Sound Velocities in FeSi at Lower Mantle Conditions and the Origin of Ultralow-Velocity Zones

The origin of ultralow-velocity zones (ULVZs) remains an open question despite recent advances in mineral physics and seismology. Here, we examine the hypothesis that FeSi formed from core-mantle chemical reactions is a plausible source of ULVZs at the core-mantle boundary (CMB). The sound velocities of B2-structured FeSi were measured up to 115(2) GPa and 1600(200) K by nuclear inelastic scattering (NIS) in laser-heated diamond anvil cells (LH-DACs). Within uncertainties, the sound velocities of B2-FeSi display negligible anharmonicity, hence validating the extrapolation of velocity-density relations (Birch's law) to P-T conditions of the CMB. The sound velocities of B2-FeSi are significantly lower compared to other candidate phases in a lowermost mantle assemblage, and the Preliminary Reference Earth Model at CMB conditions. Less than 8.4 vol% of FeSi in the aggregate is thus sufficient to explain both the velocity decrements and the high density anomaly observed in a wide range of ULVZs.ISSN:0094-8276ISSN:1944-800

High-efficiency X-ray emission spectroscopy of cold-compressed Fe2_2O3_3 and laser-heated pressurized FeCO3_3 using a von Hámos spectrometer

X-ray spectroscopy of iron-bearing compounds under high pressure and high temperature is an important tool to understand geological processes in the deep Earth. However, the sample environment using a diamond anvil cell complicates spectroscopic measurements and leads to long data acquisition times. We present a setup for resonant and non-resonant X-ray emission spectroscopy and showcase its capabilities for in situ studies at high pressure and high temperature. Spin-state imaging of laser-heated FeCO$_3$ at 75$\,$GPa via Kβ$_{1,3}$ emission spectroscopy demonstrates the great potential of this setup with measurement times within seconds for robust spin-state analysis results. The results of Kβ$_{1,3}$ emission spectroscopy of cold-compressed Fe$_2$O$_3$ reveal a two-step spin transition with the ζ-phase between 57$\,$GPa and 64$\,$GPa, having iron in different spin states at the different iron sites. The phase transition via ζ- to Θ-phase causes a delocalization of the electronic states, which is supported by 1s2p resonant X-ray emission spectroscopy

High-efficiency X-ray emission spectroscopy of cold-compressed Fe2O3 and laser-heated pressurized FeCO3 using a von Hámos spectrometer

X-ray spectroscopy of iron-bearing compounds under high pressure and high temperature is an important tool to understand geological processes in the deep Earth. However, the sample environment using a diamond anvil cell complicates spectroscopic measurements and leads to long data acquisition times. We present a setup for resonant and non-resonant X-ray emission spectroscopy and showcase its capabilities for in situ studies at high pressure and high temperature. Spin-state imaging of laser-heated FeCO3 at 75 GPa via Kβ1,3 emission spectroscopy demonstrates the great potential of this setup with measurement times within seconds for robust spin-state analysis results. The results of Kβ1,3 emission spectroscopy of cold-compressed Fe2O3 reveal a two-step spin transition with the ζ-phase between 57 GPa and 64 GPa, having iron in different spin states at the different iron sites. The phase transition via ζ- to Θ-phase causes a delocalization of the electronic states, which is supported by 1s2p resonant X-ray emission spectroscopy

High-efficiency X-ray emission spectroscopy of cold-compressed Fe2O3 and laser-heated pressurized FeCO3 using a von Hamos ´ spectrometer

X-ray spectroscopy of iron-bearing compounds under high pressure and high temperature is an important tool to understand geological processes in the deep Earth. However, the sample environment using a diamond anvil cell complicates spectroscopic measurements and leads to long data acquisition times. We present a setup for resonant and non-resonant X-ray emission spectroscopy and showcase its capabilities for in situ studies at high pressure and high temperature. Spin-state imaging of laser-heated FeCO3 at 75 GPa via Kβ1,3 emission spectroscopy demonstrates the great potential of this setup with measurement times within seconds for robust spin-state analysis results. The results of Kβ1,3 emission spectroscopy of cold-compressed Fe2O3 reveal a two-step spin transition with the ζ-phase between 57 GPa and 64 GPa, having iron in different spin states at the different iron sites. The phase transition via ζ- to Θ-phase causes a delocalization of the electronic states, which is supported by 1s2p resonant X-ray emission spectroscopy.ISSN:0267-9477ISSN:1364-554

Reflective imaging, on-axis laser heating and radiospectrometry of samples in diamond anvil cells with a parabolic mirror

We describe the use of a silver-coated 90∘ parabolic mirror of 33 mm focal length as objective for imaging, on-axis laser heating and radiospectrometric temperature measurements of a sample compressed in a diamond anvil cell in a laser heating system. There, spatial resolution and imaging quality of the parabolic mirror are similar to the one of a 10× objective. The temperature measurements between 500 and 900 nm are essentially free from chromatic aberration. The parabolic mirror was also perforated with a 220-μm hole, allowing for on-axis imaging, laser heating and incidence of X-rays simultaneously at synchrotron facilities. The parabolic mirror is thus a well-suited alternative to existing refractive and reflective objectives in laboratory and synchrotron laser heating systems.ISSN:0895-7959ISSN:1477-229

A portable on-axis laser-heating system for near-90° X-ray spectroscopy: application to ferropericlase and iron silicide

