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The structure of P21/c (Ca0.2Co0.8)CoSi2O6 pyroxene and the C2/c–P21/c phase transition in natural and synthetic Ca–Mg–Fe2+ pyroxenes

Published online by Cambridge University Press:  28 February 2018

Mario Tribaudino ,
Luciana Mantovani ,
Francesco Mezzadri ,
Gianluca Calestani  and
Geoffrey Bromiley
Mario Tribaudino*
Affiliation:
Dipartimento di Scienze Chimiche, della Vita e della Sostenibilità Ambientale, Parco Area delle Scienze 157/A, 43124 Parma, Italy
Luciana Mantovani
Affiliation:
Dipartimento di Scienze Chimiche, della Vita e della Sostenibilità Ambientale, Parco Area delle Scienze 157/A, 43124 Parma, Italy
Francesco Mezzadri
Affiliation:
Dipartimento di Scienze Chimiche, della Vita e della Sostenibilità Ambientale, Parco Area delle Scienze 157/A, 43124 Parma, Italy
Gianluca Calestani
Affiliation:
Dipartimento di Scienze Chimiche, della Vita e della Sostenibilità Ambientale, Parco Area delle Scienze 157/A, 43124 Parma, Italy
Geoffrey Bromiley
Affiliation:
School of GeoSciences, University of Edinburgh, Grant Institute, West Mains Road, Edinburgh EH9 3JW, UK
*
*E-mail: mario.tribaudino@unipr.it
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Abstract

A P21/c synthetic (Ca0.2Co0.8)CoSi2O6 pyroxene was synthesized by slow cooling from melt at high pressure. Single crystals suitable for X-ray diffraction were obtained and refined. The results were compared to those of C2/c pyroxenes along the series CaCoSi2O6–Co2Si2O6. Strong similarities in the crystal chemical mechanism of the transition with the synthetic CaFeSi2O6–Fe2Si2O6 and CaMgSi2O6–Mg2Si2O6 pyroxenes, both at an average and local level are apparent.

The results, examined together with two new refinements of pigeonite in the ureilites ALHA77257 and RKPA80239 and with a set of natural and synthetic C2/c and P21/c pyroxenes, show that the average cation radius in the M2 site is the driving force for the phase transition from C2/c to P21/c. The longest M2–O3 distances and the O3–O3–O3 angles follow the same trend, dictated only by the ionic radius in M2, in either synthetic or natural pyroxenes, regardless of the ionic radius of the M1 cations. The transition also affects the difference between bridging and non-bridging oxygen atoms and the extent of tetrahedral deformation, whereas the M1–O, M2–O1 and M2–O2 distances are unaffected by the transition and are determined only by the ionic radius of the bonding cation. The structural changes between the ionic radius and the high temperature C2/c and P21/c transitions are similar, and different to the high-pressure transition.

Analysis of natural and synthetic pyroxenes shows that the transition with composition occurs in strain free pyroxenes for a critical radius of 0.85 Å. Increasing strain stabilizes the P21/c structure to a higher temperature and larger cation radius.

Finally, our results show that the monoclinic P21/c Ca-poor clinopyroxene, i.e the mineral pigeonite, crystallizes only at conditions where the structure is HT-C2/c, and changes to the P21/c symmetry during cooling.

Keywords

pyroxenephase transitioncobaltcrystal structurehigh temperature
Type
Article
Information
Mineralogical Magazine , Volume 82 , Issue 1 , February 2018 , pp. 211 - 228
Copyright
Copyright © Mineralogical Society of Great Britain and Ireland 2018 

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Footnotes

Associate Editor: David Hibbs

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