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High-T behaviour of gedrite: thermoelasticity, cation ordering and dehydrogenation

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Abstract

The thermoelastic behaviour of a natural gedrite having the crystal-chemical formula ANa0.47 B(Na0.03 Mg1.05 Fe 2+0.86 Mn0.02 Ca0.04) C(Mg3.44 Fe 2+0.36 Al1.15 Ti 4+0.05 ) T(Si6.31 Al1.69)O22 W(OH)2 has been studied by single-crystal X-ray diffraction to 973 K (Stage 1). After data collection at 973 K, the crystal was heated to 1,173 K to induce dehydrogenation, which was registered by significant changes in unit-cell parameters, M1–O3 and M3–O3 bond lengths and refined site-scattering values of M1 and M4 sites. These changes and the crystal-chemical formula calculated from structure refinement show that all Fe2+ originally at M4 migrates into the ribbon of octahedrally coordinated sites, where most of it oxidises to Fe3+, and there is a corresponding exchange of Mg from the ribbon into M4. The resulting composition is that of an oxo-gedrite with an inferred crystal-chemical formula ANa0.47 B(Na0.03 Mg1.93 Ca0.04) C(Mg2.56 Mn 2+0.02 Fe 2+0.10 Fe 3+1.22 Al1.15 Ti 4+0.05 ) T(Si6.31 Al1.69) O22 W[O 2−1.12 (OH)0.88]. This marked redistribution of Mg and Fe is interpreted as being driven by rapid dehydrogenation at the H3A and H3B sites, such that all available Fe in the structure orders at M1 and M3 sites and is oxidised to Fe3+. Thermoelastic data are reported for gedrite and oxo-gedrite; the latter was measured during cooling from 1,173 to 298 K (Stage 2) and checked after further heating to 1,273 K (Stage 3). The thermoelastic properties of gedrite and oxo-gedrite are compared with each other and those of anthophyllite.

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Acknowledgments

Constructive comments from two anonymous reviewers helped to make our discussion clearer. MDW gratefully acknowledges financial support from the CNR in the form of a 2009 Short-Term Mobility grant that allowed him to carry out HT experiments at CNR-IGG in Pavia. The Natural History Museum (London) is also thanked for providing financial support to MDW for this research. MZ and RO acknowledge funding from the CNR project TA.P04.014.002 and the MIUR-PRIN 2009 project “Structure, microstructures and cation ordering: a window on to geological processes and geomaterial properties” to R. Oberti.

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Authors and Affiliations

  1. Dipartimento di Scienze della Terra e dell’Ambiente, Università di Pavia, via Ferrata 1, 27100, Pavia, Italy

    Michele Zema

  2. CNR-Istituto di Geoscienze e Georisorse, Unità di Pavia, via Ferrata 1, 27100, Pavia, Italy

    Michele Zema & Roberta Oberti

  3. Department of Mineralogy, The Natural History Museum, Cromwell Road, London, SW7 5BD, UK

    Mark D. Welch

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  1. Michele Zema
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  2. Mark D. Welch
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  3. Roberta Oberti
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Correspondence to Mark D. Welch.

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Communicated by M. W. Schmidt.

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Zema, M., Welch, M.D. & Oberti, R. High-T behaviour of gedrite: thermoelasticity, cation ordering and dehydrogenation. Contrib Mineral Petrol 163, 923–937 (2012). https://doi.org/10.1007/s00410-011-0706-4

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  • DOI: https://doi.org/10.1007/s00410-011-0706-4

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