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 (Syn- DB3) 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.

During the dismantling of nuclear facilities, a large quantity of radioactive concrete is generated and chelating agents are required for the decontamination process. However, disposing of environmentally persistent chelated wastes without eliminating the chelating agents might increase the rate of radionuclide migration. This paper reports a rapid and straightforward ion chromatography method for the quantification of citric acid (CA), a commonly used chelating agent. The findings demonstrate acceptable recovery yields, linearities, and reproducibilities of the simulated samples, confirming the validity of the proposed method. The selectivity of the proposed method was confirmed by effectively separating CA from gluconic acid, a common constituent in concretes. The limits of detection and quantification of the method were 0.679 and 2.059 mg·L−1, respectively, while the recovery yield, indicative of the consistency between theoretical and experimental concentrations, was 85%. The method was also employed for the quantification of CA in a real concrete sample. These results highlight the potential of this approach for CA detection in radioactive concrete waste, as well as in other types of nuclear wastes.

The disposal of spent nuclear fuel (SNF) in a deep geological repository (DGR) is a widely accepted strategy for the long-term sequestration of radiotoxic SNF. Ensuring the safety of a DGR requires the prediction of various reactions and migration behaviors of radionuclides (RNs) present in SNF within its geochemical surroundings. Understanding the dissolution behaviors of mineral phases harboring these RNs is crucial, as the levels of RNs in groundwater are basically linked to the solubility of these solid phases. Accurate measurements of solubility demand the use of welldefined solid materials characterized by chemical compositions and structures. Herein, we attempted the synthesis of sklodowskite, a magnesium-uranyl (U(VI))-silicate, employing a twostep hydrothermal synthetic approach documented previously. Subsequently, we subjected this synthesized sklodowskite to various analytical techniques, including powder X-ray diffraction (pXRD), scanning electron microscopy/energy dispersive X-ray spectrometry (SEM/EDX), and vibrational spectroscopies (FTIR and Raman). Based on our findings, we confidently identify the obtained mineral phase as sklodowskite (Mg[UO2SiO3OH]2·5H2O). This identification is primarily based on the similarity between its pXRD pattern and the reference XRD pattern of sklodowskite. Furthermore, the measured infrared and Raman spectra show the vibrational modes of UO2 2+ and SiO4 4- ions, particularly within the 700~1,100 cm-1 region, which support that the synthetic mineral has a characteristic layered uranyl-silicate structure of crystalline sklodowskite. Finally, we utilized synthetic minerals to estimate its solubility up to about three months in a model groundwater, where the dissolved species composition is analogous to that of granitic groundwater from the KAERI Underground Research Tunnel. In this presentation, we will present in detail the results of spectroscopic characterizations and the methodology employed to assess the solubility of the U(VI)-silicate solid phase.

Plutonium exhibits a variety of oxidation states and has a strong affinity for complexation with organic ligands. Isosaccharinic acid (ISA) is a major degradation product of cellulose materials present in the low to intermediate radioactive wastes. The interaction between trivalent plutonium and ISA can significantly impact the migration and containment of plutonium in the repository environment. In this study, formation of Pu(III) and ISA complexes was investigated at an ionic strength of 1 M of NaClO4 using UV-Vis absorption spectrophotometry. To exclude the effect of the Pu(III) oxidation, absorption spectra were measured within 10 min after adding ISA into Pu(III) solution and processed using HYPSPEC software for deconvolution after baseline correction. Several previous studies showed that the presence of ligands accelerates the oxidation of Pu(III) to Pu(IV). To investigate whether ISA complexation can also accelerate the Pu(III) oxidation, UV-Vis absorption spectra changes over 24 hours were analyzed as a function of the ratio of ISA to plutonium concentration.

