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.

Deep disposal facility for High-Level radioactive Waste (HLW) uses a multi-barrier system to prevent the leakage of radionuclide. As a part of the engineered barrier, bentonite is primarily considered as the main buffering material. This is due to the adsorption and swelling properties of the bentonite, which are expected to effectively impede leakage of the radionuclide. In many cases, adsorption is generally regarded as occurring only within the buffer zone. However, several research has been conducted to explore the possibility of bentonite intrusion into the Excavation- Damaged Zone (EDZ) generated during excavation processes, because of the swelling properties of the bentonite. Generally, for host rock near the deep disposal facility such as granite, groundwater flows through the fracture network. Therefore, analysis of the characteristics of the fracture network is essential for predicting the behavior of radionuclide in groundwater. Accordingly, the bentonite intrusion into the fracture network is critical for safety assessment of the deep disposal facility. To analyze this, hydro-geochemical model was established utilizing COMSOL Multiphysics and PHREEQC, observing changes of the behavior of U (VI) along fracture network due to the swelling of bentonite. Modeling was conducted with progressively changing intrusion depth of the bentonite. According to the results, the behavior of U (VI) exhibited significant changes depending on the connectivity of the fractures. Based on the distribution characteristics of the fracture network, heterogeneous groundwater flow was observed. U (VI) was transported through the preferential pathway, which indicates high connectivity, due to the rapid groundwater flow. Notably, when changing the intrusion depth of bentonite, significant differences in behavior of U (VI) were observed in the 0-20 cm case. In contrast, as the intrusion depth increased, it was observed that differences became less evident. These results indicate that changes in the properties of fracture network in EDZ due to the swelling of bentonite significantly influence the behavior of U (VI).

The effect of various physicochemical processes, such as seawater intrusion, on the performance of the engineered barrier should be closely analyzed to precisely assess the safety of high-level radioactive waste repository. In order to evaluate the impact of such processes on the performance of the engineered barrier, a thermal-hydrological-chemical model was developed by using COMSOL Multiphysics and PHREEQC. The coupling of two software was achieved through the application of a sequential non-iterative approach. Model verification was executed through a comparative analysis between the outcomes derived from the developed model and those obtained in prior investigations. Two data were in a good agreement, demonstrating the model is capable of simulating aqueous speciation, adsorption, precipitation, and dissolution. Using the developed model, the geochemical evolution of bentonite buffer under a general condition was simulated as a base case. The model domain consists of 0.5 m of bentonite and 49.5 m of granite. The uraninite (UO2) was assigned at the canister-bentonite interface as the potential source of uranium. Assuming the lifetime of canister as 1,000 years, the porewater mixing without uranium leakage was simulated for 1,000 years. After then, the uranium leakage through the dissolution of uraninite was initiated and simulated for additional 1,000 years. In the base case model, where the porewater mixing between the bentonite and granite was the only considered process, the gypsum tended to dissolve throughout the bentonite, while it precipitated in the vicinity of bentonite-granite boundary. However, the precipitation and dissolution of gypsum only showed a limited effect on the performance of the bentonite. Due to the low solubility of uraninite in the reduced environment, only infinitesimal amounts of uranium dissolved and transported through the bentonite. Additional cases considering various environmental processes, such as seawater or cement porewater intrusion, will be further investigated.

