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The crystal chemistry of Fe-bearing sphalerites: An infrared spectroscopic study

¹ Department of Mineralogy, South Australian Museum, North Terrace, Adelaide, South Australia 5000, Australia
² School of Chemistry, Physics and Earth Sciences, The Flinders University of South Australia, GPO Box 2100 Adelaide, South Australia 5000, Australia
³ Dipartimento di Scienze della Terra, Università di Pavia, Via Ferrata 1, 27100 Pavia, Italy
⁴ Department of Earth Sciences, University of Cambridge, Downing Street, Cambridge CB2 3EQ, U.K.
⁵ Research School of Chemistry, Australian National University, Canberra, ACT, 0200, Australia

Correspondence: ^* E-mail: pring.allan{at}saugov.sa.gov.au

Iron substitution into sphalerite, ZnS, has been studied systematically by infrared spectroscopy. A range of natural and synthetic compositions, (Zn_1–xFe_x)S, 0 x 0.24, were examined. The IR spectrum of pure ZnS contains a single strong absorption band at 320 cm^–1. With addition of FeS, the spectra become broader and shoulders appear. For compositions 9 mol% FeS, a splitting of the main peak occurs, and the spectra show two absorption maxima at approximately 300 and 315 cm^–1, respectively. The observation of such extra features does not correspond to the usual behavior observed in other ternary mixed crystals, where either one-, two-, or mixed-mode behavior is observed. The spectra can be deconvoluted into up to three peaks, main Peaks A and B at around 300 and 315 cm^–1, respectively, and a shoulder at around 330 cm^–1 (Peak C). The positions and area of the peaks do not change significantly with increasing Fe content. The peak at 315 cm^–1 is the main absorption peak of the host ZnS structure, and the peak at 300 cm^–1 is an impurity induced mode. An effective linewidth parameter _corr was determined by autocorrelation analysis for each spectrum, but there are no obvious trends in the values of _corr that can be interpreted in terms of an inhomogeneous distribution of Fe within the sphalerite structure.

Key Words: Fe-bearing sphalerites • infrared spectroscopy • autocorrelation analysis • solid solution