Solubility and species distributions of radionuclides in domestic groundwater conditions are required for the safety assessment of deep underground disposal system of spent nuclear fuel (SNF). Minor actinides including Am contribute significant extents to the long-term radiotoxicity of SNF. In this study, the solubility of Am was evaluated in synthetic groundwater (Syn-DB3), which were simulated for the groundwater of the DB3 site in the KAERI Underground Research Tunnel (KURT). Geochemical modeling was performed based on the ThermoChimie_11a (2022) thermochemical database from Andra to estimate the solubility and species distributions of Am in the Syn-DB3 condition. Dissolved Am concentrations in the Syn-DB3 were experimentally measured under oversaturation conditions. Am(III) stock solution in perchlorate media was sequentially diluted in Syn-DB3 to prepare 8 μM Am(III) in Syn-DB3. The pH of the solutions was adjusted to be in the range of 6.4–10.5. A portion of the samples was transferred to quartz cells for UV-Vis absorption and time-resolved laser fluorescence spectroscopy studies and the rest were stored in centrifuge tubes. The absorption spectra of the samples were monitored over 70 days and the results suggest that Am colloidal particles were formed initially in all the samples and precipitated rapidly within two days. Over the experimental period of 236 days, small volume (10 μL) of the samples in the centrifuge tubes were periodically withdrawn after centrifugation (18000 rpm, 1 hr) for the liquid scintillation counting to measure the concentrations of Am dissolved in Syn-DB3. In the end of the experiments, pH of the samples was checked again and the final dissolved Am concentrations were determined after ultrafiltration (10 kDa) to exclude the contribution of colloidal particles. In the pH range of 8-9, which is relevant to the KURT-DB3 groundwater condition, the measured dissolved Am(III) concentrations were converged to around 10-8 M. These values are higher than the solubility of AmCO3OH:0.5H2O(s), but lower than that of AmCO3OH(am). There was no indication of transformation of the amorphous phase to the crystalline phase in our observation time window.

Mobility of radionuclides (RNs) in natural water systems can be increased by complex formation with organic materials. In alkaline cement pore-water conditions, cellulose materials in radwastes such as woods and papers are degraded fast to small organic materials. As a major cellulose degradation product, isosaccharinate (ISA) has been paid attention recently due to its effect on facilitating RNs migration. ISA contains a carboxyl and four hydroxyl functional groups, which cooperatively interact to form chelating bonds with positively charged radionuclides. In our previous study, we determined thermodynamic formation constants, reaction enthalpy and entropy of trivalent americium complexes with ISA, Am(ISA)n (3-n)+ (n=1, 2), in weak acidic condition by conducting temperature-dependent UVVis absorption spectroscopy. Based on those thermodynamic constants along with the experimental results from time-resolved laser induced fluorescence spectroscopy and DFT calculations, we suggested two different chelating-modes of ISA on Am(III). It is more relevant to study Am(III)-ISA complexation under alkaline conditions around pH 12.5, which correspond to the pore-water condition of calciumsilicate- hydrate. Under the alkaline conditions, deprotonated hydroxyl groups of ISA can form more strong interactions with Am. Aquatic hydroxide group can also act as a ligand to form ternary Am(III) -ISA-OH complexes. In this study, absorption spectra of Am-ISA systems were monitored with two variations: first, pH variation (5.5–13) in the presence of constant 30 mM ISA, and second, ISA concentration variation (20 μM – 30 mM) at constant pH of 12.5. As increasing the pH at constant 30 mM ISA, absorption spectra of Am(ISA)2 + were red-shifted from 506.3 to 509.5 nm. The samples showed stable absorption spectra over 30 days. On the other hand, samples with lower ISA concentrations below 10 mM at pH 12.5, showed gradual decrease in the absorbance as sample aging time. By examining filtrates after ultrafiltration (1 kDa), we confirmed that aqueous Am(III)-ISA complexes were formed in the presence of 30 mM ISA at pH 12.5, while colloidal particles and precipitations were formed in the conditions of ISA concentrations lower than 10 mM. In this presentation, we will discuss about probable ternary complex forms of Am(III)-ISA-OH, colloidal forms, and solubility of Am(III) as a function of ISA concentration under alkaline conditions. Absorption and luminescence spectroscopic properties of the Am(III)-ISA-OH ternary system will also be presented.

