A New Incorporation Mechanism for Trivalent Actinides into Bioapatite: A TRLFS and EXAFS Study

One of the most toxic byproducts of nuclear power and weapons production is the transuranics, which have a high radiotoxicity and long biological half-life due to their tendency to accumulate in the skeletal system. This accumulation is inhomogeneous and has been associated with the chemical properties and structure of the bone material rather than its location or function. This suggests a chemical driving force to incorporation and requires an atomic scale mechanistic understanding of the incorporation process. Here we propose a new incorporation mechanism for trivalent actinides and lanthanides into synthetic and biologically produced hydroxyapatite. Time-resolved laser fluorescence spectroscopy and extended X-ray absorption fine structure have been used to demonstrate that trivalent actinides and lanthanides incorporate into the amorphous grain boundaries of apatite. This incorporation site can be used to explain patterns in uptake and distribution of radionuclides in the mammalian skeletal system

Structural Investigation of Uranium–Neptunium Mixed Oxides Using XRD, XANES, and ¹⁷O MAS NMR

Uranium–neptunium mixed dioxides are considered as fuels and targets for the transmutation of the minor actinides in fast neutron reactors. Hereafter, a local and atomic scale structural analysis was performed on a series of U_1–<i>x</i>Np_<i>x</i>O₂ (<i>x</i> = 0.01; 0.05; 0.20; 0.50; 0.75; 0.85) synthesized by the sol–gel external gelation method, for which longer range structural analysis indicates that the process yields solid solutions. The oxidation state of IV for uranium and neptunium cations was confirmed using U L_III and Np L_III edge X-ray absorption near edge structure (XANES). The atomic scale structure was probed with ¹⁷O magic angle spinning nuclear magnetic resonance (MAS NMR) for the anion. Structural distortions due to the substitution of U by the smaller Np cation were detected by ¹⁷O MAS NMR

Uranium Redox Transformations after U(VI) Coprecipitation with Magnetite Nanoparticles

Uranium redox states and speciation in magnetite nanoparticles coprecipitated with U­(VI) for uranium loadings varying from 1000 to 10 000 ppm are investigated by X-ray absorption spectroscopy (XAS). It is demonstrated that the U M₄ high energy resolution X-ray absorption near edge structure (HR-XANES) method is capable to clearly characterize U­(IV), U­(V), and U­(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 L₃ XAS and transmission electron microscopy (TEM) reveal that initially sorbed U­(VI) species recrystallize to nonstoichiometric UO_2+<i>x</i> nanoparticles within 147 days when stored under anoxic conditions. These U­(IV) species oxidize again when exposed to air. U M₄ HR-XANES data demonstrate strong contribution of U­(V) at day 10 and that U­(V) remains stable over 142 days under ambient conditions as shown for magnetite nanoparticles containing 1000 ppm U. U L₃ XAS indicates that this U­(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)