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Electronic spin states of ferric and ferrous iron in the lower-mantle silicate perovskite

  • Jung-Fu Lin EMAIL logo , Ercan E. Alp , Zhu Mao , Toru Inoue , Catherine McCammon , Yuming Xiao , Paul Chow and Jiyong Zhao
Published/Copyright: April 2, 2015
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American Mineralogist
From the journal American Mineralogist Volume 97 Issue 4

Abstract

The electronic spin and valence states of iron in lower-mantle silicate perovskite have been previously investigated at high pressures using various experimental and theoretical techniques. However, experimental results and their interpretation remain highly debated. Here we have studied a wellcharacterized silicate perovskite starting sample [(Mg0.9,Fe0.1)SiO3] in a chemically inert Ne pressure medium at pressures up to 120 GPa using synchrotron Mössbauer spectra. Analyses of the Mössbauer spectra explicitly show a high-spin to low-spin transition of the octahedral-site Fe3+ occurring at ~13-24 GPa, as evidenced from a significant increase in the hyperfine quadrupole splitting. Two quadrupole doublets of the A-site Fe2+, with extremely high-QS values of 4.1 and 3.1 mm/s, occur simultaneously with the spin transition of the octahedral-site Fe3+ and continue to develop to 120 GPa. It is conceivable that the spin-pairing transition of the octahedral-site Fe3+ causes a volume reduction and a change in the local atomic-site configurations that result in a significant increase of the quadrupole splitting in the dodecahedral-site Fe2+ at 13-24 GPa. Our results here provide a coherent explanation for recent experimental and theoretical results on the spin and valence states of iron in perovskite, and assist in comprehending the effects of the spin and valence states of iron on the properties of the lower-mantle minerals.

Keywords: Silicate perovskite; diamond-anvil cell; spin transition; lower mantle; synchrotron Mössbauer spectroscopy; high pressures
Received: 2011-9-9
Accepted: 2011-12-9
Published Online: 2015-4-2
Published in Print: 2012-4-1

© 2015 by Walter de Gruyter Berlin/Boston

Articles in the same Issue

  1. Veatchite: Structural relationships of the three polytypes
  2. Falsterite, Ca2MgMn2+2 (Fe2+0.5Fe3+0.5)4Zn4(PO4)8(OH)4(H2O)14, a new secondary phosphate mineral from the Palermo No. 1 pegmatite, North Groton, New Hampshire
  3. Pavlovskyite Ca8(SiO4)2(Si3O10): A new mineral of altered silicate-carbonate xenoliths from the two Russian type localities, Birkhin massif, Baikal Lake area and Upper Chegem caldera, North Caucasus
  4. Zaccagnaite-3R, a new Zn-Al hydrotalcite polytype from El Soplao cave (Cantabria, Spain)
  5. Incorporation of Si into TiO2 phases at high pressure
  6. TOF-SIMS and electron microprobe investigations of zoned magmatic orthopyroxenes: First results of trace and minor element analysis with implications for diffusion modeling
  7. Titanium in muscovite, biotite, and hornblende: Modeling, thermometry, and rutile activities of metapelites and amphibolites
  8. Polysaccharide-catalyzed nucleation and growth of disordered dolomite: A potential precursor of sedimentary dolomite
  9. High-pressure and high-temperature phase transitions in FeTiO3 and a new dense FeTi3O7 structure
  10. Compressibility and thermal expansion of hydrous ringwoodite with 2.5(3) wt% H2O
  11. Vibrational and elastic properties of ferromagnesite across the electronic spin-pairing transition of iron
  12. Electronic spin states of ferric and ferrous iron in the lower-mantle silicate perovskite
  13. Experimental VNIR reflectance spectroscopy of gypsum dehydration: Investigating the gypsum to bassanite transition
  14. Nature of rehydroxylation in dioctahedral 2:1 layer clay minerals
  15. Thermal behavior of afghanite, an ABABACAC member of the cancrinite group
  16. Experimental incorporation of Th into xenotime at middle to lower crustal P-T utilizing alkali-bearing fluids
  17. Sol-gel synthesis of nanocrystalline fayalite (Fe2SiO4)
  18. The heat capacity of fayalite at high temperatures
  19. Structural trends for celestite (SrSO4), anglesite (PbSO4), and barite (BaSO4): Confirmation of expected variations within the SO4 groups
  20. The dehydroxylation of serpentine group minerals
  21. Formation of nanoscale Th-coffinite
  22. Magnetic and low-temperature structural behavior of clinopyroxene-type FeGeO3: A neutron diffraction, magnetic susceptibility, and 57Fe Mössbauer study
  23. Crystal structure and thermal expansion of aragonite-group carbonates by single-crystal X-ray diffraction
  24. The lower-pressure stability of glaucophane in the presence of paragonite and quartz in the system Na2O-MgO-Al2O3-SiO2-H2O
  25. Coralloite, Mn2+Mn23+(AsO4)2(OH)2·4H2O, a new mixed valence Mn hydrate arsenate: Crystal structure and relationships with bermanite and whitmoreite mineral groups
  26. The crystal structure of metanatroautunite, Na[(UO2)(PO4)](H2O)3, from the Lake Boga Granite, Victoria, Australia
  27. Petedunnite (CaZnSi2O6): Stability and phase relations in the system CaO-ZnO-SiO2
  28. Revision of the crystal structure and chemical formula of weeksite, K2(UO2)2(Si5O13)·4H2O
  29. Electron backscatter diffraction (EBSD) analyses of phyllosilicates in petrographic thin sections
https://doi.org/10.2138/am.2012.4000
Keywords for this article
Silicate perovskite; diamond-anvil cell; spin transition; lower mantle; synchrotron Mössbauer spectroscopy; high pressures

