The mobility of uranium (U) in various disposal environments of a deep geological repository is controlled by various geochemical conditions and parameters. In particular, oxidation state of uranium is considered as a major factor to control the mobility of uranium in most of geological environments. In this study, therefore, we investigated the geochemical behaviors of uranium in grounwater samples from natural analogue study sites located in the Ogcheon Metamorphic Belt (OMB). Groundwater samples were taken using a packer system from Boeun Hoenam-myun site and Geumsan Suyoung-ri site where several boreholes were dilled with various depths. The geochemical properties and parameters such as temperature, pH, Eh, EC, and DO were directly measured in the site using an in-line measurement method. The concentrations of major cations and anions in the groundwater samples were measured by using ICP-OES (Inductively Coupled Plasma-Optical Emission Spectrometry) and IC (Ion Chromatography), respectively. The concentrations of trace elements including U and Th were measured by using ICP-MS (Inductively Coupled Plasma-Mass Spectrometry) The concentrations of U in the groundwater samples are very low for the Hoenammyun site (0.03~0.69 ppb) and Suyoung-ro site (0.39~1.74 ppb) even though the two sites are uranium deposits and redox conditions are weakly oxidizing. The speciation, saturation index (SI), pH-Eh (Poubaix) diagram were calculated using the Geochemist’s Workbench (GWB 9.0) program and the recent OECD/NEA thermochemical database for U. Calculation results for U speciation in the groundwater samples show that major dissolved uranium species in the groundwater samples are mainly as calcium uranyl carbonate complexes such as Ca2UO2(CO3)3(aq) and CaUO2(CO3)3 2- for almost all groundwater samples. The calculated results for SI and Poubaix diagram also show that the dominant uranium solid phase is a uranyl silicate mineral, uranophane (Ca(H2O)(UVIO2)2 (SiO2)2(OH)6), not uraninite (UIVO2). Since the determination of Eh values for natural groundwater samples is very difficult and uncertain work, we analyzed and discussed the effect of Eh on the geochemical behaviors of U in the groundwater. However, these calculation results are not consistent with the observation for U minerals in rock samples using electron microscopic techniques. Thus, we need further studies to explain the discrepancy between calculation and observation results.

Raman characteristics of various minerals constituting natural rocks collected from uranium deposits in Okcheon metamorphic zone in Korea are presented. Micro-Raman spectra were measured using a confocal Raman microscope (Renishaw in Via Basis). The focal length of the spectrometer was 250 mm, and a 1800 lines/mm grating was installed. The outlet of the spectrometer was equipped with a CCD (1,024256 pixel) operating at -70°C. Three objective lenses were installed, and each magnification was 10, 50, and 100 times. The diameter of the laser beam passing through the objective lens and incident on the sample surface was approximately 2 m. The laser beam power at 532 nm was 1.6 mW on the sample surface. Raman signal scattered backward from the sample surface was transmitted to the spectrometer through the same objective lens. To accurately determine the Raman peak position of the sample, a Raman peak at 520.5 cm-1 measured on a silicon wafer was used as a reference position. Since quartz, calcite, and muscovite minerals are widely distributed throughout the rock, it is easy to observe with an optical microscope, so there is no difficulty in measuring the Raman spectrum. However, it is difficult to identify the uraninite scattered in micrometer sizes only with a Raman microscope. In this case, the location of uraninite was first confirmed using SEM-EDS, and then the sample was transferred to the Raman microscope to measure the Raman spectrum. In particular, a qualitative analysis of the oxidation and lattice conditions of natural uraninite was attempted by comparing the Raman properties of a micrometer-sized natural uraninite and a laboratory-synthesized UO2 pellet. Significantly different T2g/2LO Raman intensity ratio was observed in the two samples, which indicates that there are defects in the lattice structure of natural uraninite. In addition, no uranyl mineral phases were observed due to the deterioration of natural uraninite. This result suggests that the uranium deposit is maintained in a reduced state. Rutile is also scattered in micrometer-sizes, similar to uraninite. The Raman spectrum of rutile is similar in shape to that of uraninite, making them confused. The Raman spectral differences between these two minerals were compared in detail.

Uranium (U) is a hazardous material that can lead to both chemical and radiological toxicity, including kidney damage and health issues associated with radiation exposure. In South Korea. In Korea, where shallow weathered granitic aquifers are widespread, several previous studies have reported high levels of radioactivity in shallow groundwater. This ultimately led to the closure of 60 out of 4,140 groundwater production wells in South Korea. In this study, we examined aquifers currently dedicated to drinking water supply and investigated a dataset of 11,225 records encompassing 103 environmental parameters, based on the random forest classifier. This dataset comprises 80 physical parameters associated with the hydraulic system and 23 chemical parameters linked to water-rock interactions. Among the hydraulic parameters, the presence of a coarse loamy texture in the subsoil displayed a notable positive relationship with the concentration of uranium, implying that it plays a significant role in forming redox conditions for the leaching of uranium from host rocks. Fluorine (F), a major product of water-rock interaction in granitic aquifers, exhibited a positive correlation with the distribution of uranium concentrations. The positive relationship between F concentration and uranium levels suggests that the dissolved uranium originates from groundwater interacting with granites. In conclusion, our findings indicate that two key factors, namely the infiltration capacity of soil layers and the aqueous speciation in groundwater resulting from interactions with local solids, play important roles in determining uranium concentrations in granitic aquifers.

