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Cation ordering, valence states, and symmetry breaking in the crystal-chemically complex mineral chevkinite-(Ce): X-ray diffraction and photoelectron spectroscopy studies and mechanisms of Nb enrichment

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Veröffentlicht/Copyright: 24. März 2019
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American Mineralogist
Aus der Zeitschrift American Mineralogist Band 104 Heft 4

Abstract

The crystal structures of natural Nb-rich chevkinite-(Ce) from the Biraya rare-metal deposit, Russia, crystallizing in space groups C2/m and P21/a, were solved and refined to R1 = 0.03 and R1= 0.07, respectively, from data collected with a single-crystal diffractometer. X-ray photoelectron spectroscopy was used to determine the oxidation states of the following ions: Ce3+, Fe2+, Fe3+, Ti4+, and Ti3+. Typically, Nb-rich chevkinite-(Ce) has space group C2/m, but specimens with space group P21/a were also identified. While XPS shows that both C2/m and P21/a crystal structures contain Ti4+ and Ti3+, it also indicates that Ti2+ may occur in the P21/a phases. The general formula for the Nb-rich chevkinite-(Ce) having space group C2/m is (Ce3+,La3+,Nd3+,Pr3+,Ca2+,Na+)∑4Fe2+(Fe3+,Nb5+,Al3+)∑2 (Ti4+,Ti3+,Nb5+,Mg2+)∑2(Si2O7)2O8 and with P21/a is (Ce3+,La3+,Nd3+,Pr3+,Ca2+,Na+)∑4(Fe2+,Mg2+,Ti2+)∑1 (Fe3+,Nb5+,Al3+)∑2(Ti4+,Ti3+,Nb5+)∑2(Si2O7)2O8.

It is proposed that, in addition to the substitution CFe3+ + DTi4+ ↔ CFe2+ + DNb5+, niobium can also be incorporated into chevkinite-(Ce) by the substitution 2DTi4+ ↔ DNb5+ + DTi3+, leading to substantial Nb-enrichment. The study has revealed that the distribution of cations between the various structural sites is considerably more complex than that envisaged in standard models of the chevkinite group, and that cations such as Ti can have more than one valency in the structure. Lighter elements with larger ionic radii (Mg2+) tend to occupy the D site in the C2/m crystal structure, whereas in the P21/a structure these elements (Mg2+, Ti2+) tend to enter the B site. Niobium is distributed between the C and D sites. The techniques employed provide a comprehensive representation of the distribution of cations and can be used to examine similar complexity in other mineral groups. The present study has shown that Nb can also be fractionated from residual melts.

Keywords: Chevkinite-(Ce); niobium; crystal structure; EPMA; X-ray photoelectron spectroscopy; chevkinite-group minerals; the Biraya deposit; Russia

  1. Funding: The research for this paper was in part supported by the Polish Ministry of Science and Higher Education within the Mobility Plus Fund award number 1301/ MOB/IV/2015/0. Financial support was provided by Polish National Science Centre NCN grant decision DEC-2011/03/B/ST10/05491.

Acknowledgments

We are very grateful to Stefano Merlino, Sergey Aksenov, an anonymous reviewer, and Associate Editor Alejandro Fernandez-Martinez for their very helpful comments on the manuscript, which much improved its quality. We thank the Department of Earth Sciences, Natural History Museum, London, for hosting M. Stachowicz’s year-long visit to work with M.D.W.

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Received: 2017-12-30
Accepted: 2018-12-21
Published Online: 2019-03-24
Published in Print: 2019-04-24

