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.

During the initial cooling period of spent nuclear fuel, Cs-137 and Sr-90 constitute a large portion of the total decay heat. Therefore, separating cesium and strontium from spent nuclear fuel can significantly decrease decay heat and facilitate disposition. This study presents analytical technique based on the gas pressurized extraction chromatography (GPEC) system with cation exchange resin for the separation of Sr, Cs, and Ba. GPEC is a micro-scaled column chromatography system that allows for faster separation and reduction volume of elution solvent compared to conventional column chromatography by utilizing pressurized nitrogen gas. Here, we demonstrate the comparative study of the conventional column chromatography and the GPEC method. Cation exchange resin AG 50W-X12 (200~400 mesh size) was used. The sample was prepared at a 0.8 M hydrochloric acid solution and gradient elution was applied. In this case, we used the natural isotopes 88Sr, 133Cs, and 138Ba instead of radioactive isotopes for the preliminary test. Usually, cesium is difficult to measure with ICP-OES, because its wavelengths (455.531 nm and 459.320 nm) are less sensitive. So, we used ICP-MS to determine the identification and the recovery of eluate. In this study, optimized experimental conditions and analytical result including reproducibility of the recovery, total analysis time and volume of eluents will be discussed by comparing GPEC and conventional column chromatography.

After the Fukushima accident in 2011, relevant concerns regarding the contamination of the natural environment rose abruptly. For example, water contaminated by radionuclides such as Cs and Sr may directly flow into the ocean and threaten the marine ecosystem. In this respect, costeffective and efficient decontamination techniques need to be developed and verified to remediate the contaminated water. Prussian blue (PB) is known as a representative material that can adsorb Cs by ion-trapping and is widely used for medical purposes. However, there is a limitation that PB itself is non-separable and highly mobile in aqueous system, so it needs a fixture, such as bentonite, to be collected after the adsorption. Furthermore, while the performance of PB toward Cs is relatively well known, its behavior toward Sr has rarely been reported. The object of this study is to investigate the sorption characteristics of Cs and Sr onto PB-functionalized bentonite at various conditions. The adsorbent employed in the present work was prepared by mixing bentonite, FeCl3, and K4[Fe(CN)6] at room temperature for 24 hours in the aqueous solution. The concentrations of FeCl3 and K4[Fe(CN)6] were set to a range of 5-200 % compared to the cation exchange capacity of bentonite. After that, the PB-functionalized bentonite was sieved with a mesh size of 63 μm and then reacted with the Cs and Sr solution at various liquid-to-solid (L/S) ratios of 2-10 g/L for up to 500 minutes. Moreover, synthetic seawater containing additional Cs and Sr was reacted with PBfunctionalized bentonite to characterize the ion selectivity of PB. After the completion of the adsorption experiment, a part of the adsorbent was separated and desorption of Cs and Sr with 2 M of nitric acid was performed. For the quantification of aqueous Cs and Sr concentrations, ICP-MS was employed after the filtration with a pore size of 0.45 μm. The result obtained in this study revealed a high sorption affinity of Cs and Sr onto PBfunctionalized bentonite. The analysis results also presented that the sorption reactions of Cs and Sr reached their steady state within 10 minutes of reaction time. Furthermore, the ion selectivity toward Cs and Sr was verified through sorption test with synthetic seawater. According to the high sorption affinity and selectivity, the PB-functionalized bentonite synthesized through this study is expected to be widely used for remediating the Cs- and Sr-contaminated groundwater and seawater, particularly in nuclear waste-relevant industries.

Several tests should be performed to estimate the structural and chemical stability of the radioactive waste. Among the tests in Gyeongju LILW repository, the leaching test which follows ANS 16.1 standard test method should be conducted for Cs, Sr, and Co radionuclides and must satisfy leachability index larger than 6 which applies deionized water as a leachant. However, the expected leachant inside the silo is groundwater that contains various ions and a high pH condition is predicted due to the concrete structures inside the silo. According to the chemical environment of the leachant, the chemical form of the radionuclides varies from precipitate to ion. Cobalt precipitates when the leachant has high pH environment which is similar condition to the cement-saturated leachant. Unlike the cobalt, cesium is preferred to exist as ion in the high pH condition. Therefore, the significant effect of the chemical environment of the leachant on the leachability of the radionuclides should be considered for the waste acceptance criteria of the radioactive waste repository. From the ‘NRC, Technical position on the waste form, rev1’, the leaching test method should follow the ANS 16.1 methods by using deionized water as leachant, however, a new leachant showing more aggressive leachability can be applied instead of deionized water. In the other hand, ASTM C1308 leaching test method recommends applying actual groundwater of the repository as a leachant. FT-04-020, the leaching test method of France, suggests the ion composition of the groundwater including the pH value. Therefore, the adequacy of using deionized water as leachant for the leaching test method of Cs, Sr, and Co should be re-examined. In this study, the leaching behavior of Cs, Sr, and Co under the several leachant types is estimated. The cement solidified specimen containing single Cs, Sr, and Co were manufactured. The leaching test following ANS 16.1 was performed by applying deionized water, simulated groundater, and cement-saturated groundwater. As a result, a leachability index difference according to the leachant type was discussed. The result of this study is expected to be a background data that helps understanding the actual leaching behavior of the Cs, Sr, and Co in the Gyeongju LILW repository.

