Se sorption onto Ca-type montmorillonite purified from Bentonil-WRK—a new research bentonite introduced by Korea Atomic Energy Research Institute—was examined under ambient conditions (pH 4−9, pe 7−9, I = 0.01 M CaCl2, and T = 25°C). Se(IV) was identified as the oxidation state responsible for weak sorption (Kd < 22 L∙kg−1) by forming surface complexes with edge functional groups of the montmorillonite. Thermodynamic modeling, considering reaction mechanisms of outer-sphere complexation (≡AlOH2 + + HSeO3 − ⇌ ≡AlOH3SeO3, log K = 0.50 ± 0.21), inner-sphere complexation (2≡AlOH + H2SeO3(aq) ⇌ (≡Al)2SeO3 + 2H2O(l), log K = 7.89 ± 0.51), and Ca2+-involved ternary complexation (≡AlOH + Ca2+ + SeO3 2− ⇌ ≡AlOHCaSeO3, log K = 7.69 ± 0.28) between selenite and aluminol sites of montmorillonite, acceptably reproduced the batch sorption data. Outer- and inner-sphere complexes are predominant Se(IV) forms sorbed in acidic (pH ≈ 4) and near-acidic (pH ≈ 6) regions, respectively, whereas ternary complexation accounts for Se(IV) sorption at neutral pHs under the ambient conditions. The experimental and modeling data generally extend a material-specific sorption database of Bentonil-WRK, which is essential for assessing its radionuclide retention performance as a buffer candidate of deep geological disposal system for high-level radioactive waste.

Thermodynamic sorption modeling can enhance confidence in assessing and demonstrating the radionuclide sorption phenomena onto various mineral adsorbents. In this work, Ca-montmorillonite was successfully purified from Bentonil-WRK bentonite by performing the sequential physical and chemical treatments, and its geochemical properties were characterized using X-ray diffraction, Brunauer-Emmett-Teller analysis, cesium-saturation method, and controlled continuous acidbase titration. Further, batch experiments were conducted to evaluate the adsorption properties of Cs(I) and Sr(II) onto the homoionic Ca-montmorillonite under ambient conditions, and the diffuse double layer model-based inverse analysis of sorption data was performed to establish the relevant surface reaction models and obtain corresponding thermodynamic constants. Two types of surface reactions were identified as responsible for the sorption of Cs(I) and Sr(II) onto Ca-montmorillonite: cation exchange at interlayer site and complexation with edge silanol functionality. The thermodynamic sorption modeling provides acceptable representations of the experimental data, and the species distributions calculated using the resulting reaction constants accounts for the predominance of cation exchange mechanism of Cs(I) and Sr(II) under the ambient aqueous conditions. The surface complexation of cationic fission products with silanol group slightly facilitates their sorption at pH > 8.

Radionuclides in low- and intermediate-level radioactive wastes from the decommissioning process of nuclear power plants were generally immobilized by cementation methods. Ethylenediaminetetraacetic acid (EDTA), which is extensively used as a decontamination agent, can affect the behaviors of radionuclides immobilized in cement waste forms. In this study, the effects of EDTA contained in simulated radioactive decommissioning wastes on the leaching characteristics of immobilized Co and Cs and the microstructure evolution of cement waste form. Co leaching was accelerated by the formation of Co–EDTA complexes with high mobility and solubility. Cs leaching was hindered by the ion competition with other metal–EDTA complexes for releasing from the cement waste form. Cs leaching was also retarded by carbonated layer at edge of the cement waste form, which process is facilitated by the presence of EDTA. Finally, the effects of EDTA on the leaching characteristics of immobilized Cs and Co and the microstructure evolution of the cement waste form should be considered to ensure the safety of disposal for lowand intermediate-level radioactive wastes.

