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In situ Raman vibrational spectra of siderite (FeCO3) and rhodochrosite (MnCO3) up to 47 GPa and 1100 K

  • Chao Wang , Lu’an Ren , Jesse B. Walters , Lifei Zhang and Renbiao Tao ORCID logo
Published/Copyright: January 29, 2023
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American Mineralogist
From the journal American Mineralogist Volume 108 Issue 2

Abstract

Siderite (FeCO3) and rhodochrosite (MnCO3) are two interesting carbonate minerals, which normally occur in hydrothermal deposits on deep-sea altered oceanic crust. Despite the ubiquity of carbonates in the slab, little is known of the physicochemical behavior of siderite and rhodochrosite at high-pressure (P) and high-temperature (T) conditions during slab subduction. In this study, we characterized the Raman vibrational spectra of natural siderite and rhodochrosite up to 47 GPa and 1100 K in an externally heated diamond-anvil cell (DAC). Experimental results show that the Raman frequency shifts (νi) for siderite and rhodochrosite are a function of both P and T, and the effect of the P-T cross derivative term cannot be neglected, especially at high-P and high-T conditions. Based on the functional relationship of νi-P-T, the P-T calibrants of siderite and rhodochrosite are developed, respectively. This is significant for studying the water-carbonate interaction at high P-T conditions in a DAC because the undesired change of the experimental system from traditional pressure sensors (e.g., ruby, quartz) in a reaction chamber can be avoided. Like previous studies, we observed a sharp spin transition at ~45 GPa in siderite and a phase transition from MnCO3-I to MnCO3-II at ~46 GPa for rhodochrosite at room temperature. Furthermore, we determined the isobaric and isothermal equivalents of the mode Grüneisen parameter (γiT, γiP) and the anharmonic parameter (ai) for each Raman mode of siderite and rhodochrosite. The δνi/δP, δνi/δT, γiT, γiP, and ai span a much larger value range for the external lattice modes (T, L) than internal modes (ν4, ν1) in both siderite and rhodochrosite. Combining Raman frequency shifts and the first-order Murnaghan equation of state, we also developed a method to calculate the temperature dependence of the bulk modulus (KT) for siderite and rhodochrosite, respectively.

Keywords: Siderite; rhodochrosite; Raman spectroscopy; high-P and high-T; P-T sensor; thermodynamical parameters

Funding statement: This study was supported by the National Key Research and Development Program of China (2019YFA0708501) and the NSFC Major Research Plan on West-Pacific Earth System Multispheric Interactions (project number: 92158206).

Acknowledgments

Many thanks to Chaoshuai Zhao for kindly providing the synthetic SrB4O7:Sm2+, and Freyja O’Toole for editing English. We also thank two anonymous reviewers for their constructive comments and Bin Chen (Associate Editor) for his careful editorial handling and helpful suggestions.

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Received: 2021-10-12
Accepted: 2022-02-11
Published Online: 2023-01-29
Published in Print: 2023-02-23

© 2023 Mineralogical Society of America

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https://doi.org/10.2138/am-2022-8343
Keywords for this article
Siderite; rhodochrosite; Raman spectroscopy; high-P and high-T; P-T sensor; thermodynamical parameters

Articles in the same Issue

  1. Highlights and Breakthroughs
  2. Analyses under the curve, identifying how invisible gold is held in pyrite
  3. Titanite geochemistry and textures: Implications for magmatic and post-magmatic processes in the Notch Peak and Little Cottonwood granitic intrusions, Utah
  4. Gismondine-Sr, Sr4(Al8Si8O32)·9H2O, a new strontium dominant, orthorhombic zeolite of the gismondine series from the Hatrurim Complex, Israel
  5. Lifting the cloak of invisibility: Gold in pyrite from the Olympic Dam Cu-U-Au-Ag deposit, South Australia
  6. Paragenesis and precipitation stages of Nb-Ta-oxide minerals in phosphorus-rich rare-element pegmatites (Buranga dike, Rwanda)
  7. 3D zoning of barium in alkali feldspar
  8. In situ Raman vibrational spectra of siderite (FeCO3) and rhodochrosite (MnCO3) up to 47 GPa and 1100 K
  9. Isotopic responses of magnesium to two types of dissolution-reprecipitation processes for the growth of the double-carbonate mineral norsethite
  10. Fluid-rock interaction and fluid mixing in the large Furong tin deposit, South China: New insights from tourmaline and apatite chemistry and in situ B-Nd-Sr isotope composition
  11. A neutron diffraction study of boussingaultite, (NH4)2[Mg(H2O)6](SO4)2
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  15. American Mineralogist thanks the Reviewers for 2022
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