The initial development plans for the six reactor designs, soon after the release of Generation IV International Forum (GIF) TRM in 2002, were characterized by high ambition [1]. Specifically, the sodium-cooled fast reactor (SFR) and very-high temperature reactor (VHTR) gained significant attention and were expected to reach the validation stage by the 2020s, with commercial viability projected for the 2030s. However, these projections have been unrealized because of various factors. The development of reactor designs by the GIF was supposed to be influenced by events such as the 2008 global financial crisis, 2011 Fukushima accident [2, 3], discovery of extensive shale oil reserves in the United States, and overly ambitious technological targets. Consequently, the momentum for VHTR development reduced significantly. In this context, the aims of this study were to compare and analyze the development progress of the six Gen IV reactor designs over the past 20 years, based on the GIF roadmaps published in 2002 and 2014. The primary focus was to examine the prospects for the reactor designs in relation to spent nuclear fuel burning in conjunction with small modular reactor (SMR), including molten salt reactor (MSR), which is expected to have spent nuclear fuel management potential.

The need for the development of sustainable, efficient, and green radioactive waste disposal methods is emerging with the saturation of spent nuclear waste storage facilities in the Republic of Korea. Conventional radioactive waste management methods like using cement or glass have drawbacks such as high porosity, less chemical stability, high energy consumption, carbon dioxide production, and the generation of secondary wastes, etc. To address this gigantic issue of the planet, we have designed a study to explore the potential of alternative materials having easy processability, low carbon emissions and more chemical stability such as ceramic (hydroxyapatite, HAP) and alkali-activated materials (geopolymers, GP) to capture the simulated radioactive cobalt ions from the contaminated water and directly solidify them at low temperatures. Physical and mechanical properties of HAP alone and 15wt% GP incorporated HAP (HAP-GP- 15) composite were studied and compared. The surface of both materials was fully sorbed with an excess amount of Co(II) ions in the aqueous system. Co(II) sorbed powders were separated from aqueous media using a centrifuge machine operating at 5,000 RPM for 10 minutes and dried at 100°C for 8 hours. The dried powders were then placed in stainless steel molds, and shaped into cylindrical pellets using a uniaxial press at a pressure of 1 metric ton for 1 minute. The pellets were sintered at 1,100°C for 2 hours at a heating rate of 10°C/min. Following this, the water absorption, density, porosity, and compressive strength of the polished pellets were measured using standard methods. Results showed that HAP has a greater potential for decontamination and solidification of Co(II) due to its higher density (2.65 g/cm3 > 1.90 g/cm3), less open porosity (16.2±2.9% < 42.4 ±0.9%) and high compressive strength (82.1±10.2 MPa > 6.9±0.8 MPa) values at 1,100°C compared to that of HAP-GP-15. Nevertheless, further study with different constituent ratio of HAP and GP at various temperatures is required to fully optimize the HAP-GP matrix for waste solidifications.

A comprehensive understanding of actinide coordination chemistry and its structure is essential in many aspects of the nuclear fuel cycle, such as fuel reprocessing, waste management, reactor safety, and non-proliferation efforts. Managing radioactive waste generated during the nuclear fuel cycle has recently become more important, accordingly increasing the importance of designing appropriate waste forms and storage solutions for long-term waste disposal. Compared to the increase in the need for understanding the chemistry of major radioactive elements, the information on the local structure of the radioactive elements, especially actinides, remains unknown. To probe this issue, X-ray absorption fine structure (XAFS) can be applied. By analyzing the EXAFS (extended X-ray absorption fine structure) and XANES (X-ray absorption near edge structure), the local structure around atoms can be determined. However, the radioactive properties of the nuclides hindered the measurement of EXAFS and XANES, due to the difficulties of preparation, containment, and transfer of the sample. To measure the EXAFS of various compounds regarding the back-end nuclear fuel cycle, laboratory-based EXAFS (hiXAS, HP spectroscopy) has been introduced which can measure the EXAFS and XANES at the energy range of 5-18 keV. Compounds of Copper (Cu foil, CuO samples), Zirconium (Zr foil), and Europium (Eu2O3) were used for the verification of the laboratory -based EXAFS at a given energy range. The measured EXAFS spectrum of various compounds exhibit good agreement with the theoretical data, showing an R-factor of less than 0.02. It was found that each graph has a first peak corresponding to 2.55Å for Cu foil (Cu-Cu), 1.93Å for CuO samples (Cu-O), 3.23Å for Zr foil (Zr-Zr), and from 2.32Å to 2.34Å for Eu2O3 (Eu-O), which agree well with other values from the literature. From the result, it can be implied that this equipment can be used especially in the back-end nuclear fuel cycle field to enhance the understanding of local structure in radiochemistry.

