Determination on iron species in plagioclase crystals toward the understanding on the magnetite exsolution

<p>Speciation analysis of Fe in single plagioclase crystals separated from two different gabbros was performed to understand the crystallization mechanisms of magnetite exsolution. Iron species in single crystals were measured using Fe K- and L<sub>III</sub>-edge X-ray absorption fine structure (XAFS) analysis. The K-edge pre-edge analysis showed variation in the averaged valence state of Fe in plagioclase crystals even if they had been separated from the same gabbro that was further confirmed by the L<sub>III</sub>-edge analysis. The K-edge pre-edge analysis also suggests the various degrees of contribution from tetrahedral Fe. The mixing of tetrahedral and octahedral Fe leads to an underestimation of the averaged valence state of Fe for the K-edge pre-edge analysis; thus, we adopted the L<sub>III</sub>-edge result for the valence state of Fe in plagioclase crystals. Iron K-edge extended XAFS (EXAFS) analysis of two plagioclase crystals separated from the same gabbro clearly showed different coordination environments. A weakening of EXAFS oscillation was recognized in one sample, because two Fe‒O bonds (Fe<sup>3+</sup>‒O<sub>1</sub> and Fe<sup>2+</sup>‒O2) cancelled out the oscillations of each other. The EXAFS spectrum of the other plagioclase crystal suggested a homogeneous distribution of Fe. The content of exsolved magnetite in these crystals is nearly identical, indicating that the exsolution of magnetite in plagioclase crystal had been completed before the temperature decrease that stopped the ordering of Fe ions in tetrahedral sites.</p><p>Reference: Nakada et al. (2019) G-Cubed, vol. 20 (11), 5319-5333.</p>

Performance of nearly fixed offset asymmetric channel-cut crystals for X-ray monochromators

X-ray double-crystal monochromators face a shift of the exit beam when the Bragg angle and thus the transmitted photon energy changes. This can be compensated for by moving one or both crystals accordingly. In the case of monolithic channel-cut crystals, which exhibit utmost stability, the shift of the monochromated beam is inevitable. Here we report performance tests of novel, asymmetrically cut, channel-cut crystals which reduce the beam movements by more than a factor of 20 relative to the symmetric case over the typical energy range of an EXAFS spectrum at the Cu K-edge. In addition, the presented formulas for the beam offset including the asymmetry angle directly indicate the importance of this value, which has been commonly neglected so far in the operation of double-crystal monochromators.

In situ high-temperature EXAFS measurements on radioactive and air-sensitive molten salt materials

The development at the Delft University of Technology (TU Delft, The Netherlands) of an experimental set-up dedicated to high-temperature in situ EXAFS measurements of radioactive, air-sensitive and corrosive fluoride salts is reported. A detailed description of the sample containment cell, of the furnace design, and of the measurement geometry allowing simultaneous transmission and fluorescence measurements is given herein. The performance of the equipment is tested with the room-temperature measurement of thorium tetrafluoride, and the Th—F and Th—Th bond distances obtained by fitting of the EXAFS data are compared with the ones extracted from a refinement of neutron diffraction data collected at the PEARL beamline at TU Delft. The adequacy of the sample confinement is checked with a mapping of the thorium concentration profile of molten salt material. Finally, a few selected salt mixtures (LiF:ThF4) = (0.9:0.1), (0.75:0.25), (0.5:0.5) and (NaF:ThF4) = (0.67:0.33), (0.5:0.5) are measured in the molten state. Qualitative trends along the series are discussed, and the experimental data for the (LiF:ThF4) = (0.5:0.5) composition are compared with the EXAFS spectrum generated from molecular dynamics simulations.

The hydration structure of the heavy-alkalines Rb+ and Cs+ through molecular dynamics and X-ray absorption spectroscopy: surface clusters and eccentricity

Hydration shells around Rb+ and Cs+ are not symmetric; the cation and the 1st-shell water mass center are separated by ∼0.4 Å, and this is supported by agreement between the theoretical and experimental EXAFS spectrum.

The Time-resolved and Extreme-conditions XAS (TEXAS) facility at the European Synchrotron Radiation Facility: the energy-dispersive X-ray absorption spectroscopy beamline ID24

The European Synchrotron Radiation Facility has recently made available to the user community a facility totally dedicated to Time-resolved and Extreme-conditions X-ray Absorption Spectroscopy – TEXAS. Based on an upgrade of the former energy-dispersive XAS beamline ID24, it provides a unique experimental tool combining unprecedented brilliance (up to 1014 photons s−1on a 4 µm × 4 µm FWHM spot) and detection speed for a full EXAFS spectrum (100 ps per spectrum). The science mission includes studies of processes down to the nanosecond timescale, and investigations of matter at extreme pressure (500 GPa), temperature (10000 K) and magnetic field (30 T). The core activities of the beamline are centered on new experiments dedicated to the investigation of extreme states of matter that can be maintained only for very short periods of time. Here the infrastructure, optical scheme, detection systems and sample environments used to enable the mission-critical performance are described, and examples of first results on the investigation of the electronic and local structure in melts at pressure and temperature conditions relevant to the Earth's interior and in laser-shocked matter are given.

