The disposal of spent nuclear fuel (SNF) in a deep geological repository (DGR) is a widely accepted strategy for the long-term sequestration of radiotoxic SNF. Ensuring the safety of a DGR requires the prediction of various reactions and migration behaviors of radionuclides (RNs) present in SNF within its geochemical surroundings. Understanding the dissolution behaviors of mineral phases harboring these RNs is crucial, as the levels of RNs in groundwater are basically linked to the solubility of these solid phases. Accurate measurements of solubility demand the use of welldefined solid materials characterized by chemical compositions and structures. Herein, we attempted the synthesis of sklodowskite, a magnesium-uranyl (U(VI))-silicate, employing a twostep hydrothermal synthetic approach documented previously. Subsequently, we subjected this synthesized sklodowskite to various analytical techniques, including powder X-ray diffraction (pXRD), scanning electron microscopy/energy dispersive X-ray spectrometry (SEM/EDX), and vibrational spectroscopies (FTIR and Raman). Based on our findings, we confidently identify the obtained mineral phase as sklodowskite (Mg[UO2SiO3OH]2·5H2O). This identification is primarily based on the similarity between its pXRD pattern and the reference XRD pattern of sklodowskite. Furthermore, the measured infrared and Raman spectra show the vibrational modes of UO2 2+ and SiO4 4- ions, particularly within the 700~1,100 cm-1 region, which support that the synthetic mineral has a characteristic layered uranyl-silicate structure of crystalline sklodowskite. Finally, we utilized synthetic minerals to estimate its solubility up to about three months in a model groundwater, where the dissolved species composition is analogous to that of granitic groundwater from the KAERI Underground Research Tunnel. In this presentation, we will present in detail the results of spectroscopic characterizations and the methodology employed to assess the solubility of the U(VI)-silicate solid phase.

Solubility and species distributions of radionuclides in domestic groundwater conditions are required for the safety assessment of deep underground disposal system of spent nuclear fuel (SNF). Minor actinides including Am contribute significant extents to the long-term radiotoxicity of SNF. In this study, the solubility of Am was evaluated in synthetic groundwater (Syn-DB3), which were simulated for the groundwater of the DB3 site in the KAERI Underground Research Tunnel (KURT). Geochemical modeling was performed based on the ThermoChimie_11a (2022) thermochemical database from Andra to estimate the solubility and species distributions of Am in the Syn-DB3 condition. Dissolved Am concentrations in the Syn-DB3 were experimentally measured under oversaturation conditions. Am(III) stock solution in perchlorate media was sequentially diluted in Syn-DB3 to prepare 8 μM Am(III) in Syn-DB3. The pH of the solutions was adjusted to be in the range of 6.4–10.5. A portion of the samples was transferred to quartz cells for UV-Vis absorption and time-resolved laser fluorescence spectroscopy studies and the rest were stored in centrifuge tubes. The absorption spectra of the samples were monitored over 70 days and the results suggest that Am colloidal particles were formed initially in all the samples and precipitated rapidly within two days. Over the experimental period of 236 days, small volume (10 μL) of the samples in the centrifuge tubes were periodically withdrawn after centrifugation (18000 rpm, 1 hr) for the liquid scintillation counting to measure the concentrations of Am dissolved in Syn-DB3. In the end of the experiments, pH of the samples was checked again and the final dissolved Am concentrations were determined after ultrafiltration (10 kDa) to exclude the contribution of colloidal particles. In the pH range of 8-9, which is relevant to the KURT-DB3 groundwater condition, the measured dissolved Am(III) concentrations were converged to around 10-8 M. These values are higher than the solubility of AmCO3OH:0.5H2O(s), but lower than that of AmCO3OH(am). There was no indication of transformation of the amorphous phase to the crystalline phase in our observation time window.

