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Optical absorption spectra and Fe distribution in the structures of Li-Fe micas

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Abstract

The paper proposes pioneering data on the polarized optical absorption spectra of Li-Fe micas: intermediate members of the siderophyllite-zinnwaldite-polylithionite and annite-protolithionite-zinnwaldite-trilithionite series with variable Fe and Li proportions and Li- and Fe-bearing muscovite (phengite). Based on the analysis of structural data, the complicated structure of the Fe2+ → Fe3+ charge transfer band in the mica structures is explained, and arguments are presented to justify the ascribing of its shortwave component (CTB-1, ν = 17200-14900 cm−1) to charge transfer in the pair Fe2+(M2) → Fe3+(M2) and the longwave component (CTB-2, ν = 14200-13600 cm−1) to charge transfer in the pair Fe2+(M1) Fe3+(M2). It is demonstrated that the anomalous shift of the superposition of two-component CTB toward the shortwave region, to 17000 cm−1, results from a decrease in the length of oxygen edges between adjacent M2M2 and M1M2 tetrahedrons when Li is accommodated in the mica structure. The first data are presented on the spectrum of Fe2+ ions in large distorted M3(M1) tetrahedrons (OAC Fe2+ II) in hetero-octahedral Li micas (zinnwaldite), and the behavior of the corresponding absorption bands at 11400 and 8000 cm−1 is determined. It is proved that characteristics of the optical spectra of Fe2+ ions can be used as an indicator of the structure of the octahedral layer in the mica structures. Results of the comparative analyses of spectral parameters of the Fe2+ → Fe3+ charge transfer, crystal field spectra of Fe2+ ions, and the crystal-chemical characteristics controlling them in micas of the polylithionite-siderophyllite series are completely consistent with the character of cation ordering in the crystal structures of these micas determined by X-ray diffraction analysis.

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Authors and Affiliations

  1. Semenenko Institute of Geochemistry, Mineralogy, and Ore Genesis, National Academy of Sciences of Ukraine, pr. Palladina 34, Kiev, 03142, Ukraine

    A. N. Platonov & V. M. Khomenko

  2. Fedorovskii All-Russia Institute of Mineral Resources (VIMS), Staromonetnyi per. 31, Moscow, 109017, Russia

    T. N. Shuriga

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  1. A. N. Platonov
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  2. V. M. Khomenko
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  3. T. N. Shuriga
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Correspondence to A. N. Platonov.

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Original Russian Text © A.N. Platonov, V.M. Khomenko, T.N. Shuriga, 2009, published in Geokhimiya, 2009, No. 2, pp. 184–196.

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Platonov, A.N., Khomenko, V.M. & Shuriga, T.N. Optical absorption spectra and Fe distribution in the structures of Li-Fe micas. Geochem. Int. 47, 174–185 (2009). https://doi.org/10.1134/S0016702909020050

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