Observation of aqueous Cm(III)/Eu(III) and UO 22+ nanoparticulates at concentrations approaching solubility limit by laser-induced fluorescence spectroscopy

Abstract

Eu(III), Cm(III) and the uranyl ion display intense fluorescence spectra in the visible range and the spectroscopic characteristics are dependent on the composition and structure of the individual metal complexes. In this work, we demonstrate the application of laser-induced time-resolved fluorescence spectroscopy in identification of nanoparticles of (i) Eu(III) and Cm(III) in basic solutions (pH > 10) in the presence of organic chelates including EDTA, HEDTA, NTA and oxalate and (ii) sodium uranyl phosphate after equilibration with synthetic sodium uranyl phosphate suspensions. Fluorescence spectral and SEM results indicate that Eu(III) and Cm(III) can exist as colloidal nanoparticles in filtered 0.1 M NaOH solutions. Such nanoparticles, which display largely red-shifted fluorescence spectra as compared with the aqueous complexes and unusually short fluorescence lifetimes, contribute to the measured concentrations of Eu(III)/Cm(III) in the aqueous solutions. Similarly, uranyl spectroscopic signatures indicate that the determination of the solubility of uranium phosphate minerals is prone to the presence of uranyl phosphate nanoparticles. Due to the presence of such nanoparticles, the common solubility measurements may only indicate an upper limit of the “true” solubility.