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.

The permanent disposal of discharged spent nuclear fuel (SNF) and contaminated radioactive waste generated from the subsequent chemical treatments of SNF has become a serious pending issue in many countries that operate the nuclear power plants. Among the diverse engineering solutions proposed for the disposal of high-level radioactive waste (HLW), deep geological disposal (DGD) has been considered as the most proven and safe option to prevent any significant release of radionuclides into the biosphere and to predictably ensure the long-term performance of disposal system. The DGD system consists of multiple structural components; the bentonite clay-based buffer and tunnel backfills are designed to perform the primary hydrogeochemical functions of 1) inhibiting the ingress of groundwater and reactive substances that could compromise the integrity of canister and 2) retarding the migration of released radionuclides into biosphere by providing the sufficient chemisorption sites. Montmorillonite, which is a 2:1 phyllosilicate mineral belonging to smectite group, constitutes the majority of bentonite, and it mainly predominate the swelling and chemisorption capacities of the clay material. Thus, it is essentially required to thoroughly understand the chemical interactions of major radionuclides and other important substances with montmorillonite in advance to accurately evaluate the long-term retention performance of engineered barriers and to reduce the uncertainties in the safety assessment of a deep geological repository (DGR) ultimately. Thus far, sorption of dissolved species onto mineral adsorbents has been generally described and quantified using the simple sorption-desorption distribution coefficient (Kd) concept; since any specific reaction mechanisms are not considered and reflected in the Kd concept, an empirical Kd value is intrinsically dependent on the aqueous conditions under which it was measured. In this framework, substantial scientific efforts have been made to develop a robust basis for geochemically parametrizing the sorption phenomena more reliably, and the application of thermodynamic sorption modeling (TSM), which is based on the chemical principle of mass action laws, has been studied with the aim of improving overall confidence in the description of radionuclide migration under a wide range of aquatic conditions. The disposal performance demonstration R&D division of KAERI introduced a new reference Ca-bentonite clay called Bentonil-WRK (Clariant Korea) for HLW disposal research in 2021 as the domestic Ca-bentonite sources have being depleted. We successfully separated and purified Ca-montmorillonite from the Bentonil-WRK clay, and its geochemical characteristics were meticulously studied by means of XRD, BET, CEC, FT-IR analyses and controlled acid-base titration. In this work, chemical sorption behaviors of aqueous iodide and benzoate, which are a major fission product in HLW and a model ligand of complex natural organic matters present in the deep geological environment, onto the purified Camontmorillonite were assessed under ambient conditions of S/L = 5 g/L, I = 0.01 M CaCl2, pH = 4- 9, pCO2 = 10-3.4 atm, and T = 25°C. Further, their unique adsorption envelopes and corresponding thermodynamic reaction constants refined from the diffuse double layer model (DDLM)-based inverse modeling of experimental sorption data were discussed.

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.

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.

A disposal system for spent nuclear fuel divides into two parts; (1) engineered barriers including spent nuclear fuel, canister, buffer and backfill, (2) natural barriers surrounding engineered barriers. Sorption and diffusion are main retardation mechanisms for the migration of released radionuclides. We analyzed the sorption properties of radionuclides for bentonite as a buffer material and collected/ evaluated the distribution coefficients for the purpose of safety assessment for the deep geological disposal of a spent nuclear fuel. Through this, we presented recommended distribution coefficients for radionuclides required for the safety assessment. This work included the radionuclides 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 affected various geochemical conditions such as pH/carbonates, redox potential, ionic strength, radionuclide concentration, kinds and amounts of minerals, and microbes. Among the evaluated radionuclides, Cs, Ni, Pd, and Ra is sensitive to the ionic strength, while Np, Pu, U, Se, and, Tc is sensitive to the redox condition. 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 were suggested.

Colloid Formation and Migration (CFM) project is being carried out within the Grimsel Test Site (GTS) Phase Ⅵ. Since 2008, the Korea Atomic Energy Research Institute (KAERI) has joined CFM to investigate the behavior of colloid-facilitated radionuclide transport in a generic Underground Research Laboratory (URL). The CFM project includes a long-term in-situ test (LIT) and an in-rock bentonite erosion test (i-BET) to assess the in-situ colloid-facilitated radionuclide transport through the bentonite erosion in the natural flow field. In the LIT experiment, radionuclide-containing compacted bentonite was equipped with a triple-packer system and then positioned at the borehole in the shear zone. It was observed that colloid transport was limited owing to the low swelling pressure and low hydraulic conductivity. Therefore, a postmortem analysis is being conducted to estimate the partial migration and diffusion of radionuclides. The i-BET experiment, that focuses more on bentonite erosion, was newly designed to assess colloid formation in another flow field. The i-BET experiment started with the placement of compacted bentonite rings in the double-packer system, and the hydraulic parameters and bentonite erosion have been monitored since December 2018.

