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57Fe Mössbauer measurements and electronic structure calculations on natural lawsonites

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Abstract

Three natural lawsonites from Syke Rock, Mendocino Co., Reed Ranch, Marin Co., and Blake Gardens, Sonoma Co., all from the Coast Range Region in California, were studied by 57Fe Mössbauer spectroscopy, electron microprobe analysis, and X-ray powder diffraction. The samples contain about 0.6, 1.0, and 1.4 wt% of total iron oxide, respectively. 57Fe Mössbauer spectra are consistent with the assumption that high-spin Fe3+ substitutes for Al in the octahedrally coordinated site. The Mössbauer spectrum of lawsonite from Syke Rock exhibits a second doublet with 57Fe hyperfine parameters typical for octahedrally coordinated high-spin Fe2+. Electronic structure calculations in the local spin density approximation yield quadrupole splittings for Fe3+ in quantitative agreement with experiment indicating, however, that substitution of Al by Fe3+ must be accompanied by local distortion around the octahedral site. Model calculations also reproduce the room temperature hyperfine parameters of ferrous high-spin iron assuming the substitution of Ca by Fe2+. However, it cannot be excluded that Fe2+ may occupy a more asymmetric site within the microstructural cavity occupied by Ca and a H2O molecule.

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Acknowledgments

The authors thank A. Fehler (Kiel) for the preparation of the microprobe samples and B. Mader (Kiel) for undertaking the microprobe analyses, and L. Peters for improvements in style of the first version of this article. All calculations were carried out at the Research Institute of Software Technology (RIST) in Salzburg. S.-U.W. gratefully acknowledges financial support by the Austrian Fund of Scientific Research (FWF) under the contract number P18329-N20.

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Authors and Affiliations

  1. Fachbereich Materialwissenschaften, Abteilung Mineralogie, Paris-Lodron-Universität Salzburg, Hellbrunnerstr 34, 5020, Salzburg, Austria

    S.-U. Weber, M. Grodzicki, W. Lottermoser, G. Tippelt, G. J. Redhammer, M. Bernroider & G. Amthauer

  2. Institut für Geowissenschaften, Abteilung Mineralogie, Christian-Albrechts-Universität zu Kiel, Olshausenstr. 40, 24098, Kiel, Germany

    S.-U. Weber & C. A. Geiger

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  1. S.-U. Weber
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  2. M. Grodzicki
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  3. C. A. Geiger
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  4. W. Lottermoser
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  5. G. Tippelt
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  6. G. J. Redhammer
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  7. M. Bernroider
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  8. G. Amthauer
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Correspondence to S.-U. Weber.

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Weber, SU., Grodzicki, M., Geiger, C.A. et al. 57Fe Mössbauer measurements and electronic structure calculations on natural lawsonites. Phys Chem Minerals 34, 1–9 (2007). https://doi.org/10.1007/s00269-006-0121-y

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  • DOI: https://doi.org/10.1007/s00269-006-0121-y

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