Phosphorus (P) is essential for plant growth. Arbuscular mycorrhizal fungi (AMF) aid its uptake by acquiring P from sources distant from roots in return for carbon. Little is known about how AMF colonise soil pore-space, and models of AMF-enhanced P-uptake are poorly validated.
View Article and Find Full Text PDFHere we report the results of multiple analytical techniques on sub-mm particulate material derived from Unit 1 of the Fukushima Daiichi Nuclear Power Plant to provide a better understanding of the events that occurred and the environmental legacy. Through combined x-ray fluorescence and absorption contrast micro-focused x-ray tomography, entrapped U particulate are observed to exist around the exterior circumference of the highly porous Si-based particle. Further synchrotron radiation analysis of a number of these entrapped particles shows them to exist as UO-identical to reactor fuel, with confirmation of their nuclear origin shown via mass spectrometry analysis.
View Article and Find Full Text PDFThe surface of many Old Master paintings has been affected by the appearance of whitish lead-rich deposits, which are often difficult to fully characterise, thereby hindering conservation. A paint micro-sample from Rembrandt's Homer was imaged using X-ray Diffraction Computed Tomography (XRD-CT) in order to understand the evolving solid-state Pb chemistry from the painting surface and beneath. The surface crust was identified as a complex mixture of lead sulfates.
View Article and Find Full Text PDFOne of the major obstacles in replacing the widely used zinc dialkyldithiophosphate (ZDDP) antiwear additive with a more environmentally friendly one is the difficulty of time-resolving the surface species resulting from its decomposition mechanism under high contact pressure and temperature. To tackle this issue, a newly developed miniature pin-on-disc tribotester was coupled with synchrotron X-ray absorption spectroscopy (XAS) to perform tribological tests while examining the composition of the formed triboreactive films. The results showed that in the case of bare steel surfaces the initial decomposition products are mainly zinc sulfate species, which with further shearing and heating are reduced to zinc sulfide mixed with metal oxides.
View Article and Find Full Text PDFBackground: Orthopaedic implants made of cobalt-chromium alloy undergo wear and corrosion that can lead to deposition of cobalt and chromium in vital organs. Elevated cardiac tissue cobalt levels are associated with myocardial injury while chromium is a well-established genotoxin. Though metal composition of tissues surrounding hip implants has been established, few investigators attempted to characterize the metal deposits in systemic tissues of total joint arthroplasty patients.
View Article and Find Full Text PDFThe mechanisms of metal release from the articulation at the head cup bearing and the tapered junctions of orthopaedic hip implants are known to differ and the debris generated varies in size, shape and volume. Significantly less metal is lost from the taper junction between Cobalt-Chromium-Molybdenum (CoCrMo) and Titanium (Ti) components (fretting-corrosion dominant mechanism), when compared to the CoCrMo bearing surfaces (wear-corrosion dominant mechanism). Corrosion particles from the taper junction can lead to Adverse Reactions to Metal Debris (ARMD) similar to those seen with CoCrMo bearings.
View Article and Find Full Text PDFSilver nanoparticles (Ag NPs) have been used in numerous consumer products and may enter the soil through the land application of biosolids. However, little is known about the relationship between Ag NP exposure and their bioavailability for soil organisms. This study aims at comparing the uptake and elimination kinetics of Ag upon exposures to different Ag forms (NPs and ionic Ag (as AgNO3)) in the isopod Porcellionides pruinosus.
View Article and Find Full Text PDFHeterogeneous catalysis performed in the liquid phase is an important type of catalytic process which is rarely studied in situ. Using microfocus X-ray fluorescence and X-ray diffraction computed tomography (μ-XRF-CT, μ-XRD-CT) in combination with X-ray absorption near-edge spectroscopy (XANES), we have determined the active state of a Mo-promoted Pt/C catalyst (NanoSelect) for the liquid-phase hydrogenation of nitrobenzene under standard operating conditions. First, μ-XRF-CT and μ-XRD-CT reveal the active state of Pt catalyst to be reduced, noncrystalline, and evenly dispersed across the support surface.
View Article and Find Full Text PDFCurrent bioavailability models, such as the free ion activity model and biotic ligand model, explicitly consider that metal exposure will be mainly to the dissolved metal in ionic form. With the rise of nanotechnology products and the increasing release of metal-based nanoparticles (NPs) to the environment, such models may increasingly be applied to support risk assessment. It is not immediately clear, however, whether the assumption of metal ion exposure will be relevant for NPs.
