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      Rapid oxygenation of Earth’s atmosphere 2.33 billion years ago

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          Abstract

          Continuous multiple sulfur isotope profiles from South African rocks pinpoint the Great Oxygenation Event in the geologic record.

          Abstract

          Molecular oxygen (O 2) is, and has been, a primary driver of biological evolution and shapes the contemporary landscape of Earth’s biogeochemical cycles. Although “whiffs” of oxygen have been documented in the Archean atmosphere, substantial O 2 did not accumulate irreversibly until the Early Paleoproterozoic, during what has been termed the Great Oxygenation Event (GOE). The timing of the GOE and the rate at which this oxygenation took place have been poorly constrained until now. We report the transition (that is, from being mass-independent to becoming mass-dependent) in multiple sulfur isotope signals of diagenetic pyrite in a continuous sedimentary sequence in three coeval drill cores in the Transvaal Supergroup, South Africa. These data precisely constrain the GOE to 2.33 billion years ago. The new data suggest that the oxygenation occurred rapidly—within 1 to 10 million years—and was followed by a slower rise in the ocean sulfate inventory. Our data indicate that a climate perturbation predated the GOE, whereas the relationships among GOE, “Snowball Earth” glaciation, and biogeochemical cycling will require further stratigraphic correlation supported with precise chronologies and paleolatitude reconstructions.

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          Atmospheric influence of Earth's earliest sulfur cycle

          Mass-independent isotopic signatures for delta(33)S, delta(34)S, and delta(36)S from sulfide and sulfate in Precambrian rocks indicate that a change occurred in the sulfur cycle between 2090 and 2450 million years ago (Ma). Before 2450 Ma, the cycle was influenced by gas-phase atmospheric reactions. These atmospheric reactions also played a role in determining the oxidation state of sulfur, implying that atmospheric oxygen partial pressures were low and that the roles of oxidative weathering and of microbial oxidation and reduction of sulfur were minimal. Atmospheric fractionation processes should be considered in the use of sulfur isotopes to study the onset and consequences of microbial fractionation processes in Earth's early history.
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            Dating the rise of atmospheric oxygen.

            Several lines of geological and geochemical evidence indicate that the level of atmospheric oxygen was extremely low before 2.45 billion years (Gyr) ago, and that it had reached considerable levels by 2.22 Gyr ago. Here we present evidence that the rise of atmospheric oxygen had occurred by 2.32 Gyr ago. We found that syngenetic pyrite is present in organic-rich shales of the 2.32-Gyr-old Rooihoogte and Timeball Hill formations, South Africa. The range of the isotopic composition of sulphur in this pyrite is large and shows no evidence of mass-independent fractionation, indicating that atmospheric oxygen was present at significant levels (that is, greater than 10(-5) times that of the present atmospheric level) during the deposition of these units. The presence of rounded pebbles of sideritic iron formation at the base of the Rooihoogte Formation and an extensive and thick ironstone layer consisting of haematitic pisolites and oölites in the upper Timeball Hill Formation indicate that atmospheric oxygen rose significantly, perhaps for the first time, during the deposition of the Rooihoogte and Timeball Hill formations. These units were deposited between what are probably the second and third of the three Palaeoproterozoic glacial events.
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              Mass-independent fractionation of sulfur isotopes in Archean sediments: strong evidence for an anoxic Archean atmosphere.

              Mass-independent fractionation (MIF) of sulfur isotopes has been reported in sediments of Archean and Early Proterozoic Age (> 2.3 Ga) but not in younger rocks. The only fractionation mechanism that is consistent with the data on all four sulfur isotopes involves atmospheric photochemical reactions such as SO2 photolysis. We have used a one-dimensional photochemical model to investigate how the isotopic fractionation produced during SO2 photolysis would have been transferred to other gaseous and particulate sulfur-bearing species in both low-O2 and high-O2 atmospheres. We show that in atmospheres with O2 concentrations or = 10(-5) PAL, all sulfur-bearing species would have passed through the oceanic sulfate reservoir before being incorporated into sediments, so any signature of MIF would have been lost. We conclude that the atmospheric O2 concentration must have been < 10(-5) PAL prior to 2.3 Ga.
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                Author and article information

                Journal
                Sci Adv
                Sci Adv
                SciAdv
                advances
                Science Advances
                American Association for the Advancement of Science
                2375-2548
                May 2016
                13 May 2016
                : 2
                : 5
                : e1600134
                Affiliations
                [1 ]Department of Earth, Atmospheric and Planetary Sciences, Massachusetts Institute of Technology, 77 Massachusetts Avenue, E25-608, Cambridge, MA 02139, USA.
                [2 ]State Key Laboratory of Biogeology and Environmental Geology, and School of Earth Science, China University of Geosciences, Wuhan 430074, People’s Republic of China.
                [3 ]DST-NRF (Department of Science and Technology–National Research Foundation) Centre of Excellence for Integrated Mineral and Energy Resource Analysis, Department of Geology, University of Johannesburg, P.O. Box 524, Auckland Park 2006, South Africa.
                Author notes
                [* ]Corresponding author. Email: gmluo@ 123456cug.edu.cn (G.L.); rsummons@ 123456mit.edu (R.E.S.)
                Author information
                http://orcid.org/0000-0002-2656-8951
                http://orcid.org/0000-0002-7144-8537
                Article
                1600134
                10.1126/sciadv.1600134
                4928975
                27386544
                b38ec9eb-0b32-494b-87cf-4a53bc63c824
                Copyright © 2016, The Authors

                This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license, which permits use, distribution, and reproduction in any medium, so long as the resultant use is not for commercial advantage and provided the original work is properly cited.

                History
                : 23 January 2016
                : 20 April 2016
                Funding
                Funded by: FundRef http://dx.doi.org/10.13039/100000893, Simons Foundation;
                Award ID: ID0EMDBG7317
                Award ID: N/A
                Award Recipient :
                Funded by: FundRef http://dx.doi.org/10.13039/100006195, Ames Research Center;
                Award ID: ID0EFJBG7318
                Award ID: NNA13AA90A
                Award Recipient :
                Funded by: FundRef http://dx.doi.org/10.13039/100000160, Division of Earth Sciences;
                Award ID: ID0E5OBG7319
                Award ID: EAR-1338810
                Award Recipient :
                Funded by: FundRef http://dx.doi.org/10.13039/100000160, Division of Earth Sciences;
                Award ID: ID0EXUBG7320
                Award ID: EAR-1338810
                Award Recipient :
                Funded by: CNNSF;
                Award ID: ID0ERZBG7321
                Award ID: 41472170
                Award Recipient :
                Categories
                Research Article
                Research Articles
                SciAdv r-articles
                Geochemistry
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                Mau Buenaventura

                oxygen,atmosphere,great oxidation event,goe,paleoproterozoic,sulfur isotopes

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