Safe storage of spent nuclear fuel in deep underground repositories needs an understanding of the long-term alteration (corrosion) of metal canisters and buffer materials. We conducted a small-scale laboratory alteration tests on some metal (Cu and Fe) chips by embedding them into the compacted bentonite blocks, which were placed in anaerobic water for 1 year. Some additives like lactate, sulfate, and bacteria were separately loaded into the water to promote biochemical reactions. The bentonite blocks immersed in the water were finally dismantled after 1 year, and they showed that their alteration was insignificant. However, the Cu chip exhibited some microscopic etch pits on its surface, wherein sulfur component was slightly detected. Overall, the Fe chip was more corroded than the Cu chip under the same condition. The secondary phase of the Fe chip was locally found as carbonate materials, such as siderite (FeCO3) and calcite ((Ca, Fe)CO3). These secondary products could imply that the local carbonate production around the Fe chip may be initiated by an evolution (alteration) of bentonite and a diffusive provision of biogenic CO2 gas. These laboratory scale test results suggest that the long-term alteration (corrosion) of metal canister/bentonite blocks in the engineered barrier could be possible and may be promoted by microbial activities.

Disposal methods of radioactive waste can be mainly divided into near-surface disposal and deep geological disposal. If the radioactive waste is exposed to groundwater for a long time in the disposal environment, no matter how the decommissioning waste generated from the nuclear power plant is disposed of, the radionuclides may be released from the disposal site. Decommissioning waste from nuclear power plant contains radionuclides that are harmful to ecosystem including humans. Radionuclides released from disposal site behave in a complex and sensitive manner affected by geochemical conditions such as soil, geological media and groundwater. Sorption is one of the important mechanisms to retard the migration of radionuclides in a subsurface environment. In this study, geochemical properties of groundwater were collected and analyzed in the disposal environment considering disposal method in order to evaluate the geochemical behavior of radionuclides. The formation of aqueous and precipitated species of cesium and cobalt in a disposal condition were calculated and estimated. The sorption properties were also evaluated and predicted by considering the changes in the geochemical conditions such as pH, redox potential and geological media for the safety assessment.

The deep geological disposal system is aimed to permanently isolate the high-level radioactive waste from the biosphere through a multi-barrier system composed of engineered and natural barriers. The buffer material used for the engineered barrier should have the performance to prevent and retard the migration of radionuclides to the outside of the deep disposal facility when radionuclides are released from a disposal canister by infiltration of groundwater after a long period of time. When the hydraulic conductivity of compacted bentonite is sufficiently low, the migration of radionuclides released into the surrounding rock can be significantly reduced since they are sorbed to bentonite during the diffusion process. Therefore, an investigation on diffusion of radionuclides in compacted bentonite is a fundamental task to obtain essential data for the safety assessment of the deep geological disposal system. The migration of radionuclides by diffusion can be evaluated by diffusion coefficient. In order to obtain the apparent diffusion coefficients of Sr, Sm, and Eu in compacted Ca-bentonite (1.6 g/cm3) a through-diffusion experiment have been carrying out. A cylindrical apparatus consists of a source cell with an appropriate concentration of radionuclides and diffusion cell filled with radionuclide free solution where the concentration is gradually increased by diffusion of radionuclides. The compacted bentonite was installed between the both cells. The sample used for the experiment is a Ca-type bentonite named Bentonil-WRK, and the diffusion experiment was performed under an oxidizing condition using a synthetic groundwater simulating KURT groundwater composition. The diffusion experiment will be terminated when an increasing rate of concentration of nuclides in the diffusion cell becomes constant over time. The concentration change with regard to the geochemical characteristic of the nuclide may appear to be apparently slow.In this study, the experimental results of the through-diffusion test of Sr, Sm, and Eu in the initial stage (~4 months) were presented. Through the results of the initial stage, the period of the through-diffusion experiment can be rearranged and also it is expected that the initial results provide the qualitative and quantitative diffusion properties of each nuclide.

