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Light-induced changes in molecular arsenic sulfides: State of the art and new evidence by single-crystal X-ray diffraction

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Published/Copyright: March 31, 2015
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American Mineralogist
From the journal American Mineralogist Volume 91 Issue 8-9

Abstract

Light-induced structural changes in single crystals belonging to the β-As4S4-As8S9 series and in a crystal of synthetic β-As4S3 were monitored step by step by determining the unit-cell dimensions. A marked increase of unit-cell volume as a function of exposure time was observed for all the crystals belonging to the β-As4S4-As8S9 series except for stoichiometric alacranite (As8S9). No significant change upon long exposures to light was observed for the synthetic β-As4S3 crystal. Crystal structure refinements were carried out for crystals with different composition at selected steps of the light-induced process. The structural results clearly showed that the percentage of the As4S5 molecule in the structure increases when a crystal is exposed to light. Therefore, the increment of the unit-cell volume induced by light exposure appears to be related to a random replacement of As4S5 for As4S4 in the structure according to the reaction 5As4S4 + 3O2 → 4As4S5 + 2As2O3. The results obtained in the present study combined with a critical review of data previously published indicate that the As4S4 molecule is able to incorporate sulfur to convert to As4S5 upon exposure to light, whereas either As4S- or As4S5 molecules do not go undergo any modification. It appears that the extent of sulfur incorporation is strictly controlled by the type of molecular packing as well as by the kind of molecule.

A final, complete conversion to pararealgar was observed only for pure β-As4S4, whereas nonstoichiometric As8S9-x crystals initially containing variable amounts of β-As4S4 microdomains convert only partially to pararealgar upon light exposure.

Keywords : XRD data; arsenic sulfides; crystal structure; light-induced alteration; alacranite; β-As4S4
Received: 2005-11-23
Accepted: 2006-04-05
Published Online: 2015-03-31
Published in Print: 2006-08-01

© 2015 by Walter de Gruyter Berlin/Boston

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https://doi.org/10.2138/am.2006.2165
Keywords for this article
XRD data; arsenic sulfides; crystal structure; light-induced alteration; alacranite; β-As4S4

Articles in the same Issue

  1. Low-temperature Zr mobility: An in situ synchrotron-radiation XRF study of the effect of radiation damage in zircon on the element release in H2O + HCl ± SiO2 fluids
  2. Magnetic properties, microstructure, composition, and morphology of greigite nanocrystals in magnetotactic bacteria from electron holography and tomography
  3. Site preference and local geometry of Sc in garnets: Part I. Multifarious mechanisms in the pyrope-grossular join
  4. Site preference and local geometry of Sc in garnets: Part II. The crystal-chemistry of octahedral Sc in the andradite–Ca3Sc2Si3O12 join
  5. The arrojadite enigma: I. A new formula and a new model for the arrojadite structure
  6. The arrojadite enigma: II. Compositional space, new members, and nomenclature of the group
  7. Single-crystal X-ray diffraction and temperature dependent 57Fe Mössbauer spectroscopy on the hedenbergite-aegirine (Ca,Na)(Fe2+,Fe3+)Si2O6 solid solution
  8. Stacking structures in pyrophyllite revealed by high-resolution transmission electron microscopy (HRTEM)
  9. Intensity of quartz cathodoluminescence and trace-element content in quartz from the porphyry copper deposit at Butte, Montana
  10. The fate of smectite in KOH solutions
  11. Light-induced changes in molecular arsenic sulfides: State of the art and new evidence by single-crystal X-ray diffraction
  12. Verifying and quantifying carbon Þ xation in minerals from serpentine-rich mine tailings using the Rietveld method with X-ray powder diffraction data
  13. Generation of pressures to ~60 GPa in Kawai-type apparatus and stability of MnGeO3 perovskite at high pressure and high temperature
  14. A model to predict phase equilibrium of CH4 and CO2 clathrate hydrate in aqueous electrolyte solutions
  15. Raman investigation of H2O molecule and hydroxyl groups in the channels of hemimorphite
  16. Stacking structure in disordered talc: Interpretation of its X-ray diffraction pattern by using pattern simulation and high-resolution transmission electron microscopy
  17. Electrical conductivities of pyrope-almandine garnets up to 19 GPa and 1700 °C
  18. Crystal chemistry and polytypism of tyrolite
  19. Effect of melt structure on trace-element partitioning between clinopyroxene and silicic, alkaline, aluminous melts
  20. Analysis of light lithophile elements (Li, Be, B) by laser ablation ICP-MS: Comparison between magnetic sector and quadrupole ICP-MS
  21. Stornesite-(Y), (Y, Ca)⃞2Na6(Ca,Na)8(Mg,Fe)43(PO4)36, the first terrestrial Mg-dominant member of the fillowite group, from granulite-facies paragneiss in the Larsemann Hills, Prydz Bay, East Antarctica
  22. Electron paramagnetic resonance spectroscopic study of carbonate-bearing fluorapatite: New defect centers and constraints on the incorporation of carbonate ions in apatites
  23. EXAFS signature of structural Zn at trace levels in natural and synthetic trioctahedral 2:1 phyllosilicates
  24. A neutron powder diffraction study of Fe and Ni distributions in synthetic pentlandite and violarite using 60Ni isotope
  25. Letter. Quantification of amphibole content in expanded vermiculite products from Libby, Montana U.S.A. using powder X-ray diffraction
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