Chemical state mapping of simulant Chernobyl lava-like fuel containing material using micro-focused synchrotron X-ray spectroscopy.

Uranium speciation and redox behaviour is of critical importance in the nuclear fuel cycle. X-ray absorption near-edge spectroscopy (XANES) is commonly used to probe the oxidation state and speciation of uranium, and other elements, at the macroscopic and microscopic scale, within nuclear materials. Two-dimensional (2D) speciation maps, derived from microfocus X-ray fluorescence and XANES data, provide essential information on the spatial variation and gradients of the oxidation state of redox active elements such as uranium. In the present work, we elaborate and evaluate approaches to the construction of 2D speciation maps, in an effort to maximize sensitivity to the U oxidation state at the U L3-edge, applied to a suite of synthetic Chernobyl lava specimens. Our analysis shows that calibration of speciation maps can be improved by determination of the normalized X-ray absorption at excitation energies selected to maximize oxidation state contrast. The maps are calibrated to the normalized absorption of U L3 XANES spectra of relevant reference compounds, modelled using a combination of arctangent and pseudo-Voigt functions (to represent the photoelectric absorption and multiple-scattering contributions). We validate this approach by microfocus X-ray diffraction and XANES analysis of points of interest, which afford average U oxidation states in excellent agreement with those estimated from the chemical state maps. This simple and easy-to-implement approach is general and transferrable, and will assist in the future analysis of real lava-like fuel-containing materials to understand their environmental degradation, which is a source of radioactive dust production within the Chernobyl shelter.

Redundant roles of four ZIP family members in zinc homeostasis and seed development in Arabidopsis thaliana.

Zinc (Zn) is essential for normal plant growth and development. The Zn-regulated transporter, iron-regulated transporter (IRT)-like protein (ZIP) family members are involved in Zn transport and cellular Zn homeostasis throughout the domains of life. In this study, we have characterized four ZIP transporters from Arabidopsis thaliana (IRT3, ZIP4, ZIP6, and ZIP9) to better understand their functional roles. The four ZIP proteins can restore the growth defect of a yeast Zn uptake mutant and are upregulated under Zn deficiency. Single and double mutants show no phenotypes under Zn-sufficient or Zn-limited growth conditions. In contrast, triple and quadruple mutants show impaired growth irrespective of external Zn supply due to reduced Zn translocation from root to shoot. All four ZIP genes are highly expressed during seed development, and siliques from all single and higher-order mutants exhibited an increased number of abnormal seeds and decreased Zn levels in mature seeds relative to wild type. The seed phenotypes could be reversed by supplementing the soil with Zn. Our data demonstrate that IRT3, ZIP4, ZIP6, and ZIP9 function redundantly in maintaining Zn homeostasis and seed development in A. thaliana.

Stability of solid-phase selenium species in fly ash after prolonged submersion in a natural river system.

Selenium (Se) chemistry can be very complex in the natural environment, exhibiting different valence states (-2, 0, +4, +6) representing multiple inorganic, methylated, or complexed forms. Since redox associated shifts among most of known Se species can occur at environmentally relevant conditions, it is important to identify these species in order to assess their potential toxicity to organisms. In June of 2009, researchers from the US Army Engineer Research & Development Center (ERDC) conducted investigations of the fly ash spilled 6 months previously into the Emory River at the TVA Kingston Fossil Plant, TN. Ash samples were collected on site from both the original ash pile (that did not move during the levee failure), from the spill zone (including the Emory River), and from the ash recovery ditch (ARD) containing ash removed during dredging cleanup operations. The purpose of this work was to determine the state of Se in the spilled fly ash and to assess its potential for transformation and resultant chemical stability from its prolonged submersion in the river and subsequent dredging. Sequential chemical extractions suggested that the river environment shifted Se distribution toward organic/sulfide species. Speciation studies by bulk XANES analysis on fly ash samples showed that a substantial portion of the Se in the original ash pile had transformed from inorganic selenite to a mixture of Se sulfide and reduced (organo)selenium (Se(-II)) species over the 6-month period. µ-XRF mapping data showed that significant trends in the co-location of Se domains with sulfur and ash heavy metals. Ten-d extended elutriate tests (EETs) that were bubbled continuously with atmospheric air to simulate worst-case oxidizing conditions during dredging showed no discernible change in the speciation of fly ash selenium. The enhanced stability of the organo- and sulfide-selenium species coincided with the mixture of the ash material with humic materials in the river, corresponding with notable shifts in the ash carbon- and nitrogen-functionality.

Combined application of QEM-SEM and hard X-ray microscopy to determine mineralogical associations and chemical speciation of trace metals.

We describe the application of quantitative evaluation of mineralogy by scanning electron microscopy in combination with techniques commonly available at hard X-ray microprobes to define the mineralogical environment of a bauxite residue core segment with the more specific aim of determining the speciation of trace metals (e.g., Ti, V, Cr, and Mn) within the mineral matrix. Successful trace metal speciation in heterogeneous matrices, such as those encountered in soils or mineral residues, relies on a combination of techniques including spectroscopy, microscopy, diffraction, and wet chemical and physical experiments. Of substantial interest is the ability to define the mineralogy of a sample to infer redox behavior, pH buffering, and mineral-water interfaces that are likely to interact with trace metals through adsorption, coprecipitation, dissolution, or electron transfer reactions. Quantitative evaluation of mineralogy by scanning electron microscopy coupled with micro-focused X-ray diffraction, micro-X-ray fluorescence, and micro-X-ray absorption near edge structure (mXANES) spectroscopy provided detailed insights into the composition of mineral assemblages and their effect on trace metal speciation during this investigation. In the sample investigated, titanium occurs as poorly ordered ilmenite, as rutile, and is substituted in iron oxides. Manganese's spatial correlation to Ti is closely linked to ilmenite, where it appears to substitute for Fe and Ti in the ilmenite structure based on its mXANES signature. Vanadium is associated with ilmenite and goethite but always assumes the +4 oxidation state, whereas chromium is predominantly in the +3 oxidation state and solely associated with iron oxides (goethite and hematite) and appears to substitute for Fe in the goethite structure.