Experimental investigation of FeCO3 (siderite) stability in Earth's lower mantle using XANES spectroscopy

2019 ◽  
Vol 104 (8) ◽  
pp. 1083-1091 ◽  
Author(s):  
Valerio Cerantola ◽  
Max Wilke ◽  
Innokenty Kantor ◽  
Leyla Ismailova ◽  
Ilya Kupenko ◽  
...  
Keyword(s):  
High Spin ◽  
Lower Mantle ◽  
Spin Crossover ◽  
High Spin State ◽  
Xanes Spectroscopy ◽  
Edge Structure ◽  
X Ray ◽  
Edge Features ◽  
The Stability ◽  
X Ray Absorption

Abstract 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.

Extended X-ray absorption fine structure and multiple-scattering simulation of nickel dithiolene complexes Ni[S2C2(CF3)2]2n(n= −2, −1, 0) and an olefin adduct Ni[S2C2(CF3)2]2(1-hexene)

2015 ◽  
Vol 22 (1) ◽  
pp. 124-129 ◽  
Author(s):  
Weiwei Gu ◽  
Hongxin Wang ◽  
Kun Wang
Keyword(s):  
Fine Structure ◽  
Multiple Scattering ◽  
Edge Structure ◽  
X Ray ◽  
Absorption Fine ◽  
Square Planar ◽  
Square Planar Complexes ◽  
Uv Visible ◽  
Edge Features ◽  
X Ray Absorption

A series of Ni dithiolene complexes Ni[S2C2(CF3)]2n(n= −2, −1, 0) (1,2,3) and a 1-hexene adduct Ni[S2C2(CF3)2]2(C6H12) (4) have been examined by NiK-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine-structure (EXAFS) spectroscopies. Ni XANES for1–3reveals clear pre-edge features and approximately +0.7 eV shift in the NiK-edge position for `one-electron' oxidation. EXAFS simulation shows that the Ni—S bond distances for1,2and3(2.11–2.16 Å) are within the typical values for square planar complexes and decrease by ∼0.022 Å for each `one-electron' oxidation. The changes in NiK-edge energy positions and Ni—S distances are consistent with the `non-innocent' character of the dithiolene ligand. The Ni—C interactions at ∼3.0 Å are analyzed and the multiple-scattering parameters are also determined, leading to a better simulation for the overall EXAFS spectra. The 1-hexene adduct4presents no pre-edge feature, and its NiK-edge position shifts by −0.8 eV in comparison with its starting dithiolene complex3. Consistently, EXAFS also showed that the Ni—S distances in4elongate by ∼0.046 Å in comparison with3. The evidence confirms that the neutral complex is `reduced' upon addition of olefin, presumably by olefin donating the π-electron density to the LUMO of3as suggested by UV/visible spectroscopy in the literature.

X-ray absorption near edge structures in cobalt oxides

1996 ◽  
Vol 11 (9) ◽  
pp. 2242-2256 ◽  
Author(s):  
T. Jiang ◽  
D. E. Ellis
Keyword(s):  
Wave Functions ◽  
Site Symmetry ◽  
Local Geometry ◽  
Final State ◽  
Cluster Technique ◽  
Edge Structure ◽  
X Ray ◽  
Local Electronic Structure ◽  
Edge Features ◽  
X Ray Absorption

Theoretical studies have been made of K-edge x-ray absorption near edge structure (XANES) of Co in CoO, Co(OH)2, CoTiO3, Co3O4, and CoAl2O4. Correlations of experimental near edge features with site symmetry, local geometry, local electronic structure, i.e., atomic configuration, charge transfer, and backscattering from neighboring atomic potentials are interpreted. The self-consistent Discrete Variational Xa Method (DV-Xα) within an embedded cluster technique has been used to generate the crystal potential. A multiple scattering (MS) approach is then used to solve for the final state wave function. The ground state DV wave functions are analyzed in terms of the projected density of states, whereas the final state MS continuum wave functions are analyzed through the concept of photoelectron trapping time.

scholarly journals Performance of secondary P-fertilizers in pot experiments analyzed by phosphorus X-ray absorption near-edge structure (XANES) spectroscopy

AMBIO ◽  
2017 ◽  
Vol 47 (S1) ◽  
pp. 62-72 ◽  
Author(s):  
Christian Vogel ◽  
Camille Rivard ◽  
Verena Wilken ◽  
Andreas Muskolus ◽  
Christian Adam
Keyword(s):  
Xanes Spectroscopy ◽  
Edge Structure ◽  
X Ray ◽  
Pot Experiments ◽  
X Ray Absorption ◽  
P Fertilizers