The Colloid Formation and Migration (CFM) international joint research initiative continues as a part of the GTS’s Radionuclide Retardation Programme, which has been in progress since 1984. This project focuses on examining the formation of colloids from a bentonite-engineered barrier system and exploring how these colloids impact the migration of radionuclides in fractured host rock when subjected to advective flow. Phase 1 of the project was launched in 2004 and concluded in early 2008, focusing on preliminary studies related to in-situ boundary conditions, predicting models, and supplementary lab works. Following that, Phase 2 spanned from 2008 to 2013 and aimed at fortifying the field setup by adding three new monitoring boreholes and suitable instrumentation in both the boreholes and tunnel. This phase also tested the system’s resilience while mapping the flow domain. Phase 3 kicked off in January 2014 and extended until December 2018. During this period, the Long-term In-situ Test (LIT) was introduced in May 2014, featuring a set of compacted bentonite rings laced with radionuclide tracers. These were placed in a borehole to serve as a colloid and radionuclide source. CFM Phase 4 initiative commenced in January 2019, marking the successful deployment of the i-BET (In-situ Bentonite Erosion Test). This project component involves placing approximately 50 kg of compacted bentonite in a natural water-conducting shear zone. Korea Atomic Energy Research Institute (KAERI) joined CFM in 2008 to examine the behavior of colloid generation and migration with radionuclides in the Underground Research Laboratory. The fourth phase of the CFM project was also scheduled to include a post-mortem evaluation of the LIT and additional tracer experiments in the well-mapped MI shear zone. This study aims to provide an interim update on the ongoing i-BET, a key component of Phase 4 of the CFM project. We will also discuss the current status of the post-mortem analysis for the LIT experiment. In addition, we will outline plans for the forthcoming Phase VI of the project. These plans will continue to advance our understanding of radionuclide migration and the influence of bentonite-based disposal systems.

In the high-level waste disposal systems, colloids generated through the chemical erosion of bentonite buffers can serve as critical mediators for the transport of radionuclides from the disposal environment to the biosphere. The stability of these colloids is influenced by the chemical composition of the groundwater. According to DLVO theory, the Critical Coagulation Concentration (CCC) is the ionic strength at which the total repulsive force between colloids is either less than or equal to the total attractive force. At ionic strengths lower than the CCC, electrostatic double-layer repulsion outweighs van der Waals attraction, forming a repulsive barrier between particles. Conversely, at ionic strengths higher than the CCC, attractive forces dominate, leading to particle aggregation. To investigate the CCC of bentonite colloids, this study focused on Ca-type WRK bentonite. Colloids separated from a ten g/L bentonite suspension underwent centrifugation (1,200 g for 30 minutes) and dialysis (3,500 MWCO) to produce colloid samples. After adjusting the ionic strength from 0.1 mM to 10 mM, the particle size distribution was monitored as a function of aggregation time for approximately 20 days. Rate constants, calculated based on variations in ionic strength, were used to interpret the observed results. The experimental outcomes revealed that the CCC value for WRK bentonite colloids was an order of magnitude lower with CaCl2 than with NaCl. This suggests that Ca ions have a more significant impact on colloid stability, which has implications for the longterm safety of high-level waste disposal systems.

Montmorillonite, a versatile clay mineral with a wide range of industrial applications, is often found in natural deposits with impurities that limit its effectiveness. This study investigates the use of column froth flotation as an innovative technique to improve the purity of montmorillonite by selectively removing impurities without affecting its essential properties. Column froth flotation, a well-established mineral separation method, is adapted to address the specific challenges associated with enhancing montmorillonite purity. The process involves conditioning raw montmorillonite with carefully chosen reagents to selectively separate impurities, including quartz, feldspar, and other minerals commonly found alongside montmorillonite in natural deposits. Experimental results confirm the effectiveness of column froth flotation in significantly enhancing the purity of montmorillonite. This method allows for efficient impurity removal while preserving the essential properties of montmorillonite, making it suitable for various industrial applications. The study also explores the optimal conditions and reagent choices to maximize the purification process. In conclusion, column froth flotation offers a promising avenue for enhancing montmorillonite purity without compromising its fundamental properties. This study provides valuable insights into optimizing the process for large-scale industrial applications, facilitating the development of highquality montmorillonite products tailored to specific industrial needs.

