Complex formation of uranium(IV) with phosphate and arsenate studied by spectroscopic methods

Uranium is one of the main potential contaminants in East Germany's former mining areas. Under reducing conditions uranium(IV) is stable and can be complexed by phosphate and arsenate at low pH. Due to their low water solubility no thermodynamic complex formation constants are available for the uranium(IV)-phosphate and arsenate complexes.. For example, the solubility product /1/ of U(HPO4)2·4H2O limits the uranium(IV) concentration in 1 M perchloric acid to less than 1.2 x 10-4 M. Moreover there is a general lack of information on the aqueous chemistry and thermodynamics of tetravalent actinides.
We studied the formation of these complexes at uranium concentrations between 2 x 10-6 M and 1 x 10-4 M by Laser-Induced Photoacoustic Spectroscopy and UV-vis spectroscopy in acid media. To determine the complex formation constant we measured and analyzed the spectra from 600 nm to 690 nm. The spectra were corrected for the absorption of the solvent water. The solvated uranium(IV) shows a very intensive absorption band with a maximum at 650 nm and a smaller maximum at 672 nm. We found a shoulder at 630 nm deconvoluting the absorption spectrum.
The spectrum changes with increasing phosphate and arsenate concentration. Two isosbestic points were determined at 661 nm and 670 nm in the phosphate system. In the arsenate system three isosbestic point were found to be at 628 nm, 660 nm and 667 nm.
From measurements with variable ionic strength, ligand and proton concentration the complexation reaction according to
U4+ + H3LO4 <=> UH2LO43+ + H+ (L = P, As)
was quantified
The stoichiometry of the formed phosphate and arsenate complexes was confirmed by slope analysis. The formation constant at infinite dilution in the phosphate system was found to be log b0 = 3.52 ± 0.18 using the SIT extrapolation. For the arsenate system we found the complex formation constant to be log b0 = 2.13 ± 0.32.