This study proposes the use of a cobalt-based Prussian blue analogue (Co-PBA; potassium cobalt hexacyanoferrate), as an adsorbent for the cost-effective recovery of aqueous ammonium ions. The characterization of Co-PBA involved various techniques, including Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, nitrogen adsorption-desorption analysis, and zeta potential. The prepared Co-PBA reached an adsorption equilibrium for ammonium ions within approximately 480 min, which involved both surface adsorption and subsequent diffusion into the interior. The isotherm experiment revealed a maximum adsorption capacity of 37.29 mg/g, with the Langmuir model indicating a predominance of chemical monolayer adsorption. Furthermore, the material consistently demonstrated adsorption efficiency across a range of pH conditions. Notably, adsorption was observed even when competing cations were present. Co-PBA emerges as a readily synthesized adsorbent, underscoring its efficacy in ammonium removal and selectivity toward ammonium.

In Natural Analogue Study, Concrete is one of the important engineering barrier components in the Multi-thin wall concept of radioactive waste disposal and plays the most important role in disposal sites. The concrete barrier at the disposal site loses its role as a barrier due to various deterioration phenomena such as settlement, earthquake, and ground movement, causing the disposed waste to leak into the natural ecosystem. Some of the key factor is deterioration triggered by sulfate attack. Concrete deterioration induced by sulfate is commonly manifested in an extensive scale when a concrete structure makes contact with soil or water, aggravating its performance. In this study, an accelerated concrete deterioration evaluation experiment was performed using a total of three experimental methods to evaluate the reaction between concrete and water. The first experiment was a deterioration evaluation using Demi. Water, the second was a deterioration evaluation using KURT groundwater after extraction, and the last experiment was a concrete deterioration evaluation using KURT groundwater and sodium sulfate. For all of these experiments, accelerated concrete deterioration experiments were conducted after immersion for a total of 365 days, and specimens were taken out at 30-day intervals and characterization analysis such as SEM and EDS was performed. Experimental analyzes have shown that various chemical species are generated or destroyed over time. In the future, we plan to continue to conduct a total of three concrete deterioration evaluation experiments above, and additionally evaluate the chemical reaction between bentonite and concrete.

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.

Natural analogue studies aim to understand specific processes or to make predictions regrading formation processes or environmental conditions based on information from natural phenomena on Earth. Studying geological environments similar to the disposal system can help evaluate the longterm stability of the disposal system. These studies play a crucial role in evaluating the long-term stability of deep geological repositories (DGRs) for high-level radioactive wastes, which must remain stable for extended periods. In particular, bentonite, as a vital buffer material in DGRs, is mainly composed of montmorillonite and undergoes a transformation into zeolite under specific environmental conditions, resulting in the loss of its role as a buffer material in terms of swelling property and hydraulic conductivity. In this study, bentonite samples from Pohang Basin in Korea were investigated, revealing the presence of montmorillonite and zeolite in both outcrop and drilling core samples. While it has been known that montmorillonite and zeolites can form from volcanic glass through diagenesis or hydrothermal alteration, this study revealed that these minerals are formed under distinct environmental conditions. The outcrop samples primarily consisted of montmorillonite with minor quantities of cristobalite and amorphous silicate minerals. In contrast, the drilling core samples were composed of montmorillonite, zeolites, quartz and feldspar, indicating different mineral assemblages and characteristics between the outcrop and drilling samples. This observation suggests different environmental conditions during the mineral formation process. Therefore, various experiments and analytical methods were employed to gain a deeper understanding of the phase transformation from montmorillonite to zeolites under diverse environmental conditions

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.

Deep geological disposal is generally accepted to be the most practical approach to handling radioactive wastes. Bentonite has been considered as a buffer material in deep geological disposal repositories (DGR) for high-level radioactive wastes. Evaluating the effect of short-term bentonite alteration on EBS performance has limitations in safety assessment over thousands of years. Information on bentonite characteristics under various conditions obtained from natural systems can be used to evaluate long-term safety of bentonite buffer. The purpose of this study was to investigate mineralogical and physicochemical characteristics of bentonite in the Naah mine located in Yangnam-myeon, Gyeongju-si for a natural analogue of the bentonite barrier in DGR. A total of 15 samples were collected at regular intervals from the bentonite layer and andesitic lapilli tuff (i.e., parent rock) at the boundary with the bentonite layer. The bentonite layer is located at a depth of about 1 m below the ground surface. Each sample was separated into particles < < 75 μm and particles < 2 μm through grinding and sedimentation processes. The separated subsamples were characterized mineralogically and physiochemically using various analytic techniques. Bentonite samples have a similar SiO2/Al2O3 ratio to the parent rock and a lower (Na+K)/Si ratio than the parent rock, indicating depletion of alkali components during bentonitization. The parent rock and bentonite samples have similar mineral composition (i.e., quartz, feldspars, opal-cristobalite-tridymite and montmorillonite). Results of XRD analysis on the randomly distributed particles < 2 μm indicate that bentonite is mostly composed of Ca-montmorillonite, which is a typical dioctahedral smectite. Results of FTIR and VNIR analysis indicate that montmorillonite contained in bentonite is Al-dioctahedral montmorillonite, and Al is substituted with Mg in some octahedron units. The mineralogical and physicochemical characteristics are similar regardless of sampling location. These results suggest that bentonite potentially exposed to weathering, located near the ground surface, has hardly altered.

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.

Mechanism and kinetics of Rhenium complexes as a surrogate of Technetium-99 (99Tc) is worthy of study from radioactive waste safe disposal perspective. Re(IV)-EDTA was synthesized via the reduction of Re(VII) with Sn(II) in the presence of Ethylenediaminetetracetic acid (EDTA). The Re(IV)-EDTA was then degraded by H2O2 (7–30%) at pH of 3–11 in ionic strength I = 0–2 M solution. The Re- EDTA was observed to degrade more rapidly at pH of ≤ 3–4 than one of ≥ 10–11 and remained stable at pH = 7–9. At a low acidic pH, the complex degradation process was facilitated by protonation and corresponded to the exponential model (y = k. e–nt). In contrast, at an alkaline pH, the degradation was facilitated OH– complexation with Re(IV) and corresponded to a linear model (y = –mt + C). Complex degradation followed the zero-order rate kinetics for the H+ and Re-EDTA parameters, apart from a pH of 3, for which degradation was a better fit to first order kinetics. A higher Re(IV)-EDTA stability at a pH of 7–9 demonstrated that Re(IV)-EDTA (or 99Tc(IV)-EDTA) tends to be more persistent in natural environmental conditions.

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.