A portable IR fiber laser-heating system, optimized for X-ray emission spectroscopy (XES) and nuclear inelastic scattering (NIS) spectroscopy with signal collection through the radial opening of diamond anvil cells near 90°with respect to the incident X-ray beam, is presented. The system offers double-sided on-axis heating by a single laser source and zero attenuation of incoming X-rays other than by the high-pressure environment. A description of the system, which has been tested for pressures above 100 GPa and temperatures up to 3000 K, is given. The XES spectra of laser-heated Mg0.67Fe0.33O demonstrate the potential to map the iron spin state in the pressure–temperature range of the Earth's lower mantle, and the NIS spectra of laser-heated FeSi give access to the sound velocity of this candidate of a phase inside the Earth's core. This portable system represents one of the few bridges across the gap between laser heating and high-resolution X-ray spectroscopies with signal collection near 90°

Structural and electron spin state changes in an x-ray heated iron carbonate system at the Earth's lower mantle pressures

The determination of the spin state of iron-bearing compounds at high pressure and temperature is crucial for our understanding of chemical and physical properties of the deep Earth. Studies on the relationship between the coordination of iron and its electronic spin structure in iron-bearing oxides, silicates, carbonates, iron alloys, and other minerals found in the Earth's mantle and core are scarce because of the technical challenges to simultaneously probe the sample at high pressures and temperatures. We used the unique properties of a pulsed and highly brilliant x-ray free electron laser (XFEL) beam at the High Energy Density (HED) instrument of the European XFEL to x-ray heat and probe samples contained in a diamond anvil cell. We heated and probed with the same x-ray pulse train and simultaneously measured x-ray emission and x-ray diffraction of an FeCO3 sample at a pressure of 51 GPa with up to melting temperatures. We collected spin state sensitive Fe Kβ1,3 fluorescence spectra and detected the sample's structural changes via diffraction, observing the inverse volume collapse across the spin transition. During x-ray heating, the carbonate transforms into orthorhombic Fe4C3O12 and iron oxides. Incipient melting was also observed. This approach to collect information about the electronic state and structural changes from samples contained in a diamond anvil cell at melting temperatures and above will considerably improve our understanding of the structure and dynamics of planetary and exoplanetary interiors.ISSN:2643-156

Structural and electron spin state changes in an x-ray heated iron carbonate system at the Earth's lower mantle pressures

The determination of the spin state of iron-bearing compounds at high pressure and temperature is crucial for our understanding of chemical and physical properties of the deep Earth. Studies on the relationship between the coordination of iron and its electronic spin structure in iron-bearing oxides, silicates, carbonates, iron alloys, and other minerals found in the Earth's mantle and core are scarce because of the technical challenges to simultaneously probe the sample at high pressures and temperatures. We used the unique properties of a pulsed and highly brilliant x-ray free electron laser (XFEL) beam at the High Energy Density (HED) instrument of the European XFEL to x-ray heat and probe samples contained in a diamond anvil cell. We heated and probed with the same x-ray pulse train and simultaneously measured x-ray emission and x-ray diffraction of an FeCO$_3$ sample at a pressure of 51 GPa with up to melting temperatures. We collected spin state sensitive Fe Kβ$_{1,3}$ fluorescence spectra and detected the sample's structural changes via diffraction, observing the inverse volume collapse across the spin transition. During x-ray heating, the carbonate transforms into orthorhombic Fe$_4$C$_3$O$_{12}$ and iron oxides. Incipient melting was also observed. This approach to collect information about the electronic state and structural changes from samples contained in a diamond anvil cell at melting temperatures and above will considerably improve our understanding of the structure and dynamics of planetary and exoplanetary interiors

A von Hámos spectrometer for diamond anvil cell experiments at the High Energy Density Instrument of the European X-ray Free-Electron Laser

A von Hámos spectrometer has been implemented in the vacuum interaction chamber 1 of the High Energy Density instrument at the European X-ray Free-Electron Laser facility. This setup is dedicated, but not necessarily limited, to X-ray spectroscopy measurements of samples exposed to static compression using a diamond anvil cell. Si and Ge analyser crystals with different orientations are available for this setup, covering the hard X-ray energy regime with a sub-eV energy resolution. The setup was commissioned by measuring various emission spectra of free-standing metal foils and oxide samples in the energy range between 6 and 11 keV as well as low momentum-transfer inelastic X-ray scattering from a diamond sample. Its capabilities to study samples at extreme pressures and temperatures have been demonstrated by measuring the electronic spin-state changes of (Fe₀.₅Mg₀.₅)O, contained in a diamond anvil cell and pressurized to 100 GPa, via monitoring the Fe Kβ fluorescence with a set of four Si(531) analyser crystals at close to melting temperatures. The efficiency and signal-to-noise ratio of the spectrometer enables valence-to-core emission signals to be studied and single pulse X-ray emission from samples in a diamond anvil cell to be measured, opening new perspectives for spectroscopy in extreme conditions research.ISSN:0909-0495ISSN:1600-577

Structural evolution of liquid silicates under conditions in Super-Earth interiors

International audienceMolten silicates at depth are crucial for planetary evolution, yet their local structure and physical properties under extreme conditions remain elusive due to experimental challenges. In this study, we utilize in situ X-ray diffraction (XRD) at the Matter in Extreme Conditions (MEC) end-station of the Linear Coherent Linac Source (LCLS) at SLAC National Accelerator Laboratory to investigate liquid silicates. Using an ultrabright X-ray source and a high-power optical laser, we probed the local atomic arrangement of shock-compressed liquid (Mg,Fe)SiO$_3$ with varying Fe content, at pressures from 81(9) to 385(40) GPa. We compared these findings to ab initio molecular dynamics simulations under similar conditions. Results indicate continuous densification of the O-O and Mg-Si networks beyond Earth's interior pressure range, potentially altering melt properties at extreme conditions. This could have significant implications for early planetary evolution, leading to notable differences in differentiation processes between smaller rocky planets, such as Earth and Venus, and super-Earths, which are exoplanets with masses nearly three times that of Earth