The bioreduction process from soluble U(VI) to insoluble U(IV) has been extensively studied in the field of radionuclides migration. Since acetic acid (AcOH) is widely used as an electron donor for bioreduction of U(VI), it is necessary to understand the effect of U(VI)-AcOH complexes that exist in different species depending on pH on this process. Changes in samples before and after bioreduction can be compared using time-resolved laser luminescence spectroscopy (TRLLS), which measures the characteristic luminescence spectra of different U(VI) species. Although luminescence properties of U(VI)-AcOH species were reported, experiments were conducted under conditions below pH 4.5. In this study, spectrophotometry and TRLLS for U(VI)-AcOH species (10−100 μM U(VI) and 20 mM AcOH) were performed in pH ranges extending to neutral and alkaline pH regions similar to groundwater conditions as well as acidic pH region. Two different complexes (UO2(AcO)+, UO2(AcO)2 with U(VI) and acetate ratios of 1:1, 1:2) were observed in the acidic pH region. The 1:1 complex, which appears as the pH increases, has no luminescence properties, but its presence can be confirmed because it serves to reduce the luminescence intensity of UO2 2+. In contrast, the 1:2 complex exhibits distinct luminescence properties that distinguish it from UO2 2+. The 1:3 complex (UO2(AcO)3 -) expected to appear with increasing pH was not observed. Two different complexes ((UO2)3(OH)5 +, (UO2)3(OH)7 - with U(VI) and OH ratios of 3:5, 3:7) were observed as the major species in the neutral pH region, but their luminescence lifetimes are remarkably short compared those in the absence of AcOH. Solid U(VI) particles were observed in the alkaline pH region, and they also had completely different luminescence properties from the aforementioned U(VI)-AcOH and U(VI)-hydrolysis species. Based on these results, the effect of pH in the presence of AcOH on the bioreduction process from U(VI) to U(IV) will be discussed.

The mobility of uranium (U) in the environment of a deep geological repository is controlled by various geochemical conditions and parameters. In particular, oxidation state of uranium is considered as a major factor to control the mobility of uranium in most of geological environments. In this study, therefore, we investigated the mobility of uranium in a deep geological repository by a natural analogue approach using a uranium deposit in the Ogcheon Metamorphic Belt (OMB). Uranium contents of rock samples from the study site ranged from 1.3 to 71 ppm (average 17.4 ppm). Uranium minerals found in the study site were mostly uraninite (UIVO2+x) and uranothorite ((UIV, Th)SiO4). The concentrations of U in the groundwater samples were very low (0.025~0.690 ppb) even though redox conditions are weakly oxidizing. Calculation results for U speciation in groundwater samples showed that major dissolved uranium species in the groundwater samples are mainly as calcium uranyl (UO2 2+) carbonate complexes such as Ca2UO2(CO3)3(aq) and CaUO2(CO3)3 2-. However, the activity ratios between 234U and 238U (AR(234U/238U)) showed U behavior in reducing conditions although the groundwater conditions were not reducing conditions and major dissolved U species were U(VI) species. Results from electron microscopic analyses for rock samples showed that major uranium minerals were U(IV) minerals such as uraninite and uranothorite. We could not identify other uranyl minerals and altered minerals from uraninite. This means that the geochemical condition of the study site has been maintained a reducing condition although the groundwater condition was a weakly oxidizing condition. Thus, the dissolution of uranium is strongly limited by the low solubility of uraninite. It is not obvious how the reducing condition of the study site has been maintained. Reducing agents such as pyrite, organic materials, and reducing bacteria might contribute to maintaining the reducing condition although further studies will be necessary. Results from this study imply that uranium mobility will be greatly limited by low dissolution of uraninite into groundwater if the reducing condition is well reserved. This limited mobility of uranium will be also contributed by low possibility of uraninite alteration into uranyl minerals which have a higher solubility than uraninite.

