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Sulfur speciation in dacitic melts using X-ray absorption near-edge structure spectroscopy of the S K-edge (S-XANES): Consideration of radiation-induced changes and the implications for sulfur in natural arc systems

  • Jackie M. Kleinsasser ORCID logo EMAIL logo , Brian A. Konecke , Adam C. Simon ORCID logo , Paul Northrup , Antonio Lanzirotti , Matthew Newville , Camelia Borca , Thomas Huthwelker and Francois Holtz
Published/Copyright: July 31, 2024
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American Mineralogist
From the journal American Mineralogist Volume 109 Issue 8

Abstract

The synchrotron technique of micro X-ray absorption near-edge structure spectroscopy at the sulfur K-edge (S-XANES) provides a unique opportunity to measure the proportion of different oxidation states of sulfur (S) in silicate glasses. Although applied extensively in the analysis of basaltic silicate glasses, few S-XANES studies have investigated variations in S oxidation states with fO2 in felsic silicate glasses. In addition, no study has systematically compared the S-XANES results obtained from the same samples at different photon flux densities to quantify the relationship between exposure time and changes in S speciation in silicate glass, as has been done for Fe and V. This study evaluates observed differences in S speciation measured in experimentally produced H2O-saturated dacitic glasses over a range of reducing to oxidizing conditions (from log fO2 = ΔFMQ-0.7 to ΔFMQ+3.3; FMQ is the fayalite-magnetite-quartz mineral redox buffer) and equilibrated at 1000 °C and 300 MPa.

S-XANES spectra were collected at three different photon flux densities using three microspectroscopy beamlines. As is observed in S-XANES analyses of basaltic silicate glasses, beam-induced changes to the S6+/ΣS are observed as a function of photon flux density and beam exposure time. Our results demonstrate that silicate glasses of dacitic composition undergo beam-induced photo-reduction in samples equilibrated at ΔFMQ > +1.75 and photo-oxidation if equilibrated at ΔFMQ < +1. The time required to observe beam-induced changes in the spectra varies as a function of flux density, and our study establishes an upper photon density limit at ~1.0 × 1012 photons/μm2. The S6+/ΣS calculated from spectra collected below this absorbed photon limit at intermediate flux densities (~1–4 × 109 photons/s per μm2) are affected by beam damage, as no conditions were found to be completely free of beam-induced changes. However, the S6+/ΣS ratios calculated below the limit at intermediate flux densities are consistent with thermodynamic constraints, demonstrating that S6+/ΣS ratios calculated from S-XANES spectra can be considered reliable for estimating the oxygen fugacity.

Our results carry important implications for the S budget of felsic magmas and dissolution mechanisms in evolved melts. While our results from all three flux densities show the presence of S4+ dissolved in relatively oxidized (ΔFMQ > +1.75) dacitic glass, even in the spectra exposed to the lowest photon densities, we are unable to rule out the possibility that the S4+ signal is the result of instantaneous X-ray irradiation induced beam damage using S-XANES alone. When our spectra are compared to S-XANES spectra from basaltic silicate glasses, important differences exist in the solubility of S2− and S6+ between dacitic silicate melts, pointing to differences in solubility mechanisms as melt composition changes. This study highlights the need for further investigation into beam damage systematics, presence of S4+, and the solubility mechanisms of different oxidation states of S as silicate melt composition changes.

Keywords: Sulfur; S-XANES; oxidation states; sulfate; sulfide; beam damage

Acknowledgments and Funding

We thank editor Don Baker for his patience and help along with Kalotina Geraki and an anonymous reviewer for providing feedback and suggestions that greatly improved the work presented here. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. We acknowledge the support of GeoSoilEnviroCARS (Sector 13), which is supported by the National Science Foundation–Earth Sciences (EAR-1128799), and the Department of Energy, Geosciences (DE-FG02-94ER14466). We acknowledge the Swiss Light Source at the Paul Scherrer Institut in Villigen, Switzerland, and the PHOENIX X07MB beamline for provision of synchrotron radiation beamtime. This research also used resources of the 8-BM TES beamline of the National Synchrotron Light Source II, a U.S. DOE Office of Science User Facility operated by Brookhaven National Laboratory under contract no. DE-SC0012704, and support from the Tender Energy Microspectroscopy Consortium. We thank Owen K. Neill of the Electron Microanalysis Laboratory of the University of Michigan for assistance in obtaining high-quality data from the EPMA. Financial support in the form of an International Institute Grant, a Department of Earth and Environmental Sciences Turner Award, and Rackham Graduate Student Research Grant from the University of Michigan are gratefully acknowledged as well as a National Science Foundation Graduate Research Fellowship and Society of Economic Geologists Fellowship awarded to J.M.K. The experimental work was supported by DFG (German Science Foundation) project HO 1337/43 to F.H. A.C.S acknowledges support from NSF EAR 1924142 and 2214119.

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Received: 2022-10-07
Accepted: 2023-10-18
Published Online: 2024-07-31
Published in Print: 2024-08-27

© 2024 by Mineralogical Society of America

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https://doi.org/10.2138/am-2022-8833
Keywords for this article
Sulfur; S-XANES; oxidation states; sulfate; sulfide; beam damage

Articles in the same Issue

  1. Fingerprinting the source and complex history of ore fluids of a giant lode gold deposit using quartz textures and in-situ oxygen isotopes
  2. Cu isotope fractionation between Cu-bearing phases and hydrothermal fluids: Insights from ex situ and in situ experiments
  3. Barium mobility in a geothermal environment, Yellowstone National Park
  4. Single-crystal elasticity of humite-group minerals by Brillouin scattering
  5. Sulfur speciation in dacitic melts using X-ray absorption near-edge structure spectroscopy of the S K-edge (S-XANES): Consideration of radiation-induced changes and the implications for sulfur in natural arc systems
  6. Ab initio calculations and crystal structure simulations for mixed layer compounds from the tetradymite series
  7. A fast open data reduction workflow for the electron microprobe flank method to determine Fe3+/ΣFe contents in minerals
  8. Machine learning applied to apatite compositions for determining mineralization potential
  9. Reconstructing volatile exsolution in a porphyry ore-forming magma chamber: Perspectives from apatite inclusions
  10. Incommensurate to normal phase transition in malayaite
  11. Raman spectroscopic measurements on San Carlos olivine up to 14 GPa and 800 K: Implications for thermodynamic properties
  12. Chemical and boron isotopic composition of tourmaline from the Yixingzhai gold deposit, North China Craton: Proxies for ore fluids evolution and mineral exploration
  13. Tourmaline chemical and boron isotopic constraints on the magmatic-hydrothermal transition and rare-metal mineralization in alkali granitic systems
  14. New Mineral Names
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