Mobility of radionuclides (RNs) in natural water systems can be increased by complex formation with organic materials. In alkaline cement pore-water conditions, cellulose materials in radwastes such as woods and papers are degraded fast to small organic materials. As a major cellulose degradation product, isosaccharinate (ISA) has been paid attention recently due to its effect on facilitating RNs migration. ISA contains a carboxyl and four hydroxyl functional groups, which cooperatively interact to form chelating bonds with positively charged radionuclides. In our previous study, we determined thermodynamic formation constants, reaction enthalpy and entropy of trivalent americium complexes with ISA, Am(ISA)n (3-n)+ (n=1, 2), in weak acidic condition by conducting temperature-dependent UVVis absorption spectroscopy. Based on those thermodynamic constants along with the experimental results from time-resolved laser induced fluorescence spectroscopy and DFT calculations, we suggested two different chelating-modes of ISA on Am(III). It is more relevant to study Am(III)-ISA complexation under alkaline conditions around pH 12.5, which correspond to the pore-water condition of calciumsilicate- hydrate. Under the alkaline conditions, deprotonated hydroxyl groups of ISA can form more strong interactions with Am. Aquatic hydroxide group can also act as a ligand to form ternary Am(III) -ISA-OH complexes. In this study, absorption spectra of Am-ISA systems were monitored with two variations: first, pH variation (5.5–13) in the presence of constant 30 mM ISA, and second, ISA concentration variation (20 μM – 30 mM) at constant pH of 12.5. As increasing the pH at constant 30 mM ISA, absorption spectra of Am(ISA)2 + were red-shifted from 506.3 to 509.5 nm. The samples showed stable absorption spectra over 30 days. On the other hand, samples with lower ISA concentrations below 10 mM at pH 12.5, showed gradual decrease in the absorbance as sample aging time. By examining filtrates after ultrafiltration (1 kDa), we confirmed that aqueous Am(III)-ISA complexes were formed in the presence of 30 mM ISA at pH 12.5, while colloidal particles and precipitations were formed in the conditions of ISA concentrations lower than 10 mM. In this presentation, we will discuss about probable ternary complex forms of Am(III)-ISA-OH, colloidal forms, and solubility of Am(III) as a function of ISA concentration under alkaline conditions. Absorption and luminescence spectroscopic properties of the Am(III)-ISA-OH ternary system will also be presented.

The organic complexing agents such as ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and isosaccharinic acid (ISA) can enhance the radionuclides’ solubility and have the potential to induce the acceleration of radionuclides’ mobility to a far-field from the radioactive waste repository. Hence, it is essential to evaluate the effect of organic complexing agents on radionuclide solubility through experimental analysis under similar conditions to those at the radioactive waste disposal site. In this study, five radionuclides (cesium, cobalt, strontium, iodine, and uranium) and three organic complexing agents (EDTA, NTA, and ISA) were selected as model substances. To simulate environmental conditions, the groundwater was collected near the repository and applied for solubility experiments. The solubility experiments were carried out under various ranges of pHs (7, 9, 11, and 13), temperatures (10°C, 20°C, and 40°C), and concentrations of organic complexing agents (0, 10-5, 10-4, 10-3, and 10-2 M). Experimental results showed that the presence of organic complexing agents significantly increased the solubility of the radionuclides. Cobalt and strontium had high solubility enhancement factors, even at low concentrations of organic complexing agents. We also developed a support vector machine (SVM) model using some of the experimental data and validated it using the rest of the solubility data. The root mean square error (RMSE) in the training and validation sets was 0.012 and 0.016, respectively. The SVM model allowed us to estimate the solubility value under untested conditions (e.g., pH 12, temperature 30°C, ISA 5×10-4 M). Therefore, our experimental solubility data and the SVM model can be used to predict radionuclide solubility and solubility enhancement by organic complexing agents under various conditions.

The purpose of this study is to develop and evaluate amorphous spray-dried microparticles (SDM) containing levosulpiride to increase its solubility. SDM are prepared via solvent evaporation using polyvinylpyrrolidone (PVP) as the water-soluble polymer and Cremophor RH40 as the surfactant. The SDM is prepared by varying the amounts of PVP and Cremophor RH40, and its physicochemical properties, solubility, and dissolution are confirmed. All levosulpiride-loaded SDMs converted the crystalline drug into an amorphous form, significantly improving drug solubility and dissolution compared with the drug alone. SDM consisting of drug/PVP/Cremophor RH40 in a weight ratio of 5:10:3, with increased solubility (720 ± 36 vs. 1822 ± 51 μg/mL) and dissolution rate (10.3 ± 2.2 vs. 92.6 ± 6.0%) compared with drug alone, shows potential as a commercial drug for improved oral bioavailability of levosulpiride.

The solubility and species distribution of radionuclides in groundwater are essential data for the safety assessment of deep underground spent nuclear fuel (SNF) disposal systems. Americium is a major radionuclide responsible for the long-term radiotoxicity of SNF. In this study, the solubility of americium compounds was evaluated in synthetic groundwater (Syn- DB3), simulating groundwater from the DB3 site of the KAERI Underground Research Tunnel. Geochemical modeling was performed using the ThermoChimie_11a thermochemical database. Concentration of dissolved Am(III) in Syn-DB3 in the pH range of 6.4–10.5 was experimentally measured under over-saturation conditions by liquid scintillation counting over 70 d. The absorption spectra recorded for the same period suggest that Am(III) colloidal particles formed initially followed by rapid precipitation within 2 d. In the pH range of 7.5–10.5, the concentration of dissolved Am(III) converged to approximately 2×10−7 M over 70 d, which is comparable to that of the amorphous AmCO3OH(am) according to the modeling results. As the samples were aged for 70 d, a slow equilibrium process occurred between the solid and solution phases. There was no indication of transformation of the amorphous phase into the crystalline phase during the observation period.