The deep geological repository consisting of a multi-barrier system (engineered and natural barriers) is generally designed to isolate the high-level radioactive waste. The natural barrier is outermost portion to secure safety of the disposal. Crystalline rocks are considered for potential geological repository media to retard and inhibit the migration of radionuclides when the radionuclides leak from the canister and break through the engineered barrier. Sorption and diffusion processes play a major role in retardation of the radionuclides in deep underground environment. In order to evaluate the migration of radionuclides in the safety assessment or geochemical modelling, distribution coefficient and diffusivity of radionuclides are required as input data. In this study, we performed mineralogical and geochemical analysis for a crystalline rock (e.g., granite) to use the sorption and diffusion experiment. The fresh rock samples are obtained from a deep core samples (DB-2) drilled up to 1 km from the surface at KURT (KAERI Underground Research Tunnel) site. For the optical and microscopic examination, thin sections of the rock sample were provided. The rock samples were crushed into powder size to analyze major and trace elements of the whole-rock aliquots. The powdered specimens also used for mineral identification and measurement of specific surface area. The major constituent minerals of the granite are plagioclase, quartz, and K-feldspar and the minor minerals are phlogopite, biotite, and chlorite. According to the results of geochemical analysis, the granite specimens generally contain more than 70wt% of SiO2 and 8wt% of total alkali oxides (Na2O + K2O). The trace elements normalized to primitive mantle compositions show positive Cs, Rb, U, K, and Pb anomalies and negative Nb and Ti anomalies. The rock samples have an average density of 2.62 g·cm−3 and an average porosity of 0.222%. The crushed samples represent the specific surface area of 0.2087 m2·g−1 for the 75–150 μm fraction and 0.1616 m2·g−1 for the 150–300 μm fraction by BET method, respectively. The granite specimens will be used for the sorption and diffusion experiments to evaluate the radionuclides’ geochemical behaviors. The mineralogical and geochemical properties provided in this study can be useful in understanding the sorption and diffusion processes of significant radionuclides under the geological disposal environments.

FTIR (Fourier Transform Infrared) and Raman spectra of KJ-II bentonite provided by Clariant Korea were compared with those of MX-80 bentonite. The FTIR spectra were obtained using a Nicolet 5 FTIR spectrometer (Fisher Scientific) equipped with a diamond ATR (Attenuated Total Reflection) module. The spectra were collected for 64 scans with a resolution of 4 cm−1. Raman spectra were obtained using an optical microscope (Olympus, BX43) and a spectrometer (Andor, SR- 500). The laser beam was focused using an objective lens with a magnifying power of 50. The backscattered light from the sample was collected into an optical fiber with a core diameter of 0.4 mm. The Raman signals were recorded with CCDs (Andor, DV401A-BV for 532 nm laser wavelength and DV420A-OE for 638 and 785 nm laser wavelengths). Each pixel of CCD received the signal for 1 s and its 1000 times accumulated data were collected. The FTIR spectra of the two bentonite samples are very similar. The FTIR spectra of both bentonites showed absorption bands at 3623, 3399, 3231 cm−1 in the higher wavenumber region and at 1637, 1443, 1117, 997, 914, 887, 847, 797, 611, 515, 414 cm−1 in the lower wavenumber region. A sharp band at 3623 cm−1 and the strong band at 997 cm−1 correspond to the OH stretching of structural hydroxyl groups and the Si-O stretching vibration, respectively. In addition to these clear bands, several absorption bands observed in this experiment are well matched with the results reported in various literatures. Unlike the FTIR spectrum, it is not easy to observe the Raman bands of bentonite. The reason is that strong fluorescence interferes with the Raman spectrum. The two bentonite samples showed different fluorescence intensities. In the case of MX-80 bentonite, no clear Raman band was observed due to the influence of very strong fluorescence. KJ-II bentonite showed a relatively weak fluorescence intensity and Raman bands were partially visible at around 147, 260, 397, 709, and 1279 cm−1. In particular, the band at 1279 cm−1 is wide and sturdy. It was observed that the non-powder samples showed a better quality spectra. The Raman characteristics of KJ-II bentonite, which depend on the incident laser wavelength and the sample pretreatment, are discussed in detail.

Various diffusion experiments using geologic media have been carried out and it is often assumed that aqueous diffusion is the dominant transport mechanism. However, in some cases diffusive migration has been much faster than predicted in the model simulation. To explain such results surface diffusion of sorbing species was invoked. Experimental results were generally open to interpretation but possible existence of surface diffusion, whereby sorbed radionuclides could potentially migrate at much enhanced rates, necessitated investigation. The potential for surface diffusion of some sorbing nuclides on through-diffusion experiments using domestic rocks was examined. The apparent diffusion coefficients for sorbing cations were determined from their steady-state diffusion flux through rocks disks, while effective and pore diffusion coefficients were obtained with non-sorbing tracers through the same rocks. Diffusive transport models through domestic granites and granodiorites based only on pore diffusion did not often described adequately for sorbing cations. Thus, surface diffusion should be considered. Then what was the most important measure to estimate surface diffusion? As far as we examine, the sorption reversibility provides a hint of surface diffusion. The reversible sorbing species, for example, Sr, has a remarkable surface diffusion contribution, whereas surface diffusion has a relatively small contribution for irreversibly sorbing species such as Cs and Am under domestic experimental conditions.

