Fe5S2 identified as a host of sulfur in Earth and planetary cores

Zurkowski, Claire C.; Lavina, Barbara; Case, Abigail; Swadba, Kellie; Chariton, Stella; Prakapenka, Vitali; Campbell, Andrew J.

doi:10.1016/j.epsl.2022.117650

Title: Fe₅S₂ identified as a host of sulfur in Earth and planetary cores

Abstract

Cosmochemical considerations suggest that sulfur is a candidate light alloying element in rocky planetary cores, such that the high pressure-temperature (P-T) Fe-S phase relations likely play a key role in planetary core crystallization thermodynamics. Here the iron-saturated Fe-S phase relations were investigated to 200 GPa and 3250 K using combined powder and single-crystal X-ray diffraction techniques in a laser-heated diamond anvil cell. Upon heating at 120 GPa, I-4 Fe₃S is observed to break down to form iron and a novel hexagonal Fe₅S₂ sulfide with the Ni₅As₂ structure (P6₃cm, Z=6). To 200 GPa, Fe₅S₂ and Fe are observed to coexist at high temperatures while Fe₂S polymorphs are identified with Fe at lower temperatures. An updated Fe-rich Fe-S phase diagram is presented. As this hexagonal Fe₅S₂ expresses complex Fe-Fe coordination and atomic positional disorder, crystallization of Fe₅S₂ may contribute to intricate elastic and electrical properties in Earth and planetary cores as they crystallize over time. Models of a fully crystallized Fe-rich Fe-S liquid in Earth's and Venus' core establish that Fe₅S₂ is likely the only sulfide to crystallize and may deposit in the outer third of the planets' cores as they cool. Fe₅S₂ could further serve as a host for Ni andmore »« less

Authors:

^[1]; Lavina, Barbara ^[2];

^[3];

^[3]; Prakapenka, Vitali ^[3]; Campbell, Andrew J. ^[3]

Univ. of Chicago, IL (United States); Carnegie Inst. of Science, Washington, DC (United States)
Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Univ. of Chicago, IL (United States)

Publication Date:: Wed Jun 22 00:00:00 EDT 2022

Research Org.:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC); National Science Foundation (NSF)

OSTI Identifier:: 1909606

Grant/Contract Number:: AC02-06CH11357; EAR-1634415; EAR-1651017

Resource Type:: Accepted Manuscript

Journal Name:: Earth and Planetary Science Letters

Additional Journal Information:: Journal Volume: 593; Journal ID: ISSN 0012-821X

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 58 GEOSCIENCES; diamond anvil cell; high pressure; high temperature; Earth’s core; core crystallization; iron alloys

Citation Formats


                    Zurkowski, Claire C., Lavina, Barbara, Case, Abigail, Swadba, Kellie, Chariton, Stella, Prakapenka, Vitali, and Campbell, Andrew J. Fe5S2 identified as a host of sulfur in Earth and planetary cores.  United States: N. p., 2022. 
Web.  doi:10.1016/j.epsl.2022.117650.

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                    Zurkowski, Claire C., Lavina, Barbara, Case, Abigail, Swadba, Kellie, Chariton, Stella, Prakapenka, Vitali, & Campbell, Andrew J. Fe5S2 identified as a host of sulfur in Earth and planetary cores.  United States.  https://doi.org/10.1016/j.epsl.2022.117650

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                    Zurkowski, Claire C., Lavina, Barbara, Case, Abigail, Swadba, Kellie, Chariton, Stella, Prakapenka, Vitali, and Campbell, Andrew J. Wed .  
"Fe5S2 identified as a host of sulfur in Earth and planetary cores".  United States.  https://doi.org/10.1016/j.epsl.2022.117650.  https://www.osti.gov/servlets/purl/1909606.

