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On the presence of hydrous defects in differently coloured wulfenites (PbMoO4): an infrared and optical spectroscopic study

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Abstract

Several samples of wulfenite, PbMoO4, varying in colour from colourless to yellow, orange and red, have been characterised by means of IR and optical absorption spectroscopy and by microprobe analyses. A distinct pleochroic band group with absorption maxima centred at 3,380 and 3,150 cm−1 can be seen in the IR spectra of wulfenite single-crystals, indicating the presence of hydroxyl groups. The pleochroic and thermal behaviour of the OH stretching bands along with deuteration experiments, as well as results obtained from synthetic flux-grown samples, exclude the presence of submicroscopic hydrous mineral inclusions as their primary origin. The pleochroic scheme and the band positions were used to postulate a model for the OH incorporation mode, based on the assumption of vacancies on Mo and Pb sites in the structure of this ‘nominally anhydrous mineral’. Optical absorption spectra of coloured natural samples show a broad and polarised band around 23,000–24,000 cm−1, preceding the fundamental UV absorption edge, which has been identified as the reason for the colour of the mineral. The comparison with synthetic PbMoO4 single-crystals, doped with variable amounts of Cr6+, yielded conclusive evidence that trace amounts of the CrO4 2− anion group, substituting for MoO4 2−, determine the variable colour. Besides, in one sample, trace amounts of Nd3+ have been spectroscopically identified.

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Acknowledgments

Samples were kindly provided by the mineral collection of the ‘Institut für Mineralogie und Kristallographie, Universität Wien’. Thanks are due to A. Wagner for careful sample preparation. D.T. acknowledges the award of a scholarship by the Austrian Federal Ministry of Science and Research within the frame of the Austria Exchange Service (ÖAD), Academic Mobility Unit ACM-2008-00061 and the award of a CEEPUS scholarship (CIII-RO-0038-1213). This work was supported by the projects ‘CEITEC-Central European Institute of Technology’ (CZ.1.05/1.1.00/02.0068) and GACR P207/11/0555 of the Grant Academy of the Czech Republic. We thank Henrik Skogby and Monika Koch-Müller for their reviews, which helped to significantly improve the quality of this paper.

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Authors and Affiliations

  1. Institut für Mineralogie und Kristallographie, Universität Wien, Althanstraße 14, 1090, Wien, Austria

    D. Talla, M. Wildner & A. Beran

  2. Department of Geological Sciences, Masaryk University, Kotlářská 2, 611 37, Brno, Czech Republic

    D. Talla, R. Škoda & Z. Losos

  3. CEITEC, Masaryk University, Kotlářská 2, 611 37, Brno, Czech Republic

    Z. Losos

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  1. D. Talla
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  2. M. Wildner
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  3. A. Beran
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  4. R. Škoda
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  5. Z. Losos
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Correspondence to D. Talla.

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Talla, D., Wildner, M., Beran, A. et al. On the presence of hydrous defects in differently coloured wulfenites (PbMoO4): an infrared and optical spectroscopic study. Phys Chem Minerals 40, 757–769 (2013). https://doi.org/10.1007/s00269-013-0610-8

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  • DOI: https://doi.org/10.1007/s00269-013-0610-8

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