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From structure topology to chemical composition. IX. Titanium silicates: revision of the crystal chemistry of lomonosovite and murmanite, Group-IV minerals

Published online by Cambridge University Press:  05 July 2018

F. Cámara ,
E. Sokolova ,
F. C. Hawthorne  and
Y. Abdu
F. Cámara*
Affiliation:
Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba R3T 2N2, Canada
E. Sokolova
Affiliation:
Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba R3T 2N2, Canada Institute of Geology of Ore Deposits, Petrography, Mineralogy and Geochemistry, Moscow 109017, Russia
F. C. Hawthorne
Affiliation:
Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba R3T 2N2, Canada
Y. Abdu
Affiliation:
Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba R3T 2N2, Canada
*
*E-mail: camara@crystal.unipv.it
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Abstract

The crystal structures of lomonosovite, ideally Na10Ti4(Si2O7)2(PO4)2 O4, a = 5.4170(7) Å, b = 7.1190(9) Å, c = 14.487(2) Å, a = 99.957(3)°, β = 96.711(3)°, γ = 90.360(3)°, V= 546.28(4) Å3, Dcalc. = 3.175 g cm“3, and murmanite, ideally Na4Ti4(Si2O7)2O4(H2O)4, a = 5.3875(6) Å, b = 7.0579(7) Å, c = 12.176(1) Å, a = 93.511(2)°, 0 = 107.943(4)°, y = 90.093(2)°, V = 439.55(2) Å3, Dcalc. = 2.956 g.cm∼3, from the Lovozero alkaline massif, Kola Peninsula, Russia, have been refined in the space group P1̄ (Z = 1) to R values of 2.64 and 4.47%, respectively, using 4572 and 2222 observed |F°≥ 4σF| reflections collected with a single-crystal Bruker AXS SMART APEX diffractometer with a CCD detector and Mo-Kα. radiation. Electron microprobe analysis gave empirical formulae for lomonosovite (Na9.50Mn0.16Ca0.11)Σ9.77(Ti4+2.83Nb0.51Mn0.272+Zr0.11Mg0.11Fe2+0.10Fe3+0.06Ta0.01)Σ4.00(Si2.02O7)2(P0.98O4)2(O3.50F0.50)Σ4, Z = 1, calculated on the basis of 22(O+F) a.p.f.u., with H2O determined from structure refinement and Fe3+/(Fe2++Fe3+) ratios obtained by Mössbauer spectroscopy. The crystal structures of lomonosovite and murmanite are a combination of a titanium silicate (TS) block and an intermediate (I) block. The TS block consists of HOH sheets (H-heteropolyhedral, O-octahedral), and is characterized by a planar cell based on translation vectors, t1 and t2, with t1\ ∼5.5 and t2 ∼7 Å and ttA t2 close to 90°. The TS block exhibits linkage and stereochemistry typical for Group IV (Ti = 4 a.p.f.u.) of the Ti disilicate minerals: two H sheets connect to the O sheet such that two (Si2O7) groups link to Ti polyhedra of the O sheet adjacent along tx. In murmanite and lomonosovite, the invariant part of the TS block is of composition Na4Ti4(Si2O7)2O4. There is no evidence of vacancy-dominant cation sites or (OH) groups in the O sheet of lomonosovite or murmanite. In lomonosovite, the I block is a framework of Na polyhedra and P tetrahedra which gives 2[Na3 (PO)4] p.f.u. In murmanite, there are four (H2O) groups in the intermediate space between TS blocks. In lomonosovite, TS and I blocks alternate along c. In murmanite, TS blocks are connected via hydrogen bonding. The H atoms were located and details of the hydrogen bonding are discussed.

Keywords

lomonosovitemurmanitecrystal structure refinementhydrogen bondingEMP analysisMössbauer spectroscopychemical formulaTi disilicate mineralsGroup IV
Type
Research Article
Information
Mineralogical Magazine , Volume 72 , Issue 6 , December 2008 , pp. 1207 - 1228
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2008

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Footnotes

†

Permanent address: CNR - Istituto di Geoscienze e Georisorse, Unità di Pavia, Via Ferrata 1, I-27100 Pavia, Italy

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Structure factors for lomonosovite 1

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Structure factors for lomonosovite 2

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Structure factors for murmanite 1

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Structure factors for murmanite 2

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