Effects of the Fe3+ spin transition on the properties of aluminous perovskite-New insights for lower-mantle seismic heterogeneities

Krystle Catalli, Sang-Heon Shim, Przemyslaw Dera, Vitali B. Prakapenka, Jiyong Zhao, Wolfgang Sturhahn, Paul Chow, Yuming Xiao, Hyunchae Cynn, William J. Evans

Research output: Contribution to journalArticle

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Abstract

We have measured the effects of the coupled substitution of Fe3+ and Al on the density and compressibility of mantle silicate perovskite (Pv) up to 95GPa. X-ray emission spectroscopy and synchrotron Mössbauer spectroscopy reveal a rapid increase in the population of low-spin Fe3+ in Fe3+, Al-bearing Pv over a narrow pressure range near 70GPa, which is in sharp contrast with Al-free Fe3+-bearing Pv, where Fe3+ undergoes a gradual spin transition, and with Al-free Fe2+-bearing Pv, where Fe2+ does not become low spin. At low pressure, Fe3+ and Al expand the perovskite lattice. However, near the pressure range of the abrupt increase in the low-spin population, the unit-cell volume of Fe3+, Al-bearing Pv becomes similar to that of Mg-endmember Pv, while those of Al-free Fe3+-bearing Pv and Al-free Fe2+-bearing Pv remain larger throughout the lower mantle. Consequently, Pv in Al-rich systems should have lower density in the shallow lower mantle but similar or greater density than Pv in pyrolite in the deep lower mantle, affecting the buoyancy and mechanical stability of heterogeneities. Although the Fe3+ spin transition in Pv is unlikely to cause a seismic discontinuity at mantle temperatures, it may result in a large change in bulk sound speed at 1200-1800km depth, such that a vertically extending structure with an elevated amount of Fe3+ would generate slower and faster anomalies above and below the depth of the spin transition, respectively, relative to the surrounding mantle. This may have important implications for bulk sound speed anomalies observed at similar depths in seismic tomography studies.

Original languageEnglish (US)
Pages (from-to)293-302
Number of pages10
JournalEarth and Planetary Science Letters
Volume310
Issue number3-4
DOIs
StatePublished - Oct 15 2011
Externally publishedYes

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perovskite
lower mantle
Earth mantle
Bearings (structural)
anomalies
acoustics
mantle
buoyancy
spectroscopy
compressibility
effect
silicates
discontinuity
synchrotrons
low pressure
tomography
Acoustic waves
substitutes
pyrolite
anomaly

Keywords

  • Aluminum
  • Ferric iron
  • Heterogeneities
  • Perovskite
  • Spin transition

ASJC Scopus subject areas

  • Geochemistry and Petrology
  • Geophysics
  • Earth and Planetary Sciences (miscellaneous)
  • Space and Planetary Science

Cite this

Effects of the Fe3+ spin transition on the properties of aluminous perovskite-New insights for lower-mantle seismic heterogeneities. / Catalli, Krystle; Shim, Sang-Heon; Dera, Przemyslaw; Prakapenka, Vitali B.; Zhao, Jiyong; Sturhahn, Wolfgang; Chow, Paul; Xiao, Yuming; Cynn, Hyunchae; Evans, William J.

In: Earth and Planetary Science Letters, Vol. 310, No. 3-4, 15.10.2011, p. 293-302.

Research output: Contribution to journalArticle

Catalli, Krystle ; Shim, Sang-Heon ; Dera, Przemyslaw ; Prakapenka, Vitali B. ; Zhao, Jiyong ; Sturhahn, Wolfgang ; Chow, Paul ; Xiao, Yuming ; Cynn, Hyunchae ; Evans, William J. / Effects of the Fe3+ spin transition on the properties of aluminous perovskite-New insights for lower-mantle seismic heterogeneities. In: Earth and Planetary Science Letters. 2011 ; Vol. 310, No. 3-4. pp. 293-302.
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abstract = "We have measured the effects of the coupled substitution of Fe3+ and Al on the density and compressibility of mantle silicate perovskite (Pv) up to 95GPa. X-ray emission spectroscopy and synchrotron M{\"o}ssbauer spectroscopy reveal a rapid increase in the population of low-spin Fe3+ in Fe3+, Al-bearing Pv over a narrow pressure range near 70GPa, which is in sharp contrast with Al-free Fe3+-bearing Pv, where Fe3+ undergoes a gradual spin transition, and with Al-free Fe2+-bearing Pv, where Fe2+ does not become low spin. At low pressure, Fe3+ and Al expand the perovskite lattice. However, near the pressure range of the abrupt increase in the low-spin population, the unit-cell volume of Fe3+, Al-bearing Pv becomes similar to that of Mg-endmember Pv, while those of Al-free Fe3+-bearing Pv and Al-free Fe2+-bearing Pv remain larger throughout the lower mantle. Consequently, Pv in Al-rich systems should have lower density in the shallow lower mantle but similar or greater density than Pv in pyrolite in the deep lower mantle, affecting the buoyancy and mechanical stability of heterogeneities. Although the Fe3+ spin transition in Pv is unlikely to cause a seismic discontinuity at mantle temperatures, it may result in a large change in bulk sound speed at 1200-1800km depth, such that a vertically extending structure with an elevated amount of Fe3+ would generate slower and faster anomalies above and below the depth of the spin transition, respectively, relative to the surrounding mantle. This may have important implications for bulk sound speed anomalies observed at similar depths in seismic tomography studies.",
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AU - Catalli, Krystle

