Biological regulation of atmospheric chemistry en route to planetary oxygenation
Edited by Mark H. Thiemens, University of California at San Diego, La Jolla, CA, and approved February 3, 2017 (received for review November 16, 2016)
Significance
It has been proposed that enhanced methane fluxes to Earth’s early atmosphere could have altered atmospheric chemistry, initiating a hydrocarbon-rich haze reminiscent of Saturn’s moon Titan. The occurrence, cause, and significance of haze development, however, remain unknown. Here, we test and refine the “haze hypothesis” by combining an ultra-high-resolution sulfur- and carbon-isotope dataset with photochemical simulations to reveal the structure and timing of haze development. These data suggest that haze persisted for ∼1 million years, requiring a sustained biological driver. We propose that enhanced atmospheric CH4, implied by the presence of haze, could have had a significant impact on the escape of hydrogen from the atmosphere, effectively contributing to the terminal oxidation of Earth’s surficial environments ∼2.4 billion years ago.
Abstract
Emerging evidence suggests that atmospheric oxygen may have varied before rising irreversibly ∼2.4 billion years ago, during the Great Oxidation Event (GOE). Significantly, however, pre-GOE atmospheric aberrations toward more reducing conditions—featuring a methane-derived organic-haze—have recently been suggested, yet their occurrence, causes, and significance remain underexplored. To examine the role of haze formation in Earth’s history, we targeted an episode of inferred haze development. Our redox-controlled (Fe-speciation) carbon- and sulfur-isotope record reveals sustained systematic stratigraphic covariance, precluding nonatmospheric explanations. Photochemical models corroborate this inference, showing Δ36S/Δ33S ratios are sensitive to the presence of haze. Exploiting existing age constraints, we estimate that organic haze developed rapidly, stabilizing within ∼0.3 ± 0.1 million years (Myr), and persisted for upward of ∼1.4 ± 0.4 Myr. Given these temporal constraints, and the elevated atmospheric CO2 concentrations in the Archean, the sustained methane fluxes necessary for haze formation can only be reconciled with a biological source. Correlative δ13COrg and total organic carbon measurements support the interpretation that atmospheric haze was a transient response of the biosphere to increased nutrient availability, with methane fluxes controlled by the relative availability of organic carbon and sulfate. Elevated atmospheric methane concentrations during haze episodes would have expedited planetary hydrogen loss, with a single episode of haze development providing up to 2.6–18 × 1018 moles of O2 equivalents to the Earth system. Our findings suggest the Neoarchean likely represented a unique state of the Earth system where haze development played a pivotal role in planetary oxidation, hastening the contingent biological innovations that followed.
Acknowledgments
G.I. thanks S.I., P.I., and C.L.H. for their continued support. The patience and perseverance of two anonymous reviewers is credited for significantly improving this contribution. This study was supported by Natural Environment Research Council (NERC) Fellowship NE/H016805 (to A.L.Z.) and NERC Standard Grant NE/J023485 (to A.L.Z., M.W.C., and S.W.P.). Further financial support was generously provided via a SAGES Postdoctoral & Early Career Researcher Exchange grant and The Geological Society of London’s Alan and Charlotte Welch Fund (to G.I.). For his work performed at the Jet Propulsion Laboratory, California Institute of Technology, K.H.W. acknowledges the support of a grant from the National Aeronautics and Space Administration. J.F. acknowledges funding from NASA Exobiology program Grant NNX12AD91G. S.W.P. acknowledges support from a Royal Society Wolfson Research Merit Award. Finally, this project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Programme (Grant Agreement 678812) (to M.W.C.). Final drafting was completed under the auspices of Simons Foundation collaboration on the origins of life at Massachusetts Institute of Technology.
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Published online: March 13, 2017
Published in issue: March 28, 2017
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Acknowledgments
G.I. thanks S.I., P.I., and C.L.H. for their continued support. The patience and perseverance of two anonymous reviewers is credited for significantly improving this contribution. This study was supported by Natural Environment Research Council (NERC) Fellowship NE/H016805 (to A.L.Z.) and NERC Standard Grant NE/J023485 (to A.L.Z., M.W.C., and S.W.P.). Further financial support was generously provided via a SAGES Postdoctoral & Early Career Researcher Exchange grant and The Geological Society of London’s Alan and Charlotte Welch Fund (to G.I.). For his work performed at the Jet Propulsion Laboratory, California Institute of Technology, K.H.W. acknowledges the support of a grant from the National Aeronautics and Space Administration. J.F. acknowledges funding from NASA Exobiology program Grant NNX12AD91G. S.W.P. acknowledges support from a Royal Society Wolfson Research Merit Award. Finally, this project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Programme (Grant Agreement 678812) (to M.W.C.). Final drafting was completed under the auspices of Simons Foundation collaboration on the origins of life at Massachusetts Institute of Technology.
Notes
This article is a PNAS Direct Submission.
*Sulfur-isotope ratios are conventionally reported in delta (δ) notation and reflect the permil (‰) deviation of the ratio of the least abundant isotope (33,34,36S) to the most abundant isotope (32S), relative to the same ratio in an international reference standard (Vienna Canyon Diablo Troilite, V-CDT). For example, δ34S = ((34S/32S)sample/(34S/32S)V-CDT) − 1. The majority of processes fractionate S-isotopes mass-dependently, whereby δ33S ≈ 0.515 * δ34S and δ36S ≈ 1.91 * δ34S. Departure from mass-dependent behavior, or mass-independent fractionation (MIF), is expressed in capital-delta (Δ) notation as either non-zero Δ33S [(33S/32S)sample/(33S/32S)V-CDT − ((34S/32S)sample/(34S/32S)V-CDT)0.515] or Δ36S [(36S/32S)sample/(36S/32S)V-CDT − ((34S/32S)sample/(34S/32S)V-CDT)1.9].
†
Carbon-isotope data are expressed as permil deviations from the Vienna-PeeDee Belemnite (V-PDB) standard: δ13COrg = ((13C/12CSample)/(13C/12CV-PDB)) – 1.
‡
Summation of the oxic (FeCarb, FeOx and FeMag) and anoxic Fe extractions (FePY) defines the highly reactive Fe pool (FeHR = FeCarb + FeOx + FeMag + FePY), which when normalized to the total Fe pool (FeT) and FePy permits distinction between oxic (FeHR/FeT = <0.22), ferruginous (FeHR/FeT = >0.38 and FePy/FeHR = <0.7), and euxinic (FeHR/FeT = >0.38 and FePy/FeHR = >0.8) depositional conditions. Details of mineral phases that comprise these operationally defined Fe pools and their empirical derivation are given in Methodology, Sedimentary Fe Speciation.
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Biological regulation of atmospheric chemistry en route to planetary oxygenation, Proc. Natl. Acad. Sci. U.S.A.
114 (13) E2571-E2579,
https://doi.org/10.1073/pnas.1618798114
(2017).
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