The final disposal of Spent Nuclear Fuel (SNF) will take place in a deep geological repository. The metal canister surrounding the SNF is made of cast iron and copper, designed to provide longterm containment of radionuclides. Canister is intended to be safeguarded by a multiple-barrier disposal system comprising engineered and natural barriers. Colloids and gases are mediators that can accelerate radionuclide migration and influence radionuclide behavior when radionuclides leak from the canister at the end of its service life. It is very important to consider these factors in the assessment of the long-term stability of deep dispoal repository. An experimental setup was designed to observe the acceleration of nuclide behavior due to gas-mediated transport in a simulated environment with specific temperature and pressure conditions, similar to those of a deep disposal repository. In this study, experiments were conducted to simulate gas flow within an engineered barrier under conditions reflecting 1000 years post repository closure. The experiment utilized bentonite WRK with a dry density of 1.61 g/cm³ after compaction. The compacted bentonite was subsequently saturated under a water pressure of 5 MPa, equivalent to the hydrostatic pressure found 500 meters underground. Gas was introduced into the saturated bentonite at different pressures to assess the permeation behavior of the bentonite relative to gas pressure variations. Consequently, it was observed that under specific pressures, gas permeated the saturated bentonite, ascending in the form of bubbles. Furthermore, it was noted that when a continuous flow was initiated within the bentonite, erosion took place, leading to the buoyant transportation of eroded particles upward by the bubbles. The particles transported by the bubbles had a relatively small particle size distribution, and cesium also tended to be transported by the bubbles and moved upward. When high-pressure gas is generated at the interface of the canister and the buffer, flow through the buffer can occur, and cationic nuclides such as cesium and strontium can be attached to the gas bubble and migrate. However, the pressure of the gas to break through the saturated buffer is very high, and the amount of cesium transported by the gas bubbles is very limited.

The spent fuels derived from the nuclear reactor facilities may be finally disposed in a deep underground below 500 m. It majorly has uranium with minor iodine, which is a typical anionic radionuclide. In particular, radioiodine has higher mobility from its spent fuel source. It has been well known that it could freely pass through a compacted bentonite that is one of underground engineering barriers that are used to retard some nuclide’s migration from the spent fuel. We installed a small laboratory apparatus in an anaerobic glove box imitating such an underground repository and evaluated the iodine mobility in compacted bentonites with or without copper. Some copper-bearing bentonites were prepared in two types, a copper ion-exchanged form and a copper nanoparticle-mixed one. In our study, we tried to find an effect of sulfate that has an ability to retard mobile iodine from the compacted bentonite for a long-term period. Conclusively, we found an effective way to limit the iodine release from the compacted bentonite. This condition can be achievable by exchanging the bentonite interlayer cations with copper ions or by simply mixing copper nanoparticles with bentonite powder. In those cases, soluble iodine can be easily immobilized as a solid phase (i.e., marshite (CuI)) by combining with copper via the geochemical role of sulfate and indigenous SRB (sulfate reducing bacteria) of bentonite.

A disposal system for spent nuclear fuel mainly divides into two parts; Engineered barriers include spent nuclear fuel, canister, buffer and backfill and natural barriers mean a host rock surrounding engineered barriers. If radionuclides released from a repository, they can migrate to the ecosystem. Sorption plays an important role in retarding the migration of released radionuclides. Hence, the safety assessment for the disposal of a spent nuclear fuel should consider the migration and retardation of radionuclides in geosphere. Distribution coefficient is one of input parameters for the safety assessment. In this work, distribution coefficients for crystalline rock as a natural barrier were collected and evaluated for the purpose of safety assessment for the deep geological disposal of a spent nuclear fuel. The radionuclides considered in this work are as follows; alkali and alkaline earth metals (Cs, Sr, Ba), lanthanides (Sm), actinides (Ac, Am, Cm, Np, Pa, Pu, Th U), transition elements (Nb, Ni, Pd, Tc, Zr), and others (C, Cl, I, Rn, Se, Sn). The sorption of radionuclides is influenced by various geochemical conditions such as pH/carbonates, redox potential, ionic strength, radionuclide concentration, kinds and amounts of minerals, and microbes. For the evaluation of distribution coefficients, the data from Sweden (SKB), Finland (Posiva), Switzerland (Nagra), and Japan (JAEA) were collected, analyzed, and the recommended distribution coefficients have been suggested.

