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Ruthenium isotope vestige of Earth’s pre-late-veneer mantle preserved in Archaean rocks

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Abstract

The accretion of volatile-rich material from the outer Solar System represents a crucial prerequisite for Earth to develop oceans and become a habitable planet1,2,3,4. However, the timing of this accretion remains controversial5,6,7,8. It has been proposed that volatile elements were added to Earth by the late accretion of a late veneer consisting of carbonaceous-chondrite-like material after core formation had ceased6,9,10. This view could not be reconciled with the ruthenium (Ru) isotope composition of carbonaceous chondrites5,11, which is distinct from that of the modern mantle12, or of any known meteorite group5. As a possible solution, Earth’s pre-late-veneer mantle could already have contained a fraction of Ru that was not fully extracted by core formation13. The presence of such pre-late-veneer Ru can only be established if its isotope composition is distinct from that of the modern mantle. Here we report the first high-precision, mass-independent Ru isotope compositions for Eoarchaean ultramafic rocks from southwest Greenland, which display a relative 100Ru excess of 22 parts per million compared with the modern mantle value. This 100Ru excess indicates that the source of the Eoarchaean rocks already contained a substantial fraction of Ru before the accretion of the late veneer. By 3.7 billion years ago, the mantle beneath southwest Greenland had not yet fully equilibrated with late accreted material. Otherwise, no Ru isotopic difference relative to the modern mantle would be observed. If constraints from other highly siderophile elements besides Ru are also considered14, the composition of the modern mantle can only be reconciled if the late veneer contained substantial amounts of carbonaceous-chondrite-like materials with their characteristic 100Ru deficits. These data therefore relax previous constraints on the late veneer and are consistent with volatile-rich material from the outer Solar System being delivered to Earth during late accretion.

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Fig. 1: ε100Ru data for Archaean and Palaeoproterozoic rocks, the modern mantle and chondrites.
Fig. 2: Ru isotope plot illustrating compositional differences between enstatite, ordinary, average carbonaceous, CI and CM carbonaceous chondrites, the modern mantle and the Eoarchaean mantle.
Fig. 3: Model estimates for the amount of late veneer added to the Eoarchaean mantle based on Ru isotope compositions.

Data availability

The data that support the findings of this study are available from the EarthChem library (https://doi.org/10.1594/IEDA/111462). Source data for Figs. 13 and Extended Data Fig. 14 are provided with the paper.

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Acknowledgements

We thank F. Wombacher and A. Katzemich for support in the laboratory and K. Tani and I. Nishio for help during fieldwork. This research was supported through DFG grant number FI 1704/5-1 within the priority programme SPP 1833 ‘Building a Habitable Earth’ to M.F.-G., by the European Commission through ERC grant number 669666 ‘Infant Earth’ to C.M., by the Carlsberg Foundation grant number CF18-0090 to K.S., and by Kanazawa University “SAKIGAKE 2018” to T.M. H.S. publishes with the permission of the Executive Director, Geological Survey of Western Australia.

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M.F.-G. and C.M. designed the project. M.F.-G., B.-M. E. and N.M. developed the analytical method and obtained the Ru isotope data. M.F.-G. wrote the manuscript. All authors contributed to the discussion of the results and editing of the manuscript.

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Correspondence to Mario Fischer-Gödde.

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Peer review information Nature thanks Katherine Bermingham and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data figures and tables

Extended Data Fig. 1 Ruthenium yields of the total analytical procedure and Ru yields from the distillation plotted against ε100Ru data for replicate digestions of UG-2 and southwest Greenland samples.

a, b, The accuracy of the ε100Ru data are not affected by the Ru yield of the total analytical procedure (a) or the Ru yield of the distillation (b). The grey and blue areas represent the 95% confidence intervals, and the light grey and light blue areas limited by dashed lines indicate the 2 s.d. uncertainty as stated for the calculated mean values of the Bushveld igneous complex and the IGC (Extended Data Table 1). Note that it was not possible to determine the Ru distillation yield for all replicates of the analysed samples in b for the southwest Greenland samples.