According to the Nuclear Safety and Security Commission (NSSC) Notice No. 2021-26 “Delivery Regulations for the Low- and Intermediate Level Radioactive Waste (LILW)”, the activity of 3H, 14C, 55Fe, 58Co, 60Co, 59Ni, 63Ni, 90Sr, 94Nb, 99Tc, 129I, 137Cs, 144Ce, and gross alpha must be identified. Currently, the scaling factor of the dry active waste (DAW) for LILW is applied as an indirect evaluation method in Korea. The analyses are used the destructive methods and 55Fe, 60Co, 59Ni, 63Ni, 90Sr, 94Nb, 99Tc, and 137Cs, which are classified as nonvolatile nuclides, are separated through sequential separation and then measured by gamma detector, liquid scintillation counter (LSC), alpha/beta total counter (Gas Proportional Counter, GPC), and ICP-MS. We will introduce how to apply the existing nuclide separation method and improve the measurement method to supplement it.

Korea faces decommissioning the nation’s first commercial nuclear power plant, the Kori-1 and Wolseong-1 reactors. In addition, other nuclear power plants that will continue to operate will also face decommissioning over time, so it is essential to develop independent nuclear facility decommissioning and site remediation technologies. Among these various technologies, soil decontamination is an essential not only in the site remediation after the decommissioning of the highly radioactive nuclear facility, but also in the case of site contamination caused by an accident during operation of the nuclear facility. But the soil, which is a porous material, is difficult to decontaminate because radionuclides are adsorbed into the pores. Therefore, with the current decontamination technology, it is difficult to achieve the two goals of high decontamination efficiency and secondary waste reduction at the same time. In this study, a soil decontamination process with supercritical carbon dioxide as the main solvent was presented, which has better permeability than other solvents and is easy to maintain critical conditions and change physical properties. Through prior research, a polar chelating ligand was introduced as an additive for smooth extraction reaction between radionuclides present as ions in soil and nonpolar supercritical carbon dioxide. In addition, for the purpose of continuity of the process, a candidate group of auxiliary solvents capable of liquefying the ligand was selected. In this research evaluated the decontamination efficiency by adding the selected auxiliary solvent candidates to the supercritical carbon dioxide decontamination process, and ethanol with the best characteristics was selected as the final auxiliary solvent. In addition, based on the decontamination effect under a single condition of the auxiliary solvent found in the Blank Test process, the possibility of a pre-treatment leaching process using alcohol was tested in addition to the decontamination process using supercritical carbon dioxide. Finally, in addition to the existing Cs and Sr, the possibility of decontamination process was tested by adding U nuclides as a source of contamination. As a result of this research, it is expected that by minimizing secondary waste after the process, waste treatment cost could be reduced and the environmental aspect could be contributed, and a virtuous cycle structure could be established through reuse of the separated carbon dioxide solvent. In addition, adding its own extraction capacity of ethanol used for liquefaction of solid-phase ligands is expected to maximize decontamination efficiency in the process of increasing the size of the process in the future.

During electrorefining, fission products, such as Sr and Cs, accumulate in a eutectic LiCl-KCl molten salt and degrade the efficiency of the separation process by generating high heat and decreasing uranium capture. Thus, the removal of the fission products from the molten salt bath is essential for reusing the bath, thereby reducing the additional nuclear waste. While many studies focus on techniques for selective separation of fission products, there are few studies on processing monitoring of those techniques. In-situ monitoring can be used to evaluate separation techniques and determine the integrity of the bath. In this study, laser-induced breakdown spectroscopy (LIBS) was selected as the monitoring technique to measure concentrations of Sr and Cs in 550°C LiCl-KCl molten salt. A laser spectroscopic setup for analyzing high-temperature molten salts in an inert atmosphere was established by coupling an optical path with a glove box. An air blower was installed between the sample and lenses to avoid liquid splashes on surrounding optical products caused by laser-liquid interaction. Before LIBS measurements, experimental parameters such as laser pulse energy, delay time, and gate width were optimized for each element to get the highest signal-to-noise ratio of characteristic elemental peaks. LIBS spectra were recorded with the optimized conditions from LiCl-KCl samples, including individual elements in a wide concentration range. Then, the limit of detections (LODs) for Sr and Cs were calculated using calibration curves, which have high linearity with low errors. In addition to the univariate analysis, partial least-squares regression (PLSR) was employed on the data plots to obtain calibration models for better quantitative analysis. The developed models show high performances with the regression coefficient R2 close to one and root-mean-square error close to zero. After the individual element analysis, the same process was performed on samples where Sr and Cs were dissolved in molten salt simultaneously. The results also show low-ppm LODs and an excellent fitted regression model. This study illustrates the feasibility of applying LIBS to process monitoring in pyroprocessing to minimize nuclear waste. Furthermore, this high-sensitive spectroscopic system is expected to be used for coolant monitoring in advanced reactors such as molten salt reactors.

