Startseite Influence of the octahedral cationic-site occupancies on the framework vibrations of Li-free tourmalines, with implications for estimating temperature and oxygen fugacity in host rocks
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Influence of the octahedral cationic-site occupancies on the framework vibrations of Li-free tourmalines, with implications for estimating temperature and oxygen fugacity in host rocks

  • Anke Watenphul EMAIL logo , Jochen Schlüter , Ferdinando Bosi , Henrik Skogby , Thomas Malcherek und Boriana Mihailova
Veröffentlicht/Copyright: 29. Oktober 2016
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American Mineralogist
Aus der Zeitschrift American Mineralogist Band 101 Heft 11

Abstract

Tourmalines, XY3Z6T6O18(BO3)3V3W, are excellent petrogenetic indicators as they capture the signature of the host-rock bulk composition. Raman spectra of tourmalines can be used as fingerprints for species identification and crystal-chemical analysis. While Li-bearing species are directly distinguishable by the shape of the OH-stretching vibrations, the discrimination of Mg- and Fe-dominant species can be hindered by the coexistence of at least two types of octahedrally coordinated Rn+ cations.

Thirty Li-free tourmaline samples comprising 14 different species were studied by Raman spectroscopy and electron microprobe. All nine Fe3+-bearing samples were also analyzed by single-crystal X-ray diffraction and Mössbauer spectroscopy. The Raman scattering analysis shows that Mg-dominant species can be immediately distinguished from Fe-dominant species by the shape of the vibrational modes at ~200–240 cm–1 arising from the YO6 vibrations. Trivalent Fe can be observed and quantified by shifts of the framework vibrations toward lower wavenumbers. The position of the main ZO6 vibrational mode (275–375 cm–1) can be used to determine the ZFe3+ content, while the YFe3+ content can be inferred from the position of the peak at ~315 cm–1. Fits to the data points indicate that the homovalent substitution of Fe3+ for Al3+ leads to a considerably larger downward shift of the ZO6 vibrational mode than the heterovalent substitution Mg2+ for Al3+. The intensity ratio of the two major YO6 vibrational modes (200–240 cm–1) of the fully characterized Fe3+-bearing samples reflects the amount of Y-site Mg and thus can be used to deduce the site-occupancy disorder of Mg over the Y and Z site for tourmaline species with Mg ≤2 apfu.

By combining the information from framework and OH-stretching vibrations, Raman spectroscopy alone can be used as a micrometer-scale sensitive non-destructive method for the analysis of tourmaline crystal chemistry including trivalent Fe, which is the major tracer for oxygen fugacity and central for intersite geothermometry.

Keywords: Tourmaline; Raman spectroscopy; framework vibrations; trivalent iron

Acknowledgement

Financial support by the Deutsche Forschungsgemeinschaft DFG (MI 1127/7-1 and SCHL 549/6-1) and Sapienza University of Rome (Prog. Università 2015 to F.B.) are gratefully acknowledged. The authors thank P. Stutz for sample preparation, S. Heidrich for conducting electron microprobe analysis, M. Lensing-Burgdorf for parts of the Raman spectroscopic measurements, as well as M. Ciriotti and I. Baksheev for providing sample S57 and the bosiite sample, respectively. We also thank M. Koch-Müller and J. Cempírek for their constructive reviews and G.D. Gatta for the editorial handling of the manuscript.

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Received: 2016-4-22
Accepted: 2016-7-6
Published Online: 2016-10-29
Published in Print: 2016-11-1

© 2016 by Walter de Gruyter Berlin/Boston

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https://doi.org/10.2138/am-2016-5820
Schlagwörter für diesen Artikel
Tourmaline; Raman spectroscopy; framework vibrations; trivalent iron

Artikel in diesem Heft

  1. Highlights and Breakthroughs
  2. Melts, mush, and more: Evidence for the state of intermediate-to-silicic arc magmatic systems
  3. Investigating petrologic indicators of magmatic processes in volcanic rocks
  4. Nucleation rates of spherulites in natural rhyolitic lava
  5. Review
  6. Silicic magma reservoirs in the Earth’s crust
  7. Special Collection: New Advances in Subduction Zone Magma Genesis
  8. Petrogenesis of antecryst-bearing arc basalts from the Trans-Mexican Volcanic Belt: Insights into along-arc variations in magma-mush ponding depths, H2O contents, and surface heat flux
  9. Special Collection: Apatite: A Common Mineral, Uncommonly Versatile
  10. Wayneburnhamite, Pb9Ca6(Si2O7)3(SiO4)3, an apatite polysome: The Mn-free analog of ganomalite from Crestmore, California
  11. Special Collection: Apatite: A Common Mineral, Uncommonly Versatile
  12. U-Pb LA-ICP-MS dating of apatite in mafic rocks: Evidence for a major magmatic event at the Devonian-Carboniferous boundary in the Armorican Massif (France)
  13. Special Collection: Apatite: A Common Mineral, Uncommonly Versatile
  14. Quantification of CO2 concentration in apatite
  15. Special Collection: Apatite: a Common Mineral, Uncommonly Versatile
  16. Phosphate minerals in the H group of ordinary chondrites, and fluid activity recorded by apatite heterogeneity in the Zag H3-6 regolith breccia
  17. Special Collection: Apatite: A Common Mineral, Uncommonly Versatile
  18. In situ elemental and isotopic analysis of fluorapatite from the Taocun magnetite-apatite deposit, Eastern China: Constraints on fluid metasomatism
  19. Special Collection: Geology and Geobiology of Lassen Volcanic National Park
  20. Acido-thermotolerant fungi from Boiling Springs Lake, LVNP: Potential for lignocellulosic biofuels
  21. Research Article
  22. Solid solution along the synthetic LiAISi2O6-LiFeSi2O6 (spodumene-ferri-spodumene) join: A general picture of solid solutions, bond lengths, lattice strains, steric effects, symmetries, and chemical compositions of Li clinopyroxenes
  23. Research Article
  24. Formation of hydrous stishovite from coesite in high-pressure hydrothermal environments
  25. Research Article
  26. Raman characterization of synthetic magnesian calcites
  27. Research Article
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  33. Research Article
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  35. Research Article
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  37. Book Review
  38. Book Review: Pore-Scale Geochemical Processes, RIMG Volume 80
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