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Title: Stability of iron-bearing carbonates in the deep Earth’s interior

Abstract

The presence of carbonates in inclusions in diamonds coming from depths exceeding 670 km are obvious evidence that carbonates exist in the Earth’s lower mantle. However, their range of stability, crystal structures and the thermodynamic conditions of the decarbonation processes remain poorly constrained. We investigate the behaviour of pure iron carbonate at pressures over 100 GPa and temperatures over 2,500 K using single-crystal X-ray diffraction and Mossbauer spectroscopy in laser-heated diamond anvil cells. On heating to temperatures of the Earth’s geotherm at pressures to B 50 GPa FeCO 3 partially dissociates to form various iron oxides. Furthermore, at higher pressures FeCO 3 forms two new structures— tetrairon(III) orthocarbonate Fe$$3+\atop{4}$$C3O12 and diiron(II) diiron(III) tetracarbonate Fe$$2+\atop{2}$$ Fe$$3+\atop{2}$$C4 O13, both phases containing CO4 tetrahedra. Fe4 C4 O13 is stable at conditions along the entire geotherm to depths of at least 2,500 km, thus demonstrating that self-oxidation-reduction reactions can preserve carbonates in the Earth’s lower mantle.

Authors:
 [1];  [2];  [3];  [4];  [5]; ORCiD logo [6];  [7];  [3];  [6];  [3];  [3];  [3];  [3];  [3];  [8];  [3];  [9];  [6]
  1. European Synchrotron Radiation Facility (ESRF), Grenoble (France); Univ. of Bayreuth (Germany). Bavarian Geoinstitute
  2. Univ. of Bayreuth (Germany). Bavarian Geoinstitute; Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
  3. European Synchrotron Radiation Facility (ESRF), Grenoble (France)
  4. Univ. of Milan (Italy). Dept. of Earth Sciences
  5. Center for Hydrocarbon Recovery, Moscow (Russia). Skolkovo Inst. of Science and Technology
  6. Univ. of Bayreuth (Germany). Bavarian Geoinstitute
  7. Univ. of Bayreuth (Germany). Bavarian Geoinstitute; National Univ., of Science and Technology, Moscow (Russia). Material Modeling and Development Lab.
  8. Univ. of Cologne (Germany). Inst. of Geology and Mineralogy
  9. Univ. of Chicago, IL (United States). Center for Advanced Radiation Sources
Publication Date:
Research Org.:
Univ. of Chicago, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1393163
Grant/Contract Number:  
FG02-94ER14466; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
58 GEOSCIENCES

Citation Formats

Cerantola, Valerio, Bykova, Elena, Kupenko, Ilya, Merlini, Marco, Ismailova, Leyla, McCammon, Catherine, Bykov, Maxim, Chumakov, Alexandr I., Petitgirard, Sylvain, Kantor, Innokenty, Svitlyk, Volodymyr, Jacobs, Jeroen, Hanfland, Michael, Mezouar, Mohamed, Prescher, Clemens, Rüffer, Rudolf, Prakapenka, Vitali B., and Dubrovinsky, Leonid. Stability of iron-bearing carbonates in the deep Earth’s interior. United States: N. p., 2017. Web. doi:10.1038/ncomms15960.
Cerantola, Valerio, Bykova, Elena, Kupenko, Ilya, Merlini, Marco, Ismailova, Leyla, McCammon, Catherine, Bykov, Maxim, Chumakov, Alexandr I., Petitgirard, Sylvain, Kantor, Innokenty, Svitlyk, Volodymyr, Jacobs, Jeroen, Hanfland, Michael, Mezouar, Mohamed, Prescher, Clemens, Rüffer, Rudolf, Prakapenka, Vitali B., & Dubrovinsky, Leonid. Stability of iron-bearing carbonates in the deep Earth’s interior. United States. https://doi.org/10.1038/ncomms15960
Cerantola, Valerio, Bykova, Elena, Kupenko, Ilya, Merlini, Marco, Ismailova, Leyla, McCammon, Catherine, Bykov, Maxim, Chumakov, Alexandr I., Petitgirard, Sylvain, Kantor, Innokenty, Svitlyk, Volodymyr, Jacobs, Jeroen, Hanfland, Michael, Mezouar, Mohamed, Prescher, Clemens, Rüffer, Rudolf, Prakapenka, Vitali B., and Dubrovinsky, Leonid. Wed . "Stability of iron-bearing carbonates in the deep Earth’s interior". United States. https://doi.org/10.1038/ncomms15960. https://www.osti.gov/servlets/purl/1393163.
@article{osti_1393163,
title = {Stability of iron-bearing carbonates in the deep Earth’s interior},
author = {Cerantola, Valerio and Bykova, Elena and Kupenko, Ilya and Merlini, Marco and Ismailova, Leyla and McCammon, Catherine and Bykov, Maxim and Chumakov, Alexandr I. and Petitgirard, Sylvain and Kantor, Innokenty and Svitlyk, Volodymyr and Jacobs, Jeroen and Hanfland, Michael and Mezouar, Mohamed and Prescher, Clemens and Rüffer, Rudolf and Prakapenka, Vitali B. and Dubrovinsky, Leonid},
abstractNote = {The presence of carbonates in inclusions in diamonds coming from depths exceeding 670 km are obvious evidence that carbonates exist in the Earth’s lower mantle. However, their range of stability, crystal structures and the thermodynamic conditions of the decarbonation processes remain poorly constrained. We investigate the behaviour of pure iron carbonate at pressures over 100 GPa and temperatures over 2,500 K using single-crystal X-ray diffraction and Mossbauer spectroscopy in laser-heated diamond anvil cells. On heating to temperatures of the Earth’s geotherm at pressures to B 50 GPa FeCO 3 partially dissociates to form various iron oxides. Furthermore, at higher pressures FeCO 3 forms two new structures— tetrairon(III) orthocarbonate Fe$3+\atop{4}$C3O12 and diiron(II) diiron(III) tetracarbonate Fe$2+\atop{2}$ Fe$3+\atop{2}$C4 O13, both phases containing CO4 tetrahedra. Fe4 C4 O13 is stable at conditions along the entire geotherm to depths of at least 2,500 km, thus demonstrating that self-oxidation-reduction reactions can preserve carbonates in the Earth’s lower mantle.},
doi = {10.1038/ncomms15960},
journal = {Nature Communications},
number = ,
volume = 8,
place = {United States},
year = {Wed Jul 19 00:00:00 EDT 2017},
month = {Wed Jul 19 00:00:00 EDT 2017}
}

