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 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.

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.

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.

Niobium (Nb) is present in Ni-based alloys and stainless steels used in nuclear reactors as structural materials. Nb-93 is a naturally occurring and stable isotope of niobium and Nb-94 (half-life = 20,000 years) is produced by neutron activation of Nb-93. Nb-94 can be present in waste streams from dismantling of nuclear power plants and treatment of the primary coolant circuit. Hence, the radioactive wastes containing active Nb-94 are disposed of in the repositories for low- and intermediate-level waste (LILW). Nb predominantly exhibits a pentavalent oxidation state (i.e., +V) within the stability field of water. Cementitious materials (concrete, mortar, and grout) are extensively utilized in LILW disposal systems as structural components and chemical agents for the stabilization of waste. Solubility defines the source term (i.e., upper concentration limit) in the repository system. However, the solubility behavior of Nb in cementitious systems at high pH remains ill-defined, and information available on the Nb solid phases controlling the solubility is scarce and often ambiguous. Sorption on cementbased materials is one of the main mechanisms controlling the retention of niobium(V) in a LILW repository, and distribution coefficients (Rd) are necessary to evaluate the retention capacity by sorption in the safety assessment of disposal systems. Available sorption data of Nb(V) on cement showed a large discrepancy in Rd, moreover, no sorption data is available for Nb(V) under conditions characterizing the first degradation stage of cement (young cement condition) at pH 13 – 13.5. In this context, the solubility of Nb was extensively investigated in porewater conditions representative of the cement degradation stage I, as well as in CaCl2-Ca(OH)2 systems. Special focus was given to the accurate characterization of the solubility-controlling solid niobium phases. We also studied the sorption of Nb(V) by hardened cement pastes (HCP) and calcium silicate hydrates (CSH, major hydrate of HCP). This work provides the results on Rd, sorption isotherm and sorption mechanisms of Nb(V). Besides, the impact of ISA (polyhydroxycarboxylic acid generated by the degradation of cellulose) on Nb(V) sorption and the dissolution of cement materials was investigated.

Organic complexing agents may affect the mobility of radionuclides at low- and intermediate-level radioactive waste repositories. Especially, isosaccharinic acid (ISA) is the main cellulose degradation product under high pH conditions in cement pore water. ISA can combine with radionuclides and form stable complexes that adversely influence adsorption in the concrete phase, resulting in radionuclides to leach to the near- and far-fields of repositories. This study focuses on investigating the sorption of ISA onto engineered barriers such as concrete, thereby studying adsorption isotherms of ISA on concrete and comparing various isotherm models with the experimental data. The adsorption experiment was conducted in three background solutions, groundwater (adjusted to pH 13 using NaOH), State 1 (artificial cement pore water, pH 13.3), and State 2 (artificial cement pore water, pH 12.5), in a batch system at a temperature of 20°C. Concrete was characterized using BET, Zeta-potential analyzer, XRD, XRF, and SEM-EDS. ISA concentrations were detected using HPLC. The experimental data were best fitted to one-site Langmuir isotherm; On the other hand, either two-site isotherm or Freundlich isotherm couldn’t give reasonable fitting to the experimental data. The observed ISA sorption behavior on concrete is crucial for the disposal of radioactive waste because it can significantly lower the concentration of ISA in the pore water. Although one-site Langmuir isotherm might effectively represent the sorption behavior of ISA on concrete, the underlying mechanism is still unknown, and further investigation should be done in the near future.

