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Chromium speciation in oxide-type compounds: application to minerals, gems, aqueous solutions and silicate glasses

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Abstract

Cr K-edge XANES spectra were obtained for a variety of Cr-bearing model compounds containing Cr(II), Cr(III), Cr(IV), Cr(V) and Cr(VI), in which the Cr-site symmetry is D4h, Oh and Td. The centroid position of the pre-edge feature is a better indicator of the Cr valence than the edge position. In Cr-rich oxides, higher-energy transitions must be excluded in order to refine a robust valence for Cr. The pre-edge for chromates is not unique and varies as a function of the CrO4 2− moiety distortion, which is often related to Cr-polymerization (monochromate vs. dichromate). Both the analogy with the Mn K-pre-edge information and ab initio FEFF calculations of the pre-edge feature for Cr(III) and Cr(VI) confirm the experimental trends. This methodology is applied to the Cr K-edge pre-edge feature collected in gems (emerald, spinel and ruby), the layered minerals fuchsite and kämmererite, two Cr-bearing aqueous solutions and a set of sodo-calcic silicate glasses used for bottling sparkling white wine. In emerald and fuchsite, the Cr-site is differently distorted than its ruby or spinel counterpart. In a Cr(III)-bearing aqueous solution and sodo-calcic glass, no evidence for Cr(III) with Td and C3v symmetry is detected. However, minor amounts of chromate moieties (most likely monomeric) are detected in a glass synthesized in air. Preliminary spectra for the wine bottle glass suggest that only trace amounts of chromates might possibly be present in these glasses.

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Acknowledgments

The beamline scientists at SSRL (esp. Joe Wong) and SLS (Anne-Marie Flank and Messaoud Harfouche) are greatly thanked, particularly for their help in data collection. Anonymous reviewers and associate editor Catherine McCammon made useful comments that improved the manuscript.

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Authors and Affiliations

  1. USM 201, CNRS UMR 7202, Muséum National d’Histoire Naturelle, Paris, France

    François Farges

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

    François Farges

  3. USM 201, Case Postale 52, Muséum National d’Histoire Naturelle, 61 rue Buffon, 75005, Paris, France

    François Farges

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  1. François Farges
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Farges, F. Chromium speciation in oxide-type compounds: application to minerals, gems, aqueous solutions and silicate glasses. Phys Chem Minerals 36, 463–481 (2009). https://doi.org/10.1007/s00269-009-0293-3

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