The initial radionuclide migration quantity depends on the total amount of solubilized species. Geochemical modeling based on a thermodynamic database (TDB) has been employed to assess the solubility of radionuclides. It is necessary to evaluate whether the TDB describes the domestic repository conditions appropriately. An effective way to validate the TDB-based modeling results is through direct comparisons with experimentally measured values under the conditions of interest. Here, the solubilities of trivalent Sm, Eu, and Am were measured in synthetic KURT-DB3 groundwater (Syn- DB3) and compared with modeling results based on ThermoChimie TDB. Ln2(CO3)3·xH2O(cr) (Ln = Sm, Eu) solids were introduced into the Syn-DB3 and dissolved Sm and Eu concentrations were monitored over 223 days. X-ray diffraction analysis confirmed that the crystallinity of the solid compounds was maintained throughout the experiments. The dissolved Sm and Eu concentrations at equilibrium were close to the predicted solubilities of Sm2(CO3)3(s) and Eu2(CO3)3(s) based on the ThermoChimie TDB. The Am solubility measured under oversaturated conditions was comparable to the measured Eu concentrations, although they were measured under different experimental settings. More experimental data are needed for Am-carbonate solid systems with careful characterization of the solid phases to better evaluate Am solubility in domestic groundwater conditions.

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.

Mobility of radionuclides (RNs) in natural water systems can be increased by complex formation with organic materials. In alkaline cement pore-water conditions, cellulose materials in radwastes such as woods and papers are degraded fast to small organic materials. As a major cellulose degradation product, isosaccharinate (ISA) has been paid attention recently due to its effect on facilitating RNs migration. ISA contains a carboxyl and four hydroxyl functional groups, which cooperatively interact to form chelating bonds with positively charged radionuclides. In our previous study, we determined thermodynamic formation constants, reaction enthalpy and entropy of trivalent americium complexes with ISA, Am(ISA)n (3-n)+ (n=1, 2), in weak acidic condition by conducting temperature-dependent UVVis absorption spectroscopy. Based on those thermodynamic constants along with the experimental results from time-resolved laser induced fluorescence spectroscopy and DFT calculations, we suggested two different chelating-modes of ISA on Am(III). It is more relevant to study Am(III)-ISA complexation under alkaline conditions around pH 12.5, which correspond to the pore-water condition of calciumsilicate- hydrate. Under the alkaline conditions, deprotonated hydroxyl groups of ISA can form more strong interactions with Am. Aquatic hydroxide group can also act as a ligand to form ternary Am(III) -ISA-OH complexes. In this study, absorption spectra of Am-ISA systems were monitored with two variations: first, pH variation (5.5–13) in the presence of constant 30 mM ISA, and second, ISA concentration variation (20 μM – 30 mM) at constant pH of 12.5. As increasing the pH at constant 30 mM ISA, absorption spectra of Am(ISA)2 + were red-shifted from 506.3 to 509.5 nm. The samples showed stable absorption spectra over 30 days. On the other hand, samples with lower ISA concentrations below 10 mM at pH 12.5, showed gradual decrease in the absorbance as sample aging time. By examining filtrates after ultrafiltration (1 kDa), we confirmed that aqueous Am(III)-ISA complexes were formed in the presence of 30 mM ISA at pH 12.5, while colloidal particles and precipitations were formed in the conditions of ISA concentrations lower than 10 mM. In this presentation, we will discuss about probable ternary complex forms of Am(III)-ISA-OH, colloidal forms, and solubility of Am(III) as a function of ISA concentration under alkaline conditions. Absorption and luminescence spectroscopic properties of the Am(III)-ISA-OH ternary system will also be presented.