Molten chloride salts have received considerable research attention as potential nuclear fuel and coolant candidates for molten salt reactors. However, there are several challenges, especially for structural materials due to the selective dissolution of chromium (Cr) in the molten chloride salts environment. Understanding the compatibility of uranium (U), which is used as nuclear fuel in molten salt reactors, with Cr in molten chloride salts is critical for designing the molten salt reactor structure. Therefore, in this study, the cyclic voltammetry (CV) was used to investigate the electrochemical behaviors of U and Cr. The diffusion coefficients and formal potentials were obtained. The electrochemical properties of uranium and chromium were investigated by CV in molten NaCl-MgCl2 salt at 600°C. Tungsten rods for working and counter electrode, and Ag/AgCl for reference electrode were utilized in this experiment. UCl3 made from the chemical dissolution of U rods and CrCl2 (Sigma-Aldrich, 99.99%) were used. Diffusion coefficients (D) of U and Cr were calculated by measuring reduction peak current of U3+/U and Cr2+/Cr from CV curves and using the Berzins-Delahay equation; D (U3+/U) = 3.0×10-5 cm2s-1 and D (Cr2+/Cr) = 3.3×10-5 cm2s-1. The formal potentials were also calculated by using the reduction peak potential obtained from CV results; E0’ (U3+/U) = -1.173 V and E0’ (Cr2+/Cr) = -0.321 V. The ionization tendency was investigated by comparing each reduction peak potential. The reduction peak potential Ep,c was increasing order of Ep,c (U3+/U) < Ep,c (Cr2+/Cr) < Ep,c (U4+/U3+). It can be seen that in the presence of U4+ and Cr metals, the Cr in the alloy can dissolve into Cr2+, but in the presence of U3+ and Cr metals, the Cr in the alloy does not dissolve into Cr2+. By analyzing the CV curve, diffusion coefficients and formal standard potentials were obtained. The result of comparing reduction peak potentials suggests that the nuclear fuel using U4+ should be inhibited to prevent the selective dissolution of Cr.

The ultimate objective of deep geological repositories is to achieve complete segregation of hazardous radioactive waste from the biosphere. Thus, given the possibility of leaks in the distant future, it is crucial to evaluate the capability of clay minerals to fulfill their promising role as both engineered and natural barriers. Selenium-79, a long-lived fission product originating from uranium- 235, holds significant importance due to its high mobility resulting from the predominant anionic form of selenium. To investigate the retardation behaviors of Se(IV) in clay media by sorption, a series of batch sorption experiments were conducted. The batch samples consisted of Se(IV) ions dissolved in 0.1 M NaCl solutions, along with clay minerals including kaolinite, montmorillonite, and illite-smectite mixed layers. The pH of the samples was also varied, reflecting the shift in the predominant selenium species from selenious acid to selenite ion as the environment can shift from slightly acidic to alkaline conditions. This alteration in pH concurrently promotes the competition of hydroxide ions for Se(IV) sorption on the mineral surface as the pH increases and impedes the selective attachment of selenium. The acquired experimental data were fitted through Langmuir and Freundlich sorption isotherms. From the Freundlich fit data, the distribution coefficient values of Se(IV) for kaolinite, montmorillonite, and illite-smectite mixed layer were derived, which exhibited a clear decrease from 91, 110, 62 L/kg at a pH of 3.2 to 16, 6.3, 12 L/kg at a pH of 7.5, respectively. These values derived over the pH range provide quantitative guidance essential for the safety assessment of clay mineral barriers, contributing to a more informed site selection process for deep geological repositories.

