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  - Sternemann, C.
A1  - Wilke, Max
T1  - Spectroscopy of low and intermediate Z elements at extreme conditions: in situ studies of Earth materials at pressure and temperature via X-ray Raman scattering
JF  - High pressure research
N2  - X-ray Raman scattering spectroscopy is an emerging method in the study of low and intermediate Z elements' core-electron excitations at extreme conditions in order to reveal information on local structure and electronic state of matter in situ. We discuss the capabilities of this method to address questions in Earth materials' science and demonstrate its sensitivity to detect changes in the oxidation state, electronic structure, coordination, and spin state. Examples are presented for the study of the oxygen K-, silicon L- and iron M-edges. We assess the application of both temperature and pressure in such investigations exploiting diamond anvil cells in combination with resistive or laser heating which is required to achieve realistic conditions of the Earth's crust, mantle, and core.
KW  - X-ray Raman scattering
KW  - inelastic X-ray scattering
KW  - X-ray absorption
KW  - high pressure research
KW  - diamond anvil cell
KW  - minerals
KW  - glasses
KW  - melts
KW  - Earth materials
KW  - spin transition
KW  - bonding transition
KW  - coordination transformation
KW  - oxidation state
KW  - electronic structure
Y1  - 2016
U6  - https://doi.org/10.1080/08957959.2016.1198903
SN  - 0895-7959
SN  - 1477-2299
VL  - 36
SP  - 275
EP  - 292
PB  - IOP Publ. Ltd.
CY  - Abingdon
ER  -