Phosphorus K-edge XANES spectroscopy has probably often underestimated iron oxyhydroxide-bound P in soils

2018 ◽  
Vol 25 (6) ◽  
pp. 1736-1744 ◽  
Author(s):  
Jörg Prietzel ◽  
Wantana Klysubun
Keyword(s):  
Linear Combination ◽  
Xanes Spectroscopy ◽  
Organic P ◽  
Iron Oxyhydroxide ◽  
Edge Structure ◽  
X Ray ◽  
Soil P ◽  
P Sorption ◽  
Fe Oxyhydroxides ◽  
X Ray Absorption

Phosphorus (P) K-edge X-ray absorption near-edge structure (XANES) spectra of orthophosphate (oPO4) bound to soil FeIII minerals (e.g. ferrihydrite, goethite) show a pre-edge signal at 2148–2152 eV. It is unknown whether organic P bound to FeIII oxyhydroxides also show this feature. Otherwise, Fe-bound soil P may be underestimated by P K-edge XANES spectroscopy, because a large portion of Fe oxyhydroxide-bound P in soils is organic P. K-edge XANES spectra were obtained for different organic P compounds present in soils [inositol hexaphosphate (IHP), glucose-6-phosphate (G6P), adenosine triphosphate (ATP)] after sorption to ferrihydrite or goethite and compared with spectra of oPO4 adsorbed to these minerals. P sorption to ferrihydrite increased in the sequence IHP ≪ G6P < oPO4 < ATP. P sorption to goethite increased in the sequence G6P < oPO4 ≪ ATP = IHP. Pre-edge signals in P K-edge XANES spectra of organic P adsorbed to Fe oxyhydroxides were markedly smaller compared with those of oPO4 adsorbed to these minerals and absent for FeIII oxyhydroxide-bound ATP as well as goethite-bound IHP. Linear combination fitting (LCF) performed on spectra of IHP, G6P or ATP adsorbed to ferrihydrite or goethite, using only spectra of FeIII oxyhydroxide-bound oPO4 as reference compounds for Fe-bound P, erroneously assigned >93% (ferrihydrite) or >41% (goethite) of Fe-bound P to non-Fe-bound P species. Inclusion of FeIII oxyhydroxide-bound IHP as reference compounds markedly increased the recovery of oxyhydroxide-bound organic P. Thus, Fe-bound soil P has probably often been underestimated by LCF in soil XANES studies where IHP adsorbed to ferrihydrite and to goethite were not included as reference compounds.

Using X-ray absorption near edge structure (XANES) spectroscopy to determine selenium oxidation states in animal mineral supplements and feeds

2004 ◽  
Vol 84 (2) ◽  
pp. 171-175 ◽  
Author(s):  
C. R. Christensen ◽  
J. N. Cutler ◽  
D. A. Christensen
Keyword(s):  
Oxidation State ◽  
Animal Feed ◽  
Xanes Spectroscopy ◽  
Elemental Selenium ◽  
Selenium Speciation ◽  
Edge Structure ◽  
X Ray ◽  
Mineral Supplements ◽  
Animal Feeds ◽  
X Ray Absorption

Synchrotron-based X-ray absorption near edge structure (XANES) spectroscopy is a relatively new technique within the life sciences. XANES has been utilized to identify the location, oxidation state and spatial distribution of heavy metal elements in plants , neurons, blood and DNA, but has not been widely used in the animal sciences. Selenium content in animal feeds is monitored, as both selenium deficiencies and toxicities are associated with physiological disorders. Selenium is available as an animal feed in both inorganic and organic states. The bioavailability of selenium species has been tested in numerous animal trials; however, a simple, non-destructive test for selenium speciation is not available. The objective of this study was to determine whether XANES spectroscopy could be used to determine the selenium oxidation state found in various commercial animal feed products. A comparison of absorption spectra indicated that the animal mineral supplements contained an organoselenium or selenite. The processed animal feeds had a spectral profile similar to that of elemental selenium. Further experiments are necessary to determine the implication of selenium speciation on animal physiology. Key words: Selenium speciation, mineral supplements, ruminants, non-ruminants, synchrotron, XANES, X-ray

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