This program aims to build a specialized and converged educational platform for the training of students in the back-end nuclear fuel cycle and cultivate integrated human resources encompassing majors, generations, and fields. To achieve this, we have established an infrastructure for integrated education and training in the radiochemistry and back-end nuclear fuel cycle and operated specialized educational courses linked with special lectures, experimental practices, and field trips. Firstly, to construct an integrated educational and training infrastructure for the back-end nuclear fuel cycle, we formed a committee of experts from both inside and outside the institution and built an advanced radiochemistry laboratory equipped with physical and chemical analysis instruments. Through a comprehensive educational program involving theory, experiments, and discussions, we have established an integrated curriculum across adjacent majors and interdisciplinary studies. We also operate short-term education and experimental training programs (e.g., summer and winter schools for the back-end nuclear fuel cycle). Secondly, the program has connected leading researchers domestically and internationally, as well as the next generation of scholars. The program offers long-term educational opportunities and internships targeting both undergraduate and graduate students. To support this, we continuously offer expert colloquiums and individual research internships. Through regular committee meetings and workshops, we focus on nurturing the integrated talents necessary for the back-end nuclear fuel cycle. Through this program, students from various fields are being trained as competent integrated human resources capable of addressing various issues in the back-end nuclear fuel cycle. It is expected that this will enable us to supply specialized technical personnel in the back-end nuclear field in line with mid-to-long-term demands.

High-temperature molten salts not only demonstrate exceptional thermal and chemical stability but also offer significant advantages in catalyzing chemical reactions. Consequently, they have garnered attention as a promising medium for next-generation nuclear reactors and a wide range of electrochemical processes. Nevertheless, the challenging experimental conditions in molten salts make applying conventional analytical methods to understand reaction mechanisms a formidable task. This underscores the imperative need for more intuitive approaches to investigate molten salt chemistry. One of the simplest yet potent methods involves real-time visual monitoring of the reaction system as chemical reactions progress. In light of this, we have developed an experimental system enabling real-time visual monitoring of the internal dynamics of molten salt media. This system can capture high-resolution videos and images within molten salts, surpassing existing methodologies. We have applied this system in various electrochemical experiments using the molten LiCl-KCl eutectic salt medium. Among them, this study primarily focuses on two challenging experimental scenarios that became comprehensible through our proposed system’s application: (1) the transpassivation of Zr metal and the agglomeration of potassium hexachlorozirconate (K2ZrCl6) solid salt, and (2) the solvation of electrons during the oxidation of Li metal within the molten LiCl-KCl eutectic salt.

The sustainability of the nuclear power industry hinges increasingly on the safe, long-term disposal of radioactive waste. Despite significant innovations and advancements in nuclear fuel and reactor design, the quest for a permanent solution to handle accumulating radioactive waste has received comparatively less attention. Conventionally, two widely recognized solidification methods, namely cementation for low and intermediate-level waste and vitrification for high-level waste, have been favored due to their simplicity, affordability, and availability. Recently, geopolymers have emerged as an appealing alternative, gaining attention for their minimal carbon footprint, robust chemical and mechanical properties, cost-effectiveness, and capacity to immobilize a broad spectrum of radionuclides, including radioactive organic compounds. This study delves into the synthesis of metakaolin-based geopolymers tailored for the immobilization of fission products like cesium (Cs) and molybdenum (Mo). The investigation unfolded in two key steps. In the initial step, we optimized the alkali content to prevent the occurrence of efflorescence, a potential issue. Remarkably, as the Na2O/Al2O3 ratio increased from 0.82 to 1.54, we observed significant enhancements in both compressive strength (11.45 to 27.07 MPa) and density (up to 2.23 g/cm3). This suggests the importance of careful adjustment in achieving the desired geopolymer characteristics. The second phase involved the incorporation of 2wt% of Cs and Mo, both individually and as a mixture, into the geopolymer matrix. We prepared the GP paste, which was poured into cylindrical molds and cured at 60°C for one week. To scrutinize the crystallinity, phase purity, and bonding type of the developed matrix, we employed XRD and FTIR techniques. Additionally, we conducted standard compressive strength tests (following ASTM C39/C39M-17b) to assess the stacking durability and robustness of the developed waste form, vital for storage, handling, transportation, and disposal in a deep geological repository. Furthermore, to evaluate the chemical durability, diffusivity and leaching of the GP waste matrix, we employed the ASTM standard Product Consistency Test (PCT: C 1285-02) and American nuclear society’s devised leaching test (ANS 16.1). It is noteworthy that the introduction of Cs and Cs/Mo in the GP matrix led to a reduction of more than 50% and 60% in compressive strength, respectively. This outcome may be attributed to the interference of Cs and Mo with the geopolymerization process, potentially causing the formation of new phases. However, it is crucial to emphasize that both developed matrices exhibited an acceptable normalized leaching rate of less than 10-5 g·m-2·d-1. This finding underscores the promising potential of the GP matrix for the immobilization of cationic and anionic radioactive species, paving the way for more sustainable nuclear waste management practices.