Understanding the long-term geochemical evolution of engineered barrier system is crucial for conducting safety assessment in high-level radioactive waste disposal repository. One critical scenario to consider is the intrusion of seawater into the engineered barrier system, which may occur due to global sea level rise. Seawater is characterized by its high ionic strength and abundant dissolved cations, including Na, K, and Mg. When seawater infiltrates an engineered barrier, such dissolved cations displace interlayer cations within the montmorillonite and affect to precipitation/ dissolution of accessory minerals in bentonite buffer. These geochemical reactions change the porewater chemistry of bentonite buffer and influence the reactive transport of radionuclides when it leaked from the canister. In this study, the adaptive process-based total system performance assessment framework (APro), developed by the Korea Atomic Energy Research Institute, was utilized to simulate the geochemical evolution of engineered barrier system resulting from seawater intrusion. Here, the APro simulated the geochemical evolution in bentonite porewater and mineral composition by considering various geochemical reactions such as mineral precipitation/dissolution, temperature, redox processes, cation exchange, and surface complexation mechanisms. The simulation results showed that the seawater intrusion led to the dissolution of gypsum and partial precipitation of calcite, dolomite, and siderite within the engineered barrier system. Additionally, the composition of interlayer cation in montmorillonite was changed, with an increase in Na, K, and Mg and a decrease in Ca, because the concentrations of Na, K, and Mg in seawater were 2-10 times higher than those in the initial bentonite porewater. Further studies will evaluate the geochemical sorption and transport of leaked uranium-238 and iodine-129 by applying TDB-based sorption model.

In the engineered barrier system of deep geological disposal repository, complex physicochemical phenomena occur throughout the entire disposal time, consequently impacting the safety function. The bentonite buffer, a significant component of the engineered barrier system, can be geochemically altered due to the changes in host rock groundwater, temperature, and redox condition. Such changes may have direct or indirect effects on radionuclide migration in case of canister failure. Therefore, a modeling tool that accounts for coupled thermal-hydraulic-mechanical-chemical (THMC) processes is necessary for the safety assessment. To this end, the Korea Atomic Energy Research Institute (KAERI) has developed the APro, a modeling interface for conducting safety assessment of deep geological disposal repository. The APro considers coupled THMC processes that influence radionuclide migration. Here, the solute transport considering thermal and hydraulic processes are calculated using the COMSOL multi-physics, while geochemical reactions are carried out in PHREEQC. The two software are coupled using a sequential non-iterative operator splitting approach, and transport of non-water H, non-water O, and charge were additionally considered to enhance the coupling model stability. Finally, the applicability of APro to simulate long-term geochemical evolution of bentonite was demonstrated through benchmark studies to evaluate the effects of mineral precipitation/dissolution, temperature, redox, and seawater intrusion.

APro, a modularized process-based total system performance assessment framework, was developed at the Korea Atomic Energy Research Institute (KAERI) to simulate radionuclide transport considering coupled thermal-hydraulic-mechanicalchemical processes occurring in a geological disposal system. For reactive transport simulation considering geochemical reactions, COMSOL and PHREEQC are coupled with MATLAB in APro using an operator splitting scheme. Conventionally, coupling is performed within a MATLAB interface so that COMSOL stops the calculation to deliver the solution to PHREEQC and restarts to continue the simulation after receiving the solution from PHREEQC at every time step. This is inefficient when the solution is frequently interchanged because restarting the simulation in COMSOL requires an unnecessary setup process. To overcome this issue, a coupling scheme that calls PHREEQC inside COMSOL was developed. In this technique, PHREEQC is called through the “MATLAB function” feature, and PHREEQC results are updated using the COMSOL “Pointwise Constraint” feature. For the one-dimensional advection-reaction-dispersion problem, the proposed coupling technique was verified by comparison with the conventional coupling technique, and it improved the computation time for all test cases. Specifically, the more frequent the link between COMSOL and PHREEQC, the more pronounced was the performance improvement using the proposed technique.