Dissolution behaviors of ThO2(cr) and PuO2(cr) in synthetic groundwater were investigated at room temperature (23  2°C) under atmospheric conditions. The synthetic groundwater was prepared according to the chemical composition of the KURT-DB3 groundwater. The pH and Eh of the synthetic groundwater were pH 8.9 and 0.5 V, respectively, and the major components were Na, K, Ca, Mg, Si, Cl, SO4, F and HCO3 ions. A few mg of ThO2(cr) and PuO2(cr) powder were added in the synthetic groundwater and the concentrations of Th and Pu in supernatant were monitored for 5 months of reaction time. The concentrations of Th before and after ultracentrifugation were compared, while the solid-liquid phase separation of Pu samples could not be applied due to the small volume of sample solutions. The concentrations of Th and Pu were measured by ICP-MS and alpha spectrometry, respectively. Geochemist’s Work Bench (GWB, standard, 17.0) was applied for the modeling with ThermoChimie TDB v. 11a, which was updated with the latest NEA-TDB (vol. 14). Aqueous species distributions and solubility limiting solid phases of Th and Pu under the synthetic groundwater conditions were evaluated. The results of geochemical modeling indicate that aqueous Th-OH-CO3 ternary species and Pu(IV) species are dominant in solutions equilibrated with ThO2(s) and PuO2(am, hyd), respectively. The dissolution behaviors of ThO2(cr) and PuO2(cr) are comparable to the dissolution of ThO2(aged, logKsp = 8.5) and the oxidative dissolution of PuO2(am, hyd) in the presence of PuO2(coll, hyd), respectively.

Low- and intermediate-level radioactive waste for permanent disposal often contains organic complexing agents, so-called chelating agents. Organic complexing agents, which are polycarboxylic acids, can increase the mobility of radionuclides into the environment by forming water-soluble complexes with most heavy metals. Therefore, analyzing the complexing agents in radioactive waste is crucial for comprehensive management of nuclear wastes. According to regulatory guidelines, specifically Notice No. 2021-16 issued by the Nuclear Safety and Security Commission, the determination of chelating agent content in radioactive waste materials is required to ensure proper management and safe disposal. However, only a few methods are available to analyze the chelators in various matrices such as concrete, metals, soil, and mixed solid wastes like plastics, vinyl, and rubber. Recently, we found a UV-Vis method based on an enzymatic reaction is inadequate for analyzing citric acid in radioactive waste with a complex matrix like concrete. To address this, we developed a method to determine the contents of EDTA and NTA using a UV-Vis spectrophotometer and citric acid using ion chromatography. The results showed good validity and reliability to determine the chelating agents in various radioactive wastes.

To improve the safety of nuclear fuel, research on the advanced nuclear fuel (UO2) by adding various trace elements is being conducted. For example, the addition of metals such as Mo, Cr can improve the thermal conductivity of nuclear fuel, minimizing the diffusion of fission products. Trace metal oxide additives (SiO2, Cr2O3, Al2O3, etc.) can suppress the release of fission gases. In general, complete dissolution of the fuel sample is required for chemical analysis to determine its elemental compositions. Among widely used metal oxide additives, aluminum oxide is difficult to dissolve in nitric acid due to its excellent thermal and chemical stability. In this study, we investigated on different chemical dissolution methods by applying a microwave digestion system under various acid solutions. We confirmed the validity of the digestion method by carrying out trace element analysis using an Inductively-Coupled Plasma Atomic Emission Spectrometer (ICP-AES).

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 (Syn- DB3), 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.

