Phase transitions in orthopyroxene (En90) to 49GPa from single-crystal X-ray diffraction
Abstract
Synchrotron-based high-pressure single-crystal X-ray diffraction experiments were conducted on ~Mg0.9Fe0.1SiO3 (En90) orthopyroxene crystals at room temperature to a maximum pressure of 48.5 GPa. The sample was compressed in a diamond anvil cell with a neon pressure medium and a gold pressure calibrant. In addition to the previously described orthopyroxene to β-opx transition (designated HPCEN2 in previous studies), we observe two further phase transitions at 29.9 GPa and 40.3 GPa. However, we do not observe the γ-opx phase recently described in an Fe-rich orthopyroxene composition. The structures of both of the new phases were solved in space group Pca21. While their Mg-O layers remain pyroxene-like, their Si-O layers transform in a stepwise fashion to akimotoite-like sheets, with sites in 4-, 5-, or 6-fold coordination, depending on the specific structure and layer. Due to the increased Si-O coordination number, we designate the new structures α- and β-post-orthopyroxene (α-popx and β-popx). α-popx has one Si-O layer that is entirely tetrahedral, and one layer that contains both tetrahedra and 5-coordinated Si in distorted square pyramids. β-popx retains the mixed 4- and 5-coordinated Si layer found in α-popx, while the other Si layer adopts fully octahedral coordination. The α- and β-popx structures show a progressivemore »
- Authors:
-
- Princeton Univ., NJ (United States)
- Univ. of Hawaii, Honolulu, HI (United States); Univ. of Chicago, IL (United States)
- Publication Date:
- Research Org.:
- Carnegie Inst. of Science, Washington, DC (United States). Geophysical Lab.
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1338326
- Alternate Identifier(s):
- OSTI ID: 1251985
- Grant/Contract Number:
- NA0002006
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Physics of the Earth and Planetary Interiors
- Additional Journal Information:
- Journal Volume: 244; Journal Issue: C; Journal ID: ISSN 0031-9201
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Orthopyroxene; Phase transition; Crystallography; High pressure; Single-crystal X-ray diffraction
Citation Formats
Finkelstein, Gregory J., Dera, Przemyslaw K., and Duffy, Thomas S. Phase transitions in orthopyroxene (En90) to 49GPa from single-crystal X-ray diffraction. United States: N. p., 2014.
Web. doi:10.1016/j.pepi.2014.10.009.
Finkelstein, Gregory J., Dera, Przemyslaw K., & Duffy, Thomas S. Phase transitions in orthopyroxene (En90) to 49GPa from single-crystal X-ray diffraction. United States. https://doi.org/10.1016/j.pepi.2014.10.009
Finkelstein, Gregory J., Dera, Przemyslaw K., and Duffy, Thomas S. 2014.
"Phase transitions in orthopyroxene (En90) to 49GPa from single-crystal X-ray diffraction". United States. https://doi.org/10.1016/j.pepi.2014.10.009. https://www.osti.gov/servlets/purl/1338326.
@article{osti_1338326,
title = {Phase transitions in orthopyroxene (En90) to 49GPa from single-crystal X-ray diffraction},
author = {Finkelstein, Gregory J. and Dera, Przemyslaw K. and Duffy, Thomas S.},
abstractNote = {Synchrotron-based high-pressure single-crystal X-ray diffraction experiments were conducted on ~Mg0.9Fe0.1SiO3 (En90) orthopyroxene crystals at room temperature to a maximum pressure of 48.5 GPa. The sample was compressed in a diamond anvil cell with a neon pressure medium and a gold pressure calibrant. In addition to the previously described orthopyroxene to β-opx transition (designated HPCEN2 in previous studies), we observe two further phase transitions at 29.9 GPa and 40.3 GPa. However, we do not observe the γ-opx phase recently described in an Fe-rich orthopyroxene composition. The structures of both of the new phases were solved in space group Pca21. While their Mg-O layers remain pyroxene-like, their Si-O layers transform in a stepwise fashion to akimotoite-like sheets, with sites in 4-, 5-, or 6-fold coordination, depending on the specific structure and layer. Due to the increased Si-O coordination number, we designate the new structures α- and β-post-orthopyroxene (α-popx and β-popx). α-popx has one Si-O layer that is entirely tetrahedral, and one layer that contains both tetrahedra and 5-coordinated Si in distorted square pyramids. β-popx retains the mixed 4- and 5-coordinated Si layer found in α-popx, while the other Si layer adopts fully octahedral coordination. The α- and β-popx structures show a progressive transformation towards the arrangement of Si layers found in akimotoite, a potentially important phase in the earth’s transition zone. Metastable transformations in pyroxenes are of interest for understanding possible metastability in geological environments such as subducting slabs and meteorite impacts},
doi = {10.1016/j.pepi.2014.10.009},
url = {https://www.osti.gov/biblio/1338326},
journal = {Physics of the Earth and Planetary Interiors},
issn = {0031-9201},
number = C,
volume = 244,
place = {United States},
year = {Wed Oct 29 00:00:00 EDT 2014},
month = {Wed Oct 29 00:00:00 EDT 2014}
}
Web of Science
Works referenced in this record:
Shock-induced melting of MgSiO 3 perovskite and implications for melts in Earth's lowermost mantle
journal, January 2004
- Akins, Joseph A.
