Nature 458, 750-753 (9 April 2009) | doi:10.1038/nature07858; Received 27 August 2008; Accepted 26 January 2009

Oceanic nickel depletion and a methanogen famine before the Great Oxidation Event

Kurt O. Konhauser1, Ernesto Pecoits1, Stefan V. Lalonde1, Dominic Papineau2, Euan G. Nisbet3, Mark E. Barley4, Nicholas T. Arndt5, Kevin Zahnle6 & Balz S. Kamber7

  1. Department of Earth and Atmospheric Sciences, University of Alberta, Edmonton T6G 2E3, Canada
  2. Geophysical Laboratory, Carnegie Institution of Washington, 5251 Broad Branch Road NW, Washington DC 20015, USA
  3. Department of Earth Sciences, Royal Holloway University of London, Egham, Surrey TW20 0EX, UK
  4. School of Earth and Environment, University of Western Australia, 35 Stirling Highway, Crawley, Western Australia 6009, Australia
  5. Laboratoire de Géodynamique des Chaîne Alpines, Maison de Géosciences, Université Joseph Fourier, 1381 rue de la piscine, Grenoble 38041, France
  6. NASA Ames Research Center, MS 245-3, Moffett Field, California 94035, USA
  7. Department of Earth Sciences, Laurentian University, Sudbury, Ontario P3E 2C6, Canada

Correspondence to: Kurt O. Konhauser1 Correspondence and requests for materials should be addressed to K.O.K. (Email: kurtk@ualberta.ca).

It has been suggested that a decrease in atmospheric methane levels triggered the progressive rise of atmospheric oxygen, the so-called Great Oxidation Event, about 2.4 Gyr ago1. Oxidative weathering of terrestrial sulphides, increased oceanic sulphate, and the ecological success of sulphate-reducing microorganisms over methanogens has been proposed as a possible cause for the methane collapse1, but this explanation is difficult to reconcile with the rock record2, 3. Banded iron formations preserve a history of Precambrian oceanic elemental abundance and can provide insights into our understanding of early microbial life and its influence on the evolution of the Earth system4, 5. Here we report a decline in the molar nickel to iron ratio recorded in banded iron formations about 2.7 Gyr ago, which we attribute to a reduced flux of nickel to the oceans, a consequence of cooling upper-mantle temperatures and decreased eruption of nickel-rich ultramafic rocks at the time. We measured nickel partition coefficients between simulated Precambrian sea water and diverse iron hydroxides, and subsequently determined that dissolved nickel concentrations may have reached approx400 nM throughout much of the Archaean eon, but dropped below approx200 nM by 2.5 Gyr ago and to modern day values6 (approx9 nM) by approx550 Myr ago. Nickel is a key metal cofactor in several enzymes of methanogens7 and we propose that its decline would have stifled their activity in the ancient oceans and disrupted the supply of biogenic methane. A decline in biogenic methane production therefore could have occurred before increasing environmental oxygenation and not necessarily be related to it. The enzymatic reliance of methanogens on a diminishing supply of volcanic nickel links mantle evolution to the redox state of the atmosphere.


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