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@article{osti_1909606,

  title        = {Fe5S2 identified as a host of sulfur in Earth and planetary cores},

  author       = {Zurkowski, Claire C. and Lavina, Barbara and Case, Abigail and Swadba, Kellie and Chariton, Stella and Prakapenka, Vitali and Campbell, Andrew J.},

  abstractNote = {Cosmochemical considerations suggest that sulfur is a candidate light alloying element in rocky planetary cores, such that the high pressure-temperature (P-T) Fe-S phase relations likely play a key role in planetary core crystallization thermodynamics. Here the iron-saturated Fe-S phase relations were investigated to 200 GPa and 3250 K using combined powder and single-crystal X-ray diffraction techniques in a laser-heated diamond anvil cell. Upon heating at 120 GPa, I-4 Fe3S is observed to break down to form iron and a novel hexagonal Fe5S2 sulfide with the Ni5As2 structure (P63cm, Z=6). To 200 GPa, Fe5S2 and Fe are observed to coexist at high temperatures while Fe2S polymorphs are identified with Fe at lower temperatures. An updated Fe-rich Fe-S phase diagram is presented. As this hexagonal Fe5S2 expresses complex Fe-Fe coordination and atomic positional disorder, crystallization of Fe5S2 may contribute to intricate elastic and electrical properties in Earth and planetary cores as they crystallize over time. Models of a fully crystallized Fe-rich Fe-S liquid in Earth's and Venus' core establish that Fe5S2 is likely the only sulfide to crystallize and may deposit in the outer third of the planets' cores as they cool. Fe5S2 could further serve as a host for Ni and Si as has been observed in the related meteoritic phase perryite, (Fe, Ni)8(P, Si)3, adding intricacies to elemental partitioning during core crystallization. The stability of Fe5S2 presented here is key to understanding the role of sulfur in the crystallization sequences that drive the geodynamics and dictate the structures of Earth and rocky planetary cores.},

  doi          = {10.1016/j.epsl.2022.117650},

  journal      = {Earth and Planetary Science Letters},

  number       = ,

  volume       = 593,

  place        = {United States},

  year         = {Wed Jun 22 00:00:00 EDT 2022},

  month        = {Wed Jun 22 00:00:00 EDT 2022}

}

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Title: Fe5S2 identified as a host of sulfur in Earth and planetary cores

Abstract

Citation Formats

COMPOUNDS OF THE TYPE M5X2: Pd5As2, Ni5Si2, AND Ni5P2 journal, July 1964

Elasticity and constitution of the Earth's interior journal, June 1952

Melting relationships in the Fe–Fe3S system up to the outer core conditions journal, December 2012

Crystal structure of HT-Ni5P2 and reinvestigation of isotypic Ni5As2 journal, July 2011

Phase relationships of the Fe–FeS system in conditions up to the Earth's outer core journal, May 2010

Decomposition of Fe 3 S above 250 GPa journal, September 2013

Core formation in planetesimals triggered by permeable flow journal, March 2003

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data journal, October 2011

The chemical composition of the Earth's core: Possibility of sulphur in the core journal, June 1970

A structural survey of the binary transition metal phosphides and arsenides of the d-block elements journal, January 2018

The Ni–Ni2P phase diagram at 6 GPa with implication to meteorites and super-reduced terrestrial rocks journal, October 2019

The composition of the Earth journal, March 1995

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Venus’ internal structure, temperature and core composition journal, April 2012

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Phase stabilities and spin transitions of Fe 3 (S 1−x P x ) at high pressure and its implications in meteorites journal, January 2016

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Partial melting in the iron–sulfur system at high pressure: A synchrotron X-ray diffraction study journal, June 2007

The crystal structure of Fe2S at 90 GPa based on single-crystal X-ray diffraction techniques journal, April 2022

High-Pressure Iron-Sulfur Compound, Fe3S2, and Melting Relations in the Fe-FeS System journal, March 1997

High pressure constraints on percolative core formation journal, October 1996

High-pressure and high-temperature polymorphism of iron sulfide (FeS) journal, July 1982

Why does Venus lack a magnetic field? journal, January 2002

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On the resolution of density within the Earth journal, November 2003

Lunar Troilite: Crystallography journal, January 1970

High-pressure experimental constraints of partitioning behavior of Si and S at the Mercury's inner core boundary journal, May 2021

High-pressure behavior of Fe3P and the role of phosphorus in planetary cores journal, March 2014

Advanced flat top laser heating system for high pressure research at GSECARS: application to the melting behavior of germanium journal, September 2008