Th(IV) is a stable actinide that can act as a chemical analogue of U(IV) and Pu(IV), which are important radionuclides in safety assessments of deep geological repositories (DGR). Therefore, to understand the geochemical behaviour of U(IV) and Pu(IV), batch sorption of Th(IV) onto crystalline rocks were performed in oxidising conditions. The distribution coefficients (Kd) of Th(IV) were of particular interest. Gyeongju fresh groundwater (GF) and Gyeongju brackish groundwater (GB) were obtained at the Gyeongju Low and Intermediate Level Radioactive Waste (LILW) Disposal Facility. Crystalline granite (gr) and biotite gneiss (bg) were collected in Gyeongju and Gwacheon respectively and were grounded to a particle size smaller than 150 μm. Sorption samples were continuously shaken for 7 days under 200 rpm at 25°C. The liquid-to-solid ratio (V/m) was 200 L·kg-1. Th(IV) concentrations of the sorption samples were determined by UV-Vis-NIR absorption colorimetry from the formation of Th(IV)-arsenazo III complexes. Although the method allowed the initial Th(IV) concentrations to be determined, the final Th(IV) concentrations fell below the limit of detection (LOD), 6.27×10-9 mol·L-1. Taking the LOD as the final concentrations, conservative Kd were calculated to be 4,410 L·kg-1 for GF-gr and GF-bg, and 7,830 L·kg-1 for GB-gr and GB-bg. The result indicates a strong sorption affinity of Th(IV) onto granite and biotite gneiss within Gyeongju groundwater, suggesting a similar behaviour for U(IV) and Pu(IV). Furthermore, comparison of the conservative Kd obtained from the experiment were compared with existing Kd values of Th(IV). Such analysis and comparison of Th(IV) Kd in various types of groundwater could help locate the optimal site for a DGR in South Korea.

The safe disposal of high-level radioactive waste is a critical concern in many countries, especially in the context of the increasing use of nuclear power to overcome climate change. To provide a comprehensive understanding of the behavior of the radionuclides in the crystalline natural barrier, sorption of the artificially synthesized high-level radioactive waste (HLW) leachate was conducted. Granite (-1,000 m from ground level) and biotite gneiss (-100 m from ground level) rock cores were collected from Gyeongju and Gwacheon, respectively. The rock cores were milled with a jaw crusher and steel disk mill and then sieved. The crushed rocks with a diameter of 0.6 – 1.0 mm were selected, washed three times with deionized water, and then dried. To synthesize the simulated HLW leachate, representative elements (U(VI), Se(IV), Mo(VI), and Ni(II)) were added to natural groundwater collected from Gyeongju. The kinetic sorption experiment was performed in a polypropylene bottle with a solid-to-liquid ratio of 100 g/L in the orbital shaking incubator (200 rotations per min, 25.0°C). After the sorption, the supernatants were filtered by a 0.2-μm polytetrafluoroethylene syringe filter and subsequently analyzed by inductively coupled plasma-mass spectrometry (ICP-MS). Through the kinetic change of aqueous concentration, the contact time has been determined to be 7 days. Ni(II) showed the highest distribution coefficients (Kd = 0.81 L/m2 for granite and 8 – 16 L/m2 for biotite gneiss), followed by U(VI) (Kd = 0.03 – 0.04 L/m2 for granite and 0.04 – 0.05 L/m2 for biotite gneiss). Highly mobile nuclides such as Se(IV) (Kd = 0.02 L/m2 for granite and 0.03 L/m2 for biotite gneiss) and Mo(VI) (Kd = 0.01 – 0.02 L/m2 for granite and 0.01 L/m2 for biotite gneiss) showed the lowest distribution coefficient. Our study provides insights into the migration-retention behaviors of the HLW leachate with granite and biotite gneiss in geological systems and verifies the sorption parameters, e.g., distribution coefficients, experimentally produced by other groups to ensure the safe disposal of HLW.