AU - Shim, Sang-Heon

AU - Dera, Przemyslaw

AU - Prakapenka, Vitali B.

AU - Zhao, Jiyong

AU - Sturhahn, Wolfgang

AU - Chow, Paul

AU - Xiao, Yuming

AU - Cynn, Hyunchae

AU - Evans, William J.

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N2 - We have measured the effects of the coupled substitution of Fe3+ and Al on the density and compressibility of mantle silicate perovskite (Pv) up to 95GPa. X-ray emission spectroscopy and synchrotron Mössbauer spectroscopy reveal a rapid increase in the population of low-spin Fe3+ in Fe3+, Al-bearing Pv over a narrow pressure range near 70GPa, which is in sharp contrast with Al-free Fe3+-bearing Pv, where Fe3+ undergoes a gradual spin transition, and with Al-free Fe2+-bearing Pv, where Fe2+ does not become low spin. At low pressure, Fe3+ and Al expand the perovskite lattice. However, near the pressure range of the abrupt increase in the low-spin population, the unit-cell volume of Fe3+, Al-bearing Pv becomes similar to that of Mg-endmember Pv, while those of Al-free Fe3+-bearing Pv and Al-free Fe2+-bearing Pv remain larger throughout the lower mantle. Consequently, Pv in Al-rich systems should have lower density in the shallow lower mantle but similar or greater density than Pv in pyrolite in the deep lower mantle, affecting the buoyancy and mechanical stability of heterogeneities. Although the Fe3+ spin transition in Pv is unlikely to cause a seismic discontinuity at mantle temperatures, it may result in a large change in bulk sound speed at 1200-1800km depth, such that a vertically extending structure with an elevated amount of Fe3+ would generate slower and faster anomalies above and below the depth of the spin transition, respectively, relative to the surrounding mantle. This may have important implications for bulk sound speed anomalies observed at similar depths in seismic tomography studies.

AB - We have measured the effects of the coupled substitution of Fe3+ and Al on the density and compressibility of mantle silicate perovskite (Pv) up to 95GPa. X-ray emission spectroscopy and synchrotron Mössbauer spectroscopy reveal a rapid increase in the population of low-spin Fe3+ in Fe3+, Al-bearing Pv over a narrow pressure range near 70GPa, which is in sharp contrast with Al-free Fe3+-bearing Pv, where Fe3+ undergoes a gradual spin transition, and with Al-free Fe2+-bearing Pv, where Fe2+ does not become low spin. At low pressure, Fe3+ and Al expand the perovskite lattice. However, near the pressure range of the abrupt increase in the low-spin population, the unit-cell volume of Fe3+, Al-bearing Pv becomes similar to that of Mg-endmember Pv, while those of Al-free Fe3+-bearing Pv and Al-free Fe2+-bearing Pv remain larger throughout the lower mantle. Consequently, Pv in Al-rich systems should have lower density in the shallow lower mantle but similar or greater density than Pv in pyrolite in the deep lower mantle, affecting the buoyancy and mechanical stability of heterogeneities. Although the Fe3+ spin transition in Pv is unlikely to cause a seismic discontinuity at mantle temperatures, it may result in a large change in bulk sound speed at 1200-1800km depth, such that a vertically extending structure with an elevated amount of Fe3+ would generate slower and faster anomalies above and below the depth of the spin transition, respectively, relative to the surrounding mantle. This may have important implications for bulk sound speed anomalies observed at similar depths in seismic tomography studies.

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KW - Ferric iron

KW - Heterogeneities

KW - Perovskite

KW - Spin transition

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