- Geophysical Research Letters, Vol. 31, Issue 14
Heating-induced phase transformation in zeolite brewsterite: new 4- and 5-coordinated (Si,Al) sites
journal, February 1999
- Alberti, A.; Sacerdoti, M.; Quartieri, S.
- Physics and Chemistry of Minerals, Vol. 26, Issue 3
Equations of state and thermodynamic properties of enstatite pyroxenes
journal, October 1994
- Angel, R. J.; Hugh-Jones, D. A.
- Journal of Geophysical Research: Solid Earth, Vol. 99, Issue B10
Elasticity and equation of state of orthoenstatite, MgSiO 3
journal, April 2002
- Angel, Ross J.; Jackson, Jennifer M.
- American Mineralogist, Vol. 87, Issue 4
Stability of high-density clinoenstatite at upper-mantle pressures
journal, July 1992
- Angel, R. J.; Chopelas, A.; Ross, N. L.
- Nature, Vol. 358, Issue 6384
Structural characterization of pentacoordinate silicon in a calcium silicate
journal, December 1996
- Angel, R. J.; Ross, N. L.; Seifert, F.
- Nature, Vol. 384, Issue 6608
Effective hydrostatic limits of pressure media for high-pressure crystallographic studies
journal, January 2007
- Angel, Ross J.; Bujak, Maciej; Zhao, Jing
- Journal of Applied Crystallography, Vol. 40, Issue 1
A Bond Path: A Universal Indicator of Bonded Interactions
journal, September 1998
- Bader, R. F. W.
- The Journal of Physical Chemistry A, Vol. 102, Issue 37
Theoretical study of a five-coordinated silica polymorph
journal, September 1997
- Badro, James; Teter, David M.; Downs, Robert T.
- Physical Review B, Vol. 56, Issue 10
Possible presence of high-pressure ice in cold subducting slabs
journal, December 2000
- Bina, Craig R.; Navrotsky, Alexandra
- Nature, Vol. 408, Issue 6814
Thermodynamic parameters in the Earth as determined from seismic profiles
journal, September 1981
- Brown, J. M.; Shankland, T. J.
- Geophysical Journal International, Vol. 66, Issue 3
Molecular dynamics simulations of seismic discontinuities and phase transitions of MgSiO 3 from 4 to 6-coordinated silicate via a novel 5-coordinated phase
journal, May 2001
- Chaplot, S. L.; Choudhury, N.
- American Mineralogist, Vol. 86, Issue 5-6
Metastable high-pressure transformations of orthoferrosilite Fs82
journal, August 2013
- Dera, Przemyslaw; Finkelstein, Gregory J.; Duffy, Thomas S.
- Physics of the Earth and Planetary Interiors, Vol. 221
Orthopyroxene from the Serra de Mage Meteorite; a structure-refinement procedure for a Pbca phase coexisting with a C2/c exsolved phase
journal, August 1996
- Domeneghetti, M. Chiara; Tazzoli, Vittorio; Ballaran, Tiziana Boffa
- American Mineralogist, Vol. 81, Issue 7-8
Effects of Fe-enrichment on the equation of state and stability of (Mg,Fe)SiO3 perovskite
journal, January 2013
- Dorfman, Susannah M.; Meng, Yue; Prakapenka, Vitali B.
