless time. The behaviors have been compared with temperature and molten salt composition changes to simulate the process condition variation. The distillation of the residual salt has been dominated by LiCl which is the main component of the salt and CsCl of which vapor pressure is higher than that of LiCl would be readily removed. RbCl exhibits similar vapor pressure with LiCl and maintains its composition. However, $SrCl_2$ and $BaCl_2$ of which vapor pressures are much lower than that of LiCl are concentrated with time and expected to be possibly precipitated during the distillation when the initial compositions are increased.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.18 no.2
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• pp.207-215
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• 2020

The feasibility of rare earth (RE) removal process via oxidation reactions with UCl₃ was investigated using the HSC Chemistry code to reduce the concentrations of RE in transuranic (TRU) products. The composition and thermodynamic data of TRU and RE elements contained in the reference spent fuel were examined. The reactivity was evaluated by calculating equilibrium data considering oxidation reactions with UCl₃. Both RE removal rate and TRU recovery rate were evaluated for the two cases, wherein TRU products with different RE concentrations were used. When TRU products were reacted with UCl₃, selective oxidation was driven by the difference in the Gibbs free energy of each element. The calculation results imply that the TRU/RE ratio of the final product can be increased by removing RE elements while maintaining the maximum recovery rate of TRU, which is accomplished by controlling the amount of UCl₃ injected. Since the results of this study are based on thermodynamic equilibrium data, there are many limitations to apply to the actual process. However, it is expected to be used as an important data for the process design to supply the TRU product of pyroprocessing to SFR's fuel demanding low RE concentrations.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.4 no.2
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• pp.133-138
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• 2006

Chemical wastes containing small amounts of uranium can not be disposed of them after treatment as an industrial waste, because the uranium concentration in the final dry cake exceeds the exemption level. Especially for the removal of uranium in this study, the method for immobilizing Diphosil powder within alginate beads is adopted to make a bead form from a powdered resin. Sodium alginate bead itself showed a capability to uptake uranium to above 60%, but the value was decreased to below 30% after equilibrium. The adsorption rate of uranium increased with the increasing content of Diphosil in the sodium alginate bead. Diphosil resin itself showed very fast uptake of uranium from early stages, and then the rates were leveled off. Diphosil bead showed an improved capability to uptake uranium considering the pure Diphosil content in the composite bead, and provide a considerable potential for further applications of a continuous process by using Diphosil as a bead form.

• Journal of the Korean Society of Radiology
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• v.11 no.3
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• pp.171-175
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• 2017

In the non-destructive inspection field, we invest a lot of time and resources in developing the radiation source system to ensure the safety of the workers. However, the probability of accidents is still high. In order to prevent potential radiation accidents in advance, it is necessary to directly verify the position of the radiation source, but the research is still insufficient. In this study, we developed a monitoring system that can detect the position of the radiation source in the source guide tube in the gamma-ray irradiator. The characteristics of the radiation detector are estimated by monte carlo simulation. As a result, the radiation detector for Ir-192 gamma-ray energy was analyzed to have secondary electron equilibrium at $150{\mu}m$ regardless of the semiconductor material. Also, it is expected that the gamma ray response characteristic is the best in $HgI_2$. These results are expected to be used as a basis for determining the optimal thickness of the radiation detector located in the detection part of the future monitoring system. In addition, when developing a monitoring system based on this, radiation workers can easily recognize the danger and secure safety, as well as prevent and preemptively respond to potential radiation accidents.

• Proceedings of the Korean Radioactive Waste Society Conference
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• 2005.06a
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• pp.101-109
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• 2005

In order to produce only a pH-controlled solution without discharging any unused solution, this work has developed a continuous electrolytic system with a pH-adjustment reservoir being placed before an ion exchange membrane-equipped electrolyzer, where as a target solution was fed into the pH-adjustment reservoir, some portion of the solution in the pH-adjustment reservoir was circulated through the cathodic or anodic chamber of the electrolyzer depending on the type of the ion exchange membrane used, and some other portion of the solution in the pH-adjustment reservoir was discharged from the electrolytic system through other counter chamber with its pH being controlled as acid or base. The phenomena of the pH being controlled in the system could be explained by the electro-migration of the ion species in the solution through the ion exchange membrane under a cell potential difference between anode and cathode and its consequently-occurring non-charge equilibriums and electrolytic water- split reactions in the anodic and cathodic chambers.