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Natural occurrence of monoclinic Fe3S4 nano-precipitates in pyrrhotite from the Sudbury ore deposit: a Z-contrast imaging and density functional theory study

Published online by Cambridge University Press:  02 January 2018

Huifang Xu ,
Zhizhang Shen  and
Hiromi Konishi
Huifang Xu*
Affiliation:
NASA Astrobiology Institute, Department of Geoscience, University of Wisconsin-Madison, 1215 W Dayton Street, Madison, WI 53706, USA
Zhizhang Shen
Affiliation:
NASA Astrobiology Institute, Department of Geoscience, University of Wisconsin-Madison, 1215 W Dayton Street, Madison, WI 53706, USA
Hiromi Konishi
Affiliation:
NASA Astrobiology Institute, Department of Geoscience, University of Wisconsin-Madison, 1215 W Dayton Street, Madison, WI 53706, USA
*
*E-mail: hfxu@geology.wisc.edu
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Abstract

A monoclinic form of Fe3S4, a polymorph of cubic greigite, occurs as precipitates in a sample of pyrrhotite collected from the Sudbury ore deposit. The nano-crystal precipitates are in a topotaxial relationship with the host pyrrhotite-4C (Fe7S8). The precipitate and the host pyrrhotite have a coherent (001) interface. Half of the octahedral layers in the crystal structure are fully occupied by Fe, while the other half of the octahedral layers are occupied by Fe atoms and vacancies in an ordered manner along the a axis. The crystal structure of the Fe3S4 nano-precipitates has monoclinic symmetry with a space group of I2/m. Its c dimension is 6% smaller than that of the host pyrrhotite due to the large number of vacancies in the structure. Fractional coordinates for S and Fe atoms within the unit cell are determined from Z-contrast images and density functional theory (DFT). The calculated results match the measured values very well. It is proposed that the monoclinic Fe3S4 nano-precipitates formed through ordering of vacancies in pyrrhotite with a low Fe/S ratio (i.e. <0.875) at low temperature.

Keywords

iron sulfidegreigitepyrrhotitemonoclinic Fe3S4SudburyZ-contrast imagingdensity functional theoryvacancy orderingaberration-corrected scanning transmission electron microscopymagnetic mineral
Type
Research Article
Information
Mineralogical Magazine , Volume 79 , Issue 2 , April 2015 , pp. 377 - 385
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2015

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