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Ratios of ferrous to ferric iron from nanometre-sized areas in minerals

Nature volume 396, pages 667–670 (1998)Cite this article

Abstract

Minerals with mixed valence states are widespread and form in many different rock types1. They can contain, for example, Fe2+–Fe3+ and Mn2+–Mn3+–Mn4+, with the ratios of oxidation states reflecting the redox conditions under which the host materials crystallized. The distribution of the ratio of iron (III) to total iron content (Fe3+/ΣFe) in minerals reflects the oxidation states of their host rocks and is therefore important for answering fundamental questions about the Earth's evolution and structure2,3,4,5,6,7,8. Iron is the most sensitive and abundant indicator of oxidation state, but many mineral samples are too fine-grained and heterogeneous to be studied by standard methods such as Mössbauer spectroscopy, electron microprobe, and wet chemistry. Here we report on the use of electron energy-loss spectroscopy with a transmission electron microscope to determine Fe3+/ΣFe in minerals at the nanometre scale. This procedure is efficient for determining Fe3+/ΣFe ratios of minor and major amounts of iron on a scale heretofore impossible and allows information to be obtained not only from ultra-fine grains but also, for example, at reaction fronts in minerals.

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Figure 1: Comparison of the Fe L2,3 edges of fayalite and aegerine.
Figure 2: Fe L2,3 edges of elemental Fe and selected minerals containing single-valent Fe.
Figure 3: Fe L2,3 edges of selected materials containing mixed-valent Fe.
Figure 4: Comparison of Fe3+/ΣFe from EELS and published results (from Table 1).

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Acknowledgements

We thank P. Rez and J. Bradley for discussions, and K. Righter, D. Canil and G.Gudmundsson for providing us with samples. This work was supported by the Earth Sciences Division of the US NSF.

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Authors and Affiliations

  1. Department of Geology, Arizona State University, Tempe, 85287-1404, Arizona, USA

    Laurence A. J. Garvie & Peter R. Buseck

  2. Department of Chemistry/Biochemistry, Arizona State University, Tempe, 85287-1404, Arizona, USA

    Peter R. Buseck

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  1. Laurence A. J. Garvie
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Correspondence to Laurence A. J. Garvie.

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Garvie, L., Buseck, P. Ratios of ferrous to ferric iron from nanometre-sized areas in minerals. Nature 396, 667–670 (1998). https://doi.org/10.1038/25334

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