Radioactive nickel (Ni59 and Ni63) is a major radionuclide that needs to be determined for quantifying the total radioactivity in radioactive waste disposal repository. Also, radioactive waste containing organic wastes, such as cotton and tissue can be decomposed to produce the Isosaccharinic acid (ISA) in a disposal facility. The presence of ISA in the disposal facility could increase the mobility of radionuclides. Therefore, it is necessary to confirm the mobility of Ni with the presence of ISA in the repository. This study investigated the effect of ISA on the sorption and the solubility of Ni in synthesized groundwater. The sorption test was conducted in different time intervals with Ni and ISA. Nickel nitrate hexahydrate and Ca(ISA)2 were used after purchase. Granite was used as the solid medium to simulate the major rock type of the repository. Ni and ISA solution with the medium were mixed using a platform shaker for 6 days. After 6 days, the solid parts were separated by centrifugation and additional syringe filters, and the supernatant was analyzed for Ni and ISA concentration using ICP-MS and IC, respectively. The solubility experiments were conducted at different temperatures (20, 40, and 80°C). Nickel hydroxide was used as the solubility limiting solid phase. To balance the ionic strength and confirm the effect of ISA on Ni solubility, 0.01 M of CaCl2 solution was prepared in a sample without ISA, and 0.01 M of Ca(ISA)2 solution was prepared in a sample with ISA. In solubility tests, the solution was also analyzed by ICP-MS and IC for Ni and ISA, respectively. The concentration of Ni was found to increase with ISA compared to Ni concentration without ISA. The concentration of ISA was not changed during the solubility test periods. For solubility tests, the concentration of Ni also increased according to the increase in temperature. The solid phase was characterized by XRD, FT-IR, and SEM-EDS. Based on the results of this study, the presence and effect of ISA on radioactive Ni mobility should be carefully investigated to secure the long-term safety assessment for the low and intermediate-level waste repository.

Engineered barriers (concrete and grout) in Low- and Intermediate-Level Waste (L/ILW) disposal facilities tend to degrade by groundwater or rainfall water over a long period of time. During the degradation process, radionuclides stored in the disposal facility might be released into the pore water, which can pass through the natural rock barriers (granite and sedimentary rock) and may reach the near-field and far-field. In this transportation, radionuclide might be sorbed onto the engineered and natural rock barriers. In addition, the organic complexing agent such as ethylenediaminetetraacetic acid (EDTA) and α-isosaccharinic acid (ISA), is also present in pore water, which may affect the sorption and mobility of radionuclide. In this study, the sorption and mobility of 90Sr under different conditions such as two pHs (7 and 13), different initial concentrations of organic complexing agents (from 10-5 M to 10-2 M), and solutions (groundwater, pore water, and rainfall water) were investigated in a batch system. The groundwater was collected at the L/ILW disposal facility located at Gyeongju in South Korea. The pore water and rainfall water were artificially made in the laboratory. The concrete, grout, granite, and sedimentary rock samples were collected from the same study sites from where the groundwater was collected. The rock samples were crushed to 53-150 micrometers and were characterized by XRD, XRF, SEM-EDS, BET, and zeta potential analyzer. 90Sr concentration was determined using liquid scintillation counting. The sorption of 90Sr was described by distribution coefficients (Kd) and sorption reduction factor (SRF). In the case of EDTA, the Kd values of 90Sr remained constant from 10-5 M to 10-3 M and tended to decrease at 10-2 M, while in case of ISA the Kd values decreased steadily as the concentration of ISA was increased from 10-5 M to 10-3 M; However, a sudden reduction in the Kd values were observed above 10-2 M. In comparison to EDTA, ISA gave a higher SRF of 90Sr. Therefore, from the above results, it can be concluded that the presence of ISA has a greater effect on the sorption and mobility of radionuclide in the solutions than EDTA, and the radionuclide may reach near- and far-field of the L/ILW disposal facility.

Radionuclides can be leached into groundwater or soil over a long period of time due to unexpected situations even after being permanently disposed of in a repository. Therefore, it is necessary to investigate the mobility of radionuclides for the safety assessment of radioactive waste disposal. In this study, the effects of organic complexing agents such as ethylenediaminetetraacetic acid (EDTA) and isosaccharinic acid (ISA) on the sorption behavior of 239Pu and 99Tc over cementitious (concrete and grout) and natural rock samples (granite and sedimentary rock) were investigated in batch sorption experiments. For characterization of rock samples, XRD, XRF, FT-IR, FE-SEM, BET, and Zeta-potential analyses were performed. For the evaluation of mobility, the distribution coefficient (Kd) was selected and compared. The adsorption experiment was carried out at two pHs (7 and 13), a temperature of 20°C, and a range of organic complexing agents concentrations (10-7~10-2 M and 10- 5~10-2 M for 239Pu and 99Tc, respectively). The radionuclides concentrations in adsorption samples were analyzed using ICP-MS. The Kd values for 239Pu in all rock samples reduced significantly due to the presence of EDTA, even at low concentrations such as 10-5 M. In the case of ISA, the limiting noeffect concentration was much higher than that of EDTA. On the other hand, 99Tc showed relatively lower Kd values than 239Pu, and the sorption behavior of 99Tc was almost unaffected by the organic complexing agents for all rock samples. Therefore, it is possible to assume that the increased mobility of radionuclides, especially, 239Pu, in groundwater caused by the lowering of sorption at even low concentrations of organic complexing agents may result in the transport of radionuclides to the nearand far-field location of the repository.

