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

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

Journal Article · Wed Jun 22 00:00:00 EDT 2022 · Earth and Planetary Science Letters

DOI:https://doi.org/10.1016/j.epsl.2022.117650· OSTI ID:1909606

^[1]; Lavina, Barbara ^[2]; ^[3]; ^[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)

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.

View Accepted Manuscript (DOE)

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

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

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1909606

Alternate ID(s):: OSTI ID: 1900673

Journal Information:: Earth and Planetary Science Letters, Journal Name: Earth and Planetary Science Letters Vol. 593; ISSN 0012-821X

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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58 GEOSCIENCES
Earth’s core
core crystallization
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high pressure
high temperature
iron alloys

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

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