In situ determination of Fe–Fe3S phase diagram and liquid structural properties up to 65 GPa journal, August 2008

Thermal equation of state of Fe 3 S and implications for sulfur in Earth's core: THERMAL EQUATION OF STATE OF Fe 3 S journal, June 2006

Structure and Density of FeS at High Pressure and High Temperature and the Internal Structure of Mars journal, June 1995

Crystal structure refinement with SHELXL journal, January 2015

Equation of state of Fe3S at room temperature up to 2megabars journal, March 2014

Models of the Earth's Core journal, November 1981

On the Crystal Structure of Ni5As2. journal, January 1973

Composition of the metal, schreibersite and perryite of enstatite achondrites and the origin of enstatite chondrites and achondrites journal, February 1970

Compression experiments to 126 GPa and 2500 K and thermal equation of state of Fe3S: Implications for sulphur in the Earth's core journal, March 2020

Experimental investigations of trace element fractionation in iron meteorites, II: The influence of sulfur journal, July 1983

Protracted core formation and rapid accretion of protoplanets journal, June 2014

Fe 2 S: The Most Fe‐Rich Iron Sulfide at the Earth's Inner Core Pressures journal, November 2019

Kristallstruktur von Ni31Si12 journal, May 1971

Kristallstruktur von Pd5Sb2 und Ni5As2 und einigen varianten journal, December 1970

Classification and properties of iron meteorites journal, January 1975

High pressure effects on the iron–iron oxide and nickel–nickel oxide oxygen fugacity buffers journal, September 2009

Structure of synthetic perryite, (Ni,Fe)8(Si,P)3 journal, July 1991

Preliminary reference Earth model journal, June 1981

Melting experiments on Fe–Fe 3 S system to 254 GPa journal, April 2017

Elastic anisotropy in textured hcp-iron to 112 GPa from sound wave propagation measurements journal, August 2004

Seismically determined elastic parameters for Earth’s outer core journal, June 2018

Elongation of Fe-Fe atomic pairs in the Invar alloy Fe65Ni35 journal, June 2021

High-pressure polymorphism of Fe 2 P and its implications for meteorites and Earth's core : HIGH PRESSURE BEHAVIOR OF Fe journal, May 2008

Compositional convection and stratification of Earth's core journal, January 1981

A sulfur-poor terrestrial core inferred from metal–silicate partitioning experiments journal, July 2017

Structure type and bulk modulus of Fe 3 S, a new iron-sulfur compound journal, November 2000

Measurement of the melting curve of Mg 0.9 Fe 0.1 SiO 3 at lower mantle conditions and its geophysical implications journal, October 1987

Title: Fe₅S₂ identified as a host of sulfur in Earth and planetary cores

COMPOUNDS OF THE TYPE M₅X₂: Pd₅As₂, Ni₅Si₂, AND Ni₅P₂
journal, July 1964

Elasticity and constitution of the Earth's interior
journal, June 1952

Melting relationships in the Fe–Fe3S system up to the outer core conditions
journal, December 2012

Crystal structure of HT-Ni5P2 and reinvestigation of isotypic Ni5As2
journal, July 2011

Phase relationships of the Fe–FeS system in conditions up to the Earth's outer core
journal, May 2010

Decomposition of Fe ₃ S above 250 GPa
journal, September 2013

Core formation in planetesimals triggered by permeable flow
journal, March 2003

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011

The chemical composition of the Earth's core: Possibility of sulphur in the core
journal, June 1970

A structural survey of the binary transition metal phosphides and arsenides of the d-block elements
journal, January 2018

The Ni–Ni₂P phase diagram at 6 GPa with implication to meteorites and super-reduced terrestrial rocks
journal, October 2019

The composition of the Earth
journal, March 1995

Melting Experiments on Liquidus Phase Relations in the Fe‐S‐O Ternary System Under Core Pressures
journal, May 2019

Venus’ internal structure, temperature and core composition
journal, April 2012

DIOPTAS : a program for reduction of two-dimensional X-ray diffraction data and data exploration
journal, May 2015

Phase stabilities and spin transitions of Fe ₃ (S _1−x P _x ) at high pressure and its implications in meteorites
journal, January 2016

