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Pristine and reacted surfaces of pyrrhotite and arsenopyrite as studied by X-ray absorption near-edge structure spectroscopy

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Abstract

Fe L-, S L-, and O K-edge X-ray absorption spectra of natural monoclinic and hexagonal pyrrhotites, Fe1-xS, and arsenopyrite, FeAsS, have been measured and compared with the spectra of minerals oxidized in air and treated in aqueous acidic solutions, as well as with the previous XPS studies. The Fe L-edge X-ray absorption near-edge structure (XANES) of vacuum-cleaved pyrrhotites showed the presence of, aside from high-spin Fe2+, small quantity of Fe3+, which was higher for a monoclinic mineral. The spectra of the essentially metal-depleted surfaces produced by the non-oxidative and oxidative acidic leaching of pyrrhotites exhibit substantially enhanced contributions of Fe3+ and a form of high-spin Fe2+ with the energy of the 3d orbitals increased by 0.3–0.8 eV; low-spin Fe2+ was not confidently distinguished, owing probably to its rapid oxidation. The changes in the S L-edge spectra reflect the emergence of Fe3+ and reduced density of S s–Fe 4s antibonding states. The Fe L-edge XANES of arsenopyrite shows almost unsplit e g band of singlet Fe2+ along with minor contributions attributable to high-spin Fe2+ and Fe3+. Iron retains the low-spin state in the sulphur-excessive layer formed by the oxidative leaching in 0.4 M ferric chloride and ferric sulphate acidic solutions. The S L-edge XANES of arsenopyrite leached in the ferric chloride, but not ferric sulphate, solution has considerably decreased pre-edge maxima, indicating the lesser admixture of S s states to Fe 3d orbitals in the reacted surface layer. The ferric nitrate treatment produces Fe3+ species and sulphur in oxidation state between +2 and +4.

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Acknowledgements

The authors thank Prof. R. Szargan, Dr. Lei Zhang and Dr. K.-H. Hallmeier (Leipzig University) and the staff of BESSY II and Russian-German Laboratory, particularly Dr. S. Molodtsov and Dr. D. Vyalikh, for their kind assistance with the experiment preparation and for their valuable remarks. This work was partly supported by the Russian Foundation for Basic Research, project 01-03-32687, and the bilateral program “Russian-German Laboratory at BESSY”. We thank two anonymous reviewers for helpful comments.

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  1. Institute of Chemistry and Chemical Technology SB RAS, K. Marx st., 42, Krasnoyarsk, 660049, Russia

    Yu. Mikhlin & Ye. Tomashevich

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Correspondence to Yu. Mikhlin.

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Mikhlin, Y., Tomashevich, Y. Pristine and reacted surfaces of pyrrhotite and arsenopyrite as studied by X-ray absorption near-edge structure spectroscopy. Phys Chem Minerals 32, 19–27 (2005). https://doi.org/10.1007/s00269-004-0436-5

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