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Gas-mediated trace element incorporation into rhyolite-hosted topaz: A synchrotron microbeam XAS study

  • D.R. Schaub , Paul Northrup , Hanna Nekvasil ORCID logo , Tristan Catalano and Ryan Tappero
Published/Copyright: November 30, 2023
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American Mineralogist
From the journal American Mineralogist Volume 108 Issue 12

Abstract

Magmatic gas exsolving during late-stage cooling of shallow magmas has been considered an important facilitator of low-pressure alteration and metal transport. However, the chemical properties of such gas, particularly its metal transport mechanisms and capacity, remain elusive. Trace elements in minerals produced by gas-mediated surface reaction or precipitation from gas capture details of gas composition and reaction pathways. However, interpretation of mineral trace element contents is dependent on understanding crystallographic controls on gas/mineral partitioning. This work investigates the structural accommodation of As, Mn, Ga, Ge, Fe, and Ti in vapor-deposited topaz of vesicular topaz rhyolite from the Thomas Range, Utah, through single-crystal synchrotron microbeam X-ray techniques on picogram quantities of those trace elements. X-ray absorption near edge structure (XANES) data indicates that these elements are incorporated into topaz as As5+, Fe3+, Mn3+, Ti4+, Ga3+, and Ge4+. Extended X-ray absorption fine structure (EXAFS) analysis for these trace elements, compared to EXAFS of structural Al and Si, reveals that As5+ and Ge4+ are incorporated directly into the tetrahedral site of the topaz structure, with the octahedral site accommodating Mn3+, Fe3+, Ga3+, and Ti4+. For As5+ and Fe3+, the structural impact of substitution extends to at least second neighbors (other elements were only resolvable to first neighbors). Further interpretation of the EXAFS results suggests that the substitution of Ti4+ results in increased distortion of the octahedral site, while the other trace elements induce more uniform expansion correlating in magnitude to their ionic radius. Comparison of quantified X-ray fluorescence (XRF) data for two topaz crystals from this rhyolite reveals variable trace element concentrations for As5+, Fe3+, Ga3+, and Ti4+, reflective of a source gas undersaturated in these trace elements changing in concentration over the period of topaz deposition. The identical Ge4+ content of the two topaz crystals suggests that Ge4+ in the gas was buffered by the growth of another Ge4+-bearing phase, such as quartz. The very low Mn3+ content in the topaz crystals does not reflect the abundance of Mn3+ in the gas (saturation of Mn is evidenced by coexisting bixbyite). Instead, it suggests a strong Jahn-Teller inhibitory effect to the substitution of Mn3+ for Al3+ in the distorted octahedral site of topaz. It is proposed that exsolution of an HF-enriched gas from cooling rhyolitic magma led to local scouring of Al, Si, and trace metals from the magma. Once topaz crystals nucleated, self-catalyzed reactions that recycle HF led to continued growth of topaz.

Keywords: Crystal structure; EXAFS; igneous rocks; magmatic gas; rhyolite; silicates; single-crystal EXAFS; topaz; trace elements; vapor phase; X-ray absorption spectroscopy; Experimental Halogens in Honor of Jim Webster

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

Funding statement: Support for this work was provided through grants EAR 1725212 (to H.N.) and EAR 2105876 (to H.N. and P.N.) via the Petrology and Geochemistry Program of the National Science Foundation. This research used the XFM and TES beamlines of the National Synchrotron Light Source II, and Beamline X15B of the National Synchrotron Light Source, U.S. Department of Energy (DOE) Office of Science User Facilities operated for the DOE by Brookhaven National Laboratory under Contract Nos. DE-SC0012704 and DE-AC02-98CH10886, respectively. Measurements supported by the Tender Energy Microspectroscopy Consortium.

Acknowledgments

The authors thank G. Lamble and J.-F. Lee for their help and expertise in the initial EXAFS measurements of bulk topaz (Northrup et al. 1995), which established the foundation for our current work. We appreciate Tiffany Victor’s assistance in measuring some of the oxidation state standards.

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Received: 2021-12-15
Accepted: 2021-12-23
Published Online: 2023-11-30
Published in Print: 2023-12-15

© 2023 by Mineralogical Society of America

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https://doi.org/10.2138/am-2022-8417
Keywords for this article
Crystal structure; EXAFS; igneous rocks; magmatic gas; rhyolite; silicates; single-crystal EXAFS; topaz; trace elements; vapor phase; X-ray absorption spectroscopy; Experimental Halogens in Honor of Jim Webster

Articles in the same Issue

  1. Evidence for abundant organic matter in a Neoarchean banded iron formation
  2. Electrical properties of iron sulfide-bearing dunite under pressure: Effect of temperature, composition, and annealing time
  3. Gas-mediated trace element incorporation into rhyolite-hosted topaz: A synchrotron microbeam XAS study
  4. 10.2138/am-2023-8927
  5. A dunite fragment in meteorite Northwest Africa (NWA) 11421: A piece of the Moon’s mantle
  6. 10.2138/am-2023-9054
  7. Hydrogen bond symmetrization and high-spin to low-spin transition of ε-FeOOH at the pressure of Earth’s lower mantle
  8. CURIES: Compendium of uranium Raman and infrared experimental spectra
  9. S 2 − and S 3 − radicals and the S 4 2 − polysulfide ion in lazurite, haüyne, and synthetic ultramarine blue revealed by resonance Raman spectroscopy
  10. Efect of faceting on olivine wetting properties
  11. The obscuring efect of magma recharge on the connection of volcanic-plutonic rocks
  12. In-situ study of microstructures induced by the olivine to wadsleyite transformation at conditions of the 410 km depth discontinuity
  13. Effect of pre-existing crystals and melt homogeneity on the decompression-induced crystallization of hydrous rhyodacite magma
  14. Origin of clinopyroxene-ilmenite symplectites in mafic granulites from eastern parts of the Chotanagpur granite gneissic complex, East Indian shield
  15. Single-crystal analysis of La-doped pyromorphite [Pb5(PO4)3Cl]
  16. Crystal structure of calcium-ferrite type NaAlSiO4 up to 45 GPa
  17. Revision of the CaMgSi2O6-CO2 P-T phase diagram at 3–6 GPa
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