Raman characteristics of various minerals constituting natural rocks collected from uranium deposits in Okcheon metamorphic zone in Korea are presented. Micro-Raman spectra were measured using a confocal Raman microscope (Renishaw in Via Basis). The focal length of the spectrometer was 250 mm, and a 1800 lines/mm grating was installed. The outlet of the spectrometer was equipped with a CCD (1,024256 pixel) operating at -70°C. Three objective lenses were installed, and each magnification was 10, 50, and 100 times. The diameter of the laser beam passing through the objective lens and incident on the sample surface was approximately 2 m. The laser beam power at 532 nm was 1.6 mW on the sample surface. Raman signal scattered backward from the sample surface was transmitted to the spectrometer through the same objective lens. To accurately determine the Raman peak position of the sample, a Raman peak at 520.5 cm-1 measured on a silicon wafer was used as a reference position. Since quartz, calcite, and muscovite minerals are widely distributed throughout the rock, it is easy to observe with an optical microscope, so there is no difficulty in measuring the Raman spectrum. However, it is difficult to identify the uraninite scattered in micrometer sizes only with a Raman microscope. In this case, the location of uraninite was first confirmed using SEM-EDS, and then the sample was transferred to the Raman microscope to measure the Raman spectrum. In particular, a qualitative analysis of the oxidation and lattice conditions of natural uraninite was attempted by comparing the Raman properties of a micrometer-sized natural uraninite and a laboratory-synthesized UO2 pellet. Significantly different T2g/2LO Raman intensity ratio was observed in the two samples, which indicates that there are defects in the lattice structure of natural uraninite. In addition, no uranyl mineral phases were observed due to the deterioration of natural uraninite. This result suggests that the uranium deposit is maintained in a reduced state. Rutile is also scattered in micrometer-sizes, similar to uraninite. The Raman spectrum of rutile is similar in shape to that of uraninite, making them confused. The Raman spectral differences between these two minerals were compared in detail.

Bentonite is a promising buffer material for high-level radioactive waste (HLW) disposal due to the high nuclides sorption capacity and swelling property. However, bentonite has the potential to generate colloid particles, with small particle sizes less than 1,000 nm when in contact with groundwater. The bentonite colloids easily form pseudo-colloid with the released nuclides and migrate through the water-conducting rock to the biosphere. Therefore, understanding the generation and migration of bentonite colloids is crucial in assessing the safety of the HLW repository. In this study, an artificial fracture system was prepared to investigate colloid release from compacted bentonite. A 250 mm diameter acrylic artificial fracture system was used, with 30 mm of compacted calcium bentonite installed. Artificial groundwater flow was injected into the system at a flow rate of 250 μL/h, and every 6 mL of leachate was collected by a fraction collector. A film-type pressure sensor was equipped to monitor the swelling pressure, and the swelling was observed using a digital microscope. The results indicate that the compacted bentonite formed a mineral ring originating from the swelling of the bentonite, and the end of the ring generated colloid particles due to chemical erosion. Although the release rate of colloids increased with increasing flow rate, the colloid ratio depended on the low ionic strength of the injected artificial groundwater. This work contributes to the understanding of the chemical erosion and colloid release mechanism of compacted bentonite.