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Cited by: 70 works
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Figures / Tables:

Figure 1 Figure 1: Stability diagram of FeCO3 at high P-T. Symbols and phase regions identified in experiments: magnesite-structured FeCO3 (orange dots), oxide(s) and recrystallized FeCO3 (orange-blue dots), tetrairon(III) orthocarbonate Fe4C3O12 (red triangles), diiron(II) diiron(III) tetracarbonate Fe4C4O13+ Fe4C3O12 (red-green dots), Fe4C4O12+ oxides (red-blue dots), Fe4C4O13+ oxides (green-blue dots), FeCO3 decomposition to Fe3O4+C+CO2more » (refs 29,30; dark blue area), high- and low- spin FeCO3 (dark and light orange area, respectively), incongruent melting of FeCO3 (light blue area), and formation of HP-carbonates Fe4C3O12 and Fe4C4O13 (red and green areas). The grey dashed curve is the expected mantle geotherm. The black solid lines are from refs 29,30. Black dashed lines indicate the region delimiting the spin transition in magnesio-siderite at HPHT from Liu et al. The vertical dashed black line separates the regions in which the formation of $a$-Fe2O3 and HP-Fe3O4 was observed upon incongruent melting of FeCO3.« less

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  • DOI: 10.3204/pubdb-2019-02016

Pressure driven spin transition in siderite and magnesiosiderite single crystals
text, January 2017

  • Weis, Christopher; Sternemann, Christian; Cerantola, Valerio
  • Deutsches Elektronen-Synchrotron, DESY, Hamburg
  • DOI: 10.3204/pubdb-2017-12450

High-pressure synthesis of a nitrogen-rich inclusion compound $ReN_{8}·xN_{2}$ with conjugated polymeric nitrogen chains
text, January 2018

  • Bykov, Maxim; Bykova, Elena; Koemets, Egor
  • Deutsches Elektronen-Synchrotron, DESY, Hamburg
  • DOI: 10.3204/pubdb-2018-02309

Polymerized 4-Fold Coordinated Carbonate Melts in the Deep Mantle
journal, April 2019

  • Sanloup, Chrystèle; Hudspeth, Jessica M.; Afonina, Veronika
  • Frontiers in Earth Science, Vol. 7
  • DOI: 10.3389/feart.2019.00072

Natural diamond formation by self-redox of ferromagnesian carbonate
journal, February 2018

  • Chen, Ming; Shu, Jinfu; Xie, Xiande
  • Proceedings of the National Academy of Sciences, Vol. 115, Issue 11
  • DOI: 10.1073/pnas.1720619115

Pressure driven spin transition in siderite and magnesiosiderite single crystals
text, January 2017

  • Weis, Christopher; Sternemann, Christian; Cerantola, Valerio
  • Deutsches Elektronen-Synchrotron, DESY, Hamburg
  • DOI: 10.3204/pubdb-2017-12450

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.