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Hadean age for a post-magma-ocean zircon confirmed by atom-probe tomography


The only physical evidence from the earliest phases of Earth’s evolution comes from zircons, ancient mineral grains that can be dated using the U–Th–Pb geochronometer1. Oxygen isotope ratios from such zircons have been used to infer when the hydrosphere and conditions habitable to life were established2,3. Chemical homogenization of Earth’s crust and the existence of a magma ocean have not been dated directly, but must have occurred earlier4. However, the accuracy of the U–Pb zircon ages can plausibly be biased by poorly understood processes of intracrystalline Pb mobility5,6,7. Here we use atom-probe tomography8 to identify and map individual atoms in the oldest concordant grain from Earth, a 4.4-Gyr-old Hadean zircon with a high-temperature overgrowth that formed about 1 Gyr after the mineral’s core. Isolated nanoclusters, measuring about 10 nm and spaced 10–50 nm apart, are enriched in incompatible elements including radiogenic Pb with unusually high 207Pb/206Pb ratios. We demonstrate that the length scales of these clusters make U–Pb age biasing impossible, and that they formed during the later reheating event. Our tomography data thereby confirm that any mixing event of the silicate Earth must have occurred before 4.4 Gyr ago, consistent with magma ocean formation by an early moon-forming impact4 about 4.5 Gyr ago.

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Figure 1: SEM images of growth zoning, inclusions and analysis spots for the 4.4-Gyr-old zircon.
Figure 2: APT and SIMS U–Pb data for the 4.4-Gyr-old zircon.
Figure 3: APT images of Y and Pb clusters in the 4.4-Gyr-old zircon.
Figure 4: Distribution of elements in clusters in a 4.4-Gyr-old zircon.


  1. Hanchar, J. M. & Hoskin, P. W. O. Zircon. Rev. Mineral. Geochem. 53, 1–500 (2003).

    Article  Google Scholar 

  2. Valley, J. W. The origin of habitats. Geology 36, 911–912 (2008).

    Article  Google Scholar 

  3. Wilde, S. A., Valley, J. W., Peck, W. H. & Graham, C. M. Evidence from detrital zircons for the existence of continental crust and oceans on the Earth 4.4 Gyr ago. Nature 409, 175–178 (2001).

    Article  Google Scholar 

  4. Rumble, D. et al. The oxygen isotope composition of Earth’s oldest rocks and evidence of a terrestrial magma ocean. Geochem. Geophys. Geosyst. 14, 1929–1939 (2013).

    Article  Google Scholar 

  5. Ewing, R. C. et al. Radiation effects in zircon. Rev. Mineral. Geochem. 53, 387–425 (2003).

    Article  Google Scholar 

  6. Mattinson, J. M. Zircon U–Pb chemical abrasion (‘CA-TIMS’) method: combined annealing and multi-step partial dissolution analysis for improved precision and accuracy of zircon ages. Chem. Geol. 220, 47–66 (2005).

    Article  Google Scholar 

  7. Kusiak, M. A., Whitehouse, M. J., Wilde, S. A., Nemchin, A. A. & Clark, C. Mobilization of radiogenic Pb in zircon revealed by ion imaging: Implications for early Earth geochronology. Geology 41, 291–294 (2013).

    Article  Google Scholar 

  8. Gault, B., Moody, M. P., Cairney, J. M. & Ringer, S. P. Atom Probe Microscopy. Springer Series in Materials Science 160 (Springer, 2012).

    Google Scholar 

  9. Wyche, S., Nelson, D. R. & Riganti, A. 4350–3130 Ma detrital zircons in the Southern Cross Granite–Greenstone Terrane, Western Australia: Implications for the early evolution of the Yilgarn Craton. Austral. J. Ear. Sci. 51, 31–45 (2004).

    Article  Google Scholar 

  10. Nemchin, A. A., Pidgeon, R. T. & Whitehouse, M. J. Re-evaluation of the origin and evolution of >4.2 Ga zircons from the Jack Hills metasedimentary rocks. Ear. Plan. Sci. Lett. 244, 218–233 (2006).

    Article  Google Scholar 

  11. Holden, P. et al. Mass-spectrometric mining of Hadean zircons by automated SHRIMP multi-collector and single-collector U/Pb zircon age dating: The first 100,000 grains. Int. J. Mass Spectrom. 286, 53–63 (2009).

    Article  Google Scholar 

  12. Harrison, T. M., Schmitt, A. K., McCulloch, M. T. & Lovera, O. M. Early (≥4.5 Ga) formation of terrestrial crust: Lu–Hf, δ18O, and Ti thermometry results for Hadean zircons. Ear. Plan. Sci. Lett. 268, 476–486 (2008).

