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Crystal Chemistry and Surface Configurations of Two Iron-Bearing Trioctahedral Mica-1M Polytypes

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Clays and Clay Minerals

Abstract

The crystal chemical features of the bulk and the uppermost (001) surface layers of freshly cleaved surfaces of two trioctahedral Fe-rich mica-1M (space group C2/m) polytypes, i.e. a tetraferriphlogopite from an alkaline-carbonatitic complex near Tapira, Belo Horizonte, Minas Gerais, Brazil, and an Fe2+-bearing phlogopite containing less tetrahedral Fe3+ from the Kovdor carbonatite-bearing, alkaline-ultrabasic complex, Kola Peninsula, Russia, are explored here. Mineral-surface effects were investigated by X-ray Photoelectron Spectroscopy (XPS) and compared to the bulk structure derived from single-crystal X-ray diffraction data. Based on microprobe analysis and the X-ray study, the chemical formulae are [XII](K0.99)[VI](Fe 2+0.08 Fe 3+0.15 Mg2.76Ti0.01)[IV](Fe 3+0.82 Si3.18)O10.37F0.24(OH)1.39 and [XII](K0.94Na0.06)[VI](Fe 2+0.17 Fe 3+0.05 Mg2.75Mn0.01Ti0.05)[IV](Fe 3+0.16 Al0.84Si3.00)O10.21F0.35(OH)1.44 for tetraferriphlogopite and Fe-bearing phlogopite, respectively. The tetrahedrally coordinated sites of the two minerals differ, where Fe-for-Si substitution is at 20.5% in tetra-ferriphlogopite and at 4% in Fe-bearing phlogopite.

The bulk study showed that Fe3+ substitution increases the tetrahedral sheet thickness and the mean tetrahedral edge lengths in tetra-ferriphlogopite compared to Fe-bearing phlogopite. The tetrahedral rotation angle (α) changes remarkably from tetra-ferriphlogopite (α = 10.5°) to the Fe-bearing phlogopite (α = 8.5°), thus indicating a significantly greater initial lateral sheet misfit (leading to a greater tetrahedral ring distortion) between the tetrahedral and the octahedral sheets in the tetra-ferriphlogopite compared to Fe-bearing phlogopite. The Fe3+ substitution for Si and the differences in lateral dimensions of the tetrahedral and octahedral sheets affect the tetrahedral flattening angle (τ), with τ = 109.9° for tetraferriphlogopite and τ = 110.7° for Fe-bearing phlogopite.

The binding energy (BE) of photoelectron peaks in XPS is dependent on the chemical state of atoms and on their local environment at the near surface. The Mg in both phlogopites is bonded to F, with the BE of Mg1s increasing as coordinated oxygen atoms are substituted by fluorine. For Fe-rich phlogopite (BE = 1306.8 eV), the binding energy is greater than for tetra-ferriphlogopite (BE = 1305.9 eV), and this is consistent with the bulk composition having greater F-for-OH substitution in Fe-rich phlogopite (F0.35vs. tetra-ferriphlogopite, F0.24 atoms per formula unit).

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Authors and Affiliations

  1. Dipartimento di Scienze Chimiche e Geologiche, Università di Modena e Reggio Emilia, Largo S. Eufemia 19, 41121, Modena, Italy

    Chiara Elmi & Maria Franca Brigatti

  2. Department of Earth and Environmental Sciences, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois, 60607-7059, USA

    Stephen Guggenheim

  3. Dipartimento di Ingegneria “Enzo Ferrari”, Università di Modena e Reggio Emilia, Via Vignolese 905, 41125, Modena, Italy

    Luca Pasquali, Monica Montecchi & Stefano Nannarone

  4. IOM INFM-CNR Area Science Park, Building MM, S.S. 14, Km 163.5, 34012, Basovizza (TS), Italy

    Luca Pasquali, Monica Montecchi & Stefano Nannarone

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  1. Chiara Elmi
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  2. Maria Franca Brigatti
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  3. Stephen Guggenheim
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Correspondence to Stephen Guggenheim.

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Elmi, C., Brigatti, M.F., Guggenheim, S. et al. Crystal Chemistry and Surface Configurations of Two Iron-Bearing Trioctahedral Mica-1M Polytypes. Clays Clay Miner. 62, 243–252 (2014). https://doi.org/10.1346/CCMN.2014.0620401

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  • DOI: https://doi.org/10.1346/CCMN.2014.0620401

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