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A pre-edge analysis of Mn K-edge XANES spectra to help determine the speciation of manganese in minerals and glasses

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Abstract

High-resolution manganese K-edge X-ray absorption near edge structure spectra were collected on a set of 40 Mn-bearing minerals. The pre-edge feature information (position, area) was investigated to extract as much as possible quantitative valence and symmetry information for manganese in various “test” and “unknown” minerals and glasses. The samples present a range of manganese symmetry environments (tetrahedral, square planar, octahedral, and cubic) and valences (II to VII). The extraction of the pre-edge information is based on a previous multiple scattering and multiplet calculations for model compounds. Using the method described in this study, a robust estimation of the manganese valence could be obtained from the pre-edge region at 5% accuracy level. This method applied to 20 “test” compounds (such as hausmannite and rancieite) and to 15 “unknown” compounds (such as axinite and birnessite) provides a quantitative estimate of the average valence of manganese in complex minerals and silicate glasses.

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Acknowledgments

We gratefully acknowledge Arnaud Papin (formerly at CNRS, Orléans), Ina Reiche (Laboratoire de Recherche des Musées de France, UMR171 CNRS, Paris), and Antoine Bézos (IPGP, Paris) for providing some of the samples from their Ph.D. work. We also thank the mineral collections of the Ecole des Mines de Paris (J.M. Le Cleac’h and A. Djemai), the Centre Canadien de la Nature in Ottawa (P. Piilonen), the Laboratoire de Minéralogie-Cristallographie de Paris (“Sorbonne collection”; J.C. Bouillard), and Stanford University for providing some of the specimens used in this study (the others are from the private collection of François Farges). The staffs of SSRL (especially Joe Rodgers, Cathy Knotts, and Michelle Steger) and ESRF (especially Jean Susini on ID21) are thanked for their help. Helpful discussions with John R. Rehr (University of Washington at Seattle, USA) on FEFF calculations and P. Glatzel (ESRF, Grenoble, France) on multiplet calculations are also acknowledged.

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Authors and Affiliations

  1. European Synchrotron Radiation Facility, 38043, Grenoble, France

    E. Chalmin

  2. Unité Minéralogie-Pétrologie, Muséum National d’Histoire Naturelle and CNRS UMR 7160, Paris, France

    F. Farges

  3. Department of Geological and Environmental Sciences, Stanford University, Stanford, CA, 94305-2115, USA

    F. Farges & G. E. Brown Jr

  4. Stanford Synchrotron Radiation Laboratory, SLAC, 2575 Sand Hill Road, MS 69, Menlo Park, CA, 94025, USA

    G. E. Brown Jr

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  1. E. Chalmin
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Communicated by J. Hoefs.

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Chalmin, E., Farges, F. & Brown, G.E. A pre-edge analysis of Mn K-edge XANES spectra to help determine the speciation of manganese in minerals and glasses. Contrib Mineral Petrol 157, 111–126 (2009). https://doi.org/10.1007/s00410-008-0323-z

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