Complexation of Cm(III)/Eu(III) with silicates in basic solutions

Abstract

Summary The complexation of Cm(III) and Eu(III) with dissolved silica was studied by solubility measurement and time resolved laser fluorescence spectroscopy (TRLFS) in basic solutions over a range of total silica concentrations and ionic strengths (NaNO3). In initial experiments on the solubility of Eu(OH)3 in silicate containing solutions we observed a rapid increase in the soluble Eu(III) concentration under basic conditions. The Eu(III)/Cm(III) silicate complexes that formed caused a significant increase of the hypersensitive 5 D 0 → 2 F 2 band around 615 nm relative to the non-hypersensitive 5 D 0 → 7 F 1 band at 592 nm for Eu(III). Further studies of Eu(III) and Cm(III) containing solutions showed a shift of the fluorescence spectral maximum from 594 nm to up to 607 nm for Cm(III) along with a significant increase of fluorescence intensities. The fluorescence lifetimes for Eu(III) species increased from 115 μs to 1.8 ms in 3.0 M and 5.0 M NaNO3, corresponding to full coordination, and from 68 μs to 202 μs for Cm(III) in 0.1 M NaNO3, consistent with the removal of 6–7 water molecules upon silicate complexation. The variations of the fluorescence intensity and the concentrations of the monomeric and polymeric silicates suggested that in basic silicate solutions, Eu(III)/Cm(III) mainly complexes with polysilicates.