- Earth and Planetary Science Letters, Vol. 361
The coordination numbers of Na and K atoms in low albite and microcline as determined from a procrystal electron-density distribution
journal, December 1996
- Downs, Robert T.; Andalman, Aaron; Hudacsko, Marc
- American Mineralogist, Vol. 81, Issue 11-12
A comparison of procrystal and ab initio model representations of the electron-density distributions of minerals
journal, June 2002
- Downs, R. T.; Gibbs, G. V.; Boisen Jr, M. B.
- Physics and Chemistry of Minerals, Vol. 29, Issue 5
Preliminary reference Earth model
journal, June 1981
- Dziewonski, Adam M.; Anderson, Don L.
- Physics of the Earth and Planetary Interiors, Vol. 25, Issue 4
Internally consistent thermodynamic data and equilibrium phase relations for compounds in the system MgO-SiO 2 at high pressure and high temperature
journal, January 1990
- Fei, Yingwei; Saxena, Surendra K.; Navrotsky, Alexandra
- Journal of Geophysical Research, Vol. 95, Issue B5
Toward an internally consistent pressure scale
journal, May 2007
- Fei, Y.; Ricolleau, A.; Frank, M.
- Proceedings of the National Academy of Sciences, Vol. 104, Issue 22
Two-dimensional detector software: From real detector to idealised image or two-theta scan
journal, January 1996
- Hammersley, A. P.; Svensson, S. O.; Hanfland, M.
- High Pressure Research, Vol. 14, Issue 4-6, p. 235-248
Metastability of enstatite in deep subducting lithosphere
journal, November 1994
- Hogrefe, A.; Rubie, D. C.; Sharp, T. G.
- Nature, Vol. 372, Issue 6504
High-pressure phase transitions in MgSiO3 orthoenstatite studied by atomistic computer simulation
journal, April 2008
- Jahn, S.
- American Mineralogist, Vol. 93, Issue 4
Ortho/clinoenstatite transition
journal, May 1991
- Kanzaki, Masami
- Physics and Chemistry of Minerals, Vol. 17, Issue 8
Corrections to tabulated anomalous-scattering factors
journal, March 1990
- Kissel, L.; Pratt, R. H.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 46, Issue 3
In situ measurements of sound velocities and densities across the orthopyroxene → high-pressure clinopyroxene transition in MgSiO3 at high pressure
journal, October 2004
- Kung, Jennifer; Li, Baosheng; Uchida, Takeyuki
- Physics of the Earth and Planetary Interiors, Vol. 147, Issue 1
Pentacoordinate silicon intermediate states during silicate condensation and decondensation. Crystallographic support
journal, October 1984
- Liebau, F.
- Inorganica Chimica Acta, Vol. 89, Issue 1
Pressure-induced metastable phase transition in orthoenstatite (MgSiO3) at room temperature: a Raman spectroscopic study
journal, September 2003
- Lin, Chung-Cherng
- Journal of Solid State Chemistry, Vol. 174, Issue 2
Survival of pyropic garnet in subducting plates
journal, November 2008
- Nishi, Masayuki; Kato, Takumi; Kubo, Tomoaki
- Physics of the Earth and Planetary Interiors, Vol. 170, Issue 3-4
Reversals of the orthoenstatite-clinoenstatite transition at high pressures and high temperatures
journal, January 1990
- Pacalo, R. E. G.; Gasparik, T.
- Journal of Geophysical Research, Vol. 95, Issue B10
Pyroxenes: comparisons of real and ideal structural topologies*
journal, August 1973
- Papike, J. J.; Prewitt, C. T.; Sueno, S.
- Zeitschrift für Kristallographie, Vol. 138, Issue 138
Re-investigation of the crystal structure of enstatite under high-pressure conditions
journal, September 2012
- Periotto, B.; Balic-Zunic, T.; Nestola, F.