BX90: A new diamond anvil cell design for X-ray diffraction and optical measurements
journal, December 2012

Chemical classification of iron meteorites—X. Multielement studies of 43 irons, resolution of group IIIE from IIIAB, and evaluation of Cu as a taxonomic parameter
journal, April 1984

Partial melting in the iron–sulfur system at high pressure: A synchrotron X-ray diffraction study
journal, June 2007

The crystal structure of Fe2S at 90 GPa based on single-crystal X-ray diffraction techniques
journal, April 2022

High-Pressure Iron-Sulfur Compound, Fe3S2, and Melting Relations in the Fe-FeS System
journal, March 1997

High pressure constraints on percolative core formation
journal, October 1996

High-pressure and high-temperature polymorphism of iron sulfide (FeS)
journal, July 1982

Why does Venus lack a magnetic field?
journal, January 2002

X-ray Photoelectron and Absorption Spectroscopy of Metal-Rich Phosphides M ₂ P and M ₃ P ( M = Cr−Ni)
journal, November 2008

On the resolution of density within the Earth
journal, November 2003

Lunar Troilite: Crystallography
journal, January 1970

High-pressure experimental constraints of partitioning behavior of Si and S at the Mercury's inner core boundary
journal, May 2021

High-pressure behavior of Fe3P and the role of phosphorus in planetary cores
journal, March 2014

Advanced flat top laser heating system for high pressure research at GSECARS: application to the melting behavior of germanium
journal, September 2008

In situ determination of Fe–Fe3S phase diagram and liquid structural properties up to 65 GPa
journal, August 2008

Thermal equation of state of Fe ₃ S and implications for sulfur in Earth's core: THERMAL EQUATION OF STATE OF Fe ₃ S
journal, June 2006

Structure and Density of FeS at High Pressure and High Temperature and the Internal Structure of Mars
journal, June 1995

Crystal structure refinement with SHELXL
journal, January 2015

Equation of state of Fe3S at room temperature up to 2megabars
journal, March 2014

Models of the Earth's Core
journal, November 1981

On the Crystal Structure of Ni5As2.
journal, January 1973

Composition of the metal, schreibersite and perryite of enstatite achondrites and the origin of enstatite chondrites and achondrites
journal, February 1970

Compression experiments to 126 GPa and 2500 K and thermal equation of state of Fe3S: Implications for sulphur in the Earth's core
journal, March 2020

Experimental investigations of trace element fractionation in iron meteorites, II: The influence of sulfur
journal, July 1983

Protracted core formation and rapid accretion of protoplanets
journal, June 2014

Fe ₂ S: The Most Fe‐Rich Iron Sulfide at the Earth's Inner Core Pressures
journal, November 2019

Kristallstruktur von Ni31Si12
journal, May 1971

Kristallstruktur von Pd5Sb2 und Ni5As2 und einigen varianten
journal, December 1970

Classification and properties of iron meteorites
journal, January 1975

High pressure effects on the iron–iron oxide and nickel–nickel oxide oxygen fugacity buffers
journal, September 2009

Structure of synthetic perryite, (Ni,Fe)8(Si,P)3
journal, July 1991

Preliminary reference Earth model
journal, June 1981

Melting experiments on Fe–Fe 3 S system to 254 GPa
journal, April 2017

Elastic anisotropy in textured hcp-iron to 112 GPa from sound wave propagation measurements
journal, August 2004

Seismically determined elastic parameters for Earth’s outer core
journal, June 2018

Elongation of Fe-Fe atomic pairs in the Invar alloy Fe65Ni35
journal, June 2021

High-pressure polymorphism of Fe ₂ P and its implications for meteorites and Earth's core : HIGH PRESSURE BEHAVIOR OF Fe
journal, May 2008

Compositional convection and stratification of Earth's core
journal, January 1981

A sulfur-poor terrestrial core inferred from metal–silicate partitioning experiments
journal, July 2017

Structure type and bulk modulus of Fe ₃ S, a new iron-sulfur compound
journal, November 2000

Measurement of the melting curve of Mg _0.9 Fe _0.1 SiO ₃ at lower mantle conditions and its geophysical implications
journal, October 1987