1 research outputs found
Uranium Redox Transformations after U(VI) Coprecipitation with Magnetite Nanoparticles
Uranium
redox states and speciation in magnetite nanoparticles
coprecipitated with UĀ(VI) for uranium loadings varying from 1000 to
10āÆ000 ppm are investigated by X-ray absorption spectroscopy
(XAS). It is demonstrated that the U M<sub>4</sub> high energy resolution
X-ray absorption near edge structure (HR-XANES) method is capable
to clearly characterize UĀ(IV), UĀ(V), and UĀ(VI) existing simultaneously
in the same sample. The contributions of the three different uranium
redox states are quantified with the iterative transformation factor
analysis (ITFA) method. U L<sub>3</sub> XAS and transmission electron
microscopy (TEM) reveal that initially sorbed UĀ(VI) species recrystallize
to nonstoichiometric UO<sub>2+<i>x</i></sub> nanoparticles
within 147 days when stored under anoxic conditions. These UĀ(IV) species
oxidize again when exposed to air. U M<sub>4</sub> HR-XANES data demonstrate
strong contribution of UĀ(V) at day 10 and that UĀ(V) remains stable
over 142 days under ambient conditions as shown for magnetite nanoparticles
containing 1000 ppm U. U L<sub>3</sub> XAS indicates that this UĀ(V)
species is protected from oxidation likely incorporated into octahedral
magnetite sites. XAS results are supported by density functional theory
(DFT) calculations. Further characterization of the samples include
powder X-ray diffraction (pXRD), scanning electron microscopy (SEM)
and Fe 2p X-ray photoelectron spectroscopy (XPS)