Neptunium (Np) is one of the daughter elements included in the decay chain of Pu. The quantitative analysis of Np isotopes is required for radioactive waste characterization, research on actinide chemistry, etc. Np-237 has a long half-life (2.144 million years), but its daughter Pa-233 has a relatively short half-life (26.975 days). For this reason, after a sufficient time elapses following the chemical preparation process of the analyte, the two nuclides are in radiation equilibrium in the sample. Np-237 emits alpha-rays while Pa-233 emits beta-rays. Both nuclides also emit gamma- and X-rays. In this study, alpha-rays were measured using liquid scintillation counting (LSC) method and alpha spectrometry. Gamma-spectrometry with a HPGe detector was used for the analysis of gammaand X-rays. In addition, we compared the radiometric results with quantitative analysis of Np using UV-Vis absorption spectrometry. The LSC method and the HPGe gamma-spectroscopy do not require extensive sample preparation procedures. Alpha spectroscopy requires a standard material spiking, separation by coprecipitation, and disk-type sample preparation procedure to obtain measurement efficiency and recovery factor. A reference material sample with a concentration of 5.8 mM was analyzed by the four analysis methods, and all of the measured results agreed well within a difference level of 4%.

Nuclear spent fuel (SNF) disposal in deep geological repositories is considered as one of sound options for the long-term and safe sequestration of radiotoxic SNF and the sustainable use of nuclear energy. The chemical behaviors of various radionuclides originated from SNF should be well understood to evaluate the migrational behaviors of radionuclides and their reactions and interactions with various geochemical components. Formation of secondary minerals, colloids, other insoluble precipitates is of interest since the concentrations of radionuclides in groundwaters can be limited by the solubility of those solid phases. Particularly when evaluating their solubility, the use of well-defined solid materials in terms of chemical composition and molecular structure is crucial to obtain reliable measurement results. In this study, a synthetic calcium uranyl silicate (Ca-U(VI)-silicate, or uranophane) was prepared and characterized by using various analytical methods including powder X-ray diffraction (pXRD), scanning electron microscopy/energy dispersive X-ray spectrometry (SEM/EDX), and vibrational (FTIR and Raman) spectroscopies. Uranyl silicate minerals are significant to the disposal of nuclear wastes. Our simulation demonstrates that uranophane (Ca[UO2SiO3OH]2·5H2O), one having a U:Si ratio of 1:1, can be a mineral species limiting U(VI) solubility under groundwater conditions in Korea. For the preparation of Ca-U(VI)-silicate, we applied a two-step hydrothermal synthetic procedure reported in literature with modification. Briefly, we conclude that the obtained mineral phase is the ‘α-uranophane’; our characterization results show that the structural and spectroscopic properties of the synthetic Ca-U(VI)-silicate agree well with those of α-uranophane. For instance, the pXRD patterns obtained from the solid show nearly identical diffraction peak positions with those from the reference XRD pattern. From IR and Raman spectroscopy it is noticed that the stretching modes of UO2 2+ and SiO4 4- ions result in strong absorption bands in a region of 700 ~ 1,100 cm-1. Elemental compositions of the synthetic solids were also estimated by using EDX analysis, which results in a Ca:U:Si ratio close to 1:2:2 on average. However, we found that it is difficult to obtain good crystallinity of uranophane, which can be observable by using SEM and its image analysis. We believe that this work serves as a model study to provide synthetic routes of radionuclide-related mineral phases and applicable solid phase characterization methods. In the presentation, the potential use of the U(VI)-silicate solid phase for the upcoming groundwater solubility measurements will be discussed. Keywords: Hexavalent Uranium, Silicate

