• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.7 no.3
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• pp.133-141
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• 2009

Study on the chemical speciation of uranium(VI) species, ${UO_2}^{2+}$, $UO_2(OH)^+$, ${(UO_2)}_2{(OH)_2}^{2+}$, ${(UO_2)}_3{(OH)_5}^+$, has been peformed by using time-resolved laser-induced fluorescence spectroscopy. Speciation sensitivity which depends on the excitation wavelength was investigated. We obtained the speciation sensitivity in the order of $10^{-9}$ M concentration of U(VI) compounds at the excitation wavelength of 266 nm. The fluorescence spectrum and lifetime of ${UO_2}^{2+}$ were carefully measured at pH 1 and ion strength of 0.1 M. The spectrum showed the four characteristic peaks located around 488, 509, 533, 559nm and the fluorescence lifetime of $1.92{\pm}0.17{\mu}s$. The wavelength shifts of fluorescence peaks and the change of lifetimes for uranium hydrolysis compounds were compared with those of ${UO_2}^{2+}$. We report on the characteristic features, the shifts of peaks to the longer wavelength direction and the prolonged lifetimes, in the fluorescence of the U(VI) hydrolysis compounds.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.16 no.4
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• pp.397-410
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• 2018

When considering the long-term safety assessment of spent-nuclear fuel management, americium is one of the most radio-toxic actinides. Although spectroscopic methods are widely used for the study of actinide chemistry, application of those methods to americium chemistry has been limited. Herein, we purified $^{241}Am$ to obtain a highly pure stock solution required for spectroscopic studies. Quantitative and qualitative analyses of purified $^{241}Am$ were carried out using liquid scintillation counting, and gamma and alpha radiation spectrometry. Highly sensitive absorption spectrometry coupled with a liquid waveguide capillary cell and time-resolved laser fluorescence spectroscopy were employed for the study of Am(III) hydrolysis and oxalate (Ox) complexation. $Am^{3+}$ ions under acidic conditions exhibit maximum absorbance at 503 nm, with a molar absorption coefficient of $424{\pm}8cm^{-1}{\cdot}M^{-1}$. $Am(OH)_3(s)$ colloidal particles formed under near neutral pH conditions were identified by monitoring the absorbance at around 506-507 nm. The formation of ${Am(Ox)_3}^{3-}$ was detected by red-shifts of the absorption and luminescence spectra of 4 and 5 nm, respectively. In addition, considerable enhancements of the luminescence intensities were observed. The luminescence lifetime of ${Am(Ox)_3}^{3-}$ increased from 23 to 56 ns, which indicates that approximately six water molecules are replaced by carboxylate ligands in the inner-sphere of the Am(III). These results suggest that ${Am(Ox)_3}^{3-}$ is formed through the bidentate coordination of the oxalate ligands.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.9 no.4
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• pp.207-217
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• 2011

In this study the complex formation reactions between uranium(VI) and 2,6-dihydroxybenzoate (DHB) as a model ligand of humic acid were investigated by using UV-Vis spectrophotometry and time-resolved laser-induced fluorescence spectroscopy (TRLFS). The analysis of the spectrophotometric data, i.e., absorbance changes at the characteristic charge-transfer bands of the U(VI)-DHB complex, indicates that both 1:1 and 1:2 (U(VI):DHB) complexes occur as a result of dual equilibria and their distribution varies in a pH-dependent manner. The stepwise stability constants determined (log $K_1$ and log $K_2$) are $12.4{\pm}0.1$ and $11.4{\pm}0.1$. Further, the TRLFS study shows that DHB plays a role as a fluorescence quencher of U(VI) species. The presence of both a dynamic and static quenching process was identified for all U(VI) species examined, i.e., ${UO_2}^{2+}$, $(UO_2)_2{(OH)_2}^{2+}$, and $(UO_2)_3{(OH)_5}^+$. The fluorescence intensity and lifetimes of each species were measured from the time-resolved spectra at various ligand concentrations, and then analyzed based on Stern-Volmer equations. The static quenching constants (log $K_s$) obtained are $4.2{\pm}0.1$, $4.3{\pm}0.1$, and $4.34{\pm}0.08$ for ${UO_2}^{2+}$, $(UO_2)_2{(OH)_2}^{2+}$, and $(UO_2)_3{(OH)_5}^+$, respectively. The results of Stern-Volmer analysis suggest that both mono- and bi-dentate U(VI)-DHB complexes serve as groundstate complexes inducing static quenching.