Free oxygen began to accumulate in Earth’s surface environments between 3.0 and 2.4 billion years ago. Links between oxygenation and changes in the composition of continental crust during this time are suspected, but have been difficult to demonstrate. Here we constrain the average composition of the exposed continental crust since 3.7 billion years ago by compiling records of the Cr/U ratio of terrigenous sediments. The resulting record is consistent with a predominantly mafic crust prior to 3.0 billion years ago, followed by a 500- to 700-million-year transition to a crust of modern andesitic composition. Olivine and other Mg-rich minerals in the mafic Archaean crust formed serpentine minerals upon hydration, continuously releasing O2-scavenging agents such as dihydrogen, hydrogen sulfide and methane to the environment. Temporally, the decline in mafic crust capable of such process coincides with the first accumulation of O2 in the oceans, and subsequently the atmosphere. We therefore suggest that Earth’s early O2 cycle was ultimately limited by the composition of the exposed upper crust, and remained underdeveloped until modern andesitic continents emerged.
Subscribe to Journal
Get full journal access for 1 year
only $4.92 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
Canfield, D. E. The early history of atmospheric oxygen. Annu. Rev. Earth Planet. Sci. 33, 1–36 (2005).
Lyons, T. W., Reinhard, C. T. & Planavsky, N. J. The rise of oxygen in Earth’s early ocean and atmosphere. Nature 506, 307–315 (2014).
Farquhar, J., Bao, H. & Thiemens, M. Atmospheric influence of Earth’s earliest sulfur cycle. Science 289, 756–759 (2000).
Anbar, A. D. et al. A whiff of oxygen before the Great Oxidation Event? Science 317, 1903–1906 (2007).
Frei, R., Gaucher, C., Poulton, S. & Canfield, D. E. Fluctuations in Precambrian atmospheric oxygenation recorded by chromium isotopes. Nature 461, 250–253 (2009).
Planavsky, N. J., Bekker, A., Rouxel, O. & Lyons, T. W. Iron isotope composition of some Archean and Proterozoic iron formations. Geochim. Cosmochim. Acta 80, 158–169 (2012).
Kendall, B. et al. Pervasive oxygenation along late Archaean ocean margins. Nat. Geosci. 3, 647–652 (2010).
Crowe, S. A. et al. Atmospheric oxygenation three billion years ago. Nature 501, 535–538 (2013).
Kamber, B. S. Archean mafic-ultramafic oceanic landmasses and their effect on ocean-atmosphere chemistry. Chem. Geol. 274, 19–28 (2010).
Kasting, J. F. What caused the rise of atmospheric O2? Chem. Geol. 362, 13–25 (2013).
Lee, C.-T. et al. Two-step rise of atmospheric oxygen linked to the growth of continents. Nat. Geosci. 9, 417–424 (2016).
Konhauser, K. O. et al. Oceanic nickel depletion and a methanogen famine before the Great Oxidation Event. Nature 458, 750–753 (2009).
Condie, K. C. Earth as an Evolving Planetary SystemCh. 2, 1st edn, 11–58 (Elsevier, 2005).
Tang, M., Chen, K. & Rudnick, R. L. Archean upper crust transition from mafic to felsic marks the onset of plate tectonics. Science 351, 372–375 (2016).
Kamber, B. The evolving nature of terrestrial crust from the Hadean, through the Archean, into the Proterozoic. Precambrian Res. 258, 48–82 (2015).
Nutman, A. P. On the scarcity of >3900 Ma detrital zircons in >3500 Ma metasediments. Precambrian Res. 105, 93–114 (2001).
Hawkesworth, C. J. et al. The generation and evolution of the continental crust. J. Geol. Soc. Lond. 167, 229–248 (2010).
McLennan, S. M. & Taylor, S. R. Th and U in sedimentary rocks: crustal evolution and sedimentary recycling. Nature 285, 621–624 (1980).
Taylor, S. R. & McLennan, S. M. The geochemical evolution of the continental crust. Rev. Geophys. 33, 241–265 (1995).
Garçon, M. et al. Erosion of Archean continents: the Sm–Nd and Lu–Hf isotopic record of Barberton sedimentary rocks. Geochim. Cosmochim. Acta 206, 216–235 (2017).
Rosing, M. T. & Frei, R. U-rich Archaean sea-floor sediments from Greenland indications of >3700 Ma oxygenic photosynthesis. Earth Planet. Sci. Lett. 217, 237–244 (2004).
