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 ∼400 nM throughout much of the Archaean eon, but dropped below ∼200 nM by 2.5 Gyr ago and to modern day values6 (∼9 nM) by ∼550 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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We thank M. Labbe for sample preparation, G. Chen and A. Simonetti for assistance with LA-ICP-MS analyses in the Radiogenic Isotope Facility at the University of Alberta, and S. Matveev for assistance with electron microprobe analyses. Field assistance by W. Mueller is acknowledged for Hunter Mine Group samples. Samples from the Loch Maree Group were provided by A. Wright. Funding was provided by the Natural Science and Engineering Research Council of Canada (NSERC) to K.O.K., the Canada Research Chairs Program to B.S.K., the Australian Research Council (ARC) to M.E.B., and NASA Exobiology and Evolutionary Biology Program individually to D.P. and K.Z. This manuscript was improved by discussions with R. Buick, J. Kasting and M. Lesher, and reviews by R. Frei and M. Saito.
Author Contributions BIF samples were provided by K.O.K., E.P., B.S.K. and D.P. E.P. performed LA-ICP-MS and electron microprobe analysis and S.V.L. conducted sorption experiments. K.O.K., S.V.L., E.P. and B.S.K. produced the manuscript with significant contributions from all co-authors. Specifically, insights into komatiites were provided by E.G.N., N.T.A. and M.E.B.; early Earth tectonics by M.E.B. and B.S.K.; and GOE and methanogens by D.P. and K.Z.
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Konhauser, K., Pecoits, E., Lalonde, S. et al. Oceanic nickel depletion and a methanogen famine before the Great Oxidation Event. Nature 458, 750–753 (2009). https://doi.org/10.1038/nature07858
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