Fate of Lu(III) sorbed on 2-line ferrihydrite at pH 5.7 and aged for 12 years at room temperature. II: insights from STEM-EDXS and DFT calculations

Abstract

Transformation products of two-line ferrihydrite associated with Lu(III) were studied after 12 years of aging using aberration-corrected high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM), high-efficiency energy-dispersive X-ray spectroscopy (EDXS), and density functional theory (DFT). The transformation products consisted of hematite nanoparticles with overgrown goethite needles. High-efficiency STEM-EDXS revealed that Lu is only associated with goethite needles, and atomic-resolution HAADF-STEM reveals structural incorporation of Lu within goethite, partially replacing structural Fe sites. This finding corroborates those recently obtained by AsFlFFF and EXAFS spectroscopy on the same sample (Finck et al. 2018). DFT calculations indicate that Lu incorporation within goethite or hematite are almost equally likely, suggesting that experimental parameters such as temperature and reaction time which affect reaction kinetics, play important roles in determining the Lu uptake. It seems likely that these results may be transferable to predict the behavior of chemically homologous trivalent actinides.