This study demonstrated a rapid and simple method for the determination of seven anions including halides and oxyhalides from the KURT underground water sample by capillary electrophoresis with UV detection. In nuclear waste disposal, some anions such as iodine, selenium, and technetium have been of great concern due to its high mobility and toxicity with a long half-life. It has been needed for a reliable analysis of anionic speciation because the high mobility of anions is easily affected by environmental conditions especially pH and salinity of underground water. Here this project is to develop a fast separation of seven anions including iodide, iodate, and selenite using capillary electrophoresis. The electroosmotic flow (EOF) was suppressed using a poly (ethyleneglycol) -coated capillary (DB-WAX capillary). As a result, anions migrated depending on their mobility under a reverse polarity condition (-15 kV) and the analysis time was within 15 min. UV detection was used at 200 nm. The RSDs for migration time were between 0.7% and 1.3% except for selenite of 5.1%. The RSDs for peak area were obtained between 2.9% and 7.4%. The calibration curves were linear from 10 to 200 mg/L with correlation coefficients greater than 0.9952. The LODs were 7.3, 10.9, 11.3, 12.9, 13.0, 13.9, and 17.4 mg/L for iodide, nitrate, bromide, selenite, bromate, tungstate and iodate. The KURT underground water sample spiked with seven anions at 50 mg/L were analyzed. The recoveries of spiked KURT sample ranged from 93.4% to 99.3%. The proposed method was successfully applied to determine seven anions in underground water sample.

Radiation from spent nuclear fuel (SNF) is one of key factors affecting the dissolution process of SNF and the source term from repository. The dissolution rate of uranium dioxide (UO2) matrix of SNF is expected to control the release of radionuclides from SNF in contact with water under geological disposal conditions. Based on the oxidative dissolution mechanism, the solubility of UO2 can increase significantly if the reducing environment near the fuel surface is altered by water radiolysis caused by radiation from SNF. Therefore, the analysis of water radiolysis products such as radicals (·OH, ·OH2, eaq, ·H) and molecules (H3O+, H2, H2O2) is perquisite for studies on the rate of such dissolution process to determine oxidation/dissolution mechanism and related rate constants. In this study we examined the two-known spectroscopic methods developed for H2O2 determination; one is the luminol-based chemiluminescence (luminol-CL) method and the other is the spectrophotometry using ferrous oxidation-xylenol orange complexation (FOX). Their applicability for quantitative analysis of H2O2 in potential aqueous samples from SNF dissolution studies was evaluated in terms of the analytical dynamic range (ADR), the limit of detection (LOD) and the interfering effects of various metal ions possibly present in real samples. The luminol-CL method exploits the chemiluminescence reaction caused by luminol; when in the presence of a metallic catalyst (e.g., Cu2+, Co2+), luminol emits a blue light (425 nm) at pH 10- 11 in response to oxidizing agents such as hydrogen peroxide. Although a flow-through reaction system is routinely employed to enhance the analytical sensitivity we achieved the ADR up to ~200 μM and LOD < 1 μM by a batch-wise CL detection using conventional cuvette cells and an intensified charge-coupled device (ICCD). Interestingly, it turned out that the interfering effects of other metal ions (e.g., UO2 2+, U4+, Fe2+ and Fe3+) is minimal, which should be advantageous for the luminol-CL method to be employed for samples potentially containing other metal ions. On the other hand, the FOX method spectrophotometrically analyzes H2O2 based on the difference in color (or absorption spectra) of Fe-xylenol orange (XO) complexes. Initially, the Fe2+-XO complex was provided in working solutions at pH 3, which was subsequently mixed with samples having H2O2 and allowed for quantitative oxidation of Fe2+ to Fe3+. Typically, by monitoring the absorbance of Fe3+-XO complex at 560-580 nm (λmax) the ADR up to ~100 μM and LOD ~1.6 μM were achieved. However, it is found that interfering effects from M3+ and M4+ ions are significant; these interfering metal ions can form XO complexes so as to directly contribute the measured absorbance. In contrast, the influence from M2+ ions was found to be negligible. To summarize we conclude that both methods can be applied for H2O2 determination for aqueous samples taken from SNF dissolution tests. However, prior to applying the FOX method the metal ion composition in those samples should be thoroughly identified not to overestimate the H2O2 concentration of samples. More details of underlying chemical reactions in both methods will be discussed in the presentation.

