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Abstract: Implant-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. Microfocus X-ray spectroscopy using a synchrotron beam is useful in addressing both these issues. Using this technique we compared tissue from failed MOM hips with: (1) tissue from metal-on-polyethylene (MOP) hips; (2) chemical standards; (3) metal discs cut from MOM hips. The most abundant implant-related species in all MOM hip tissues contained Cr. Comparison with standards revealed the chemical form was Cr(III) phosphate, which did not vary with manufacturer type (four types analysed) or level of blood metal ions. Cobalt (Co) and molybdenum (Mo) were occasionally present in areas of high Cr. Co was normally found in a metallic state in the tissue, while Mo was found in an oxidized state. The variety of metallic species may have arisen from corrosion, wear or a combination of both. No evidence of Cr(VI) was seen in the tissues examined.

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Abstract: This work describes the application of microfocus X-ray absorption spectroscopy (XAS) and X-ray photo-emission electron microscopy (XPEEM) to the study of the complex mineralogical intergrowths within the Santa Catharina meteorite. The Santa Catharina meteorite of this study (BM52283 from the meteorite collection of the Natural History Museum, London, UK) primarily comprises a taenite bulk host phase (Fe:Ni ratio = 70.9 ± 0.8%:29.1 ± 0.8%) with a set of oxide-bearing cloudy zone textured regions (Fe:Ni:O ratio = 40.4 ± 0.3%:49.0 ± 0.7%:10.6 ± 0.8% at the core and Fe:Ni:O ratio = 34.4 ± 1.5%:42.7 ± 0.6%:22.9 ± 1.8% towards the rims) and numerous schreibersite (Fe:Ni:P ratio = 38.6 ± 1.6%:38.4 ± 0.9%:23.0 ± 0.5%) inclusions. Between the schreibersite and the taenite are rims up to 50 μm across of Ni-rich kamacite (Fe:Ni ratio = 93.4 ± 0.4%:6.6 ± 0.5%). No chemical zoning or spatial variations in the Fe and Ni speciation was observed within either the schreibersite or the kamacite phases. The oxide-bearing cloudy zone textured regions mostly comprise metallic Fe-Ni alloy, predominantly tetrataenite. Within the oxide phases, the Fe is predominantly, but not entirely, tetrahedrally co-ordinated Fe3+ and the Ni is octahedrally co-ordinated Ni2+. Structural analysis supports the suggestion that non-stoichiometric Fe2NiO4 trevorite is the oxide phase. The trevorite:tetrataenite ratio increases at the edges of the oxide-bearing cloudy zone textured regions indicating increased oxidation at the edges of these zones. The spatial resolution of the XPEEM achieved was between 110 and 150 nm, which precluded the study of either the previously reported ∼ 10 nm precipitates of tetrataenite within the bulk taenite or any antitaenite.

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Abstract: Timescales of magma chamber assembly and recharge are investigated here by applying 1D and 2D diffusion modeling techniques to high-resolution maps of titanium in quartz from a large-volume ignimbrite eruption in the Taupo Volcanic Zone, New Zealand. We compare quartz zonation patterns and associated diffusion timescales from the ?340?ka Whakamaru super-eruption (magma volume ?1000?km3) with the Younger Toba Tuff super-eruption, 74?ka (2000?km3), Sumatra, and the smaller volume ?50?ka Earthquake Flat eruption (10?km3), Okataina Caldera Complex, New Zealand. Two principal timescales are presented: that of chamber recharge and eruption triggering events, and that of magma generation (involving long-term assembly, stirring and reactivation). Synchrotron micro-X-ray fluorescence maps of core–rim quartz transects provide a high-resolution record of magma chamber conditions throughout quartz crystallization. Quartz crystals from the Whakamaru magma display complex zonation patterns indicating fluctuating pressure–temperature conditions throughout the crystallization history. Toba and Earthquake Flat, in contrast, display simple quartz-zoning patterns and record slightly longer periods of crystal residence in the chamber that fed the eruption. We apply Lattice Boltzmann 2D diffusion modeling to reconstruct the timescales of quartz crystal zonation, accounting for crystal boundary complexities. Quartz crystal orientation is also accounted for by using geometry constraints from the synchrotron data. Our calculations suggest that crystal-mush reactivation for the main Whakamaru magma reservoir occured over a period of the order of 103–104 years. Both the Earthquake Flat and Toba eruptions experienced a significant recharge event (causing a temperature and pressure change), which occurred within ?100 years of eruption. In comparison, the complex Whakamaru quartz zoning patterns suggest that the magma body experienced numerous thermal and compositional fluctuations in the lead-up to eruption. The final magma recharge event, which most probably triggered the eruption, occurred within ?10–60 years of the eruption. Even though the volume of these systems spans two orders of magnitude, there does not appear to be a relationship between magma volume and diffusion timescale, suggesting similar histories before eruption.

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Abstract: Disregulation of transition metal ions is implicated in many neurodegenerative disorders, and altered status may both affect disease progression and hold biomarker potential. The analytical challenges in this field often lead to isolated evidence for altered concentration, distribution, chemical or mineral state, limiting the conclusions that can be drawn. Combining methods that are highly sensitive to a range of these properties can give new insight.