The dissolution mechanism of sulphur in hydrous silicate melts. I: Assessment of analytical techniques in determining the sulphur speciation in iron-free to iron-poor glasses

Kevin Klimm*, Simon C. Kohn, Luke A. O'Dell, Roman E. Botcharnikov, Mark E. Smith

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

59 Citations (Scopus)

Abstract

S K-edge XANES, lambda (SK alpha) wavelength shift, S-33 MAS NMR and Raman spectroscopy have been applied to a series of experimentally synthesised hydrous sulphur bearing silicate glasses to determine the oxidation state of sulphur dissolved in the glass. Glasses investigated include soda-lime glass (SLG), K2Si4O9 (KSG) and albitic (Albite) and trondhjemitic (TROND) glass compositions. The four spectroscopic techniques are compared with each other to investigate the applicability of each technique as a method to determine the sulphur oxidation state and structural aspects of sulphur dissolution in silicate melts.

XANES and Raman spectroscopy provide the most comprehensive information on the S-speciation and S6+ and S2- (plus S4+ in the case of XANES) can be detected. XANES allows detection of S-species at lower concentrations (

The linear combination of XANES spectra of glasses containing either only S2- or S6+ provides direct constraints on the S6+/Sigma S of glasses containing a mixture of S2- and S6+. In addition the Raman intensities of bands related to S6+ and S2- can also be used to quantify S6+/Sigma S and determined values are in good agreement with those obtained by XANES at least for S contents of >150 ppm. XANES and Raman both show that the dissolution of S2- is different in Fe-free and Fe-bearing hydrous glasses. In Fe-free glasses S2- is present as SH- and H2S whereas Fe-S complexes are observed in the presence of Fe. (C) 2012 Elsevier B.V. All rights reserved.

Original languageEnglish
Pages (from-to)237-249
Number of pages13
JournalChemical Geology
Volume322
DOIs
Publication statusPublished - 5 Sept 2012

Keywords

  • X-RAY-ABSORPTION
  • VIBRATIONAL SPECTROSCOPY
  • S K-edge XANES
  • FLUID INCLUSIONS
  • WAVELENGTH SHIFTS
  • OXIDATION-STATE
  • lambda (SK alpha) wavelength shift
  • Raman spectroscopy
  • Sulphur oxidation state
  • S-33 MAS NMR
  • RAMAN-SPECTROSCOPY
  • BOROSILICATE WASTE GLASSES
  • INDIVIDUAL PHASES
  • Silicate glass
  • XANES SPECTROSCOPY

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  • SULPHUR DEGASSING FROM VOLACANOES

    Kohn, S. C. (Principal Investigator)

    1/06/051/10/08

    Project: Research

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