This study aimed to develop an efficient recycling process for wastewater generated from soil-washing used to remediate uranium (U(VI))-contaminated soil. Under acidic conditions, U(VI) ions leached from the soil were precipitated and separated through neutralization using hydrazine (N2H4). N2H4, employed as a pH adjuster, was decomposed into nitrogen gas (N2), water (H2O), and hydrogen ions (H+) by hydrogen peroxide (H2O2). The residual N2H4 was precipitated when the pH was adjusted using sulfuric acid (H2SO4) to recycle the wastewater in the soil-washing process. This purified wastewater was reused in the soil-washing process for a total of ten cycles. The results confirmed that the soil-washing performance for U(VI)-contaminated soil was maintained when using recycled wastewater. All in all, this study proposes an efficient recycling process for wastewater generated during the remediation of U(VI)-contaminated soil.

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.

Bacterial metabolisms influence the behavior of uranium (U) in deep geological repository (DGR) system because bacteria are ubiquitous in the natural environment. Nevertheless, most studies for the U(VI) bioreduction have focused on a few model bacterium, such as Shewanella putrefaciens, Desulfovibrio desulfuricans, and Geobacter sulfurreducens. In this study, the potential of aqueous U(VI) ((U(VI)aq) reduction by indigenous bacteria was examined under anaerobic conditions with addition of 20 mM sodium acetate for 24 weeks. Three different indigenous bacterial communities obtained from granitic groundwater at depths of 44–60 m (S1), 92–116 m (S2), and 234–244 m (S3) were applied for U(VI)aq reduction experiments. The S2 groundwater contained the highest U concentration of 885.4 μg/L among three groundwater samples, where U mainly existed in the form of Ca2UO2(CO3)3(aq). The S2 groundwater amended 20 mM of sodium acetate was used for the U(VI)aq bioreduction experiment. Variations in the U(VI)aq concentration and redox potential were monitored for 24 weeks to compare U(VI)aq removal efficiency in response to indigenous bacteria. The U(VI)aq removal efficiencies varied among three indigenous bacteria: 57.8% (S3), 43.1% (S2), and 37.7% (S1). The presence of the thermodynamically stable uranyl carbonate complex resulted in the incomplete U(VI)aq removal. Significant shifts in indigenous bacterial communities were observed through highthroughput 16S rRNA gene sequencing analysis. Two SRB species, Thermodesulfovibrio yellowstonii and Desulfatirhabdium butyrativorans, were dominant in the S3 sample after the anaerobic reaction, which enhanced the bioreduction of U(VI)aq. The precipitates produced by bacterial activity were determined to be U(IV)-silicate nanoparticles by a transmission electron microscope (TEM)-energy dispersive spectroscope (EDS) analysis. These results demonstrated that considerable U immobilization is possible by stimulating the activity of indigenous bacteria in the DGR environment.

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.

Montmorillonite plays a key role in engineered barrier systems in the high-level radioactive waste repository because of its large sorption capacity and high swelling pressure. However, the sorption capacity of montmorillonite can be largely varied dependent on the surrounding environments. This study conducted the batch simulation for U(VI) sorption on Na-montmorillonite by utilizing the cation exchange and surface complexation coupled (2SP-NE-SC/CE) model and evaluated the effects of physicochemical properties (i.e., pH, temperature, competing cations, U(VI) concentration, and carbonate species) on U(VI) sorption. The simulation demonstrated that the U(VI) sorption was affected by physicochemical properties: the pH and temperature relate to aqueous U(VI) speciation, the competing cations relate to the cation exchange process and selectivity, the U(VI) concentration relates to saturation at sorption sites. For example, the Kd (L kg−1) of Na-montmorillonite represented the largest values of 2.7×105 L kg−1 at neutral pH condition and had significantly decreased at acidic pH<3, showing non-linear and diverse U(VI) sorption at the ranged pH from 2 to 11. Additionally, the U(VI) sorption on montmorillonite significantly decreased in presence of carbonate species. The U(VI) sorption for long-term in actual porewater chemistry and temperature of high-level radioactive waste repository represented that the sorption capacity of Na-montmorillonite was affected by various external properties such as concentration of competing cation, temperature, pH, and carbonate species. These results indicate that geochemical sorption capacity of bentonite should be evaluated by considering both geological and aquifer environments in the high-level radioactive waste repository.