A deep geological disposal system, which consists of the engineered and natural barrier components, is the most proven and widely adopted concept for a permanent disposal of the high level radioactive waste (HLW) thus far. The clay-based engineered barrier is designed to not only absorb mechanical stress caused by the geological activities, but also prevent inflow of groundwater to canister and outflow of radionuclides by providing abundant sorption sites. The principal mineralogical constituent of the clay material is montmorillonite, which is a 2:1 phyllosilicate having two tetrahedral sheets of SiO2 sandwiching an octahedral sheet of Al2O3. The stacking of SiO2 and Al2O3 sheets form the layered structures, and ion-exchange and water uptake reactions occur in the interlayer space. In order to reliably assess the radionuclide retention capacity of engineered barrier under wide geochemical conditions relevant to the geological disposal environments, sorption mechanisms between montmorillonite and radionuclides should be explicitly investigated in advance. Thus far, sorption behavior of mineral adsorbents with radionuclides has been quantified by the sorption-desorption distribution coefficient (Kd), which is simply defined as the ratio of radionuclide concentration in the solid phase to that in the equilibrium solution; the Kd value is conditional, and there have been scientific efforts to develop geochemically robust bases for parameterizing the sorption phenomena more reliably. In this framework, application of thermodynamic sorption model (TSM), which is theoretically based on the concept of widely accepted equilibrium models for aquatic chemistry, offers the potential to improve confidence in demonstration of radionuclide sorption reactions on the mineral adsorbents. Specifically, it is generally regarded in the TSM that coordination of radionuclides on montmorillonite takes place at the surficial aluminol and silanol groups while their ion-exchange reactions occur in the interlayer space also. The effects of electrical charge on the surface reactions are additionally corrected in accordance with the numerous theories of electrochemical interface. The present work provides an overview of the current status of application of TSM for quantifying sorption behaviors of radionuclides on montmorillonite and experimental results for physical separation and characterization of Ca-montmorillonite from the newly adopted reference bentonite (Bentonil- WRK) by means of XRD, BET, FTIR, CEC measurement, and acid-base titration. The determined mineralogical and chemical properties of the montmorillonite obtained will be used as input parameters for further sorption studies of radionuclides with the Bentonil-WRK montmorillonite.

The decommissioning of a nuclear power plant generates large amounts of radioactive waste, which is of several types. Radioactive concrete powder is classified as low-level waste, which can be disposed of in a landfill. However, its safe disposal in a landfill requires that it be immobilized by solidification using cement. Herein, a safety assessment on the disposal of solidified radioactive concrete powder waste in a conceptual landfill site is performed using RESRAD. Furthermore, sensitivity analyses of certain selected input parameters are conducted to investigate their impact on exposure doses. The exposure doses are estimated, and the relative impact of each pathway on them during the disposal of this waste is assessed. The results of this study can be used to obtain information for designing a landfill site for the safe disposal of low-level radioactive waste generated from the decommissioning of a nuclear power plant.

Safe storage of spent nuclear fuel in deep underground repositories necessitates an understanding of the long-term alteration of metal canisters and buffer materials. A small-scale laboratory alteration test was performed on metal (Cu or Fe) chips embedded in compacted bentonite blocks placed in anaerobic water for 1 year. Lactate, sulfate, and bacteria were separately added to the water to promote biochemical reactions in the system. The bentonite blocks immersed in the water were dismantled after 1 year, showing that their alteration was insignificant. However, the Cu chip exhibited some microscopic etch pits on its surface, wherein a slight sulfur component was detected. Overall, the Fe chip was more corroded than the Cu chip under the same conditions. The secondary phase of the Fe chip was locally found as carbonate materials, such as siderite (FeCO3) and calcite ((Ca, Fe)CO3). These secondary products can imply that the local carbonate occurrence on the Fe chip may be initiated and developed by an evolution (alteration) of bentonite and a diffusive provision of biogenic CO2 gas. These laboratory scale results suggest that the actual long-term alteration of metal canisters/bentonite blocks in the engineered barrier could be possible by microbial activities.