Source data

Extended Data Fig. 2 Ruthenium isotope plot showing the ln values of the measured raw ratios for 99Ru/101Ru and 100Ru/101Ru obtained for 100 ng ml−1 Ru sample solutions and associated Alfa Aesar Ru bracketing standards.

The measured isotope ratios are shown as raw ratios uncorrected for mass-dependent fractionation and are normalized to reference ratios R and R’. Two distinct mass fractionation lines can be observed. The slopes for both lines are indistinguishable within error and are in very good agreement with the predicted slope of 0.5, which would be expected if the exponential law could accurately correct the mass-dependent fractionation (see Methods for details). Most importantly, the samples purified by distillation fall on the same respective mass fractionation line as their associated Alfa Aesar bracketing standards. This clearly demonstrates that the Ru distillation does not induce any unaccounted mass-fractionation effects for the samples in comparison with the bracketing standards. The shift observed for samples and associated standards plotting on a distinct mass fractionation array was caused by a maintenance on the mass spectrometer in May 2019, during which a Faraday cup was changed. However, this does not affect the accuracy of the isotopic data because the analysed samples and their associated bracketing standards are shifted by the same magnitude, and the isotopic data are expressed as ε values from the bracketing standards.

Source data

Extended Data Fig. 3 Ruthenium isotope data obtained for 100 ng ml−1 Alfa Aesar Ru standard solutions doped with variable amounts of Ni and S.

a, b, The effect of Ni argide interferences on the measured ε100Ru (a) and ε98Ru (b) isotopic compositions of a 100 ng ml−1 Ru standard solution doped with varying amounts of Ni. The accuracy of the measured isotopic compositions is not affected for samples with Ni/Ru <10−2. c, d, High amounts of S (S/Ru = 5) in the analysed sample solutions have no effect on the accuracy of the measured ε100Ru (c) and ε96Ru (d) data. Vertical dashed lines in c and d indicate the range of S/Ru ratios in the analysed samples. The blue areas indicate the external reproducibility of the method as defined by 2 s.d. of the replicate digestions and repeated analysis of the UG-2 reference sample (see Methods).

Source data

Extended Data Fig. 4 Ruthenium isotope plots illustrating systematic compositional differences between EC, OC and CI, modern mantle and the pre-late-veneer mantle in comparison with mixing lines calculated between the modern mantle composition and isotopic variations caused by variable contributions of s-process Ru nuclides, a fissiogenic Ru component and variations of nuclear field-shift induced isotope fractionations.

a, Ruthenium isotope data for the Eoarchaean mantle of southwest Greenland, the modern mantle and the three types of carbonaceous chondrite in comparison with a mixing line calculated between the composition of the modern mantle (ε102Ru = ε100Ru = 0) and an s-process component34 (dashed line) and the slope calculated for a nuclear field shift-induced (NSF) fractionation51 (solid black line). b, Ruthenium isotope composition of the Eoarchaean mantle in comparison with mixing lines calculated between the composition of the modern mantle (ε96Ru = ε100Ru = 0) and a fissiogenic Ru component53 (dotted line), an s-process component34 (dashed line) and the slope calculated for an NSF isotope fraction51 (solid black line).

Source data

Extended Data Table 1 Ruthenium isotope data for ultramafic rocks
Extended Data Table 2 Ruthenium concentration data, details about the NiS procedure and Re–Os isotope data for ultramafic rocks
Extended Data Table 3 Parameters for mixing model shown in Fig. 3 and resulting ε100Ru values for pre-late-veneer mantle endmember composition

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Fischer-Gödde, M., Elfers, BM., Münker, C. et al. Ruthenium isotope vestige of Earth’s pre-late-veneer mantle preserved in Archaean rocks. Nature 579, 240–244 (2020). https://doi.org/10.1038/s41586-020-2069-3

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