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Smoking gun for thallium geochemistry in volcanic arcs: Nataliyamalikite, TlI, a new thallium mineral from an active fumarole at Avacha Volcano, Kamchatka Peninsula, Russia

  • Victor Okrugin , Michael Favero , Amelia Liu , Barbara Etschmann , Ekaterina Plutachina , Stuart Mills , Andrew G. Tomkins , Mariaya Lukasheva , Vladimir Kozlov , Svetlana Moskaleva , Mikhail Chubarov and Joël Brugger EMAIL logo
Published/Copyright: July 31, 2017
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American Mineralogist
From the journal American Mineralogist Volume 102 Issue 8

Abstract

This paper describes the new mineral nataliyamalikite, the orthorhombic form of thallium iodide (TlI), from high-temperature fumaroles from the Avacha volcano, Kamchatka Peninsula, Russia. We also present some chemical analyses showing extreme enrichment of Tl in the volcanic gases at the Avacha volcano, and a review of thallium geochemistry that highlights the fascinating processes that led to the formation of nataliyamalikite.

Nataliyamalikite occurs as pseudo-cubic nanocrystals (≤0.5 µm) within vacuoles in an As-(Te)-rich amorphous sulfur matrix and rarely as irregularly shaped aggregates up to ~50 µm in diameter within the amorphous sulfur matrix. Associated minerals include an unidentified Tl-As-S mineral, barite, and rare inclusions of a Re-Cu-bearing phase. The mean empirical composition based on four EDS analyses is Tl1.00(I0.95Br0.03Cl0.02), corresponding to the ideal formula TlI. Nataliyamalikite crystallizes in the orthorhombic system, space group Cmcm, which is consistent with the low-temperature (<175 °C) synthetic TlI polymorph. EBSD data reveal that some grains retain the cubic symmetry (Pm3m) of the high-temperature polymorph, although most analyzed grains display the orthorhombic symmetry. Single-crystal X-ray studies of material extracted by the focused ion beam-scanning electron microscopy (FIB-SEM) technique, and carried out on the MX2 macromolecular beamline of the Australian Synchrotron, determined the following cell dimensions: a = 4.5670(9), b = 12.803(3), c = 5.202(1) Å, V = 304.2(1) Å3, and Z = 4. The six strongest calculated X-ray reflections and their relative intensities are: 3.31 (100), 2.674 (73), 3.20 (43), 2.601 (28), 2.019 (21), and 2.284 Å (19). The combination of EBSD analysis (providing an efficient test of the crystallinity and crystal symmetry of a population of micrometer-sized grains) and synchrotron single-crystal X-ray micro-diffraction (beam size ~7.5 µm) on micro-aggregates extracted using FIB-SEM opens the way to the characterization of challenging specimen—in this case, the sulfur matrix is highly beam sensitive, and the nataliyamalikite grains could not be isolated using optical microscopy.

The high-temperature (>600 °C) sulfidic (~1.2 wt% S) vapors at Avacha are extremely enriched in thallium; with 34 ppm, they contain an order of magnitude more Tl than the richest volcanic gases analyzed to date and ~100× more Tl than most metal-rich fumarolitic fluids associated with volcanic arcs. The formation of nataliyamalikite illustrates the complex processes that control thallium geochemistry in magmatic arc systems. Thallium minerals have now been reported in andesitic (Avacha), basaltic (Tolbachik, Kamchatka), as well as rhyolitic (Vulcano, Eolian Islands, Italy) volcanoes. Ultimately, these thallium minerals result from the transfer of thallium from subducted sediments to volcanic gases in arc volcanoes. We suggest that the extremely thallium-enriched vapors from which nataliyamalikite formed result from complex and transient interactions between Tl-rich sulfosalt melts and magmatic vapors, a process that may be important in controlling metal distribution in boiling epithermal systems.

Keywords: Nataliyamalikite; new mineral; thallium; fumaroles; vapor transport; Avacha Volcano; Kamchatka Peninsula; Russia

Acknowledgments

We acknowledge the support of MCEM for access to FIB–SEM facilities, and the Australian Synchrotron for beamtime. Jason Price from the Australian Synchrotron is thanked for help with processing the data. Chairman Ulf Hålenius and members of IMA-CNMMN are gratefully acknowledged for feedback on the new mineral proposal. Stefan Ansermet (Lausanne, Switzerland) helped with fieldwork at Avacha in Summer 2015, and Natalja Malik contributed samples and geochemical data. Kurt Hollocher generously granted permission to use his graphics as the background for Figure 6. The manuscript benefitted from insightful reviews by Andrew Christy and an anonymous reviewer.