View Article and Find Full Text PDFThe cellular and subcellular distributions of trace elements can provide important clues to understanding how the elements are transported and stored in plant cells, but mapping their distributions is a challenging task. The distributions of arsenic, iron, zinc, manganese and copper, as well as physiologically related macro-elements, were mapped in the node, internode and leaf sheath of rice (Oryza sativa) using synchrotron X-ray fluorescence (S-XRF) and high-resolution secondary ion mass spectrometry (NanoSIMS). Although copper and silicon generally showed cell wall localization, arsenic, iron and zinc were strongly localized in the vacuoles of specific cell types.
View Article and Find Full Text PDFWe have used synchrotron-based X-ray fluorescence and absorption techniques to establish both metal distribution and complexation in mature wheat grains. In planta, extended X-ray absorption fine structure (EXAFS) spectroscopy reveals iron phytate and zinc phytate structures in aleurone cells and in modified aleurone cells in the transfer region of the grain: iron is coordinated octahedrally by six oxygen atoms and fewer than two phosphorous atoms. Zinc is coordinated tetrahedrally by four oxygen atoms and approximately 1.
View Article and Find Full Text PDFFluid catalytic cracking (FCC) is the main conversion process used in oil refineries. An X-ray microscopy method is used to show that metal poisoning and related structural changes in the zeolite active material lead to a non-uniform core–shell deactivation of FCC catalyst particles. The study links the detrimental effect of V and Ni poisoning with zeolite destruction and dealumination in a spatial manner within a single FCC catalyst particle.
View Article and Find Full Text PDFSome types of metal-on-metal (MOM) hip replacements have unacceptably high rates of failure, such as the Ultima TPS MOM hip, with 13.8% failure at 5 years. This has been attributed to an inflammatory reaction following the release of cobalt (Co) and chromium (Cr) from the bearing surfaces and modular junctions.
View Article and Find Full Text PDFThe deposition of gold at the interface between immiscible electrolyte solutions has been investigated using reduction of tetrachloroaurate or tetrabromoaurate in 1,2-dichloroethane, with aqueous phase hexacyanoferrate as reducing agent. In a clean environment without defects present at the interface, the Au(III) complex was reduced to the Au(I) complex, but no solid phase formation could be observed. A deposition process could only be observed through the addition of artificial nucleation sites in the form of palladium nanoparticles at the interface.
View Article and Find Full Text PDFShales play an important role in many earth system processes including coastal erosion, and they form the foundations of many engineering structures. The geobiology of the interior of pyrite-containing receding shale cliffs on the coast of northeast England was examined. The surface of the weathered shales was characterised by a thin layer of disordered authigenic iron oxyhydroxides and localised acicular, platy and aggregated gypsum, which was characterised by Raman spectroscopy, XAS and SEM.
View Article and Find Full Text PDFImplant-derived material from metal-on-metal (MOM) hip arthroplasties may be responsible for an unexplained tissue inflammatory response. The chemical form of the metal species in the tissues is predominantly chromium (Cr), but the currently used techniques have not been able to determine whether this is Cr(III) phosphate or Cr(III) oxide. The analytical challenge must overcome the fact that the metal in the tissues is at a relatively low concentration and tissue preparation or the microscopy beam used can affect the results.
View Article and Find Full Text PDFBacteria are abundant in many natural and engineered environments where they are thought to exert important controls on the cycling, mobility, bioavailability, and toxicity of metal contaminants. In order to probe their role in moderating the behavior of lanthanides, pH-dependent adsorption edges of 13 individual lanthanides and yttrium to the Gram-negative bacterium Pantoea agglomerans were used to generate discrete site surface complexation constants. The calculated surface complexation constants were compared with stability constants estimated using linear free energy relationships based on a number of hydroxyl-containing ligands.
View Article and Find Full Text PDFThis study investigated Zn adsorption to an extracellular polymeric substance (EPS)-producing bacterial strain, Bacillus licheniformis S-86. Batch metal adsorption experiments and spectroscopic (EXAFS) analysis were conducted using both native (EPS-covered) cells and EPS-free cells in order to assess the contribution made by EPS to metal adsorption by this strain. Thermodynamic modelling of the macroscopic adsorption data indicated that Zn complexation to both native and EPS-free cells was predominantly to carboxyl (pK(a)5.
View Article and Find Full Text PDFTechnetium, uranium and neptunium may all occur in the environment in more than one oxidation state (IV or VII, IV or VI and IV or V respectively). The surface of mackinawite, the first-formed iron sulfide phase in anoxic conditions, can promote redox changes so a series of laboratory experiments were carried out to explore the interactions of Tc, U and Np with this mineral. The products of reaction were characterised using X-ray absorption spectroscopy.
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