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Abstract: Cerium oxide nanoparticles (CeO2NPs), used in some diesel fuel additives to improve fuel combustion efficiency and exhaust filter operation, have been detected in ambient air and concerns have been raised about their potential human health impact. The majority of CeO2NP inhalation studies undertaken to date have used aerosol particles of larger sizes than the evidence suggests are emitted from vehicles using such fuel additives. Hence, the objective of this study was to investigate the effects of inhaled CeO2NP aerosols of a more environmentally relevant size, utilizing a combination of methods, including untargeted multi-omics to enable the broadest possible survey of molecular responses and synchrotron X-ray spectroscopy to investigate cerium speciation. Male Sprague–Dawley rats were exposed by nose-only inhalation to aerosolized CeO2NPs (mass concentration 1.8 mg/m3, aerosol count median diameter 40 nm) for 3 h/d for 4 d/week, for 1 or 2 weeks and sacrificed at 3 and 7 d post-exposure. Markers of inflammation changed significantly in a dose- and time-dependent manner, which, combined with results from lung histopathology and gene expression analyses suggest an inflammatory response greater than that seen in studies using micron-sized ceria aerosols. Lipidomics of lung tissue revealed changes to minor lipid species, implying specific rather than general cellular effects. Cerium speciation analysis indicated a change in Ce3+/Ce4+ ratio within lung tissue. Collectively, these results in conjunction with earlier studies emphasize the importance of aerosol particle size on toxicity determination. Furthermore, the limited effect resolution within 7 d suggested the possibility of longer-term effects.

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Abstract: One 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 in situ 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. The mixed base layer seems to enhance the tenacity of the subsequently formed zinc phosphate layers composing the main bulk of the protective triboreactive film. This base layer was not observed in the case of coated substrates with hydrogenated diamond-like carbon (a-C:H DLC) coating, which results in the formation of less durable films of small volume barely covering the contacting surfaces and readily removed by shear. Comprehensive decomposition pathways and kinetics for the ZDDP triboreactive films are proposed, which enable the control and modification of the ZDDP triboreactive films.

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Abstract: This manuscript presents the current status and technical details of the Spectroscopy Village at Diamond Light Source. The Village is formed of four beamlines: I18, B18, I20-Scanning and I20-EDE. The village provides the UK community with local access to a hard X-ray microprobe, a quick-scanning multi-purpose XAS beamline, a high-intensity beamline for X-ray absorption spectroscopy of dilute samples and X-ray emission spectroscopy, and an energy-dispersive extended X-ray absorption fine-structure beamline. The optics of B18, I20-scanning and I20-EDE are detailed; moreover, recent developments on the four beamlines, including new detector hardware and changes in acquisition software, are described.

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Abstract: Corrosion products generated in artificial pits of zirconium were characterized in–situ by synchrotron X-ray diffraction and X-ray absorption near edge structure (XANES) in physiological saline, with and without addition of 4% albumin and/or 0.1% H2O2. Zr metal fragments and tetragonal ZrO2 particles were detected in aggregated black corrosion products away from the corrosion front. At the corrosion front, a ZrOCl2⋅8H2O salt layer of a few hundreds of microns thickness was formed. Coarsened ZrOCl2⋅8H2O crystallites were found farther out into the solution. The Zr solution species were confirmed to be in a tetravalent state by XANES. TEM imaging of the corrosion products revealed heterogeneity of the morphology of the Zr metal fragments and confirmed their size to be less than a few microns. The formation and speciation of Zr corrosion products were found not affected by the presence of H2O2 and/or albumin in physiological saline. Furthermore, bulk Zr electrochemistry identified that the presence of H2O2 and/or albumin did not affect passive current densities and pitting potentials of the bulk Zr surface. Therefore, it is concluded that the pitting susceptibility and pit chemistry of Zr in physiological saline were unaffected by the presence of H2O2, albumin or their combinations.

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Abstract: Two flow-through experiments were conducted to assess serpentinization of intact dunite cores. Permeability and fluid chemistry indicate significantly more reaction during the second experiment at 200°C than the first experiment at 150°C. Permeability decreased by a factor of 2.4 and 25 during the experiments at 150 and 200°C, respectively. Furthermore, hydrogen and methane concentrations exceeded 600 µmol/kg and 300 µmol/kg during the 200°C experiment, and were one and two orders of magnitude higher, respectively, than the 150°C experiment. Fe K-edge X-ray absorption near edge structure analyses of alteration minerals demonstrated Fe oxidation that occurred during the 200°C experiment. Vibrating sample magnetometer measurements on post-experimental cores indicated little to no magnetite production, suggesting that the hydrogen was largely generated by the oxidation of iron as olivine was converted to ferric iron (Fe(III)) serpentine and/or saponite. Scanning electron microscopy images suggested secondary mineralization on the post-experimental core from the 200°C experiment, portraying the formation of a secondary phase with a honeycomb-like texture as well as calcite and wollastonite. Scanning electron microscopy images also illustrated dissolution along linear bands through the interiors of olivine crystals, possibly along pathways with abundant fluid inclusions. Energy dispersive X-ray spectroscopy identified Cl uptake in serpentine, while Fourier transform-infrared spectroscopy suggested the formation of serpentine, saponite, and talc. However, no change was observed when comparing pre- and post-experimental X-ray computed tomography scans of the cores. Furthermore, (ultra) small angle neutron scattering datasets were collected to assess changes in porosity, surface area, and fractal characteristics of the samples over the ≈ 1 nm- to 10 µm-scale range. The results from the 200°C post-experimental core generally fell within the range of values for the two pristine samples and the 150°C post-experimental core that underwent negligible reaction, indicating that any change from reaction was smaller than the natural variability of the dunite. Even though there was little physical evidence of alteration, the initial stage of serpentinization at 200°C was sufficiently significant to have a dramatic effect on flow fields in the core. Furthermore, this experiment generated significant dissolved hydrogen concentrations, while simulating open system dynamics. Even though open systems prevent elevated hydrogen concentrations due to continual loss of hydrogen, we speculate that this process is responsible for stabilizing ferric Fe-rich serpentine in nature, while also oxidizing more ferrous Fe (Fe(II)) iron and cumulatively generating more hydrogen than would be possible in a closed system.