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.

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 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 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.

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.

Bentonite, which mostly consists of montmorillonite, is considered as a suitable buffer material for disposal of high-level radioactive wastes in deep geological repository due to its high swelling capacity, low permeability, and strong retention capacity of radionuclide migration. Alkaline and saline solutions originated from degradation of cementitious material and seawater intrusion, respectively, may cause the changes in mineralogical and chemical properties of montmorillonite with various processes such as cation exchange within the interlayer, dissolution of montmorillonite, and precipitation of second minerals. In this study, montmorillonite alteration under alkaline and saline environments and its influences on retention of cesium and iodide by bentonite buffer were investigated. The reactions of bentonite (Bentonil-WRK) with alkaline solutions (0.1 M KOH and NaOH) and simulated saline solution were performed for 7 days in batch experiments at 25°C. After the experiments, reacted bentonite samples were characterized by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR) spectroscopy, Short Wavelength Infrared (SWIR) spectrometry. The concentrations of cesium and iodide dissolved in the solutions were analyzed using an inductively coupled plasma mass spectrometer (ICP–MS). The XRD patterns showed significant decrease in the interlayer space of montmorillonite after the reaction with alkaline solution due to cation exchange and change in hydration status at the interlayer. The retention of cesium and iodide in alkaline and saline solutions were affected by montmorillonite alteration and ion competition. Therefore, the montmorillonite alteration affecting the nuclide retention capacity and long-term stability of bentonite buffer should be considered in the safety assessment of long-term geological disposal performance.

Numerous low-and intermediate level radioactive wastes were generated from the decommissioning processes of nuclear power plants. Radionuclides such as Co and Cs contained in decommissioning wastes should be immobilized to prevent the release of radionuclides from the wastes due to its harmful impacts on ecosystem by high radioactivity and long half-life. Ethylenediaminetetraacetic acid (EDTA) used as decontamination agent can be contained in cement waste during decommissioning process of nuclear power plants. In addition, EDTA can be stably and strongly bound with radionuclides, resulting in the acceleration of the nuclide release from solidified cement matrix. Here, we investigated the effects of EDTA on leaching behaviors of Co and Cs immobilized in the cement specimen. The leaching tests were performed according to the ANS 16.1 “Measurement of the leachability of solidified low-level radioactive wastes by a short-term test procedure”. From the results, an increase in the EDTA content in the cement specimen led to an increase in Co leaching, whereas a decrease in Cs leaching. Leaching of Cs was dominantly controlled by diffusion from the pore space of the cement specimen to the solution. The effective diffusion coefficient and leachability index of nuclide were determined using the diffusion-release models of ANS 16.1. The results of present study can be used in the safety assessment for disposal of the radioactive waste generated by decommissioning of nuclear power plants.