- American Mineralogist, Vol. 97, Issue 10
β ‐diopside, a new ultrahigh‐pressure polymorph of CaMgSi 2 O 6 with six‐coordinated silicon
journal, December 2012
- Plonka, Anna M.; Dera, Przemyslaw; Irmen, Peyton
- Geophysical Research Letters, Vol. 39, Issue 24
Combined method for ab initio structure solution from powder diffraction data
journal, October 1999
- Putz, H.; Schön, J. C.; Jansen, M.
- Journal of Applied Crystallography, Vol. 32, Issue 5
Phase Transformations and Differentiation in Subducted Lithosphere: Implications for Mantle Dynamics, Basalt Petrogenesis, and Crustal Evolution
journal, November 1982
- Ringwood, A. E.
- The Journal of Geology, Vol. 90, Issue 6
Enthalpy of formation of CaSi 2 O 5, a quenched high-pressure phase with pentacoordinate silicon
journal, February 2001
- Schoenitz, M.; Navrotsky, A.; Ross, N.
- Physics and Chemistry of Minerals, Vol. 28, Issue 1
High-pressure phase transitions in tetrahedrally coordinated chain structures
journal, January 2003
- Serghiou, G.
- Journal of Raman Spectroscopy, Vol. 34, Issue 7-8
A short history of SHELX
journal, December 2007
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
Low orthopyroxene from a lunar deep crustal rock: A new Pyroxene polymorph of space group P21ca
journal, May 1974
- Smyth, Joseph R.
- Geophysical Research Letters, Vol. 1, Issue 1
NMR evidence for five-coordinated silicon in a silicate glass at atmospheric pressure
journal, June 1991
- Stebbins, Jonathan F.
- Nature, Vol. 351, Issue 6328
Pentacoordinate silicon in high-pressure crystalline and glassy phases of calcium disilicate (CaSi 2 O 5 )
journal, August 1999
- Stebbins, J. F.; Poe, B. T.
- Geophysical Research Letters, Vol. 26, Issue 16
Isothermal equation of state for gold with a He-pressure medium
journal, September 2008
- Takemura, K.; Dewaele, A.
- Physical Review B, Vol. 78, Issue 10
Mixing properties of the enstatite-ferrosilite solid solution: I. A macroscopic perspective [Mixing properties of the enstatite-ferrosilite solid solution: I. A macroscopic perspective]
journal, June 2002
- Tarantino, Serena C.; Domeneghetti, M. Chiara; Carpenter, Michael A.
- European Journal of Mineralogy, Vol. 14, Issue 3
Stagnation of subducting slabs in the transition zone due to slow diffusion in majoritic garnet
journal, March 2013
- van Mierlo, W. L.; Langenhorst, F.; Frost, D. J.
- Nature Geoscience, Vol. 6, Issue 5
Change from sixfold to fivefold coordination of silicate polyhedra: Insights from first-principles calculations of
journal, April 1999
- Warren, M. C.; Redfern, S. A. T.; Angel, R.
- Physical Review B, Vol. 59, Issue 14
Spectroscopic Evidence for Pressure-Induced Coordination Changes in Silicate Glasses and Melts
journal, February 1988
- Williams, Q.; Jeanloz, R.
- Science, Vol. 239, Issue 4842
The orthorhombic to high- P monoclinic phase transition in Mg-Fe Pyroxenes: Can it produce a seismic discontinuity?
journal, April 1998
- Woodland, Alan B.
- Geophysical Research Letters, Vol. 25, Issue 8
A new pyroxene structure at high pressure; single-crystal X-ray and Raman study of the Pbcn-P2 1 cn phase transition in protopyroxene
journal, March 1999
- Yang, Hexiong; Finger, Larry W.; Conrad, Pamela G.
- American Mineralogist, Vol. 84, Issue 3
Pressure impact on the structure, elasticity, and electron density distribution of CaSi O
journal, May 2013
- Yu, Yonggang G.; Angel, Ross J.; Ross, Nancy L.
- Physical Review B, Vol. 87, Issue 18
Local structure variations observed in orthoenstatite at high pressures
journal, September 2011
- Zhang, D.; Jackson, J. M.; Sturhahn, W.
- American Mineralogist, Vol. 96, Issue 10
A new high-pressure phase transition in natural Fe-bearing orthoenstatite
journal, June 2012
- Zhang, J. S.; Dera, P.; Bass, J. D.
