Speciation Studies of Metals in Trace Concentrations: The Mononuclear Uranyl(VI) Hydroxo Complexes


Speciation Studies of Metals in Trace Concentrations: The Mononuclear Uranyl(VI) Hydroxo Complexes

Drobot, B.; Bauer, A.; Steudtner, R.; Tsushima, S.; Bok, F.; Patzschke, M.; Raff, J.; Brendler, V.

A direct luminescence spectroscopic experimental setup for the determination of complex stability constants of mononuclear uranyl(VI) hydrolysis species is presented. The occurrence of polynuclear species is prevented using a low uranyl(VI) concentration of 10-8M (2.4 ppb). Time-resolved laser-induced fluorescence spectra were recorded in a pH range from 3 to 10.5. Deconvolution with parallel factor analysis (PARAFAC) resulted in three hydrolysis complexes. A tentative assignment was based on thermodynamic calculations: UO2+2 - 1:0 (aquo ion), UO2(OH)+ - 1:1, UO2(OH)2 - 1:2, UO2(OH)-3 - 1:3. An implementation of a Newton-Raphson algorithm into PARAFAC allowed a direct extraction of complex stability constants during deconvolution yielding log(ß1 M, 1 °C)1:1 =-4.4, log(ß1 M, 1 °C)1:2 =-11.7, log(ß1 M, 1 °C)1:3 =-21.6. Extrapolation to standard conditions gave: log(ß0)1:1 =-3.7, log(ß0)1:2 =-10.4 and log(ß0)1:3 =-20.1. Luminescence characteristics (band position, lifetime) of the individual mononuclear hydroxo species were derived to serve as reference data set for further investigations. A correlation of luminescence spectroscopic features with Raman frequencies was demonstrated for the mononuclear uranyl(VI) hydroxo complexes for the first time. Thereby a signal-to-structure correlation was achieved and the complex assignment validated.

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Publ.-Id: 22521