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Crystal chemistry of spinels in the system MgAl2O4-MgV2O4-Mg2VO4

  • Ferdinando Bosi EMAIL logo , Henrik Skogby , Rosa Anna Fregola and Ulf Hålenius
Published/Copyright: March 4, 2016
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American Mineralogist
From the journal American Mineralogist Volume 101 Issue 3

Abstract

Eight spinel single-crystal samples belonging to the spinel sensu stricto-magnesiocoulsonite series (MgAl2O4-MgV2O4) were synthesized and crystal-chemically characterized by X-ray diffraction, electron microprobe and optical absorption spectroscopy. Site populations show that the tetrahedrally coordinated site (T) is populated by Mg and minor Al for the spinel sensu stricto compositions, and only by Mg for the magnesiocoulsonite compositions, while the octahedrally coordinated site (M) is populated by Al, V3+, minor Mg, and very minor amounts of V4+. The latter occurs in appreciable amounts in the Al-free magnesium vanadate spinel, T(Mg)M(Mg0.26V1.483+V0.264+)O4, showing the presence of the inverse spinel VMg2O4. The studied samples are characterized by substitution of Al3+ for V3+ and (Mg2++V4+) for 2V3+ described in the system MgAl2O4-MgV2O4-VMg2O4.

The present data in conjunction with data from the literature provide a basis for quantitative analyses of two solid-solution series MgAl2O4-MgV23+O4 and MgV23+O4-V4+Mg2O4. Unit-cell parameter increases with increasing V3+ along the series MgAl2O4-MgV2O4 (8.085–8.432 Å), but only slightly increases with increasing V3+ along the series VMg2O4-MgV2O4 (8.386–8.432 Å). Although a solid solution could be expected between the MgAl2O4 and VMg2O4 end-members, no evidence was found. Amounts of V4+ are nearly insignificant in all synthetic Al-bearing vanadate spinels, but are appreciable in Al-free vanadate spinel.

An interesting observation of the present study is that despite the observed complete solid-solution along the MgAl2O4-MgV2O4 and MgV2O4-VMg2O4 series, the spinel structure seems to be unable to stabilize V4+ in any intermediate members on the MgAl2O4-Mg2VO4 join even at high oxygen fugacities. This behavior indicates that the accommodation of specific V-valences can be strongly influenced by crystal-structural constraints, and any evaluation of oxygen fugacities during mineral formation based exclusively on V cation valence distributions in spinel should be treated with caution. The present study underlines that the V valency distribution in spinels is not exclusively reflecting oxygen fugacities, but also depends on activities and solubilities of all chemical components in the crystallization environment.

Keywords: Vanadate spinel; magnesiocoulsonite; electron microprobe; crystal synthesis; X-ray diffraction; optical absorption spectroscopy

Special collection papers can be found online at http://www.minsocam.org/MSA/AmMin/special-collections.html.

Acknowledgments

The authors appreciate constructive reviews by Thomas Armbruster and an anonymous reviewer, and the manuscript handling by the Associate Editor Kristina Lilova. Chemical analyses were carried out with the kind assistance of M. Serracino to whom the authors express their gratitude. F.B. is grateful to financial support from the project Università Sapienza 2014. R.A.F. is grateful to the Swedish Museum of Natural History that partly funded her visit at Stockholm laboratories for this project.

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  1. Manuscript handled by Kristina Lilova.

Received: 2015-7-23
Accepted: 2015-10-18
Published Online: 2016-3-4
Published in Print: 2016-3-1

© 2016 by Walter de Gruyter Berlin/Boston

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https://doi.org/10.2138/am-2016-5508
Keywords for this article
Vanadate spinel; magnesiocoulsonite; electron microprobe; crystal synthesis; X-ray diffraction; optical absorption spectroscopy

Articles in the same Issue

  1. Editorial
  2. The most-cited journal in mineralogy and petrology (and what scientists can learn from baseball)
  3. Fluids in the Crust
  4. Fluids in the crust during regional metamorphism: Forty years in the Waterville limestone
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  7. Research Article
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  10. Constraints on the early delivery and fractionation of Earth’s major volatiles from C/H, C/N, and C/S ratios
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  13. Special Collection: Advances in Ultrahigh-Pressure Metamorphism
  14. Multi-stage barite crystallization in partially melted UHP eclogite from the Sulu belt, China
  15. Spinels Renaissance: The Past, Present, and Future of those Ubiquitous Minerals and Materials
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