© 2019 Walter de Gruyter GmbH, Berlin/Boston

Artikel in diesem Heft

  1. Introduction
  2. Deep carbon cycle through five reactions
  3. Earth in five reactions: Grappling with meaning and value in science
  4. In-situ iron isotope analyses reveal igneous and magmatic-hydrothermal growth of magnetite at the Los Colorados Kiruna-type iron oxide-apatite deposit, Chile
  5. Carbon and nitrogen isotopes and mineral inclusions in diamonds from chromitites of the Mirdita ophiolite (Albania) demonstrate recycling of oceanic crust into the mantle
  6. Geochronology and trace element mobility in rutile from a Carboniferous syenite pegmatite and the role of halogens
  7. The incorporation of chlorine into calcium amphibole
  8. Crystal size distribution of amphibole grown from hydrous basaltic melt at 0.6–2.6 GPa and 860–970 °C
  9. Role of micropores, mass transfer, and reaction rate in the hydrothermal alteration process of plagioclase in a granitic pluton
  10. Lead diffusion in CaTiO3: A combined study using Rutherford backscattering and TOF-SIMS for depth profiling to reveal the role of lattice strain in diffusion processes
  11. On growth and form of etched fission tracks in apatite: A kinetic approach
  12. High-pressure behavior of liebenbergite: The most incompressible olivine-structured silicate
  13. Phase transition of wadsleyite-ringwoodite in the Mg2SiO4-Fe2SiO4 system
  14. Cation ordering, valence states, and symmetry breaking in the crystal-chemically complex mineral chevkinite-(Ce): X-ray diffraction and photoelectron spectroscopy studies and mechanisms of Nb enrichment
  15. Meyrowitzite, Ca(UO2)(CO3)2⋅5H2O, a new mineral with a novel uranyl-carbonate sheet
  16. Letter
  17. Discovery of the first natural hydride
  18. Synthesis of pigeonites for spectroscopic studies
  19. Presentation of the 2018 Roebling Medal of the Mineralogical Society of America to E. Bruce Watson
  20. Acceptance of the 2018 Roebling Medal of the Mineralogical Society of America
  21. Presentation of the Dana Medal of the Mineralogical Society of America for 2018 to Jörg Hermann
  22. Acceptance of the Dana Medal of the Mineralogical Society of America for 2018
  23. New Mineral Names
  24. Book Review
https://doi.org/10.2138/am-2019-6457
Schlagwörter für diesen Artikel
Chevkinite-(Ce); niobium; crystal structure; EPMA; X-ray photoelectron spectroscopy; chevkinite-group minerals; the Biraya deposit; Russia

Artikel in diesem Heft

  1. Introduction
  2. Deep carbon cycle through five reactions
  3. Earth in five reactions: Grappling with meaning and value in science
  4. In-situ iron isotope analyses reveal igneous and magmatic-hydrothermal growth of magnetite at the Los Colorados Kiruna-type iron oxide-apatite deposit, Chile
  5. Carbon and nitrogen isotopes and mineral inclusions in diamonds from chromitites of the Mirdita ophiolite (Albania) demonstrate recycling of oceanic crust into the mantle
  6. Geochronology and trace element mobility in rutile from a Carboniferous syenite pegmatite and the role of halogens
  7. The incorporation of chlorine into calcium amphibole
  8. Crystal size distribution of amphibole grown from hydrous basaltic melt at 0.6–2.6 GPa and 860–970 °C
  9. Role of micropores, mass transfer, and reaction rate in the hydrothermal alteration process of plagioclase in a granitic pluton
  10. Lead diffusion in CaTiO3: A combined study using Rutherford backscattering and TOF-SIMS for depth profiling to reveal the role of lattice strain in diffusion processes
  11. On growth and form of etched fission tracks in apatite: A kinetic approach
  12. High-pressure behavior of liebenbergite: The most incompressible olivine-structured silicate
  13. Phase transition of wadsleyite-ringwoodite in the Mg2SiO4-Fe2SiO4 system
  14. Cation ordering, valence states, and symmetry breaking in the crystal-chemically complex mineral chevkinite-(Ce): X-ray diffraction and photoelectron spectroscopy studies and mechanisms of Nb enrichment
  15. Meyrowitzite, Ca(UO2)(CO3)2⋅5H2O, a new mineral with a novel uranyl-carbonate sheet
  16. Letter
  17. Discovery of the first natural hydride
  18. Synthesis of pigeonites for spectroscopic studies
  19. Presentation of the 2018 Roebling Medal of the Mineralogical Society of America to E. Bruce Watson
  20. Acceptance of the 2018 Roebling Medal of the Mineralogical Society of America
  21. Presentation of the Dana Medal of the Mineralogical Society of America for 2018 to Jörg Hermann
  22. Acceptance of the Dana Medal of the Mineralogical Society of America for 2018
  23. New Mineral Names
  24. Book Review
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