One of the promising candidates for heat transfer fluid is molten chloride salts. They have been studied in various fields such as the electrolyte of pyroprocessing, the molten salt reactor coolant, and the energy storage system media. Main considerations for utilizing molten chloride salts are the compatibility of salts with structural materials. The corrosion behavior of structural materials in molten chloride salts must be understood to identify suitable materials against the corrosive environment. In this study, the corrosion behavior of a candidate structural material, Hastelloy N, in molten LiCl- KCl salt at 500°C were investigated by the electrochemical impedance spectroscopy (EIS) method. The sheet type of Hastelloy N was utilized as the working electrode in LiCl-KCl to measure the EIS data for 100 hours with 5 hours of time intervals. The EIS data were measured in the frequency range from 104 Hz to 10-2 Hz with the AC signal (amplitude = 20 mV) at open circuit potential. The capacitance semicircle observed in Nyquist plots for all periods indicates that charge-transfer controlled reactions occur. As the immersion time progresses, the radius of the semicircle in Nyquist plots and the impedance and phase angle in Bode plots decrease. These behaviors suggest a decreasing reaction resistance and the corrosion reactions are accelerated with the immersion time. The EIS data were fitted using the equivalent circuit to achieve quantitative results. Two capacitor-resistor components were considered due to the overlapped shape of two valleys in phase angle. The depressed shape of the semicircle in Nyquist plots led to the use of the constant phase element(Q) instead of the capacitor. Therefore, R(Q(R(QR))) circuit was selected to fit the EIS data. Fitting results show that the charge transfer resistance decreases dramatically within 1 day and then converges. The film resistance shows no clear trends, but the increase of the film admittance value indicates the decreased film thickness. Consequently, the film appears to exist like the oxide layer but it does not act as a protective layer. The real-time EIS data were measured in molten salt and provides the corrosion behavior over time. The corrosion mitigation strategy should consider that the corrosion of Hastelloy N accelerates over time and its intrinsic film cannot act as the protective layer. The next steps of this study are to evaluate other candidate structural materials and to demonstrate the presence of the film.

An elevated temperature is expected at the deep geological repository (DGR) due to the decay heat from spent nuclear fuel and the positive geothermal gradient. The resulting elevated temperature would change the aqueous speciation and surface complexation of uranium, which is the major component in spent nuclear fuel. Since sorption reactions of uranium species on natural minerals determine the extent of uranium retardation, in this work the temperature-dependent adsorption of hexavalent uranium, U(VI), was studied by choosing alumina as the basic component mineral for complex aluminosilicates. Time-resolved laser fluorescence spectroscopy (TRLFS) was used to assess the dissolved and adsorbed U(VI) species on γ-Alumina in the pH range of 6.5–9.0 at temperatures of 25 to 70°C. Initial concentrations of U(VI), carbonate and calcium were 89 μM, 25 mM, and 3.0 mM, respectively. The parallel factor analysis (PARAFAC) was used for chemical speciation by spectrum deconvolution. In addition, a separate solution system with higher U(VI) concentrations (0.1 mM, 1.0 mM) and carbonate concentration of 25 mM was studied with attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy for adsorbed species at 25°C. The electrophoretic mobility measurements were also conducted at 25°C to assess the coordination mechanism of adsorbed species at 25°C. The uranyl hydrolysis species and uranyl tricarbonato species coexist in solution at 25°C. At the same temperature, both species were found to be adsorbed. ATR-FTIR could confirm the adsorption of uranyl tricarbonato species at 25°C, and the electrophoretic mobility measurements suggested that the reaction mechanism is an inner-sphere coordination. However, in comparison with aqueous speciation at 25°C, at elevated temperatures the available pH range of uranyl tricarbonato species was narrow and that for uranyl hydrolysis species was wider. It was evident that two hydrolysis species are adsorbed at elevated temperatures, but no tricarbonato species. The enhanced U(VI) adsorption was observed with temperatures. This could result from the transition of dominance from the concurrent adsorption of uranyl hydrolysis species and uranyl tricarbonato species to two hydrolysis species. It was seen that the trend of enthalpy of adsorption was endothermic. Combining the present results with temperature-dependent adsorption studies on silica and aluminosilicates, a reliable SCM for the subsurface system can be proposed to explain U(VI) migration.