The disposal of spent nuclear fuel (SNF) in a deep geological repository (DGR) is a widely accepted strategy for the long-term sequestration of radiotoxic SNF. Ensuring the safety of a DGR requires the prediction of various reactions and migration behaviors of radionuclides (RNs) present in SNF within its geochemical surroundings. Understanding the dissolution behaviors of mineral phases harboring these RNs is crucial, as the levels of RNs in groundwater are basically linked to the solubility of these solid phases. Accurate measurements of solubility demand the use of welldefined solid materials characterized by chemical compositions and structures. Herein, we attempted the synthesis of sklodowskite, a magnesium-uranyl (U(VI))-silicate, employing a twostep hydrothermal synthetic approach documented previously. Subsequently, we subjected this synthesized sklodowskite to various analytical techniques, including powder X-ray diffraction (pXRD), scanning electron microscopy/energy dispersive X-ray spectrometry (SEM/EDX), and vibrational spectroscopies (FTIR and Raman). Based on our findings, we confidently identify the obtained mineral phase as sklodowskite (Mg[UO2SiO3OH]2·5H2O). This identification is primarily based on the similarity between its pXRD pattern and the reference XRD pattern of sklodowskite. Furthermore, the measured infrared and Raman spectra show the vibrational modes of UO2 2+ and SiO4 4- ions, particularly within the 700~1,100 cm-1 region, which support that the synthetic mineral has a characteristic layered uranyl-silicate structure of crystalline sklodowskite. Finally, we utilized synthetic minerals to estimate its solubility up to about three months in a model groundwater, where the dissolved species composition is analogous to that of granitic groundwater from the KAERI Underground Research Tunnel. In this presentation, we will present in detail the results of spectroscopic characterizations and the methodology employed to assess the solubility of the U(VI)-silicate solid phase.

Solubility and species distributions of radionuclides in domestic groundwater conditions are required for the safety assessment of deep underground disposal system of spent nuclear fuel (SNF). Minor actinides including Am contribute significant extents to the long-term radiotoxicity of SNF. In this study, the solubility of Am was evaluated in synthetic groundwater (Syn-DB3), which were simulated for the groundwater of the DB3 site in the KAERI Underground Research Tunnel (KURT). Geochemical modeling was performed based on the ThermoChimie_11a (2022) thermochemical database from Andra to estimate the solubility and species distributions of Am in the Syn-DB3 condition. Dissolved Am concentrations in the Syn-DB3 were experimentally measured under oversaturation conditions. Am(III) stock solution in perchlorate media was sequentially diluted in Syn-DB3 to prepare 8 μM Am(III) in Syn-DB3. The pH of the solutions was adjusted to be in the range of 6.4–10.5. A portion of the samples was transferred to quartz cells for UV-Vis absorption and time-resolved laser fluorescence spectroscopy studies and the rest were stored in centrifuge tubes. The absorption spectra of the samples were monitored over 70 days and the results suggest that Am colloidal particles were formed initially in all the samples and precipitated rapidly within two days. Over the experimental period of 236 days, small volume (10 μL) of the samples in the centrifuge tubes were periodically withdrawn after centrifugation (18000 rpm, 1 hr) for the liquid scintillation counting to measure the concentrations of Am dissolved in Syn-DB3. In the end of the experiments, pH of the samples was checked again and the final dissolved Am concentrations were determined after ultrafiltration (10 kDa) to exclude the contribution of colloidal particles. In the pH range of 8-9, which is relevant to the KURT-DB3 groundwater condition, the measured dissolved Am(III) concentrations were converged to around 10-8 M. These values are higher than the solubility of AmCO3OH:0.5H2O(s), but lower than that of AmCO3OH(am). There was no indication of transformation of the amorphous phase to the crystalline phase in our observation time window.

Dissolution behaviors of ThO2(cr) and PuO2(cr) in synthetic groundwater were investigated at room temperature (23  2°C) under atmospheric conditions. The synthetic groundwater was prepared according to the chemical composition of the KURT-DB3 groundwater. The pH and Eh of the synthetic groundwater were pH 8.9 and 0.5 V, respectively, and the major components were Na, K, Ca, Mg, Si, Cl, SO4, F and HCO3 ions. A few mg of ThO2(cr) and PuO2(cr) powder were added in the synthetic groundwater and the concentrations of Th and Pu in supernatant were monitored for 5 months of reaction time. The concentrations of Th before and after ultracentrifugation were compared, while the solid-liquid phase separation of Pu samples could not be applied due to the small volume of sample solutions. The concentrations of Th and Pu were measured by ICP-MS and alpha spectrometry, respectively. Geochemist’s Work Bench (GWB, standard, 17.0) was applied for the modeling with ThermoChimie TDB v. 11a, which was updated with the latest NEA-TDB (vol. 14). Aqueous species distributions and solubility limiting solid phases of Th and Pu under the synthetic groundwater conditions were evaluated. The results of geochemical modeling indicate that aqueous Th-OH-CO3 ternary species and Pu(IV) species are dominant in solutions equilibrated with ThO2(s) and PuO2(am, hyd), respectively. The dissolution behaviors of ThO2(cr) and PuO2(cr) are comparable to the dissolution of ThO2(aged, logKsp = 8.5) and the oxidative dissolution of PuO2(am, hyd) in the presence of PuO2(coll, hyd), respectively.