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Received: 2016-12-15
Accepted: 2017-4-10
Published Online: 2017-7-31
Published in Print: 2017-8-28

© 2017 by Walter de Gruyter Berlin/Boston

Articles in the same Issue

  2. How many boron minerals occur in Earth’s upper crust?
  3. Outlooks in Earth and Planetary Materials
  4. Network analysis of mineralogical systems
  5. Special collection: From magmas to ore deposits
  6. Geochemistry of the Cretaceous Kaskanak Batholith and genesis of the Pebble porphyry Cu-Au-Mo deposit, Southwest Alaska
  7. Special collection: From magmas to ore deposits
  8. Physicochemical controls on bismuth mineralization: An example from Moutoulas, Serifos Island, Cyclades, Greece
  9. Special collection: Earth analogs for martian geological materials and processes
  10. Geochemistry and mineralogy of a saprolite developed on Columbia River Basalt: Secondary clay formation, element leaching, and mass balance during weathering
  11. Special collection: Apatite: A common mineral, uncommonly versatile
  12. An ab-initio study of the energetics and geometry of sulfide, sulfite, and sulfate incorporation into apatite: The thermodynamic basis for using this system as an oxybarometer
  13. Special collection: Dynamics of magmatic processes
  14. The role of modifier cations in network cation coordination increases with pressure in aluminosilicate glasses and melts from 1 to 3 GPa
  16. Nitrides and carbonitrides from the lowermost mantle and their importance in the search for Earth’s “lost” nitrogen
  18. Accounting for the species-dependence of the 3500 cm−1 H2Ot infrared molar absorptivity coefficient: Implications for hydrated volcanic glasses
  20. A finite strain approach to thermal expansivity’s pressure dependence
  22. Ilmenite breakdown and rutile-titanite stability in metagranitoids: Natural observations and experimental results
  24. Single-crystal equations of state of magnesiowüstite at high pressures
  26. Analysis of erionites from volcaniclastic sedimentary rocks and possible implications for toxicological research
  28. Reconstructive phase transitions induced by temperature in gmelinite-Na zeolite
  30. Smoking gun for thallium geochemistry in volcanic arcs: Nataliyamalikite, TlI, a new thallium mineral from an active fumarole at Avacha Volcano, Kamchatka Peninsula, Russia
  32. How to facet gem-quality chrysoberyl: Clues from the relationship between color and pleochroism, with spectroscopic analysis and colorimetric parameters
  33. Letter
  34. Mn-Fe systematics in major planetary body reservoirs in the solar system and the positioning of the Angrite Parent Body: A crystal-chemical perspective
  35. Letter
  36. Dolomite-IV: Candidate structure for a carbonate in the Earth’s lower mantle
  37. Book Review
  38. Book Review
https://doi.org/10.2138/am-2017-6057
Keywords for this article
Nataliyamalikite; new mineral; thallium; fumaroles; vapor transport; Avacha Volcano; Kamchatka Peninsula; Russia

Articles in the same Issue

  2. How many boron minerals occur in Earth’s upper crust?
  3. Outlooks in Earth and Planetary Materials
  4. Network analysis of mineralogical systems
  5. Special collection: From magmas to ore deposits
  6. Geochemistry of the Cretaceous Kaskanak Batholith and genesis of the Pebble porphyry Cu-Au-Mo deposit, Southwest Alaska
  7. Special collection: From magmas to ore deposits
  8. Physicochemical controls on bismuth mineralization: An example from Moutoulas, Serifos Island, Cyclades, Greece
  9. Special collection: Earth analogs for martian geological materials and processes
  10. Geochemistry and mineralogy of a saprolite developed on Columbia River Basalt: Secondary clay formation, element leaching, and mass balance during weathering
  11. Special collection: Apatite: A common mineral, uncommonly versatile
  12. An ab-initio study of the energetics and geometry of sulfide, sulfite, and sulfate incorporation into apatite: The thermodynamic basis for using this system as an oxybarometer
  13. Special collection: Dynamics of magmatic processes
  14. The role of modifier cations in network cation coordination increases with pressure in aluminosilicate glasses and melts from 1 to 3 GPa
  16. Nitrides and carbonitrides from the lowermost mantle and their importance in the search for Earth’s “lost” nitrogen
  18. Accounting for the species-dependence of the 3500 cm−1 H2Ot infrared molar absorptivity coefficient: Implications for hydrated volcanic glasses
  20. A finite strain approach to thermal expansivity’s pressure dependence
  22. Ilmenite breakdown and rutile-titanite stability in metagranitoids: Natural observations and experimental results
  24. Single-crystal equations of state of magnesiowüstite at high pressures
  26. Analysis of erionites from volcaniclastic sedimentary rocks and possible implications for toxicological research
  28. Reconstructive phase transitions induced by temperature in gmelinite-Na zeolite
  30. Smoking gun for thallium geochemistry in volcanic arcs: Nataliyamalikite, TlI, a new thallium mineral from an active fumarole at Avacha Volcano, Kamchatka Peninsula, Russia
  32. How to facet gem-quality chrysoberyl: Clues from the relationship between color and pleochroism, with spectroscopic analysis and colorimetric parameters
  33. Letter
  34. Mn-Fe systematics in major planetary body reservoirs in the solar system and the positioning of the Angrite Parent Body: A crystal-chemical perspective
  35. Letter
  36. Dolomite-IV: Candidate structure for a carbonate in the Earth’s lower mantle
  37. Book Review
  38. Book Review
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