The sorption behavior of Se(IV) on montmorillonite clay, a promising buffer and backfill material, was investigated in the presence of aquatic fulvic acid. Selenium-79 is one of the major radioactive nuclides which are long-lived and highly mobile in subsurface environments. Moreover, it is highly toxic even in small amounts, so the selenium quantity in soil and groundwater should be assessed. Although natural organic matters such as humic and fulvic acids are present in the environment, the influence of natural organic matters on Se(IV) migration has not yet been extensively studied. The batch sorption experiments were performed under oxic conditions. Suwannee River III standard aquatic fulvic acid (International Humic Substances Society) was used to build an organicrich environment. The N2 – BET surface area of the montmorillonite (Clay Minerals Society) was 97 ± 5 m2·g−1. The montmorillonite suspensions with/without fulvic acid were equilibrated with air before adding Na2SeO3. The solid-to-liquid ratio was 5 g·L−1, the ionic medium was 0.1 M NaCl, fulvic acid concentration was 50 mg·L−1, and the final pH was 3. The horizontal vial roller was used to prevent the clay from sinking. After 7 days of sorption at room temperature, the suspensions were centrifuged at 10,600 g for 15 min and filtered through 0.2 μm PTFE filters. The colloidal fulvic selenide and free Se(IV) concentrations were entirely measured by inductively coupled plasma–mass spectrometry (ICP-MS). The sorption results were fitted with Langmuir and Freundlich models. At concentrations lower than 20 μM, the distribution coefficients (Kd) were 50 ± 9 L·kg−1 without fulvic acid, and 36 ± 5 L·kg−1 with 50 mg·L−1 fulvic acid. For the concentrations between 20 and 100 μM, the Kd values without and with fulvic acid were 16 ± 7 L·kg−1 and 10 ± 1 L·kg−1, respectively. As a result, it turned out that fulvic acid interferes with the sorption of Se(IV) on montmorillonite in competition with the selenite anion. This indicates that such organic matter may facilitate the migration of selenium in deep geological groundwaters.

Garnet is one of the promising ceramic waste forms for immobilizing radioactive wastes. It has an A3 [VIII]B2 [VI]T3 [IV]O12 structure, so it can accommodate various cations of different sizes and coordination. Silicon usually occupies the centers of the tetrahedron structural site (T[IV]O4) in natural garnet. However, substitution of the T-site with iron, which has a relatively large ionic radius, causes the expansion of a unit cell volume of garnet and allows the incorporation of large cations such as actinides at other sites. Relatively few leaching data have been reported for ferrite garnet waste forms to date. In this study, we synthesized gadolinium-iron-garnet and evaluated the leaching property using cerium as a surrogate for actinide elements. The test specimens were made by cold pressing and sintering process. Three different standard leaching tests were performed as follows. The PCT-A (ASTM C1285) was performed for 7 days at 90°C to the crushed sample (0.149 to 0.074 mm). The ANSI/ANS-16.1 standard leach test was performed at ambient conditions for 5 days with constant replacement of leachate. Finally, the MCC-1 (ASTM C1220) test was performed for 28 days at 90°C with different types of leachants such as ultrapure water, brine, and silicate water. The last two leaching tests were conducted on monolithic specimens. After the end of the test, leachate was analyzed by inductively coupled plasma mass spectroscopy (Agilent, ICP-MS 7700S).