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Crystal structure and Raman spectroscopic studies of OH stretching vibrations in Zn-rich fluor-elbaite

  • Adam Pieczka ORCID logo EMAIL logo , Andreas Ertl , Bożena Gołębiowska , Piotr Jeleń , Jakub Kotowski , Krzysztof Nejbert , Marcin Stachowicz and Gerald Giester
Published/Copyright: October 28, 2020
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American Mineralogist
From the journal American Mineralogist Volume 105 Issue 11

Abstract

Zinc-rich fluor-elbaite from Piława Górna, Poland, was studied by electron microprobe (EPMA), single-crystal X‑ray difraction (SREF), and Raman spectroscopy (RS) to check the possibility of the application of RS to draw crystal-chemical conclusions for Al-rich and Li-bearing tourmalines on basis of the O–H stretching vibrations in the spectral range 3400–3800 cm–1. This tourmaline, forming a thin metasomatic zone around gahnite, features varying compositions with a ZnO content reaching in the studied fragment of 5.70(12) wt%. The crystal structure of this Zn-rich fluor-elbaite [a = 15.921(1), c = 7.127(1) Å] was refined with a R1 value of 1.67%. Its formula was determined on the basis of electron-microprobe and structure refinement as X(Na0.84◻0.14Ca0.01)Σ1.00Y(Al1.06Li0.84Zn0.69Fe0.322+Mn0.09Σ3.00ZAl6BO33TSi6O18V(OH)3WF0.65OH0.26O0.09.The deconvolution of the O–H stretching vibration bands, performed by fitting of an input model of component bands with Gaussian function shapes for the empirical spectrum, indicates that each of the three maxima assigned for VOH bonded to YAl3+, Y2+, and YLi+ and with the total integral intensity of at least 75% of the total OH content could be resolved into 1 to 3 bands, depending on the X-site occupation (vacancies, Na+, and Ca2+). The deconvolution indicates further that several low intense bands of WO–H modes above a Raman shift of 3600 cm–1, totally reaching ≤25%, are dependent on the occupation of triplets of YYY cations bonded to the hydroxyl. These WO–H modes are also influenced by the X-site occupation. Due to ordering of all octahedral cations (except Al) at the Y site and a complete occupation of the Z site by Al and the V site by OH, it seems possible to evaluate the Li and OH contents in a Al-rich and Li-bearing tourmaline directly from the Raman spectrum. By using the ratio VOHIYAlZAlZAl/(VOHIYZZ + WOHIYYY) as evaluated from RS, corresponding to the ratio YAl/V+WOH in the crystal, the formula of the Zn-rich fluor-elbaite can be calculated as X(Na0.85□0.14Ca0.01)∑1.00Y(Al1.11Y1.112+Li0.78)∑3.00ZAl6(BO3)3(Si6O18)(OH)3(F0.65OH0.13O0.22),where Y2+ = Zn + Fe + Mn. The formula, determined only on basis of EPMA and deconvolution of RS in the O–H stretching bands, corresponds very well (≤1 SD range of EPMA) to the formula determined on basis of EPMA and SREF. This result implicates that the O–H stretching vibrations, measured by Raman spectroscopy, could be applied for Al-rich and Li-bearing tourmalines as a useful tool for providing additional information for determining the crystal-chemical formula. It is also very helpful when crystal structural data are not available.

Keywords: Zn-rich fluor-elbaite; structure refinement; Raman spectroscopy; OH stretching vibrations; lithium content; hydroxyl content; Lithium; Beryllium; and Boron: Quintessentially Crustal

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

Acknowledgments and Funding

We thank two anonymous reviewers and the technical reviewer for their comments that were very helpful to improve the manuscript. We are also very indebted to Edward S. Grew for the careful editorial handling. This study was supported by the National Science Centre (Poland) grant 2015/19/B/ST10/01809 and AGH UST grant 16.16.140.315, both to A.P., and in part by the Austrian Science Fund (FWF) project no. P31049-N29 (A.E.).

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Received: 2019-11-09
Accepted: 2020-04-13
Published Online: 2020-10-28
Published in Print: 2020-11-25

© 2020 Walter de Gruyter GmbH, Berlin/Boston

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  1. Parageneses of TiB2 in corundum xenoliths from Mt. Carmel, Israel: Siderophile behavior of boron under reducing conditions
  2. Crystal structure and Raman spectroscopic studies of OH stretching vibrations in Zn-rich fluor-elbaite
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  13. Magmatic haggertyite in olivine lamproites of the West Kimberley region, Western Australia
  14. Trace elements in sulfides from the Maozu Pb-Zn deposit, Yunnan Province, China: Implications for trace-element incorporation mechanisms and ore genesis
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https://doi.org/10.2138/am-2020-7360
Keywords for this article
Zn-rich fluor-elbaite; structure refinement; Raman spectroscopy; OH stretching vibrations; lithium content; hydroxyl content; Lithium; Beryllium; and Boron: Quintessentially Crustal

Articles in the same Issue

  1. Parageneses of TiB2 in corundum xenoliths from Mt. Carmel, Israel: Siderophile behavior of boron under reducing conditions
  2. Crystal structure and Raman spectroscopic studies of OH stretching vibrations in Zn-rich fluor-elbaite
  3. Crystal structure of Ag-exchanged levyne intergrown with erionite: Single-crystal X-ray diffraction and Molecular Dynamics simulations
  4. Br diffusion in phonolitic melts: Comparison with fluorine and chlorine diffusion
  5. Crystal chemistry and microfeatures of gadolinite imprinted by pegmatite formation and alteration evolution
  6. A new occurrence of corundum in eucrite and its significance
  7. Zircon survival in shallow asthenosphere and deep lithosphere
  8. Reconsidering initial Pb in titanite in the context of in situ dating
  9. Solubility of Na2SO4 in silica-saturated solutions: Implications for REE mineralization
  10. Vanadium micro-XANES determination of oxygen fugacity in olivine-hosted glass inclusion and groundmass glasses of martian primitive shergottite Yamato 980459
  11. Donwilhelmsite, [CaAl4Si2O11], a new lunar high-pressure Ca-Al-silicate with relevance for subducted terrestrial sediments
  12. Magnetite texture and trace-element geochemistry fingerprint of pulsed mineralization in the Xinqiao Cu-Fe-Au deposit, Eastern China
  13. Magmatic haggertyite in olivine lamproites of the West Kimberley region, Western Australia
  14. Trace elements in sulfides from the Maozu Pb-Zn deposit, Yunnan Province, China: Implications for trace-element incorporation mechanisms and ore genesis
  15. Letter
  16. New pressure-induced phase transition to Co2Si-type Fe2P
  17. Effects of small crystallite size on the thermal infrared (vibrational) spectra of minerals
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