The solubility and species distribution of radionuclides in groundwater are essential data for the safety assessment of deep underground spent nuclear fuel (SNF) disposal systems. Americium is a major radionuclide responsible for the long-term radiotoxicity of SNF. In this study, the solubility of americium compounds was evaluated in synthetic groundwater (Syn- DB3), simulating groundwater from the DB3 site of the KAERI Underground Research Tunnel. Geochemical modeling was performed using the ThermoChimie_11a thermochemical database. Concentration of dissolved Am(III) in Syn-DB3 in the pH range of 6.4–10.5 was experimentally measured under over-saturation conditions by liquid scintillation counting over 70 d. The absorption spectra recorded for the same period suggest that Am(III) colloidal particles formed initially followed by rapid precipitation within 2 d. In the pH range of 7.5–10.5, the concentration of dissolved Am(III) converged to approximately 2×10−7 M over 70 d, which is comparable to that of the amorphous AmCO3OH(am) according to the modeling results. As the samples were aged for 70 d, a slow equilibrium process occurred between the solid and solution phases. There was no indication of transformation of the amorphous phase into the crystalline phase during the observation period.

Carbonates are inorganic ligands that are abundant in natural groundwater. They strongly influence radionuclide mobility by forming strong complexes, thereby increasing solubility and reducing soil absorption rates. We characterized the spectroscopic properties of Am(III)-carbonate species using UV-Vis absorption and time-resolved laser-induced fluorescence spectroscopy. The deconvoluted absorption spectra of aqueous Am(CO3)2 − and Am(CO3)3 3− species were identified at redshifted positions with lower molar absorption coefficients compared to the absorption spectrum of aqua Am3+. The luminescence spectrum of Am(CO3)3 3− was red-shifted from 688 nm for Am3+ to 695 nm with enhanced intensity and an extended lifetime. Colloidal Am(III)-carbonate compounds exhibited absorption at approximately 506 nm but had non-luminescent properties. Slow formation of colloidal particles was monitored based on the absorption spectral changes over the sample aging time. The experimental results showed that the solubility of Am(III) in carbonate solutions was higher than the predicted values from the thermodynamic constants in OECD-NEA reviews. These results emphasize the importance of kinetic parameters as well as thermodynamic constants to predict radionuclide migration. The identified spectroscopic properties of Am(III)-carbonate species enable monitoring time-dependent species evolution in addition to determining the thermodynamics of Am(III) in carbonate systems.

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.

아메리슘(Am)은 사용후핵연료의 장기 방사성 독성에 크게 영향을 주기 때문에 고준위 방사성 폐기물 처분의 장기 안전성 평가에 필수적으로 고려되어야 할 원소이다. 분광학적 방법을 이용한 일부 악티나이드 원소의 화학반응 연구가 활발히 진행되고 있는 반면, 아메리슘에 대한 연구는 아직까지 미비한 상황이다. 이 연구에서는 고순도의 시료를 필요로 하는 화학반응 연구를 위하여 241Am 시료를 정제한 후, 액체섬광계수기와 감마선 및 알파선 스펙트럼을 이용하여 정량과 정성분석을 하였다. 액체 광도파 모세관 셀을 이용한 고감도의 UV-Vis 흡수 분광학과 시간분해 레이저 형광 분광학을 이용하여 Am(Ⅲ) 가수분해물과 옥살레이트(oxalate, Ox) 착물반응을 조사하였다. 산성조건에서 Am3+은 503 nm에서 최대 흡수봉우리를 보이며, 몰흡광계수는 424 ± 8 cm-1·M-1임을 확인하였다. 중성 이상의 pH 조건에서 형성되는 Am(OH)3(s) 콜로이드 입자에서는 506-507 nm 파장에서 최대 흡수봉우리가 관측되었다. Am(Ox)3 3- 착물은 Am3+에 비교하여 흡수 및 발광스펙트럼이 각 각 4와 5 nm정도 장파장으로 이동하였고 몰흡광계수와 발광세기도 크게 증가하였다. Am(Ox)3 3-의 발광수명은 23에서 56 ns으로 증가하였고 이는 Am(Ⅲ)의 내부권에 결합하고 있던 약 여섯 개의 물분자가 옥살레이트의 카르복실기로 치환되었음을 의미한다. 이 결과로부터 Am(Ox)3 3-은 각 옥살레이트 리간드가 두 자리 결합(bidentate)을 하고 있다는 것을 제안하였다.