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Crystallographic and spectroscopic characterization of a natural Zn-rich spinel approaching the endmember gahnite (ZnAl2O4) composition

Published online by Cambridge University Press:  05 July 2018

V. D’Ippolito ,
G. B. Andreozzi ,
F. Bosi ,
U. Hålenius ,
L. Mantovani ,
D. Bersani  and
R. A. Fregola
V. D’Ippolito*
Affiliation:
Dipartimento di Scienze della Terra, Sapienza Università di Roma, Italy
G. B. Andreozzi
Affiliation:
Dipartimento di Scienze della Terra, Sapienza Università di Roma, Italy
F. Bosi
Affiliation:
Dipartimento di Scienze della Terra, Sapienza Università di Roma, Italy
U. Hålenius
Affiliation:
Department of Geosciences, Swedish Museum of Natural History, Stockholm, Sweden
L. Mantovani
Affiliation:
Dipartimento di Fisica e Scienze della Terra “Macedonio Melloni”, Università di Parma, Italy
D. Bersani
Affiliation:
Dipartimento di Fisica e Scienze della Terra “Macedonio Melloni”, Università di Parma, Italy
R. A. Fregola
Affiliation:
Dipartimento di Scienze della Terra e Geoambientali, Università di Bari, Italy
*
* E-mail: veronica.dippolito@uniroma1.it
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Abstract

The crystal chemistry of a natural, gem-quality, blue-grey Zn-rich spinel crystal from Jemaa, Kaduna State, Nigeria, was studied using electron microprobe, single-crystal X-ray diffraction, optical absorption and Raman spectroscopies. The composition of the crystal approaches the gahnite endmember (ZnAl2O4), ∼94 mol.%, with the remainder being dominated by a hercynite component (FeAl2O4). The unit-cell dimension is 8.0850(3) Å and the tetrahedral and octahedral bond distances are determined as T–O 1.9485(6) Å and M–O 1.9137(3) Å. Crystal chemical analysis resulted in the empirical structural formula T(Zn0.94Fe2+0.03Al0.03)M (Al1.96Fe2+0.03Fe3+0.01)O4, which shows Zn and Al almost fully ordered in the tetrahedrally and octahedrally coordinated T and M sites, respectively. Raman spectra obtained using the excitation of the blue 473.1 nm line of a Nd:YAG laser display three of the five Raman-active modes predicted for the general oxide spinel group of minerals. These are the Eg mode at 420.6 cm–1 and the T2g modes at 510 cm–1 and 661 cm–1, due to vibrations in the AlO6 octahedra. Optical absorption spectra recorded in the UV/VIS-NIR-MIR range 2000 29000 cm–1 show a dominant absorption band at ∼5000 cm–1 which is caused by spin-allowed electronic d–d transitions in Fe2+ located at the T sites. The blue-grey hue exhibited by the sample is mainly due to spin-forbidden electronic transitions in TFe2+ and to MFe2+ ↔MFe3+ intervalence charge transfer, and the poor saturation of the colour is due to the small concentration of Fe2+ and Fe3+.

Keywords

blue spinelgahnitecation orderingelectron microprobecrystal-structure refinementRaman spectroscopyoptical absorption spectroscopy
Type
Research Article
Information
Mineralogical Magazine , Volume 77 , Issue 7 , October 2013 , pp. 2941 - 2953
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2013

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