A deep geological repository for disposal of high-level radioactive waste (HLW) consists of the canister, buffer material, and natural rock. If radionuclides leak from a disposal container, it can pass through buffer materials and rock, and move into the biosphere. Transport and migration of radionuclides in the rock differently were affected by the fracture type, filling minerals in the fracture, and the chemical and hydraulic properties of the groundwater. In this study, aperture distribution in fractured granite block was investigated by hydraulic test and CFD analysis. The fractured rock block (1 m × 0.6 m × 0.6 m), which is simulated as natural barrier, was prepared from Iksan, Jeollabuk-do. 9 test holes were drilled and packer system was installed to perform hydraulic test at the surface of fracture. 3D model simulated for aperture distribution of rock block was made using results of hydraulic test. And then, CFD analysis was performed to evaluate the co-relation between experiment results and analysis results using FLUENT code.

The safe disposal of high-level radioactive waste (HLW), including the discharged spent nuclear fuel (SNF) and contaminated by-products produced from relevant chemical treatments, has become a serious pending problem for numerous countries that operate the nuclear power plants. The deep geological disposal (DGD) has thus far been considered the most proven and viable solution for isolation of the HLW and preventing any significant release of radionuclides into the biosphere. The DGD system consists of the multiple engineered and natural barrier components. Among them, the montmorillonite-based buffer and tunnel backfills are designed to perform the two major geochemical functions: 1) preventing the ingress of groundwater and any chemicals that compromise the safety of waste canister and 2) retarding the migration of released radionuclides by providing sufficient chemisorption sites. Therefore, it is essential to investigate the sorption mechanism of radionuclides onto montmorillonite and develop a thermodynamic reaction model in advance in order to accurately predict the long-term performance of engineered barriers and to reduce the uncertainties in the safety assessment of a deep geological repository (DGR) ultimately; thus far, sorption of chemical species onto mineral adsorbents has been widely described based on the concept of sorption-desorption distribution coefficient (Kd), the value of which is intrinsically conditional, and active scientific efforts have been made to develop robust thermodynamic sorption models which offer the potential to improve confidence in demonstration of radionuclide migration under a wide range of geochemical conditions. The natural montmorillonites are generally classified into Na-type or Ca-type according to its exchangeable cation, and the Ca-montmorillonite containing clays are being considered as candidate materials for the engineered barriers of DGR in several countries; they generally have advantages of higher thermal conductivity and lower price than the Na-montmorillonite based clays, but their sorption capacities are still comparable. In this framework, we aimed to investigate the chemical interactions of Ca-montmorillonite with selenite [Se(IV)], which is a major oxyanionic species in terms of HLW disposal, and develop a reliable thermodynamic sorption model (TSM). The present work summarizes the characterization of Ca-montmorillonite separated from the newly adopted reference bentonite (Bentonil-WRK) by means of XRD, BET, FTIR, CEC measurement, and acid-base titration. Further, its sorption behaviors with aqueous selenite species under aqueous conditions of S/L = 5 g/L, I = 0.01-0.1 m CaCl2, pH = 4.5-8.5, pCO2 = 10-3.5 atm, and T = 25°C were examined, and the resulting thermodynamic data are discussed as well.

Bentonite is a potential buffer material of multi-barrier systems in high-level radioactive wastes repository. Montmorillonite, the main constituent of the bentonite, is 2:1 type aluminosilicate clay mineral with high swelling capacity and low permeability. Montmorillonite alteration under alkaline and saline conditions may affect the physico-chemical properties of the bentonite buffer. In this study, montmorillonite alteration by interaction with synthetic alkaline and saline solution and its retention capacity for cesium and iodide were investigated. The experiments were performed in three different batches (Milli-Q water, alkaline water, and saline water) doped with cesium and iodide for 7 days. Alteration characteristics and nuclide retention capacity of original- and reacted bentonite was analyzed by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR) spectroscopy, Scanning Electron Microscope (SEM), Nuclear Magnetic Resonance (NMR) and Cation Exchange Capacity (CEC) analysis. From the results, cesium retention occurred differently depending on the presence of competing ions such as K, Na, and Mg ions in synthetic solutions, while iodide was negligibly removed by bentonite. Montmorillonite alteration mainly occurred as cation exchange and zeolite minerals such as merlinoite and mordenite were new-formed during alkaline alteration of the montmorillonite. CEC value of reacted bentonite increased by formation of the zeolite minerals under alkaline conditions.