Articles in the same Issue

  1. Veatchite: Structural relationships of the three polytypes
  2. Falsterite, Ca2MgMn2+2 (Fe2+0.5Fe3+0.5)4Zn4(PO4)8(OH)4(H2O)14, a new secondary phosphate mineral from the Palermo No. 1 pegmatite, North Groton, New Hampshire
  3. Pavlovskyite Ca8(SiO4)2(Si3O10): A new mineral of altered silicate-carbonate xenoliths from the two Russian type localities, Birkhin massif, Baikal Lake area and Upper Chegem caldera, North Caucasus
  4. Zaccagnaite-3R, a new Zn-Al hydrotalcite polytype from El Soplao cave (Cantabria, Spain)
  5. Incorporation of Si into TiO2 phases at high pressure
  6. TOF-SIMS and electron microprobe investigations of zoned magmatic orthopyroxenes: First results of trace and minor element analysis with implications for diffusion modeling
  7. Titanium in muscovite, biotite, and hornblende: Modeling, thermometry, and rutile activities of metapelites and amphibolites
  8. Polysaccharide-catalyzed nucleation and growth of disordered dolomite: A potential precursor of sedimentary dolomite
  9. High-pressure and high-temperature phase transitions in FeTiO3 and a new dense FeTi3O7 structure
  10. Compressibility and thermal expansion of hydrous ringwoodite with 2.5(3) wt% H2O
  11. Vibrational and elastic properties of ferromagnesite across the electronic spin-pairing transition of iron
  12. Electronic spin states of ferric and ferrous iron in the lower-mantle silicate perovskite
  13. Experimental VNIR reflectance spectroscopy of gypsum dehydration: Investigating the gypsum to bassanite transition
  14. Nature of rehydroxylation in dioctahedral 2:1 layer clay minerals
  15. Thermal behavior of afghanite, an ABABACAC member of the cancrinite group
  16. Experimental incorporation of Th into xenotime at middle to lower crustal P-T utilizing alkali-bearing fluids
  17. Sol-gel synthesis of nanocrystalline fayalite (Fe2SiO4)
  18. The heat capacity of fayalite at high temperatures
  19. Structural trends for celestite (SrSO4), anglesite (PbSO4), and barite (BaSO4): Confirmation of expected variations within the SO4 groups
  20. The dehydroxylation of serpentine group minerals
  21. Formation of nanoscale Th-coffinite
  22. Magnetic and low-temperature structural behavior of clinopyroxene-type FeGeO3: A neutron diffraction, magnetic susceptibility, and 57Fe Mössbauer study
  23. Crystal structure and thermal expansion of aragonite-group carbonates by single-crystal X-ray diffraction
  24. The lower-pressure stability of glaucophane in the presence of paragonite and quartz in the system Na2O-MgO-Al2O3-SiO2-H2O
  25. Coralloite, Mn2+Mn23+(AsO4)2(OH)2·4H2O, a new mixed valence Mn hydrate arsenate: Crystal structure and relationships with bermanite and whitmoreite mineral groups
  26. The crystal structure of metanatroautunite, Na[(UO2)(PO4)](H2O)3, from the Lake Boga Granite, Victoria, Australia
  27. Petedunnite (CaZnSi2O6): Stability and phase relations in the system CaO-ZnO-SiO2
  28. Revision of the crystal structure and chemical formula of weeksite, K2(UO2)2(Si5O13)·4H2O
  29. Electron backscatter diffraction (EBSD) analyses of phyllosilicates in petrographic thin sections
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