TY - JOUR A1 - Kaa, Johannes M. A1 - Sternemann, Christian A1 - Appel, Karen A1 - Cerantola, Valerio A1 - Preston, Thomas R. A1 - Albers, Christian A1 - Elbers, Mirko A1 - Libon, Lelia A1 - Makita, Mikako A1 - Pelka, Alexander A1 - Petitgirard, Sylvain A1 - Plückthun, Christian A1 - Roddatis, Vladimir A1 - Sahle, Christoph J. A1 - Spiekermann, Georg A1 - Schmidt, Christian A1 - Schreiber, Anja A1 - Sakrowski, Robin A1 - Tolan, Metin A1 - Wilke, Max A1 - Zastrau, Ulf A1 - Konopkova, Zuzana T1 - Structural and electron spin state changes in an x-ray heated iron carbonate system at the Earth's lower mantle pressures JF - Physical review research N2 - 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 K beta(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 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. Y1 - 2022 U6 - https://doi.org/10.1103/PhysRevResearch.4.033042 SN - 2643-1564 VL - 4 IS - 3 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Weis, Christopher A1 - Spiekermann, Georg A1 - Sternemann, Christian A1 - Harder, Manuel A1 - Vanko, Gyorgy A1 - Cerantola, Valerio A1 - Sahle, Christoph J. A1 - Forov, Yury A1 - Sakrowski, Robin A1 - Kupenko, Ilya A1 - Petitgirard, Sylvain A1 - Yavas, Hasan A1 - Bressler, Christian A1 - Gawelda, Wojciech A1 - Tolan, Metin A1 - Wilke, Max T1 - Combining X-ray K beta(1,3), valence-to-core, and X-ray Raman spectroscopy for studying Earth materials at high pressure and temperature BT - the case of siderite JF - Journal of analytical atomic spectrometry N2 - X-ray emission and X-ray Raman scattering spectroscopy are powerful tools to investigate the local electronic and atomic structure of high and low Z elements in situ. Notably, these methods can be applied for in situ spectroscopy at high pressure and high temperature using resistively or laser-heated diamond anvil cells in order to achieve thermodynamic conditions which appear in the Earth's interior. We present a setup for combined X-ray emission and X-ray Raman scattering studies at beamline P01 of PETRA III using a portable wavelength-dispersive von Hamos spectrometer together with the permanently installed multiple-analyzer Johann-type spectrometer. The capabilities of this setup are exemplified by investigating the iron spin crossover of siderite FeCO3 up to 49.3 GPa by measuring the Fe M2,3-edge and the Fe Kβ1,3 emission line simultaneously. With this setup, the Fe valence-to-core emission can be detected together with the Kβ1,3 emission line providing complementary information on the sample's electronic structure. By implementing a laser-heating device, we demonstrate the strength of using a von Hamos type spectrometer for spin state mapping at extreme conditions. Finally, we give different examples of low Z elements' absorption edges relevant for application in geoscience that are accessible with the Johann-type XRS spectrometer. With this setup new insights into the spin transition and compression mechanisms of Earth's mantle materials can be obtained of importance for comprehension of the macroscopic physical and chemical properties of the Earth's interior. Y1 - 2018 U6 - https://doi.org/10.1039/c8ja00247a SN - 0267-9477 SN - 1364-5544 VL - 34 IS - 2 SP - 384 EP - 393 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Cerantola, Valerio A1 - Wilke, Max A1 - Kantor, Innokenty A1 - Ismailova, Leyla A1 - Kupenko, Ilya A1 - McCammon, Catherine A1 - Pascarelli, Sakura A1 - Dubrovinsky, Leonid S. T1 - Experimental investigation of FeCO3 (siderite) stability in Earth's lower mantle using XANES spectroscopy JF - American mineralogist : an international journal of earth and planetary materials N2 - We studied FeCO3 using Fe K-edge X-ray absorption near-edge structure (XANES) spectroscopy at pressures up to 54 GPa and temperatures above 2000 K. First-principles calculations of Fe at the K-edge in FeCO3 were performed to support the interpretation of the XANES spectra. The variation of iron absorption edge features with pressure and temperature in FeCO3 matches well with recently reported observations on FeCO3 at extreme conditions, and provides new insight into the stability of Fe-carbonates in Earth's mantle. Here we show that at conditions of the mid-lower mantle, ~50 GPa and ~2200 K, FeCO3 melts and partially decomposes to high-pressure Fe3O4. Carbon (diamond) and oxygen are also inferred products of the reaction. We constrained the thermodynamic phase boundary between crystalline FeCO3 and melt to be at 51(1) GPa and ~1850 K. We observe that at 54(1) GPa, temperature-induced spin crossover of Fe2+ takes place from low to high spin such that at 1735(100) K, all iron in FeCO3 is in the high-spin state. A comparison between experiment and theory provides a more detailed understanding of FeCO3 decomposition observed in X-ray absorption spectra and helps to explain spectral changes due to pressure-induced spin crossover in FeCO3 at ambient temperature. KW - Deep carbon cycle KW - siderite KW - decomposition KW - melting KW - spin transition KW - Earth in Five Reactions: A Deep Carbon Perspective Y1 - 2019 U6 - https://doi.org/10.2138/am-2019-6428 SN - 0003-004X SN - 1945-3027 VL - 104 IS - 8 SP - 1083 EP - 1091 PB - Mineralogical Society of America CY - Chantilly ER - TY - JOUR A1 - Weis, Christopher A1 - Sternemann, Christian A1 - Cerantola, Valerio A1 - Sahle, Christoph J. A1 - Spiekermann, Georg A1 - Harder, Manuel A1 - Forov, Yury A1 - Kononov, Alexander A1 - Sakrowski, Robin A1 - Yavas, Hasan A1 - Tolan, Metin A1 - Wilke, Max T1 - Pressure driven spin transition in siderite and magnesiosiderite single crystals JF - Scientific reports Y1 - 2017 U6 - https://doi.org/10.1038/s41598-017-16733-3 SN - 2045-2322 VL - 7 PB - Nature Publ. Group CY - London ER -