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    XANES evidence for sulphur speciation in Mn-, Ni- and W-bearing silicate melts

    135024_18646_W6213_revised.pdf (2.724Mb)
    Access Status
    Open access
    Authors
    Evans, Katy
    O'Neil, H.
    Mavrogenes, J.
    Keller, N.
    Jang, L.
    Lee, J.
    Date
    2009
    Type
    Journal Article
    
    Metadata
    Show full item record
    Citation
    Evans, Katy and O'Neil, Hugh and Mavrogenes, John and Keller, Nicole and Jang, Ling and Lee, J. 2009. XANES evidence for sulphur speciation in Mn-, Ni- and W-bearing silicate melts. Geochimica et Cosmochimica Acta. 73 (22): pp. 6847-6867.
    Source Title
    Geochimica et Cosmochimica Acta
    DOI
    10.1016/j.gca.2009.08.013
    ISSN
    00167037
    Faculty
    Department of Applied Geology
    Faculty of Science and Engineering
    WA School of Mines
    Remarks

    The link to the journal’s home page is: http://www.elsevier.com/wps/find/journaldescription.cws_home/212/description#description. Copyright © 2009 Elsevier B.V. All rights reserved

    URI
    http://hdl.handle.net/20.500.11937/27945
    Collection
    • Curtin Research Publications
    Abstract

    S K edge XANES and Mn, W and Ni XANES and EXAFS spectra of silicate glasses synthesised at 1400 degrees C and 1 bar with compositions in the CaO-MgO-Al2O3-SiO2-S plus MnO, NiO, or WO3 systems were used to investigate sulphur speciation in silicate glasses. S K-edge spectra comprised a composite peak with an edge between 2470 and 2471.4 eV, which was attributed to S2-, and a peak of variable height with an edge at 2480.2 to 2480.8 eV, which is consistent with the presence of S+6. The latter peak was attributed to sample oxidation during sample storage. W-rich samples produced an additional lower energy peak at 2469.8 eV that is tentatively attributed to the existence of S 3p orbitals hybridised with the W 5d states. Deconvolution of the composite peak reveals that the composite peak for Mn-bearing samples fits well to a model that combines three Lorentzians at 2473.1, 2474.9 and 2476.2 eV with an arctan edge step. The composite peak for W-bearing samples fits well to the same combination plus an additional Lorentzian at 2469.8 eV. The ratio of the proportions of the signal accounted for by peaks at 2473.1eV and 2476.2eV correlates with Mn:Ca molar ratios, but not with W:Ca ratios. Spectra from Ni-bearing samples were qualitatively similar but S levels were too low to allow robust quantification of peak components. Some part of the signal accounted for by the 2473.1 eV peak was therefore taken to record the formation of Mn-S melt species, while the 2469.8 peak is interpreted to record the formation of W-S melt species. The 2474.9 eV and 2476.2 eV peaks were taken to be dominated by Ca-S and Mg-S interactions. However, a 1:1 relationship between peak components and specific energy transitions is not proposed. This interpretation is consistent with known features of the lower parts of the conduction band in monosulphide minerals and indicates a similarity between sulphur species in the melts and the monosulphides. S XANES spectra cannot be reproduced by a combination of the spectra of the component element monosulphides. Mn-, W- and Ni- XANES and EXAFS for synthetic glasses without sulphide exsolution did not show any sensitivity to the presence of sulphur, which is unsurprising as S:O ratios were sufficiently low that metals would be mostly co-ordinated by O. Mn EXAFS spectra were consistent with divalent Mn in 5 co-ordinated Mn-O melt species. W spectra were consistent with tetrahedrally co-ordinated hexavalent W, most likely in scheelite-like melt species, and Ni spectra were consistent with [4] co-ordinated divalent Ni. These results indicate lower coordinations for both W and Ni than those inferred by some previous workers. Cation coordination may reflect the proportion of non-bridging oxygens, which is lower in the Ca-rich and Al-poor samples investigated here than for previous studies.

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