    Article  Google Scholar 

  13. Cavosie, A. J., Valley, J. W. & Wilde, S. A. in Earth’s Oldest Rocks (eds van Kranendonk, M. J., Smithies, R. H. & Bennett, V. C.) The oldest terrestrial mineral record: A review of 4400 to 4000 Ma detrital zircons from the Jack Hills, Western Australia. Devel. Precam. Geol. 15, 91–111 (2007)

  14. Whitehouse, M. J. & Kamber, B. S. On the overabundance of light rare earth elements in terrestrial zircons and its implication for Earth’s earliest magmatic differentiation. Ear. Plan. Sci. Lett. 204, 333–346 (2002).

    Article  Google Scholar 

  15. Parrish, R. R. & Noble, S. R. Zircon U–Th–Pb geochronology by isotope dilution—thermal ionization mass spectrometry (ID-TIMS). Rev. Mineral. Geochem. 53, 183–213 (2003).

    Article  Google Scholar 

  16. Hoskin, P. W. O. Trace-element composition of hydrothermal zircon and the alteration of Hadean zircon from the Jack Hills, Australia. Geochim. Cosmochim. Acta 69, 637–648 (2005).

    Article  Google Scholar 

  17. Tilton, G. R. Volume diffusion as a mechanism for discordant lead ages. J. Geophys. Res. 65, 178–190 (1960).

    Google Scholar 

  18. Nasdala, L. et al. Metamictization of natural zircon: Accumulation versus thermal annealing of radioactivity-induced damage. Contrib. Mineral. Petrol. 141, 125–144 (2001).

    Article  Google Scholar 

  19. Romer, R. L. Alpha-recoil in U–Pb geochronology: Effective sample size matters. Contrib. Mineral Petrol. 145, 481–491 (2003).

    Article  Google Scholar 

  20. Utsunomiya, S. et al. Nanoscale occurrence of Pb in an Archean zircon. Geochim. Cosmochim. Acta. 68, 4679–4686 (2004).

    Article  Google Scholar 

  21. Cavosie, A. J., Wilde, S. A., Liu, D., Valley, J. W. & Weiblen, P. W. Internal zoning and U–Th–Pb chemistry of the Jack Hills detrital zircons: a mineral record of early Archean to Mesoproterozoic (4348–1576 Ma) magmatism. Precamb. Res. 135, 231–279 (2004).

    Article  Google Scholar 

  22. Valley, J. W. et al. Elemental and isotopic tomography at single-atom-scale in 4.0 and 2.4 Ga zircons. Trans. Am. Geophys. Un. abstr. V12A-05 (2012).

  23. Pidgeon, R. T. & Wilde, S. A. The interpretation of complex zircon U–Pb systems in Archaean granitoids and gneisses from the Jack Hills, Narryer Gneiss Terrane, Western Australia. Precam. Res. 91, 309–332 (1998).

    Article  Google Scholar 

  24. Cherniak, D. J. Diffusion in accessory minerals: zircon, titanite, apatite, monazite and xenotime. Rev. Mineral Geochem. 72, 827–869 (2010).

    Article  Google Scholar 

  25. Clayton, R. N. Oxygen isotopes in meteorites. Treat. Geochem. 1, 1–14 (2007).

    Google Scholar 

  26. Valley, J. W., Ushikubo, T. & Kita, N. T. In situ analysis of three oxygen isotopes and OH in ALH 84001: Further evidence of two generations of carbonates. Lunar Planet. Sci. Conf. 38, abstr. #1147 (2007).

    Google Scholar 

  27. Valley, J. W. & Kita, N. T. In situ oxygen isotope geochemistry by ion microprobe. Min. Assoc. Can. 41, 19–63 (2009).

    Google Scholar 

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This research was supported by NSF-EAR0838058, DOE-93ER14389 and the NASA Astrobiology Institute. T.C., D.R., D.F.L., D.J.L. and P.C. thank their colleagues at CAMECA in Madison, Wisconsin, for their contribution to these efforts. WiscSIMS is partly supported by NSF-EAR1053466.

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Authors and Affiliations



J.V. initiated this project, selected samples, assisted in data reduction and interpretation, and wrote most of the paper. A.C. and S.W. dated the 4.4-Gyr-old zircon by SIMS, and assisted in interpretation and rewriting. TU made SIMS analysis of trace elements and SEM images, and assisted in interpretation. D.R. performed data analysis of APT data, and assisted in interpretation. D.F.L. prepared samples by FIB. D.J.L., P.C. and T.K. performed atom-probe analysis and assisted in interpretation. D.M. conducted EBSD analysis and SEM imaging of the zircon. M.S. assisted in analysis and interpretation. All authors reviewed and approved this paper.

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Correspondence to John W. Valley.

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Valley, J., Cavosie, A., Ushikubo, T. et al. Hadean age for a post-magma-ocean zircon confirmed by atom-probe tomography. Nature Geosci 7, 219–223 (2014).

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