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 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.

Uranium inventory in Boeun aquifer is facing the artificial reservoir that intended for supplying water to nearby cities (40-70 m apart) where, toxic radionuclides might mobile and enter the reservoir. In order to understand U mobility in the system, groundwater and fracture filling materials (FFMs) were analyzed for microbial signatures, C, O, Fe, S and U-series isotopes. The δ18O-H2O and 14C signatures suggested groundwater was originated from upland recharges dominantly and not affected by mixing with the surface water. However, the 234U/238U activity ratios (ARs) and 230Th/234U ARs in FFMs ranged from 0.93 to 1.67 and from 0.22 to 1.97, respectively, indicating that U was mobile along the fractures. In shallow FFMs, the U accumulations (~157 mg/kg) were found with Fe enrichments (~226798 mg/kg) and anomalies of δ56Fe and δ57Fe, implied U mobility in shallow depths was associated with Fe-rich environment. Also, in the shallow depths, Fe-oxidizers, Gallionella was prevailing in groundwater while Acidovorax was abundant near U ore depth. The Fe-rich environment in shallow depths was formed by pyrite dissolution, demonstrated using δ34S-SO4 and δ18O-SO4 distribution. Conclusively, the Fe-rich aquifer was capable of immobilizing the dissolved U through biotic and abiotic processes, without significant discharge into the nearby reservoir.

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.

Uranium (U) is hazardous material can cause chemical and radiological toxicity, e.g., kidney toxicity and health effects associated with radiation. In Korea, where shallow weathered granitic aquifers are ubiquitous, several previous studies have reported high level of radioactivity in shallow groundwater. This eventually led to the closure of 60 out of 4,140 groundwater production wells in South Korea. Here, we examined aquifers currently dedicated for drinking water supply and investigated the 11,225 dataset of 103 environmental parameters. This dataset includes 80 physical parameters associated with the hydraulic system and 23 chemical parameters associated with waterrock interactions. Among hydraulic parameters, coarse loamy texture in subsoil displayed a notable relation with U concentration level, implied it is controlling the leaching of U from host rocks. Fluorine (F), is one of major products from water-rock interaction in granitic aquifer, exhibited high correlation with U concentration distribution. Positive relation of F concentration with uranium level suggested the dissolved U originated from groundwater interacted with granites. Conclusively, we found that infiltration capacity of soil layers and (2) aqueous speciation in groundwater formulated by interaction of groundwater with local solids, played important role for U concentration in granitic aquifer.

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.