Surface Alteration of Pentlandite and Spectroscopic Evidence for Secondary Violarite Formation

S. Richardson and D. J. Vaughan
Department of Geological Sciences, Aston University, Birmingham B4 7ET
Department of Geology, The University, Manchester M13 9PL

Abstract: Synthetic pentlandite surfaces were subjected to oxidation by a range of inorganic oxidants, and the resultant alteration of the surface studied by a range of surface-sensitive spectroscopic techniques. The oxidants used were air during heating to relatively low temperatures (150°C), steam, ammonium hydroxide, hydrogen peroxide, and sulphuric acid. Electrochemical oxidation was also undertaken. X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), conversion electron Mössbauer spectroscopy (CEMS), and spectral reflectance measurements were used to characterize the surface compositions. New data for the binding energies of core electrons in pentlandite and violarite, based on the fitted XPS spectra, are proposed. For pentlandite and violarite respectively, values of 707.3 eV and 708.4 eV for the Fe 2p3/2, 853.0 eV and 853.2 eV for the Ni 2p3/2, and 161.2 eV for the S 2p in both sulphides, were obtained. After oxidation the pentlandite surfaces indicated nickel enrichment in the subsurface, with the formation of violarite. The immediate oxidized surface, of approximately 10Å thickness, indicated a range of iron oxides and hydroxides (Fe3O4, Fe2O3 and FeOOH, with possible Fe1−xO and Fe(OH)3), nickel oxide (NiO), and iron sulphates (FeSO4, Fe2(SO4)3). The proportions of the phases present in the surface layer are inferred to be a consequence of both the strength of the oxidant employed, and the thermodynamic stability of the phases, as can be illustrated using partial pressure and Eh/pH diagrams. A sequence of oxidation is proposed, accounting for the sub-surface enrichment in violarite, and the development of the oxidized surface, which is inferred to have a major affect on the rates of oxidation.

Keywords: pentlandite • violarite • sulphides • surface • XPS • AES • Mössbauer • spectroscopy

Mineralogical Magazine; April 1989 v. 53; no. 370; p. 213-222; DOI: 10.1180/minmag.1989.053.370.08
© 1989, The Mineralogical Society
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