Sorption of U(VI) on muscovite. Comparing SCM modeling with spectroscopic and microscopic results.

The sorption of uranyl(VI) on muscovite was studied with the diffuse double layer model (DDLM). The required values for the surface site density, the surface acidity constants, the specific surface area, and the experimental sorption data were determined in [1].
The modeling favored the formation of two uranyl surface complexes. Both surfave complexes were simultaneously calculated with FITEQL [2]. The first one is a monodentate mononuclear surface complex:

XOH + UO22+ = (XO-UO22+)+ + H+

The second surface complex is a bidentate mononuclear surface complex:

X(OH)2 + UO22+ = (XO22-UO22+)+ + 2 H+

The results of the SCM (surface complexation model) modeling were compared with results obtained from extended x-ray absorption fine structure spectroscopy (EXAFS), high-resolution transmission electron microscopy (HRTEM), and time resolved laser induced fluorescence spectroscopy (TRLFS).
An EXAFS sample representing the sorption of U(VI) on muscovite at pH 5.8 with an initial U concentration of 1H10-4 M indicated that U(VI) is bound to the muscovite surface as an outer-sphere complex, as indicated by the missing Si/Al to U distance.
HRTEM investigations, representing the sorption of uranium on muscovite at pH 6.5 using an initial U concentration of 5H10-4 M, showed sorbed uranium particles on the muscovite surface. The particles were 5 to 10 nm in diameter. Diffraction patterns of these nano-sized particles gave indication for schoepite and metallic uranium.
TRLFS studies conducted with a muscovite suspension at pH 6.5 using an initial uranium concentration of 1×10-5 M revealed the presence of an uranium-muscovite surface species with a fluorescence lifetime of 120 ns ± 10 ns.

References

[1] Arnold, T. et al. (2001) Sorption Behavior of U(VI) on Phyllite: Experiment and Modeling. Journal of Contaminant Hydrology 47, 219-231.

[2] Herbelin, A. and Westall, J. (1996) FITEQL A Computer Program for Determination of Chemical Equilibrium Constants from Exp. Data, Version 3.2. Rep. 96-01, Dep. of Chem., Oregon St. Uni., Corvallis, Oregon.