27 research outputs found

    INFLUENCE OF NATURAL AND SYNTHETIC ORGANIC LIGANDS ON THE STABILITY AND MOBILITY OF REDUCED TC(IV)

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    The primary objectives were (1) to quantify the interactions of organic ligands with Tc(IV) through the generation of thermodynamic (complexation) and kinetic parameters needed to assess and predict the mobility of reduced Tc(IV) at DOE contaminated sites; and (2) to determine the impact of organic ligands on the mobility and fate of reduced Tc(IV) under field geochemical conditions

    Chemical Trends in Solid Alkali Pertechnetates

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    Insight into the solid-state chemistry of pure technetium-99 (99Tc) oxides is required in the development of a robust immobilization and disposal system for nuclear waste stemming from the radiopharmaceutical industry, from the production of nuclear weapons, and from spent nuclear fuel. However, because of its radiotoxicity and the subsequent requirement of special facilities and handling procedures for research, only a few studies have been completed, many of which are over 20 years old. In this study, we report the synthesis of pure alkali pertechnetates (sodium, potassium, rubidium, and cesium) and analysis of these compounds by Raman spectroscopy, X-ray absorption spectroscopy (XANES and EXAFS), solid-state nuclear magnetic resonance (static and magic angle spinning), and neutron diffraction. The structures and spectral signatures of these compounds will aid in refining the understanding of 99Tc incorporation into and release from nuclear waste glasses. NaTcO4 shows aspects of the relatively higher electronegativity of the Na atom, resulting in large distortions of the pertechnetate tetrahedron and deshielding of the 99Tc nucleus relative to the aqueous TcO4 –. At the other extreme, the large Cs and Rb atoms interact only weakly with the pertechnetate, have closer to perfect tetrahedral symmetry at the Tc atom, and have very similar vibrational spectra, even though the crystal structure of CsTcO4 is orthorhombic while that of RbTcO4 is tetragonal. Further trends are observed in the cell volume and quadrupolar coupling constant

    Integrated Computational and Experimental Protocol for Understanding Rh(III) Speciation in Hydrochloric and Nitric Acid Solutions

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    Platinum group metals (PGMs), including rhodium, generated by the fission of <sup>235</sup>U are present in significant quantities within spent nuclear fuel located on power generation sites in the United States, the amount of which is expected to exceed natural reserves by 2030. Yet, spent fuel raffinates are highly acidic media that may result in complex speciation of the PGM. This work provides an understanding of Rh­(III) speciation up to 9 M HCl and HNO<sub>3</sub>, and utilizes a combination of ultraviolet–visible (UV-vis) and capillary zone electrophoresis data, along with computationally predicted thermochemistry and simulated UV-vis spectra to approximate the relative concentrations of potential species in solution as a function of acid concentration. One Rh­(III) species, [Rh­(NO<sub>3</sub>)<sub>3</sub>], is observed under all conditions in HNO<sub>3</sub> and for Rh­(III) concentrations smaller than 10<sup>–3</sup> M. In contrast, a variety of chloridated Rh­(III) species may exist simultaneously in a HCl medium. The species [RhCl<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]<sup>+</sup> and [RhCl<sub>3</sub>(H<sub>2</sub>O)<sub>3</sub>] are observed in HCl solutions of concentrations ranging from 0 to 1 M; the species [RhCl<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub>]<sup>−</sup>, [RhCl<sub>5</sub>(H<sub>2</sub>O)]<sup>2–</sup>, and [Rh<sub>2</sub>Cl<sub>9</sub>]<sup>3–</sup> are observed between 2 and 9 M HCl

    Synthesis and Crystal Structures of Volatile Neptunium(IV) β‑Diketonates

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    Production of certified reference materials in support of domestic nuclear forensics programs require volatile precursors for introduction into electromagnetic isotopic separation instruments. β-Diketone chelates of tetravalent actinides are known for their high volatility, but previously developed synthetic approaches require starting material (NpCl<sub>4</sub>) that is prohibitively difficult and hazardous to prepare. An alternative strategy was developed here that uses controlled potential electrolysis to reduce neptunium to the tetravalent state in submolar concentrations of hydrochloric acid. Four different β-diketone ligands of varying degrees of fluorination were reacted with an aqueous solution of Np<sup>4+</sup>. Products of this reaction were characterized via X-ray diffraction and infrared spectroscopy, and were found to be neutral 8-coordinate complexes that adopt square antiprismatic crystal geometry. Synthesis of Np β-diketonates by this approach circumvents the necessity of using NpCl<sub>4</sub> in tetravalent Np coordination compound synthesis. The volatility of the complexes was assessed using thermogravimetric analysis, where the temperature of sublimation was determined to be in the range of 180° to 205 °C. The extent of fluorination did not appreciably alter the sublimation temperature of the complex. Thermal decomposition of these compounds was not observed during sublimation. High volatility and thermal stability of Np β-diketonates make them ideal candidates for gaseous introduction into isotopic separation instruments

    Association of mutations in FLNA with craniosynostosis

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    Mutations of FLNA, an X-linked gene that encodes the cytoskeletal protein filamin A, cause diverse and distinct phenotypes including periventricular nodular heterotopia and otopalatodigital spectrum disorders (OPDS). Craniofacial abnormalities associated with OPDS include supraorbital hyperostosis, down-slanting palpebral fissures and micrognathia; craniosynostosis was previously described in association with FLNA mutations in two individual case reports. Here we present four further OPDS subjects who have pathological FLNA variants and craniosynostosis, supporting a causal link. Together with the previously reported patients, frontometaphyseal dysplasia was the most common clinical diagnosis (four of six cases overall); five patients had multiple suture synostosis with the sagittal suture being the most frequently involved (also five patients). No genotype–phenotype correlation was evident in the distribution of FLNA mutations. This report highlights the need to consider a filaminopathy in the differential diagnosis of craniosynostosis, especially in the presence of atypical cranial or skeletal features
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