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Thermal expansion of minerals in the tourmaline supergroup

  • Guy L. Hovis , Mario Tribaudino ORCID logo , Caitlin Altomare and Ferdinando Bosi ORCID logo
Published/Copyright: May 31, 2023
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American Mineralogist
From the journal American Mineralogist Volume 108 Issue 6

Abstract

The thermal behavior of 15 natural tourmaline samples has been measured by X-ray powder diffraction from room temperature to ~930 °C. Axial thermal expansion is generally greater along the c crystallographic axis (αc 0.90–1.05 × 10–5/K) than along the a crystallographic axis and the symmetrically equivalent b axis (αa 0.47–0.60 × 10–5/K). Ferro-bearing samples show lower expansion along a than in other tourmalines. In povondraite the thermal expansion along the c axis is higher than in other tourmalines, whereas along a it is lower [αa = 0.31(2) and αc = 1.49(3) × 10–5/K]. Volume expansion in the tourmaline-supergroup minerals is relatively low compared with other silicates such as pyroxenes and amphiboles. Volume also exhibits a relatively narrow range of thermal expansion coefficients (1.90–2.05 × 10–5/K) among the supergroup members. An interpretation for the small changes in thermal expansion in a compositionally heterogeneous group like tourmaline is that all members, except povondraite, share a framework of dominantly ZAlO6 polyhedra that limit thermal expansion. Povondraite, with a framework dominated by ZFe3+O6 polyhedra, displays thermal expansion that is different from other members of the group.

Unit-cell dimensions of tourmalines having significant Fe2+ deviate from linearity above 400 °C on plots against temperature (T); along with the resulting substantial reduction in unit-cell volume, these efects are likely the result of deprotonation/oxidation processes. Lithium-rich and Fe2+-free tourmalines deviate similarly at T > 600 °C. In Li- and Fe2+-free tourmalines, no such deviation is observed up to the highest temperatures of our experiments. It is not clear whether this is due to cation order-disorder over Y and Z sites that occurs during the highest temperature measurements, a phenomenon that is apparently inhibited (at least in the short term) in Li-free/Mg-rich samples. If so, this must occur at a relatively rapid rate, as no difference in unit-cell values was detected at 800 °C after heating in both one- and 12-h experiments on Na-rich rossmanite.

Keywords: Tourmaline; thermal expansion; modeling; systematics; unit-cell parameters; X-ray diffraction

Acknowledgments and funding

One of the original purposes of this thermal expansion work was to involve undergraduate students at Lafayette College in meaningful research. Participating students have been coauthors of previous thermal expansion papers (Hovis et al. 2021; Tribaudino et al. 2022). One such student who focused largely on thermal expansion in the tourmaline system is coauthor of the present work; those results also have been published as a senior honors thesis at Lafayette College (Altomare 2014) and a Geological Society of America abstract (Altomare and Hovis 2014).

This thermal expansion research would not have been possible without financial support from the U.S. National Science Foundation, Earth Sciences Division, for both the X-ray equipment and student participation via grants EAR-1019809 and EAR-1028953. We are grateful as well for support from the Excel Scholars Program of Lafayette College. A Sapienza University of Rome grant (Prog. Università 2020 to F. Bosi) is also gratefully acknowledged. We could not have done this work without the tourmaline samples so generously contributed by Jeff Post and Paul Powhat (National Museum of Natural History), Frank Hawthorne (University of Manitoba), George Rossman (Caltech), George Harlow (American Museum of Natural History), and Raquel Alonso Perez and Kevin Czaja (Mineralogical and Geological Museum at Harvard University). Finally, we greatly appreciate the thoughtful reviews of this paper by Eleanor Berryman and Andreas Ertl.

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Received: 2022-05-06
Accepted: 2022-06-27
Published Online: 2023-05-31
Published in Print: 2023-06-27

© 2023 by Mineralogical Society of America

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https://doi.org/10.2138/am-2022-8580
Keywords for this article
Tourmaline; thermal expansion; modeling; systematics; unit-cell parameters; X-ray diffraction

Articles in the same Issue

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  2. Incorporation of chlorine in nuclear waste glasses using high-pressure vitrification: Solubility, speciation, and local environment of chlorine
  3. Experimental constraints on miscibility gap between apatite and britholite and REE partitioning in an alkaline melt
  4. Thermal expansion of minerals in the tourmaline supergroup
  5. Viscosity of Earth’s inner core constrained by Fe–Ni interdiffusion in Fe–Si alloy in an internal-resistive-heated diamond anvil cell
  6. The distribution of carbonate in apatite: The environment model
  7. Low-temperature crystallography and vibrational properties of rozenite (FeSO4·4H2O), a candidate mineral component of the polyhydrated sulfate deposits on Mars
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  14. Single-crystal UV/Vis absorption spectroscopy of aluminosilicate garnet: Part III. {Fe2+} + [Fe3+] → {Fe3+} + [Fe2+] intervalence charge transfer
  15. A novel method for experiments in a one-atmosphere box furnace
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