Characterization of Chloroquine-Ferriheme Solution Structure Using EXAFS and MD

The complex formed between the antimalarial drug chloroquine (CQ) and its target iron(III)protoporphyrin IX (ferriheme) in aqueous solution is of considerable importance in understanding its mechanism of antimalarial activity. Recently, convincing evidence showed that CQ induces the μ-oxo dimeric form of ferriheme in aqueous solution, but the structure of this complex in solution is uncertain.[1] Molecular dynamics (MD) simulations in aqueous solution were used to model the structure of μ-oxo ferriheme and two possible conformations of the CQ-ferriheme complex, one in which CQ π-stacked with the unligated face of ferriheme and the other in which CQ was docked between the porphyrin rings. The EXAFS spectrum of μ-oxo ferriheme obtained from frozen solution strongly supported the hydrated structure determined from MD simulation where an excellent fit to the spectrum was only obtained when incorporating waters of hydration at regions identified by computation. On the other hand, the EXAFS spectrum recorded on the dried solid of μ-oxo ferriheme required no solvating waters to produce excellent agreement with the crystal structure of μ-oxo ferrihaem dimethyl ester.[2] The EXAFS spectrum recorded on a frozen aqueous solution of the CQ-ferriheme complex was able to distinguish between the two conformations modeled computationally. Fits to the EXAFS spectrum using the π-stacked structure produced poor agreement while those obtained using the docked conformation reproduced the spectrum well. This indicated that the latter is the most likely form of the CQ-ferriheme complex in aqueous solution.

Synchrotron X-Ray Absorption Spectroscopy Study of Self-Assembled Nanoparticles Synthesized from Fe(acac)3and Pt(acac)2

The synchrotron X-ray absorption technique was used to complement electron microscopy in the investigation of nanoparticles synthesized from the coreduction of iron acetylacetonate, Fe(acac)3and platinum acetylacetonate, Pt(acac)2. A much higher Pt composition than Fe leads to an extended X-ray absorption fine structure (EXAFS) spectrum for the sample that differs from that of fcc FePt nanoparticles. Most importantly, X-ray absorption near-edge structure (XANES) spectra clearly indicate the existence ofα-Fe2O3and Pt metal. Since these monodisperse nanoparticles have a diameter of around 4 nm and tend to self-assemble into hexagonal arrangements, they can be modeled as Pt-rich cores with anα-Fe2O3shell stabilized by organic surfactants.

XAFS of Pu and Hf LIII Edge in Lanthanide-Borosilicate Glass

Lanthanide-Borosilicate (LaBS) glass capable to dissolve up to ∼10 wt.% PuO2 is designed for immobilization of plutonium-bearing wastes. The sample of LaBS glass with a target chemical composition (wt %): 9.0 Al2O3, 11.8 B2O3, 12.2 Gd2O3, 6.3 HfO2, 17.2 La2O3, 13.6 Nd2O3, 9.5 PuO2, 18.1 SiO2, 2.3 SrO was prepared from PuO2 powder and mechanically activated mixture of chemicals at 1500 °C. The obtained product was visually homogeneous. Xraydiffraction of the as-prepared glass showed that it mostly consists of a vitreous phase withsmall amounts of crystalline PuO2 (or PuO2-HfO2 solid solution with minor HfO2), britholite andan oxide with a fluorite structure and a composition close to GdHfO1.75. The crystalline fractionincreased after storage for ∼1 year. Magnitude of the FT of EXAFS spectrum at Pu LIII edgeshows that the peak due to first coordination sphere is much more intense than that of the secondshell. This indicates that though some Pu entered crystalline phases (mainly distorted PuO2), itsmajor fraction remained in the vitreous phase. Fit of the spectrum (R-factor = 0.02) gives thefollowing distances: R (Pu-O1)1 = 1.98 (σ = 0.04), R (Pu-O1)2 = 2.18 (σ = 0.04), R (Pu-O1)3= 2.35, R (Pu-Pu) = 3.72 (σ = 0.04), R (Pu-O2) = 4.4 (σ = 0.06). Oxygen environment ofthe Pu4+ ions in the vitreous phase resembles axially squeezed tetragonal pyramid with acoordination number ∼5. The distances ∼2.35 and ∼4.4 correspond to the pairs Pu-O in thefirst and the second shells in the crystalline PuO2. The distance ∼3.72 corresponds to the Pu-Pu and/or Pu-M (M = Ln, Hf) distances. EXAFS spectra of Hf show that Hf is present mostly in thevitreous phase with major neighbors at 2.17 and ∼3.2 A.