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Sb5+ and Sb3+ substitution in segnitite: A new sink for As and Sb in the environment and implications for acid mine drainage

  • Stuart J. Mills EMAIL logo , Barbara Etschmann , Anthony R. Kampf , Glenn Poirier and Matthew Newville
Published/Copyright: July 2, 2014
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American Mineralogist
From the journal American Mineralogist Volume 99 Issue 7

Abstract

A sample of Sb-rich segnitite from the Black Pine mine, Montana, U.S.A., has been studied by microprobe analyses, single-crystal X-ray diffraction, and μ-EXAFS and XANES spectroscopy. Linear combination fitting of the spectroscopic data provided Sb5+:Sb3+ = 85(2):15(2), where Sb5+ is in octahedral coordination substituting for Fe3+ and Sb3+ is in tetrahedral coordination substituting for As5+. Based upon this Sb5+:Sb3+ ratio, the microprobe analyses yielded the empirical formula Pb1.02 H1.02(Fe3+2.36Sb5+0.41Cu2+0.27)Σ3.04(As5+1.78Sb3+0.07S6+0.02)Σ1.88O8(OH)6.00. The crystal structure refinement and bond valence analysis are consistent with these cation site assignments. The formation of Sb-rich segnitite opens new possibilities for Sb sinks within the supergene zone. Segnitite may, in fact, be an ideal host for the sequestering of several toxic elements for pH < 2. At higher pH values, As is more likely to be incorporated into schwertmannite and ferrihydrite.

Keywords: μ-EXAFS; XANES; crystal structure; segnitite; antimony; valency; alunite supergroup; oxidized zone
Published Online: 2014-7-2
Published in Print: 2014-7-1

© 2014 by Walter de Gruyter Berlin/Boston

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https://doi.org/10.2138/am.2014.4834
Keywords for this article
μ-EXAFS; XANES; crystal structure; segnitite; antimony; valency; alunite supergroup; oxidized zone

Articles in the same Issue

  1. Highlights and Breakthroughs
  2. An alternative to alteration and melting processes in the Earth: Reaction between hydrogen (H2) and oxide components in the Earth in space and time
  3. The crystallographic and petrogenetic significance of pegmatite phosphates
  4. Small grains and big implications: Accessory Ti- and Zr-minerals as petrogenetic indicators in HP and UHP marbles
  5. What Lurks in the Martian Rocks and Soil? Investigations of Sulfates, Phosphates, and Perchlorates
  6. Natural Fe-bearing oxides and sulfates from the Rio Tinto Mars analog site: Critical assessment of VNIR reflectance spectroscopy, laser Raman spectroscopy, and XRD as mineral identification tools
  7. Dissolution rates of amorphous Al- and Fe-phosphates and their relevance to phosphate mobility on Mars
  8. Stability and spectroscopy of Mg sulfate minerals: Role of hydration on sulfur isotope partitioning
  9. Synthesis and characterization of the Mars-relevant phosphate minerals Fe- and Mg-whitlockite and merrillite and a possible mechanism that maintains charge balance during whitlockite to merrillite transformation
  10. Minerals in the Human Body
  11. Determination of the concentration of asbestos minerals in highly contaminated mine tailings: An example from abandoned mine waste of Crètaz and Èmarese (Valle d’Aosta, Italy)
  12. Spinels Renaissance: The past, present, and future of those ubiquitous minerals and materials
  13. Pressure-volume equation of state for chromite and magnesiochromite: A single-crystal X-ray diffraction investigation
  14. The systematics of the spinel-type minerals: An overview
  15. Chemistry and Mineralogy of Earth’s Mantle
  16. Formation of SiH4 and H2O by the dissolution of quartz in H2 fluid under high pressure and temperature
  17. Identifying the spin transition in Fe2+-rich MgSiO3 perovskite from X-ray diffraction and vibrational spectroscopy
  18. Mantle-derived guyanaite in a Cr-omphacitite xenolith from Moses Rock diatreme, Utah
  19. Pluton assembly and the genesis of granitic magmas: Insights from the GIC pluton in cross section, Sierra Nevada Batholith, California
  20. First-principles molecular dynamics simulations of MgSiO3 glass: Structure, density, and elasticity at high pressure
  21. A new UHP metamorphic complex in the ~1.8 Ga Nagssugtoqidian Orogen of West Greenland
  22. Visible and short-wave infrared reflectance spectroscopy of REE fluorocarbonates
  23. Volatile abundances of coexisting merrillite and apatite in the martian meteorite Shergotty: Implications for merrillite in hydrous magmas
  24. Sb5+ and Sb3+ substitution in segnitite: A new sink for As and Sb in the environment and implications for acid mine drainage
  25. First-principles elasticity of monocarboaluminate hydrates
  26. Substitution of Ti3+ and Ti4+ in hibonite (CaAl12O19)
  27. Exploring the effect of lithium on pegmatitic textures: An experimental study
  28. XANES measurements of Cr valence in olivine and their applications to planetary basalts
  29. Z-contrast imaging and ab initio study on “d” superstructure in sedimentary dolomite
  30. Influence of temperature, pressure, and chemical composition on the electrical conductivity of granite
  31. Ti- and Zr-minerals in calcite-dolomite marbles from the ultrahigh-pressure Kimi Complex, Rhodope mountains, Greece: Implications for the P-T evolution based on reaction textures, petrogenetic grids, and geothermobarometry
  32. Ab initio thermodynamic and thermophysical properties of sapphirine end-members in the join Mg4Al8Si2O20-Mg3Al10SiO20
  33. The relation between Li ↔ Na substitution and hydrogen bonding in five-periodic singlechain silicates nambulite and marsturite: A single-crystal X-ray study
  34. Natural analogs of belite sulfoaluminate cement clinkers from Negev Desert, Israel
  35. Australian sedimentary opal-A and its associated minerals: Implications for natural silica sphere formation
  36. The 2H and 3R polytypes of sabieite, NH4Fe3+(SO4)2, from a natural fire in an oil-bearing shale near Milan, Ohio
  37. Letter
  38. Te-rich raspite, Pb(W0.56Te0.44)O4, from Tombstone, Arizona, U.S.A.: The first natural example of Te6+ substitution for W6+
  39. New Mineral Names
  40. Book Review
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