Several countries have been operating radioactive waste disposal (RWD) programs to construct their own repositories and have used natural analogues (NA) studies directly or indirectly to ensure the reliability of the long-term safety of deep geological disposal (DGD) systems. A DGD system in Korea has been under development, and for this purpose a generic NA study is necessary. The Korea Atomic Energy Research Institute has just launched the first national NA R&D program in Korea to identify the role of NA studies and to support the safety case in the RWD program. In this article, we review some cases of NA studies carried out in advanced countries considering crystalline rocks as candidate host rocks for high-level radioactive waste disposal. We examine the differences among these case studies and their roles in reflecting each country’s disposal repository design. The legal basis and roadmap for NA studies in each country are also described. However because the results of this analysis depend upon different environmental conditions, they can be only used as important data for establishing various research strategies to strengthen the NA study environment for domestic disposal system research in Korea.

Disposal methods of radioactive waste can be mainly divided into near-surface disposal and deep geological disposal. If the radioactive waste is exposed to groundwater for a long time in the disposal environment, no matter how the decommissioning waste generated from the nuclear power plant is disposed of, the radionuclides may be released from the disposal site. Decommissioning waste from nuclear power plant contains radionuclides that are harmful to ecosystem including humans. Radionuclides released from disposal site behave in a complex and sensitive manner affected by geochemical conditions such as soil, geological media and groundwater. Sorption is one of the important mechanisms to retard the migration of radionuclides in a subsurface environment. In this study, geochemical properties of groundwater were collected and analyzed in the disposal environment considering disposal method in order to evaluate the geochemical behavior of radionuclides. The formation of aqueous and precipitated species of cesium and cobalt in a disposal condition were calculated and estimated. The sorption properties were also evaluated and predicted by considering the changes in the geochemical conditions such as pH, redox potential and geological media for the safety assessment.

In south Korea, most of uranium deposits are distributed in the Ogcheon belt, which is one of two late Precambrian to Paleozoic fold belts (the Imjingang and Ogcheon belts). A study site of the Ogcheon metamorphic belt (OMB) in Hoenam-myun, Boeun-gun was selected for the natural analogue study by preliminary site investigation for several candidate study sites. Three boreholes were drilled in the site and some rock cores and groundwater samples were taken from the boreholes. Various analytical studies for the samples are now being performed. Thus, in this study, various basic characteristics of the study site such as occurrence, geological, mineralogical, and chemical properties were investigated for a future study. Base rocks containing uranium in the OMB are usually black slate and coaly slate. Coaly slate usually shows a higher content of uranium and larger grain size of uranium than black slate. Uranium minerals found in the OMB are uraninite, uranothorite, brannerite, ekanite, coffinite, francevillite, uranophane, autunite, and torbernite depending on the base rock types. Uranothorite is abundant in black slate whereas uraninite is mostly abundant in coaly slate. Chemical compositions of the solid and groundwater samples from the study site were also analyzed by using ICP-MS/OES (Inductively Coupled Plasma Mass Spectrometry) and XRF (X-ray Fluorescence). This will contribute to determine uranium minerals in the solid samples and uranium speciation in the groundwater. The results of this study will contribute to performing future natural analogue studies in domestic uranium deposits and provide basic information and knowledge for understanding long-term geochemical behaviors of radionuclides in a high-level radioactive repository.

Time-resolved laser fluorescence spectroscopy (TRLFS) and excitation-emission matrix (EEM) spectroscopy were used to study the interaction of U(VI) and natural organic matters (NOMs) in groundwater. Various types of groundwaters (DB-1, DB-3 from KURT site and OB-1, OB-3 from a U deposit in Ogcheon metamorphic belt) were used as samples. Pulsed Nd-YAG laser at 266 nm (Continuum Minilite) was used as the light source of TRLFS. The laser pulse energy of 1.0 mJ was fixed for all measurements. The luminescence spectrum was recorded using a gated intensified chargecoupled device (Andor, DH-720/18U03 iStar 720D) attached to the spectrograph (Andor, SR-303i). EEM spectra were measured using a spectrofluorometer (Horiba Scientific, Aqualog) equipped with a 150 W ozone-free xenon arc lamp. Excitation spectra were recorded by scanning the excitation wavelength from 200 to 500 nm. Emission spectra were measured using a CCD in the wavelength range of 242–823 nm. In the case of the recently collected DB-1 samples, it was observed that the U and NOM quantities decreased compared to the samples collected before 2016. For some DB-1 samples, the amount of dissolved organic carbon indicating the presence of NOM was significantly reduced, and changes consistent with this phenomenon were observed in the EEM spectrum. The time-resolved luminescence characteristics (peak wavelengths and lifetime) of U(VI) in the DB-1 samples agree well with those of Ca2UO2(CO3)3(aq). This U(VI) species remains stable, even in samples taken five years ago. The estimated amounts of U and NOM from the spectroscopic data of DB-3, OB-1, and OB-3 samples are relatively low compared to DB-1 samples. When a known amount of U(VI) was mixed in each groundwater, the time-resolved luminescence spectrum exhibited a characteristic spectral shape different from the expected luminescence intensity. This phenomenon is presumed to be due to the interaction between U(VI) and NOM in groundwater. The results of this study suggest that the chemical speciation of NOM as well as U(VI) is required to understand U behavior in groundwater.