The analysis of uranium migration is crucial for the accurate safety assessment of high-level radioactive waste (HLW) repository. Previous studies showed that the migration of the uranium can be affected by various physical and chemical processes, such as groundwater flow, heat transfer, sorption/ desorption and, precipitation/dissolution. Therefore, a coupled Thermal-Hydrological-Chemical (THC) model is required to accurately simulate the uranium migration near the HLW repository. In this study, COMSOL-PHREEQC coupled model was used to simulate the uranium migration. In the model, groundwater flow, heat transfer, and non-reactive solute transport were calculated by COMSOL, and geo-chemical reaction was calculated by PHREEQC. Sorption was primarily considered as geo-chemical reaction in the model, using the concept of two-site protolysis nonelctrostatic surface complexation and cation exchange (2 SP NE SC/CE). A modified operator splitting method was used to couple the results of COMSOL and PHREEQC. Three benchmarks were done to assess the accuracy of the model: 1) 1D transport and cation exchange model, 2) cesium transport in the column experiment done by Steefel et al. (2002), and 3) the batch sorption experiment done by Fernandes et al. (2012), and Bradbury and Baeyens (2009). Three benchmark results showed reliable matching with results from the previous studies. After the validation, uranium 1D transport simulation on arbitrary porewater condition was conducted. From the results, the evolution of the uranium front with sequentially saturating sites was observed. Due to the limitation of operator splitting method, time step effect was observed, which caused the uranium to sorbed at further sites then it should. For further study, 3 main tasks were proposed. First, precipitation/ dissolution will be added to the reaction part. Second, multiphase flow will be considered instead of single phase Darcy flow. Last, the effect of redox potential will be considered.

Montmorillonite plays a key role in engineered barrier systems in the high-level radioactive waste repository because of its large sorption capacity and high swelling pressure. However, the sorption capacity of montmorillonite can be largely varied dependent on the surrounding environments. This study conducted the batch simulation for U(VI) sorption on Na-montmorillonite by utilizing the cation exchange and surface complexation coupled (2SP-NE-SC/CE) model and evaluated the effects of physicochemical properties (i.e., pH, temperature, competing cations, U(VI) concentration, and carbonate species) on U(VI) sorption. The simulation demonstrated that the U(VI) sorption was affected by physicochemical properties: the pH and temperature relate to aqueous U(VI) speciation, the competing cations relate to the cation exchange process and selectivity, the U(VI) concentration relates to saturation at sorption sites. For example, the Kd (L kg−1) of Na-montmorillonite represented the largest values of 2.7×105 L kg−1 at neutral pH condition and had significantly decreased at acidic pH<3, showing non-linear and diverse U(VI) sorption at the ranged pH from 2 to 11. Additionally, the U(VI) sorption on montmorillonite significantly decreased in presence of carbonate species. The U(VI) sorption for long-term in actual porewater chemistry and temperature of high-level radioactive waste repository represented that the sorption capacity of Na-montmorillonite was affected by various external properties such as concentration of competing cation, temperature, pH, and carbonate species. These results indicate that geochemical sorption capacity of bentonite should be evaluated by considering both geological and aquifer environments in the high-level radioactive waste repository.

The design of the high-level radioactive waste (HLW) repository is made for isolating the HLW from the groundwater system by using artificial and natural barriers. Granite is usually considered to be a great natural barrier for the HLW repository in various countries including Sweden, Canada, and Korea due to its low hydraulic permeability. However, many fractures that can act as conduits for groundwater and radionuclides exist in granite. Furthermore, the decay heat generated by the HLW can induce groundwater acceleration through the fracture. Since the direction, magnitude, and lasting time of the heat-induced groundwater flow can be differed depending on the fracture geometry, the effect of fracture geometry on the groundwater flow around the repository should be carefully analyzed. In this study, groundwater models were conducted with various fracture geometries to quantify the effect of various properties of fractures (or fracture networks) on the heat-induced groundwater flow. In all models, the pressure around the repository only lasted for a short period after it peaked at 0.1 years. In contrast, the temperature lasted for 10,000 years after the disposal inducing the convective groundwater flow. Single fracture models with different orientations were conducted to evaluate the variations in groundwater velocities around the repository depending on the fracture slope. According to the results, the groundwater velocity on the fracture was the fastest when the regional groundwater flow direction and the fracture direction coincided. In double fracture models, various inclined fractures were added to the horizontal fracture. Due to the intersecting, the groundwater flow velocity showed a discontinuous change at the intersecting point. Lastly, the discrete fracture network models were conducted with different fracture densities, length distributions, and orientations. According to the modeling results, the groundwater flow was significantly accelerated when the fracture network density increased, or the average fracture length increased. However, the effect of the fracture orientation was not significant compared to the other two network properties.