Oze, C., Bird, D. & Fendorf, S. Genesis of hexavalent chromium from natural sources in soil and groundwater. Proc. Natl Acad. Sci. USA 104, 6544–6549 (2007).
Dhuime, B., Wuestefeld, A. & Hawkesworth, C. J. Emergence of modern continental crust about 3 billion years ago. Nat. Geosci. 8, 552–555 (2015).
Næraa, T. et al. Hafnium isotope evidence for a transition in the dynamics of continental growth 3.2 Gyr ago. Nature 485, 627–630 (2012).
Flament, N., Coltice, N. & Rey, P. F. A case for late-Archean continental emergence from thermal evolution models and hypsometry. Earth Planet. Sci. Lett. 275, 326–336 (2008).
Heubeck, C. & Lowe, D. R. Depositional and tectonic setting of the Archean Moodies Group, Barberton Greenstone Belt, South Africa. Precambrian Res. 68, 257–290 (1994).
Kröner, A. & Compston, W. Ion microprobe ages of zircons from early Archean granite pebbles and greywacke, Barberton Greenstone Belt, Southern Africa. Precambrian Res. 38, 367–380 (1988).
Frei, R. et al. Oxidative elemental cycling under the O2 Eoarchean atmosphere. Sci. Rep. 6, 21058 (2016).
Planavsky, N. J. et al. Evidence for oxygenic photosynthesis half a billion years before the Great Oxidation Event. Nat. Geosci. 7, 283–286 (2014).
Cottrell, E. & Kelley, K. A. The oxidation state of Fe in MORB glasses and the oxygen fugacity of the upper mantle. Earth Planet. Sci. Lett. 305, 270–282 (2011).
Sleep, N. H., Meibom, A., Fridriksson, T., Coleman, R. G. & Bird, D. K. H2-rich fluids from serpentinization: geochemical and biotic implications. Proc. Natl Acad. Sci. USA 101, 12818–12823 (2004).
Frost, B. R. & Beard, J. S. On silica activity and serpentinization. J. Petrol. 48, 1351–1368 (2007).
Berndt, M. E., Allen, D. E. & Seyfried, W. E. Reduction of CO2 during serpentinization of olivine at 300 °C and 500 bar. Geology 24, 351–354 (1996).
McCollom, T. M. & Seewald, J. S. A reassessment of the potential for reduction of dissolved CO2 to hydrocarbons during serpentinization of olivine. Geochim. Cosmochim. Acta 65, 3769–3778 (2001).
Schrenk, M. O., Brazelton, W. J. & Lang, S. Q. in Carbon in Earth, Reviews in Mineralogy 75 (eds Hazen, R. M., Jones, A. P. & Baross, J. A.) 575–606 (Mineralogical Society of America, 2013).
Canfield, D. E. A new model for Proterozoic ocean chemistry. Nature 396, 450–453 (1998).
Catling, D. C., Zahnle, K. J. & McKay, C. P. Biogenic methane, hydrogen escape, and the irreversible oxidation of early Earth. Science 293, 839–843 (2001).
Kump, L. R. & Barley, M. E. Increased subaerial volcanism and the rise of atmospheric oxygen 2.5 billion years ago. Nature 448, 1033–1036 (2007).
Kelsey, C. H. Calculation of the CIPW norm. Mineral. Mag. 34, 276–282 (1965).
Ludwig, K. Berkeley Geochron. Center Spec. Publ. 5 User’s manual for Isoplot 3.75. 1–75 (Berkeley Geochronology Center, 2012).
Careful and constructive comments from P. R. D. Mason and M. Tang, as well as fruitful discussions with E. Kooijman, allowed us to improve the quality of the manuscript substantially. The research was financially supported by the Natural Sciences and Engineering Research Council of Canada, Discovery Grant RGPIN-2015-04080 to M.A.S.
The authors declare no competing financial interests.
About this article
Cite this article
Smit, M., Mezger, K. Earth’s early O2 cycle suppressed by primitive continents. Nature Geosci 10, 788–792 (2017). https://doi.org/10.1038/ngeo3030
Anoxic continental surface weathering recorded by the 2.95 Ga Denny Dalton Paleosol (Pongola Supergroup, South Africa)
Geochimica et Cosmochimica Acta (2021)
National Science Review (2021)
Precambrian Research (2021)
Science China Earth Sciences (2021)
The Diverse Planetary Ingassing/Outgassing Paths Produced over Billions of Years of Magmatic Activity
Space Science Reviews (2021)