With respect to the geologic repository, intrusion of groundwater has been considered as a major factor that can transfer radionuclides to the natural environment. Moreover, the migration of radionuclides in the natural groundwater system is significantly influenced by the interaction between the radionuclides and groundwater constituents. Among various hydrogeochemical reactions, hydrolysis is one of the major reactions that can affect the aqueous solubility of radionuclides. Therefore, a precise understanding of relevant chemical thermodynamic behavior is of cardinal importance for the reliable prediction of migration/retardation behavior of radionuclides in the natural groundwater system. The objective of the present work is to investigate the solubility behavior of Nd(OH)3(s) to provide relevant chemical thermodynamic data of Nd(III) as a chemical analogy of major radiotoxic elements such as Am(III) and Cm(III). All the experiments were performed with Ar gas-filled glovebox under inert atmospheric condition. The aqueous Nd(III) solution was prepared by dissolution of 0.5 g NdCl3·6H2O (Sigma-Aldrich) in 10 ml of deionized water. The Nd(III) solid phase was precipitated by dropwise addition of ca. 10 ml of 4 M NaOH (Sigma-Aldrich). The Nd(III) precipitate was identified to be crystalline Nd(OH)3(s) nanorod by using XRD and TEM. For the solubility experiment, the solid Nd(OH)3(s) was equilibrated at the pH range from 5.0 to 9.0 at 0.1 M NaCl condition. The total concentration of the Nd(III) was quantified by using UV/Vis absorption spectroscopy and ICP-MS after the phase separation. In the present work, the solubility behavior of the solid Nd(OH)3(s) phase was investigated by using colorimetric analysis. The chemical thermodynamic data obtained in this study are expected to enhance the reliability of solubility prediction for the trivalent lanthanides and actinides.

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.

Radioactive contamination of soil on the site of a nuclear facility has a characteristic that radioactive nuclides are adsorbed into the pores between soil particles, making it quite difficult to decontaminate. For this reason, research on the development of various decontamination processes is being actively conducted. In this study, among various decontamination studies, a soil decontamination process using supercritical carbon dioxide was presented. The decontamination process uses supercritical carbon dioxide as the main solvent, which has a higher penetration power than other materials. Therefore, the process consists of the process of desorbing and extracting the target radionuclides between particles of soil. However, since nuclides exist as ions in the soil, polar chelating ligand material was introduced as an additive to nonpolar supercritical carbon dioxide for smooth chemical reactions in the soil. Thereafter, from the viewpoint of improving process continuity and efficiency, an alcohol material was introduced as an auxiliary solvent for liquefaction of chelating ligand in a solid state. Through prior research on the selection of a solvent for liquefaction of chelating ligand, ethanol and 2-propanol were finally selected based on whether the chelating ligand was dissolved. However, if the auxiliary solvent in which the chelating ligand is dissolved is to be combined with radionuclides in the soil, it must first be well dissolved in supercritical carbon dioxide, the main solvent. Therefore, in this study, the solubility of ethanol and 2-propanol in supercritical carbon dioxide was measured and the suitability was evaluated. The temperature conditions were carried out at 40°C, the same as the previously designed decontamination process, and the measurement was conducted by adjusting the pressure and volume through a syringe pump and a variable volume device. In addition, solubility was measured based on the observation of the ‘cloud point’ in which the image becomes cloudy and then bright. As a result of the experiment, several solubility points were measured at a pressure of 150 bar or less. If the flow rate ratio of supercritical carbon dioxide and auxiliary solvent derived from the results is applied to the soil decontamination process, it is expected that the process efficiency will increase in the future.