Nuclear spent fuel (SNF) disposal in deep geological repositories is considered as one of sound options for the long-term and safe sequestration of radiotoxic SNF and the sustainable use of nuclear energy. The chemical behaviors of various radionuclides originated from SNF should be well understood to evaluate the migrational behaviors of radionuclides and their reactions and interactions with various geochemical components. Formation of secondary minerals, colloids, other insoluble precipitates is of interest since the concentrations of radionuclides in groundwaters can be limited by the solubility of those solid phases. Particularly when evaluating their solubility, the use of well-defined solid materials in terms of chemical composition and molecular structure is crucial to obtain reliable measurement results. In this study, a synthetic calcium uranyl silicate (Ca-U(VI)-silicate, or uranophane) was prepared and characterized by using various analytical methods including powder X-ray diffraction (pXRD), scanning electron microscopy/energy dispersive X-ray spectrometry (SEM/EDX), and vibrational (FTIR and Raman) spectroscopies. Uranyl silicate minerals are significant to the disposal of nuclear wastes. Our simulation demonstrates that uranophane (Ca[UO2SiO3OH]2·5H2O), one having a U:Si ratio of 1:1, can be a mineral species limiting U(VI) solubility under groundwater conditions in Korea. For the preparation of Ca-U(VI)-silicate, we applied a two-step hydrothermal synthetic procedure reported in literature with modification. Briefly, we conclude that the obtained mineral phase is the ‘α-uranophane’; our characterization results show that the structural and spectroscopic properties of the synthetic Ca-U(VI)-silicate agree well with those of α-uranophane. For instance, the pXRD patterns obtained from the solid show nearly identical diffraction peak positions with those from the reference XRD pattern. From IR and Raman spectroscopy it is noticed that the stretching modes of UO2 2+ and SiO4 4- ions result in strong absorption bands in a region of 700 ~ 1,100 cm-1. Elemental compositions of the synthetic solids were also estimated by using EDX analysis, which results in a Ca:U:Si ratio close to 1:2:2 on average. However, we found that it is difficult to obtain good crystallinity of uranophane, which can be observable by using SEM and its image analysis. We believe that this work serves as a model study to provide synthetic routes of radionuclide-related mineral phases and applicable solid phase characterization methods. In the presentation, the potential use of the U(VI)-silicate solid phase for the upcoming groundwater solubility measurements will be discussed. Keywords: Hexavalent Uranium, Silicate

Elucidating the redox behavior of actinide elements in aqueous solution is important for the safety assessments of nuclear waste disposal. Despite ongoing endeavors for decades, some points of uranium and plutonium redox mechanism are ambiguous and unclear. In this study, the electrochemical redox behaviors of U(VI) and Pu(III and VI) ions in perchloric acid media were investigated by using a gold (Au) working electrode via cyclic voltammetry (CV) and cyclic square wave voltammetry (CSWV) with the temperature control (10–55°C). The cyclic voltammograms of U(V/VI), Pu(III/IV) and Pu(V/VI) redox couple were transformed to semi-integral form to calculate the diffusion coefficient and formal potential in the electrochemical quasi-reversibility prevailed system. The CSWV was additionally used for a more precise interpretation of the redox mechanism. From the investigation of the redox chemistry of U(VI) ions, a clear U(V/VI) redox peak and one unidentified oxidation peak appear around pH 2. With the temperature control and CSWV, the relevance of the oxidation peak and U(IV) was confirmed. In the case of voltammetry of Pu(VI) solution, Pu(V/VI) redox peak and an additional reduction peak appear. The redox behavior resposible for this additional reduction peak are also examined. The cyclic voltammograms of Pu(III) solution show a clear reversible redox reaction of Pu(III/IV) couple. With the temperature control, using the change of formal potential at ionic strength 1 M (ClO4 −), thermodynamic parameters of conditional molar enthalpy and entropy change were evaluated in this system.

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.

Complexation of actinides and lanthanides with carboxylic organic ligands is known to facilitate migration of radionuclides from deep geological disposal systems of spent nuclear fuel. In order to examine the ligand-dependent structures of trivalent actinides and lanthanides, a series of Eu(III)-aliphatic dicarboxylate compounds, Eu2(oxalate)3(H2O)6, Eu2(malonate)3(H2O)6, and Eu2(succinate)3(H2O)2, were synthesized and characterized by using X-ray crystallography and time-resolved laser fluorescence spectroscopy. Powder X-ray diffraction results captured the transition of the coordination modes of aliphatic dicarboxylate ligands from side-on to end-on binding as the carbon chain length increases. This transition is illustrated in malonate bindings involving a combination of side-on and end-on modes. Strongly enhanced luminescence of these solid compounds, especially on the hypersensitive peak, indicates a low site symmetry of these solid compounds. Luminescence lifetimes of the compounds were measured to be increased, which is ascribed to the displacement of water molecules in the innersphere of Eu center upon bindings of the organic ligands. The numbers of remaining bound water molecules estimated from the increased luminescence lifetimes were in good agreement with crystal structures. The excitation-emission matrix spectra of these crystalline polymers suggest that oxalate ligands promote the sensitized luminescence of Eu(III), especially in the UV region. In the case of malonate and succinate ligands, charge transfer occurs in the opposite direction from Eu(III) to the ligands under UV excitation, resulting in weaker luminescence.

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.