An elevated temperature is expected at the deep geological repository (DGR) due to the decay heat from spent nuclear fuel and the positive geothermal gradient. The resulting elevated temperature would change the aqueous speciation and surface complexation of uranium, which is the major component in spent nuclear fuel. Since sorption reactions of uranium species on natural minerals determine the extent of uranium retardation, in this work the temperature-dependent adsorption of hexavalent uranium, U(VI), was studied by choosing alumina as the basic component mineral for complex aluminosilicates. Time-resolved laser fluorescence spectroscopy (TRLFS) was used to assess the dissolved and adsorbed U(VI) species on γ-Alumina in the pH range of 6.5–9.0 at temperatures of 25 to 70°C. Initial concentrations of U(VI), carbonate and calcium were 89 μM, 25 mM, and 3.0 mM, respectively. The parallel factor analysis (PARAFAC) was used for chemical speciation by spectrum deconvolution. In addition, a separate solution system with higher U(VI) concentrations (0.1 mM, 1.0 mM) and carbonate concentration of 25 mM was studied with attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy for adsorbed species at 25°C. The electrophoretic mobility measurements were also conducted at 25°C to assess the coordination mechanism of adsorbed species at 25°C. The uranyl hydrolysis species and uranyl tricarbonato species coexist in solution at 25°C. At the same temperature, both species were found to be adsorbed. ATR-FTIR could confirm the adsorption of uranyl tricarbonato species at 25°C, and the electrophoretic mobility measurements suggested that the reaction mechanism is an inner-sphere coordination. However, in comparison with aqueous speciation at 25°C, at elevated temperatures the available pH range of uranyl tricarbonato species was narrow and that for uranyl hydrolysis species was wider. It was evident that two hydrolysis species are adsorbed at elevated temperatures, but no tricarbonato species. The enhanced U(VI) adsorption was observed with temperatures. This could result from the transition of dominance from the concurrent adsorption of uranyl hydrolysis species and uranyl tricarbonato species to two hydrolysis species. It was seen that the trend of enthalpy of adsorption was endothermic. Combining the present results with temperature-dependent adsorption studies on silica and aluminosilicates, a reliable SCM for the subsurface system can be proposed to explain U(VI) migration.

To predict the long-term behaviors of actinides in aqueous environments, complexation behaviors of actinides should be understood. Various organic ligands of chelating aromatic structure appearing in humic substances are known to form stable aqueous complexes. In this study, a benzene diol (or catechol) derivative, i.e., 4-nitrocatechol (nCA) is selected and its chemical equilibria including acid dissociation and complexation with U(VI) ion were examined using spectroscopic methods. In addition, the effect of ionic strength (Is) on those equilibria was evaluated by adjusting the level of NaClO4 in aqueous solutions. First, the experiments to determine the acid dissociation constant (pKa) of nCA were carried out in aqueous solutions with different ionic strengths from 0.01–2.0 M. The acid dissociation constants of nCA (pKa1) were measured to 6.73 ± 0.07, 6.69 ± 0.03, 6.38 ± 0.03, 6.09 ± 0.12, and 6.04 ± 0.07 at Is = 0.01, 0.1, 0.5, 1.0, and 2.0, respectively. These results were confirmed through the UV-Vis absorption spectral data analysis using the HypSpec program. As the pKa1 decreases as the ionic strength increases, except for Is = 2.0, these data were further analyzed with SIT (Specific ion Interaction Theory). Typically, as the solution becomes basic, a red shift is shown in the absorption spectrum. This effect can be understood from the intramolecular charge transfer (ICT) occurring in the deprotonated structures of nCA. At higher pH similar trends were also observed for measurement of pKa2. However, the determination of pKa2 is found not to be straightforward since a dimer formation equilibrium of nCA was observed as the ionic strength increased. This phenomenon will be discussed in detail with other supporting experimental results. Second of all, the complexation between the U(VI) and nCA in aqueous solutions was also examined. It was shown that nCA can easily form complexes with U(VI) ions at a wide range of pH via the deprotonation of their hydroxyl groups. U(VI)-nCA complexation will be further characterized by UV-Vis spectroscopy, IR and NMR by varying the solution ionic strength. The metal-ligand binding stoichiometry will be confirmed, for example, through the Job’s method. Finally, the acid dissociations constant and stability constants that were determined in this study will be used to provide species diagrams of aqueous U(VI)-nCA systems at a wide range of pH considering the effect of solution ionic strengths.

Deep geological repository (DGR) has been considered as a globally accepted strategy to dispose high-level radioactive wastes. During long storage periods of 100,000 years, uranium (U) could be migrated through fractures in deep granite aquifers and interact with indigenous bacteria under anaerobic condition. Anaerobic bacteria can reduce U(VI) and further precipitate in the form of U(IV)-oxide minerals by transferring electrons through c-type cytochrome. In this point of view, a comprehensive understanding of uranium-microorganisms interaction is necessary to guarantee the safety of high-level radioactive waste disposal. Although diverse bacterial communities are present in DGR environment, a number of studies have been focused on some model bacteria, such as Desulfovibrio, Geobacter, and Shewanella spp.. In this study, indigenous bacterial community in deep granitic groundwater at 234–244 m was inoculated to sterile uranium-contaminated granitic groundwater amended with 20 mM of sodium acetate, and then incubated under anaerobic condition for 12 weeks. Bio-reduction of U(VI) to U(IV) by indigenous bacteria in uranium-contaminated groundwater was investigated during whole operation period. Initial U(VI) concentration of 885.4 μg·L−1 gradually decreased to 586.1 μg·L−1, resulting in approximately 33.8% of aqueous U(VI) removal efficiency. Oxidation-reduction potential (ORP) value was gradually decreased from 175.4 mV to –243.0 mV after the incubation of 12 weeks. The decrease in ORP value was attributed to the presence of aerobic bacteria and facultative anaerobic bacteria in indigenous bacterial community. The shift in bacterial community structure was observed by 16S rRNA gene high-throughput sequencing analysis. Proteobacteria (55.6%), Firmicutes (24.1%), Actinobacteria (5.5%), and Bacteroidetes (5.4%) were dominant in initial indigenous bacterial community, while Proteobacteria (94.8%) was found to be the only abundant phylum after the reaction. In addition, great increase in the relative abundance of sulfate-reducing bacteria (SRB) was observed: the relative abundance of SRB increased from 11.4% to 44.3% after the reaction. This result indicates that the SRB played a key role in the removal of aqueous U(VI). This finding shows the potential of aqueous U(VI) removal by indigenous bacteria in DGR environment.