Polycarboxylic ether-based high-range water reducer (PCE) has been proposed to use due to the operational advantages of reduced water content and increased fluidity of cementitious mixtures. But the concern about using PCE can increase the mobility of radionuclides as well. Nuclear Decommissioning Authority (NDA) showed that the PCE formulations increased radionuclide solubility in free solution. Solubility of U(VI), 239Pu, 241Am with the cementitious materials tested with 3:1 pulverized fuel Ash/Ordinary Portland Cement (PFA:OPC) and 9:1 Ground Granulated Blast Furnace Slag/OPC (GGBS:OPC) with PCE that increased at least one and, in some cases, more than three orders of magnitude (between 10-9 and 10-4 mol dm-3) for these radionuclides in the cement-equilibrated solution. It is possible that the relatively low molecular weight substances present in the PCE cement mixture increase the solubility of radionuclides. In addition, the organic substances that are easily miscible with water can contribute to increase the solubility. In this study, several radionuclides (Nb, Ni, Pd, Zr, and Sn) that may be present in intermediate and low-level waste (LIW) repositories were selected based on the half-life and the estimated dose accordingly, and the solubility tests were conducted with and without PCE in solution. To simulate the field condition of the underground repository, synthetic groundwater was prepared based on the recipe by the KAERI Underground Research Tunnel (KURT) DB-3 GW and used as a solvent. The solubility limiting solid phase (SLSP) of each radionuclide was determined using Geochemist’s WorkBench (GWB) model. The selected solid phases are Ni(OH)2, ZrSiO4, Nb2O5, Pd(metal), and SnO2, respectively, and the solubility experiments were conducted with 1.0wt% of PCE per total weight and 0.5 g / 250 ml of selected radionuclide’s SLSP for 90 days at room temperature (25°C). Compared with and without PCE presence in solution, the selected radionuclides also showed an increased solubility with the presence of water reducing agent like PCE. This results can be used to correctly estimate the mobility of target radionuclides with the presence of PCE in repository environments.

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.

Organic complexing agents which are contained in the radioactive waste can form the complex with radionuclides and enhance the solubility of radionuclides. The mobility of radionuclides to the far-field from the repository will be increased by radionuclide-ligand complex formation. Therefore, the assessment of the radionuclides’ solubility should be performed in the presence of organic complexing agents. In this study, five radionuclides (cobalt, strontium, iodine, cesium, and uranium) and three organic complexing agents (ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and isosaccharinic acid (ISA)) were selected as model radionuclides and organic complexing agents, respectively. For simulating the in-situ condition, the groundwater near the repository was collected and applied in solubility experiments and the solubility was measured in various environmental conditions such as different pHs (7, 9, 11, and 13), temperatures (10°C, 20°C, and 40°C), and a range of organic complexing agent concentrations (10-5, 10-4, 10-3, and 10-2 M). In cases of cesium and iodine, they were very soluble in all conditions, and the effect on their solubilities was not observed. However, at high pHs, cobalt and strontium showed lower solubilities than at neutral pH and the solubility enhancement by the organic complexing agents was significant. Moreover, the effects of each organic ligand showed obvious differences and were in the order of EDTA > NTA > ISA. The solubility of uranium was increased with increasing the organic ligand concentration at lower pHs, but the organic complexing agents did not cause a remarkable difference at high pHs. According to these results, the presence of complexing agents could enhance the radionuclides’ solubility and increase the potential to release the radionuclides to the far-field from the repository. Solubility experiments of other major radionuclides in the repository are in progress.

Technetium (Tc) is a long-lived radioactive isotope, which exists as TcO4 - with high solubility under oxidative condition. The solubility of Tc is fundamental to assess the safety of radioactive waste repository in the case of a leakage of radioactive wastes. Cellulosic materials (paper, wood, cotton, etc.) contaminated by radionuclides are disposed of in low-level and intermediate-level radioactive waste repositories. Cellulose can be decomposed under anaerobic and alkaline conditions when cement pore water is saturated, and then isosaccharinic acid (ISA) is generated as a degradation product of cellulose. ISA forms complexations with radionuclides in solution and affects the solubilities of radionuclides. Therefore, the effect of ISA should be accurately evaluated to predict and assess the mobility of radionuclides in repository environments. In this study, batch tests were conducted to confirm the effect of ISA on the solubility of Rhenium(IV) Oxide. Herein, rhenium was used as a non-radioactive analog of Tc due to their similar chemical properties. Deionized water (DIW) and 0.1 M NaOH solution in pH 12.5 were used as background solutions, and ISA concentration was varied to 1~20 mM using Ca(ISA)2 and NaISA, respectively. The batch tests were conducted under both aerobic and anaerobic conditions. The whole batch tests under anaerobic conditions were performed in the glove box using oxygen purged DIW with a high purity nitrogen gas (99.9%) and low oxygen concentration (< 0.5 ppm). As a result, the rhenium concentration decreases as more ISA is dissolved in the solution, which shows the contrary effect of ISA on the solubility of other metals and radionuclides (e.g., Co, Th, Fe, Ni, etc.). It is assumed that the reducing capacity of ISA decreases the rhenium dissolution in the solution. Additional characterization of the oxidation state of rhenium oxide and the mechanism will be tested and presented.