EDUKEM project - first spectroscopic insights into the U(IV)/U(VI) speciation in concentrated NaCl solution

This work is embedded into the EDUKEM project, a collaboration with GRS Braunschweig and KIT-INE. Its major purpose is the provision of quality assured thermodynamic data for both tetra- and hexavalent uranium. This shall enable a better assessment of speciation and solubility limits in diluted to highly saline solutions as expected near nuclear waste repositories.
Respective experiments are based on parallel developments in electrochemical and spectroscopic tools being complementary to each other. In such a way difficult to access, systems and conditions should be explored to obtain an integral overview about aqueous uranium chemistry. This especially holds for reducing conditions. This will not only promote the characterization of complex system, e.g., encountered in nuclear waste management, but also allow a fingerprinting of unknown substances and mixtures.
We started to investigate the spectroscopic characteristics of 0.01M U(IV) and U(VI) in different background media (ClO4-, Cl-, SO42-, PO43-, CO32-) using UV/vis and fluorometry. The U(VI) was reduced by potentiostatic electrolysis using Ag/AgCl reference electrode. The reduction was monitored by UV/vis spectroscopy. The residual content of U(VI) was less than 1 %. We observed no formation of precipitations under the experimental conditions with exception of the PO43- system. There, we changed the uranium/ligand ratio from 1:100 to 1:5000 to suppress uranium phosphate precipitation. In general, the UV/vis spectra show variations in intensities and peak shifts to higher wavelengths in dependence of complexation strength in following order ClO4– < Cl– < SO42– < PO43– < CO32–.
In contrast to U(VI), which is often quenched by ions in the solution such as chloride, we obtained a luminescence spectrum of U4+ in 0.1 M HCl excited by λexc = 245 nm at a temperature of 1°C. The obtained luminescence spectrum is similar to the luminescence spectra of the free U4+ ion in acidic published by Kirishima et al. [1]. Under the experimental conditions, hydrolysis species as well as a complex formation between U(IV) and chloride should occur. The UV/vis spectra show spectral modifications which could be induced by the hydrolysis species. However, the luminescence spectra do not show spectral modifications.
In case of U(VI), first TRLFS results show the capabilities of fluorescence spectroscopy even in high chloride concentrated solutions to study U(VI) speciation. Despite the high concentration of 3 M chloride, a luminescence spectrum could be recorded in presence of carbonate in the alkaline pH region. Comparing the position of these bands with literature, we suggest a U(VI) complexation by carbonate [2].
The preliminary results of this study and of Bader et al. [3] shown that chloride quench mechanism for U(IV) and U(VI) luminescence is not fully understood yet in literature. Therefore, further studies will be performed on the spectroscopic behavior and chemistry of U(IV) as well as for U(VI) in highly concentrated chloride solutions.

Literature:

1. A. Kirishima et al., “Luminescence properties of tetravalent uranium in aqueous solution” Radiochim. Acta, 92, 705-710 (2004).
2. Z. Wang et al., “Cryogenic laser induced fluorescence characterization of U(VI) in Hanford vadose zone pore waters“, Environ. Sci. Technol., 38, 5591-5597 (2004).
3. M. Bader et al., “Biosorption of uranium on the cells of the halophilic archaea Halobacterium noricense DSM 15987 under highly saline conditions”, Abstract – ABC-Salt IV Workshop 2015 – Heidelberg, Germany.