In the geochemical field, the chemical speciation of hexavalent uranium (U(VI)) has been widely investigated by performing measurements to determine its luminescence properties, namely the excitation, emission, and lifetime. Of these properties, the excitation has been relatively overlooked in most time-resolved laser fluorescence spectroscopy (TRLFS) studies. In this study, TRLFS and continuous-wave excitation–emission matrix spectroscopy are adopted to characterize the excitation properties of U(VI) surface species that interact with amorphous silica. The luminescence spectra of U(VI) measured from a silica suspension and silica sediment showed very similar spectral shapes with similar lifetime values. In contrast, the excitation spectra of U(VI) measured from these samples were significantly different. The results show that distinctive excitation maxima appeared at approximately 220 and 280 nm for the silica suspension and silica sediment, respectively.

용존 6가 우라늄은 다양한 화학종으로 존재하며, 화학종의 분포는 수용액의 pH에 의존한다. 산성 및 중성 근처의 pH 환경 에서는 대표적으로 UO2 2+, UO2OH+, (UO2)2(OH)2 2+, (UO2)3(OH)5 + 화학종이 공존한다. 수용액 속에 비결정성 실리카가 콜로이드 성질의 부유입자 상태로 존재할 때 용존 화학종은 실리카 표면에 쉽게 흡착된다. 이 연구에서는 표면 흡착 화학종의 분 포가 용존 화학종의 분포를 따르는지 조사하였다. 시료의 pH 값이 3.5-7.5인 조건에서 3종의 용존 화학종(UO2 2+, UO2OH+, (UO2)3(OH)5 +)과 2종의 표면 흡착 화학종(≡SiO2UO2, ≡SiO2(UO2)OH‐ 또는 ≡SiO2(UO2)3(OH)5 ‐)의 시간 분해 발광(luminescence) 스펙트럼을 측정하였다. pH 변화에 따른 각 화학종의 스펙트럼 변화 양상을 비교한 결과로 표면 흡착 U(VI) 화학종의 분포는 용존 U(VI) 화학종의 분포와 다르다는 것을 확인하였다.

This study is the process of finding answers to the following questions. Cultural content is needed to study Vietnamese language? Do Vietnamese language learners feel the need for classes using cultural content? Do Vietnamese teachers use cultural contents in class? In order to find out the answer, I conducted a questionnaire survey on Vietnamese students in Chungnam Foreign Language High School, interviewed teachers and analyzed the case examples. As a result of the questionnaires and interviews, it was found that the necessity of cultural contents development in Vietnamese language education is a requirement for both teachers and learners. Based on these results, we developed a case study on cultural education contents for Vietnamese language education. However, the model of teaching Vietnamese language utilizing cultural contents needs to be developed through more diverse academic analysis. Its effectiveness should also be investigated in depth. We will propose this as a future research project.

KURT(KAERI Underground Research Tunnel) 지하수에 존재하는 천연 유기물질과 6가 우라늄(U(VI))화학종의 상호작용을 레이저 분광학 기술을 이용하여 조사하였다. 지하수 시료에 266 nm 파장의 레이저 빛을 입사시켜 자외선 및 파란색 파장 영 역에서 방출되는 천연 유기물질의 발광 스펙트럼을 관측하였다. 0.034-0.788 mg·L-1 농도 범위의 우라늄이 함유된 지하수에 서는 녹색 파장 영역에서 방출되는 U(VI) 화학종의 발광 스펙트럼을 측정하였다. 지하수에 함유된 U(VI) 화학종의 발광 특 성(피크 파장 및 발광 수명)이 실험실에서 제조한 표준용액에 함유된 Ca2UO2(CO3)3(aq)의 발광 특성과 매우 유사하다는 것 을 확인하였다. 지하수에 존재하는 U(VI) 화학종의 발광 세기는 표준용액에 함유된 같은 농도의 Ca2UO2(CO3)3(aq)의 발광 세기에 비해 약하다. 표준용액의 Ca2UO2(CO3)3(aq)를 천연 유기물질이 함유된 지하수에 섞었을 때에도 Ca2UO2(CO3)3(aq)의 발광 세기가 감소한다. 이러한 현상의 원인을 지하수의 천연 유기물질과 Ca-U(VI)-탄산염 화학종의 상호작용으로 인해 비 발광성 U(VI) 착물이 형성되기 때문인 것으로 설명하였다.