The fundamental characteristics of groundwater colloids, such as composition, concentration, size, and stability, were analyzed using granitic groundwater samples taken from the KAERI Underground Research Tunnel (KURT) site by such analytical methods as inductively coupled plasma-mass spectrometry, field emission-transmission electron microscopy, a liquid chromatography-organic carbon detector, and dynamic light scattering technique. The results show that the KURT groundwater colloids are mainly composed of clay minerals, calcite, metal (Fe) oxide, and organic matter. The size and concentration of the groundwater colloids were 10–250 nm and 33–64 μg·L−1, respectively. These values are similar to those from other studies performed in granitic groundwater. The groundwater colloids were found to be moderately stable under the groundwater conditions of the KURT site. Consequently, the groundwater colloids in the fractured granite system of the KURT site can form stable radiocolloids and increase the mobility of radionuclides if they associate with radionuclides released from a radioactive waste repository. The results provide basic data for evaluating the effects of groundwater colloids on radionuclide migration in fractured granite rock, which is necessary for the safety assessment of a high-level radioactive waste repository.

Several previous simulation studies using various geochemical models have been carried out in several major analogue sites. The cases are beneficial when these studies provided the possibility of testing the geochemical models to be used to describe the migration of radionuclides in a future radioactive waste repository system. It was possible to interpret the complex transport behaviour of radionuclides such as uranium and thorium in an environment. We organize major natural analogue study sites from the previous literatures that provided information on the general geochemistry of the sites, in terms of groundwater composition and mineralogy. Also, we calculated aqueous speciation and the solid phases most likely to control their solubilities. The results obtained from the previous studies and this study vary depending on the tools used and on the conceptual models followed. Also, the results differed from the actual measured concentrations of trace metals or radionuclide analogues. The results obtained from these tests identify the main mathematical limitations of available geochemical models. However, the modelling results using a geochemical code with the thermodynamic database simulated well the observed behaviour of radionuclides, especially to identify the dominant processes controlling actinide mobilization and fixation. It was a useful outcome in terms of building confidence on the current geochemical tools to predict the concentrations of radionuclide analogues once the major geochemical characteristics were known. This study allows improving specific aspects of geochemical modelling using major natural analogue sites.

Uranium isotopes (238U, 235U, and 234U) found in natural environments and their activity ratios (235U/238U and 234U/238U) have been used as an important tool in investigating various geological processes, especially in natural analogue studies. Occurrence and fractionation of uranium isotopes in nature between 238U, 235U, and 234U were investigated. Various measurement methods have been used for the determination of isotopic ratios and geochronology. Thus, we reviewed and summarized the measurement methods such as alpha spectrometry, gamma spectrometry, thermal ionization mass spectrometry (TIMS), secondary ion mass spectrometry (SIMS) with sensitive high resolution ion microprobe (SHRIMP), and multiple-collector inductively coupled plasma mass spectrometry (MCICPMS). Research status of natural analogue studies carried out using uranium isotopes and their isotopic ratios were also reviewed and summarized in terms of long-term behaviors of radionuclides in various foreign uranium deposits as analogues of high-level radioactive waste repositories. Research results for mineralogical, geochemical, and biogeochemical behaviors of uranium in various natural analogue sites were collected and analyzed to investigate the migration and retardation processes of uranium through geological media. These long-term behaviors of uranium and uranium isotopes include dissolution/precipitation of uranium minerals, interactions of uranium with various fracture minerals including sorption and incorporation, redox reactions by minerals and microbes, and hydrological groundwater flow thorough rock fracture systems including identification of flow paths and groundwater circulation. The results of this study will contribute to performing future natural analogue studies in domestic uranium deposits and provide basic information and knowledge for understanding long-term geochemical and geochronological behaviors of radionuclides in a high-level radioactive repository.

The decommissioning of a nuclear power plant generates large amounts of radioactive waste, which is of several types. Radioactive concrete powder is classified as low-level waste, which can be disposed of in a landfill. However, its safe disposal in a landfill requires that it be immobilized by solidification using cement. Herein, a safety assessment on the disposal of solidified radioactive concrete powder waste in a conceptual landfill site is performed using RESRAD. Furthermore, sensitivity analyses of certain selected input parameters are conducted to investigate their impact on exposure doses. The exposure doses are estimated, and the relative impact of each pathway on them during the disposal of this waste is assessed. The results of this study can be used to obtain information for designing a landfill site for the safe disposal of low-level radioactive waste generated from the decommissioning of a nuclear power plant.