- American Mineralogist, Vol. 97, Issue 7
Elasticity and lattice dynamics of enstatite at high pressure: ELASTICITY AND LATTICE DYNAMICS OF EN87
journal, August 2013
- Zhang, Dongzhou; Jackson, Jennifer M.; Chen, Bin
- Journal of Geophysical Research: Solid Earth, Vol. 118, Issue 8
Pressure-induced Pbca-P21/c phase transition of natural orthoenstatite: Compositional effect and its geophysical implications
journal, May 2013
- Zhang, J. S.; Reynard, B.; Montagnac, G.
- American Mineralogist, Vol. 98, Issue 5-6
Pressure-induced Pbca–P21/c phase transition of natural orthoenstatite: The effect of high temperature and its geophysical implications
journal, March 2014
- Zhang, Jin S.; Reynard, Bruno; Montagnac, Gilles
- Physics of the Earth and Planetary Interiors, Vol. 228
Works referencing / citing this record:
Metastable silica high pressure polymorphs as structural proxies of deep Earth Silicate Melts
text, January 2018
- Bykova, Elena; Bykov, Maxim; Cernok, Ana
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Compressional Behavior of Hydrous Orthoenstatite: Insight into the Nature of LVZ under Continental Plate
journal, January 2020
- Hua, Florian Tian-Siang; Dera, Przemyslaw; Kung, Jennifer
- Minerals, Vol. 10, Issue 1
High‐Pressure γ ‐CaMgSi 2 O 6 : Does Penta‐Coordinated Silicon Exist in the Earth's Mantle?
journal, November 2017
- Hu, Yi; Kiefer, Boris; Bina, Craig R.
- Geophysical Research Letters, Vol. 44, Issue 22
Phase Transitions in Orthoenstatite and Subduction Zone Dynamics: Effects of Water and Transition Metal Ions
journal, April 2018
- Xu, Jingui; Zhang, Dongzhou; Fan, Dawei
- Journal of Geophysical Research: Solid Earth, Vol. 123, Issue 4
An Experimental Investigation of the Relative Strength of the Silica Polymorphs Quartz, Coesite, and Stishovite
journal, April 2019
- Hunt, Simon A.; Whitaker, Matthew L.; Bailey, Edward
- Geochemistry, Geophysics, Geosystems, Vol. 20, Issue 4
High pressure phase transitions of paracelsian BaAl2Si2O8
journal, September 2019
- Gorelova, Liudmila A.; Pakhomova, Anna S.; Krivovichev, Sergey V.
- Scientific Reports, Vol. 9, Issue 1
Pentacoordinated silicon in the high-pressure modification of datolite, CaBSiO 4 (OH)
journal, January 2018
- Gorelova, Liudmila A.; Pakhomova, Anna S.; Aprilis, Georgios
- Inorganic Chemistry Frontiers, Vol. 5, Issue 7
A New High-Pressure Phase Transition in Natural Gedrite
journal, October 2019
- Yong, Tommy; Bina, Craig R.; Finkelstein, Gregory J.
- Crystals, Vol. 9, Issue 10
High pressure phase transitions of paracelsian $BaAl_{2}Si_{2}O_{8}$
text, January 2019
- Gorelova, Liudmila A.; Pakhomova, Anna S.; Krivovichev, Sergey V.
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Metastable silica high pressure polymorphs as structural proxies of deep Earth silicate melts
journal, November 2018
- Bykova, E.; Bykov, M.; Černok, A.
- Nature Communications, Vol. 9, Issue 1
High-pressure single-crystal X-ray diffraction and synchrotron Mössbauer study of monoclinic ferrosilite
journal, February 2019
- Solomatova, Natalia V.; Alieva, Ayya; Finkelstein, Gregory J.
- Comptes Rendus Geoscience, Vol. 351, Issue 2-3
Compressional Behavior of Hydrous Orthoenstatite: Insight into the Nature of LVZ under Continental Plate
journal, January 2020
- Hua, Florian Tian-Siang; Dera, Przemyslaw; Kung, Jennifer
- Minerals, Vol. 10, Issue 1
High Pressure Single Crystal Diffraction at PX^2
journal, January 2017
- Zhang, Dongzhou; Dera, Przemyslaw K.; Eng, Peter J.
- Journal of Visualized Experiments, Issue 119