• 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.