For the safety assessment of the high-level radioactive waste (HLRW) disposal, the thermodynamic data such as solubility products, formation constants of complexes, redox equilibrium constants of radionuclides, and their reaction enthalpy and entropy are required. In order to recommend and summarize the reliable data, thermodynamic databases (TDB) have been persistently developed through the OECD-NEA TDB projects and an updated TDB of actinides has been recently published in 2020. To date, reliable data for Pu reactions are scarce due to the possibility of coexistence of four different oxidation states, Pu(III-VI) by redox equilibria in solutions. To determine the thermodynamic data for the reaction of each Pu oxidation state, it is necessary to precisely control the oxidation state and quantitatively analyze all reactants, products and bi-products by using highly sensitive speciation techniques. Since 2004, the nuclear chemistry research team in KAERI has been focused on developing techniques for the sensitive chemical speciation by using laser-based spectroscopy and determining thermodynamic data of actinides such as U, Pu, Am. In this paper, chemical speciation and thermodynamic studies on Pu in KAERI are reviewed. A combination of a commercial spectrophotometer and a capillary cell was adopted for a sensitive chemical speciation of Pu(III-VI) in solutions. A sensitive detection of trace amount of Pu colloids was carried out with the laser-induced breakdown detection (LIBD) system. Pu(VI) complexation with hydroxide or carbonate ions were investigated under strong oxidation conditions controlled with hypochlorite (NaOCl). The solubility product of Pu(OH)3(am) and formation constant of Pu(III)-OH speices were determined by a combination of wet-chemistry experiments and several analysis methods of spectrophotometry, LIBD, radiometry under a strong reducing condition controlled by electrochemistry. More recently, we reported the reaction enthalpy and entropy data for the formation of Pu(OH)2+ and the dissolution of Pu(OH)3(am). A preliminary data for reaction between Pu(III) and organic matter will be presented.

The fundamental characteristics of groundwater colloids, such as composition, concentration, size, and stability, were analyzed using granitic groundwater samples taken from the KAERI Underground Research Tunnel (KURT) site by such analytical methods as inductively coupled plasma-mass spectrometry, field emission-transmission electron microscopy, a liquid chromatography-organic carbon detector, and dynamic light scattering technique. The results show that the KURT groundwater colloids are mainly composed of clay minerals, calcite, metal (Fe) oxide, and organic matter. The size and concentration of the groundwater colloids were 10–250 nm and 33–64 μg·L−1, respectively. These values are similar to those from other studies performed in granitic groundwater. The groundwater colloids were found to be moderately stable under the groundwater conditions of the KURT site. Consequently, the groundwater colloids in the fractured granite system of the KURT site can form stable radiocolloids and increase the mobility of radionuclides if they associate with radionuclides released from a radioactive waste repository. The results provide basic data for evaluating the effects of groundwater colloids on radionuclide migration in fractured granite rock, which is necessary for the safety assessment of a high-level radioactive waste repository.

Elucidating the redox behavior of actinide elements in aqueous solution is important for the safety assessments of nuclear waste disposal. Despite ongoing endeavors for decades, some points of uranium and plutonium redox mechanism are ambiguous and unclear. In this study, the electrochemical redox behaviors of U(VI) and Pu(III and VI) ions in perchloric acid media were investigated by using a gold (Au) working electrode via cyclic voltammetry (CV) and cyclic square wave voltammetry (CSWV) with the temperature control (10–55°C). The cyclic voltammograms of U(V/VI), Pu(III/IV) and Pu(V/VI) redox couple were transformed to semi-integral form to calculate the diffusion coefficient and formal potential in the electrochemical quasi-reversibility prevailed system. The CSWV was additionally used for a more precise interpretation of the redox mechanism. From the investigation of the redox chemistry of U(VI) ions, a clear U(V/VI) redox peak and one unidentified oxidation peak appear around pH 2. With the temperature control and CSWV, the relevance of the oxidation peak and U(IV) was confirmed. In the case of voltammetry of Pu(VI) solution, Pu(V/VI) redox peak and an additional reduction peak appear. The redox behavior resposible for this additional reduction peak are also examined. The cyclic voltammograms of Pu(III) solution show a clear reversible redox reaction of Pu(III/IV) couple. With the temperature control, using the change of formal potential at ionic strength 1 M (ClO4 −), thermodynamic parameters of conditional molar enthalpy and entropy change were evaluated in this system.