Concrete is one of the largest wastes, by volume, generated during the decommissioning of nuclear facilities, which significantly influences the projected costs for the disposal of decommissioning wastes. Concrete consists of aggregates and a cement binder. In radioactive concrete, the radioisotopes are mainly associated with the cement component. If the radioactive isotope can be separated from the concrete to below the clearance criteria, the volume of radioactive concrete waste could be reduced effectively. We were studied to separate the radioactive materials from the concrete by using the thermomechanical and chemical treatment processes, sequentially. From the study, separated aggregate could be treated to achieve the clearance level. However, these processes generate a large volume of secondary acidic radioactive wastewater, which might be a critical problem to reduce the volume of radioactive concrete waste. In this research, separating the 137Cs and 90Sr from dissolved concrete wastewater to below the discharge criteria by precipitation method, it would be released to the environment under industrial waste guidelines. The experiments were conducted to using a simulated radioactive wastewater, formed by the dissolution of concrete within HCl, which was spiking the 137Cs and 90Sr, respectively. In addition, we applied the chemical precipitation methods with wastewater, using ferrocyanide for 137Cs and BaSO4 coprecipitation for 90Sr. As a result, targeted radionuclides could be removed to the discharge level (137Cs: 0.05 Bq·ml−1, 90Sr: 0.02 Bq·ml−1) by precipitation method. Therefore, it could reduce the secondary wastewater effectively by precipitation method and enhance the additional volume reduction for radioactive concrete waste.

본 연구는 고온 열분해를 통한 Cs, Sr 등 고방사성핵종의 고정화를 위하여 각각 Cs이 흡착된 CHA (K형 Chabazite zeolite)-Cs, CHA-PCFC (potassium cobalt ferrocyanide)-Cs 및 Sr이 흡착된 4A-Sr, BaA-Sr 등의 제올라이트 계에서 TGA 및 XRD에 의한 배소 온도 변화에 따른 상변환을 고찰하였다. CHA-Cs 제올라이트 계의 경우 900℃ 까지는 CHA-Cs의 형태를 유지하고 있으며, 1,000℃에서 무정형 단계를 거친 후 1,100℃에서 pollucite (CsAlSi2O6)로 재결정 되었다. 반면에 CHA-CFC-Cs 제올라이 트 계는 700℃ 까지는 CHA-PCFC-Cs 형태를 유지하고 있으나, 900∼1,000℃ 사이에서 구조가 파괴되어 무정형으로 상변환 된 후 1,100℃에서 pollucite로 재결정 되었다. 한편 4A-Sr 제올라이트 계의 경우 700℃ 까지는 4A-Sr의 구조를 유지하고 있 으며, 800℃에서 무정형으로 상변환 된 다음 900℃에서는 Sr-feldspar (SrAl2Si2O8, hexagonal)으로, 1,100℃에서 SrAl2Si2O8 (triclinic)로 재결정 되었다. 그러나 BaA-Sr 제올라이트 계의 경우는 500℃ 이하부터 구조가 파괴되기 시작하여 500∼900℃ 에서 무정형 단계를 거친 후, 1,100℃에서 Ba/Sr-feldspar (Ba0.9Sr0.1Al2Si2O8 및 Ba0.5Sr0.5Al2Si2O8 공존)로 재결정 되었다. 상기 제올라이트 계 모두 온도 증가에 따라 탈수/(분해)→ 무정형→ 재결정의 단계를 거쳐 광물상으로 재결정 되었으며, 고온 열 분해 과정에서의 Cs 및 Sr의 휘발성, 침출성 등의 추가 연구가 요구되지만 각 제올라이트 계에 흡착된 Cs 및 Sr은 pollucite나 Sr-feldspar, Ba/Sr-feldspar 등으로 광물화 하여 Cs과 Sr을 배소체/(고화체) 내에 완전히 고정화 시킬 수 있을 것으로 보인다.