Multiple sorptive sites on natural illitic clays (e.g., frayed edge [FES], type II [TS], and planar sites [PS]) play an important role to diverse 137Cs immobilization in soil and aquifer environments. This study investigated the Cs sorption capabilities of 10 natural illitic clays at ranged Cs concentrations (1 ×10−7 to 1×10−3 mol·L−1) under various competing potassium concentration (distilled water to 1×10−1 mol·L−1). Additionally, multisite cation exchange model was performed to evaluate the best-fit sorption model and optimize the sorption capacities and affinities of multiple sorptive sites for Cs. Here, the experimental Cs sorption isotherms varied among 10 illtic clays, indicating different sorption capacities of Cs on illitic clays. The best-fit sorption model exhibited that variable Cs sorption of 10 illitic clays was significantly related to the sorption capacities at the FES (1.76 × 10−5 to 1.12×10−4 eq·kg−1), TS (1.59×10−3 to 9.76×10−3 eq·kg−1), and PS (2.14×10−2 to 1.51×10−1 eq·kg−1), respectively. The FES predominantly contributed to Cs sorption at low aqueous concentrations, whereas the TS and PS sorbed Cs at high concentrations. These sorption capabilities of multiple sorptive sites were correlated to illite contents and crystallinity of illitic clays, implicating that such parameters could be key factors to predict the Cs sorption for natural illitic clays in soil and aquifer environments. Finally, 1-D transport simulations represented that the severe Cs retardation occurred at low Cs concentration, implying that the FES predominantly affected to Cs transport in actual radioactive contamination sites (i.e., where low Cs concentration prevails), compared to the TS and/or PS.

본 연구는 원자력 중대 사고 시, 환경에 유출된 방사성 세슘의 확산을 억제하기 위해 충북 영동 지역 일라이트의 활용 가능성을 평가하였다. 영동 일라이트는 운모질 편암의 열수변질 작용에 의해 형성되었으며, 주요 구성 광물은 석영, 장석, 일라이트이다. 저농도 세슘 용액을 사용한 회분식 흡착 실험 결과, 영동 일라이트의 흡착 분배 계수(Kd)는 약 4,200 L kg-1으로 다른 점토 광물에 비해 비교적 높은 값을 가지며, 이는 일라이트에 존재하는 풍화된 모서리면(FES)의 영향으로 판단된다. 영동 일라 이트와 세슘의 흡착등온선은 비선형 흡착 특성을 나타내며 단일 표면 한계 흡착 능력이 250,000 μg kg-1으로 우수한 흡착능을 보여주어 방사성 세슘 흡착제로서의 사용 가능성을 입증하였다. 이러한 결 과는 추후 방사능 누출 사고 등의 긴급 상황 발생 시, 영동 지역 일라이트를 오염 확산 방지 및 정화 작업에 사용하기 위한 평가 자료로 활용될 것으로 기대된다.

본 연구는 원자력 중대 사고 시, 환경에 유출된 방사성 세슘의 확산을 억제하기 위해 충북 영동 지역 일라이트의 활용 가능성을 평가하였다. 영동 일라이트는 운모질 편암의 열수변질 작용에 의해 형성되었으며, 주요 구성 광물은 석영, 장석, 일라이트이다. 저농도 세슘 용액을 사용한 회분식 흡착 실험 결과, 영동 일라이트의 흡착 분배 계수(Kd)는 약 4,200 L kg-1으로 다른 점토 광물에 비해 비교적 높은 값을 가지며, 이는 일라이트에 존재하는 풍화된 모서리면(FES)의 영향으로 판단된다. 영동 일라 이트와 세슘의 흡착등온선은 비선형 흡착 특성을 나타내며 단일 표면 한계 흡착 능력이 250,000 μg kg-1으로 우수한 흡착능을 보여주어 방사성 세슘 흡착제로서의 사용 가능성을 입증하였다. 이러한 결 과는 추후 방사능 누출 사고 등의 긴급 상황 발생 시, 영동 지역 일라이트를 오염 확산 방지 및 정화 작업에 사용하기 위한 평가 자료로 활용될 것으로 기대된다.