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Sulfur isotopic signature of Earth established by planetesimal volatile evaporation

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Abstract

How and when Earth’s volatile content was established is controversial with several mechanisms postulated, including planetesimal evaporation, core formation and the late delivery of undifferentiated chondrite-like materials. The isotopes of volatile elements such as sulfur can be fractionated during planetary accretion and differentiation and thus are potential tracers of these processes. Using first-principles calculations, we examine sulfur isotope fractionation during core formation and planetesimal evaporation. We find no measurable sulfur isotope fractionation between silicate and metallic melts at core-forming conditions, indicating that the observed light sulfur isotope composition of the bulk silicate Earth relative to chondrites cannot be explained by metal–silicate fractionation. Our thermodynamic calculations show that sulfur evaporates mostly as H2S during planetesimal evaporation when nebular H2 is present. The observed bulk Earth sulfur isotope signature and abundance can be reproduced by evaporative loss of about 90% sulfur mainly as H2S from molten planetesimals before nebular H2 is dissipated. The heavy sulfur isotope composition of the Moon relative to the Earth is consistent with evaporative sulfur loss under 94–98% saturation condition during the Moon-forming giant impact. In summary, volatile evaporation from molten planetesimals before Earth’s formation probably played a key role in establishing Earth’s volatile element content.

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Fig. 1: Sulfur isotope compositions (δ34S) of planetary materials.
Fig. 2: Equilibrium sulfur isotope fractionation factors (103lnα of 34S/32S) between silicate and metallic melts.
Fig. 3: Sulfur isotope fractionation caused by volatile loss during planetesimal evaporation and the Moon-forming impact.
Fig. 4: Schematic diagram of sulfur isotopic behaviours during evaporation on small precursor bodies and during the Moon-forming impact.

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Data availability

The data that support the findings of this study are available in the article and Supplementary Information files. All new data associated with this paper will be made publicly available at https://doi.org/10.6084/m9.figshare.16566336.v1.

Code availability

The Vienna Ab Initio Simulation Package is a proprietary software available for purchase at https://www.vasp.at/.

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Acknowledgements

This work is supported by the Strategic Priority Research Program (B) of the Chinese Academy of Sciences (XDB41000000), Natural Science Foundation of China (41925017 and 41721002), and the Fundamental Research Funds for the Central Universities (WK2080000144). W.W. acknowledges support from the UCL–Carnegie Postdoctoral Scholarship. S.H. and M.L. acknowledge support from NSF AST-1910955 and EAR-1942042. Part of the calculations were conducted at the Supercomputing Center of the University of Science and Technology of China.

Author information

Authors and Affiliations

  1. Laboratory of Seismology and Physics of Earth’s Interior, School of Earth and Space Sciences, University of Science and Technology of China, Hefei, China

    Wenzhong Wang & Zhongqing Wu

  2. Department of Earth Sciences, University College London, London, UK

    Wenzhong Wang & John P. Brodholt

  3. Earth and Planets Laboratory, Carnegie Institution for Science, Washington, DC, USA

    Wenzhong Wang & Michael J. Walter

  4. International Center for Planetary Science, College of Geosciences, Chengdu University of Technology, Chengdu, China

    Chun-Hui Li

  5. CAS Key Laboratory of Crust–Mantle Materials and Environments, School of Earth and Space Sciences, University of Science and Technology of China, Hefei, China

    Chun-Hui Li & Fang Huang

  6. Centre for Earth Evolution and Dynamics, University of Oslo, Oslo, Norway

    John P. Brodholt

  7. Department of Geoscience, University of Nevada, Las Vegas, NV, USA

    Shichun Huang

  8. Department of Physics and Astronomy, University of Nevada, Las Vegas, NV, USA

    Min Li

  9. College of Physics, Jilin Normal University, Siping, China

    Min Li

  10. CAS Center for Excellence in Comparative Planetology, USTC, Hefei, China

    Zhongqing Wu & Fang Huang

  11. National Geophysical Observatory at Mengcheng, USTC, Hefei, China

    Zhongqing Wu

  12. State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Beijing, China

    Shui-Jiong Wang

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  1. Wenzhong Wang
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Contributions

W.W. and C.-H.L. conceived and designed this project. W.W. performed the theoretical calculations. S.H. and M.L. did the GRAINS calculations. W.W. wrote the manuscript with the help of C.-H.L., and all authors contributed to the discussion of the results and revision of the manuscript.

Corresponding authors

Correspondence to Wenzhong Wang or Chun-Hui Li.

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Peer review information Nature Geoscience thanks Yuan Li and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Rebecca Neely, in collaboration with the Nature Geoscience team.

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Extended data

Extended Data Fig. 1

Radial distribution functions g(r) and coordination numbers (CN) for S-O, S-Mg, and S-Si pairs in Mg32Si32O96SO2 silicate melt at different pressures.

Extended Data Fig. 2

Radial distribution functions g(r) and coordination numbers (CN) for S-O, S-Mg, and S-Si pairs in Mg32Si32O95S silicate melt at different pressures.

Extended Data Fig. 3

Radial distribution function g(r) and coordination number (CN) for S-Fe pair in Fe97S3 metallic melt at different pressures.

Extended Data Fig. 4

Radial distribution function g(r) and coordination number (CN) for S-Mg/Fe/Si/Ca/Al/O in Mg41Ca2Fe5Si32Al4O117 melt at 46.59 GPa and S-Fe/Ni/Si/C/O pairs in Fe87Ni4Si10O2C2S3 melt at 41.81 GPa.

Extended Data Fig. 5 Average force constants <F > of S in silicate and metallic melts at different pressures.

Mg32Si32O95S and Mg32Si32O96SO2 represent the S-bearing silicate melts under extremely reducing and oxidizing conditions, respectively. The green star and pentagon are the <F > of S in Mg41Ca2Fe5Si32Al4O117S and Fe87Ni4Si10O2C2S3 melts, respectively.

Extended Data Fig. 6

The reduced partition function ratios (103lnβ) of 34S/32S of Fe97S3, Mg32Si32O95S, and Mg32Si32O96SO2 melts at 0, 30, 60, 90 GPa.

Extended Data Fig. 7 The fractions of major S species in the vapour phase at 1e-4 bar and different temperatures (1000-1600 K).

(a) solar abundance, (b) solar abundance with H concentration decreased by one order of magnitude, (c) solar abundance with H concentration decreased by four orders of magnitude.

Extended Data Fig. 8 Equilibrium sulfur isotope fractionation factors (103lnαvapor-melt of 34S/32S) between vapour phase and silicate melt (Mg32Si32O95S).

The 103lnβ of silicate melt is derived from the force constant of S in Mg32Si32O95S silicate melt. The 103lnβ of vapour phase is estimated based on the <F > of each important S species (Extended Data Table 1) and their fractions in the vapour phase (Extended Data Table 2).

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Supplementary Information

Supplementary text, Tables 1 and 2 and Figs. 1–6.

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Wang, W., Li, CH., Brodholt, J.P. et al. Sulfur isotopic signature of Earth established by planetesimal volatile evaporation. Nat. Geosci. 14, 806–811 (2021). https://doi.org/10.1038/s41561-021-00838-6

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