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.

Molten salt consisting primarily of eutectic LiCl-KCl is currently being used in electrorefiners in the Fuel Conditioning Facility at Idaho National Laboratory. Options are currently being evaluated for storing this salt outside of the argon atmosphere hot cell. The hygroscopic nature of eutectic LiCl-KCl makes is susceptible to deliquescence in air followed by extreme corrosion of metallic cannisters. In this study, the effect of occluding the salt into a zeolite on water sorption/desorption was tested. Two zeolites were investigated: Na-Y and zeolite 4A. Na-Y was ineffective at occluding a high percentage of the salt at either 10 or 20wt% loading. Zeolite-4A was effective at occluding the salt with high efficiency at both loading levels. Weight gain in salt occluded zeolite-4A (SOZ) from water sorption at 20% relative humidity and 40℃ was 17wt% for 10% SOZ and 10wt% for 20% SOZ. In both cases, neither deliquescence nor corrosion occurred over a period of 31 days. After hydration, most of the water could be driven off by heating the hydrated salt occluded zeolite to 530℃. However, some HCl forms during dehydration due to salt hydrolysis. Over a wide range of temperatures (320–700℃) and ramp rates (5, 10, and 20℃ min−1), HCl formation was no more than 0.6% of the Cl− in the original salt.

Under anoxic conditions, this study investigated removal of dissolved As(III) by Si and Al oxides including natural sand, chemically washed sand (silica), alumina, and activated alumina. Despite the similar surface area, natural sand showed greater extents of As(III) sorption than chemically washed sand. This was likely due to the high reactivity of Fe(oxyhydr)oxide impurities on the surface of natural sand. For both sands, As(III) sorption was the greatest at pH 7.1, in agreement with the weakly dissociating tendency of arsenous acid. Also, the least sorption was observed at pH 9.6. At basic pH, elevated silicate, which originated from the dissolution of silica in sands, would compete with As(III) for sorption. Due to the highest surface area, activated alumina was found to quantitatively immobilize the initially added As(III) (6.0×10−7 -2.0×10−5 M). Alumina showed As(III) sorption compared to or greater than chemically washed sand, although the former had less than 6% of the surface of area the latter. The greater reactivity of alumina than chemically washed sand can be explained by using the shared charge of oxygen.

The sorption of Eu on MX-80 bentonite in Na–Ca–Cl solutions is investigated at a molal proton concentration (pHm) range of 3 to 10 and an ionic strength (I) range of 0.1 to 6 m (mol·kgw−1). The sorption equilibrium of Eu on MX-80 is achieved within 14 to 21 d at I = 0.1 and 6 m. The sorption distribution coefficient (Kd) values of Eu for MX-80 increase as pHm increases from 3 to 6 for all I values, and they are independent of pHm between 8 and 10 at I ≥ 0.5 m. Meanwhile, at I = 0.1 m, the Kd value at pHm = 10 is slightly lower than those at pHm = 8 and 9. The Kd values are not affected by the I values between 0.5 m and 6 m, whereas the Kd value at I = 0.1 m is greater than those at I ≥ 0.5 m, except at pHm = 10. A two-site protolysis nonelectrostatic surface complexation and cation exchange sorption model is applied to the Eu sorption data for I ≤ 4 m, and the equilibrium constants of the sorption reactions are estimated.

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.

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.