Fluctuations in Precambrian atmospheric oxygenation recorded by chromium isotopes
Open accessAbstract
Geochemical data suggest that oxygenation of the Earth's atmosphere occurred in two broad steps. The first rise in atmospheric oxygen is thought to have occurred between approximately 2.45 and 2.2 Gyr ago, leading to a significant increase in atmospheric oxygen concentrations and concomitant oxygenation of the shallow surface ocean. The second increase in atmospheric oxygen appears to have taken place in distinct stages during the late Neoproterozoic era ( approximately 800-542 Myr ago), ultimately leading to oxygenation of the deep ocean approximately 580 Myr ago, but details of the evolution of atmospheric oxygenation remain uncertain. Here we use chromium (Cr) stable isotopes from banded iron formations (BIFs) to track the presence of Cr(VI) in Precambrian oceans, providing a time-resolved picture of the oxygenation history of the Earth's atmosphere-hydrosphere system. The geochemical behaviour of Cr is highly sensitive to the redox state of the surface environment because oxidative weathering processes produce the oxidized hexavalent [Cr(VI)] form. Oxidation of reduced trivalent [Cr(III)] chromium on land is accompanied by an isotopic fractionation, leading to enrichment of the mobile hexavalent form in the heavier isotope. Our fractionated Cr isotope data indicate the accumulation of Cr(VI) in ocean surface waters approximately 2.8 to 2.6 Gyr ago and a likely transient elevation in atmospheric and surface ocean oxygenation before the first great rise of oxygen 2.45-2.2 Gyr ago (the Great Oxidation Event). In approximately 1.88-Gyr-old BIFs we find that Cr isotopes are not fractionated, indicating a decline in atmospheric oxygen. Our findings suggest that the Great Oxidation Event did not lead to a unidirectional stepwise increase in atmospheric oxygen. In the late Neoproterozoic, we observe strong positive fractionations in Cr isotopes (delta(53)Cr up to +4.9 per thousand), providing independent support for increased surface oxygenation at that time, which may have stimulated rapid evolution of macroscopic multicellular life.
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Isotopes of Cu, Cr, Fe, U, Mo, and Se indicate an anoxic Archean atmosphere.
“Using similar arguments of O2-sensitive weathering, transport, and fractionation, isotopes of Cu (76), Cr (77), Fe (78), U (79), Mo [e.g., (80, 81)], and Se (82) indicates an anoxic Archean atmosphere.”
From The Archean atmosphere (2020) · cites this paper as [77]
Those authors argued that increases in δ53Cr of +0.04 to +0.29‰ in iron formations at 2.7 and again at 1.8 Ga are the direct result of Cr(III) oxidation to Cr(VI), and that this oxidation must have been catalyzed by oxidized Mn2+ as MnO2.
“Those authors argued that increases in δ 53 Cr of +0.04 to +0.29‰ in IFs at 2.7, and again at 1.8 Ga, are the direct result of Cr(III) being oxidized to Cr(VI) and that oxidation of Cr must have been catalyzed by oxidized Mn 2+ in the form of MnO2.”
From Trace elements at the intersection of marine biological and geochemical evolution (2016) · cites this paper as Frei et al., 2009
Muted δ53Cr variations (-0.3 to +0.3‰) at this time were taken as indicative of Cr cycling in reduced form, in contrast with highly variable values coincident with ocean oxygenation in the Neoproterozoic (up to +4.9‰).
“Muted δ 53 Cr variations (-0.3 to +0.3‰) at this time were taken as being indicative of Cr cycling in reduced form (Konhauser et al., 2011), in contrast with highly variable values coincident with ocean oxygenation in the Neoproterozoic (up to +4.9‰; Frei et al., 2009).”
From Trace elements at the intersection of marine biological and geochemical evolution (2016) · cites this paper as Frei et al., 2009
Small variations in Cr isotope composition in 2.8-2.6 Ga iron formations were first suggested to document brief pulses in atmospheric oxygen, which mobilized Cr via oxidative weathering and led to Cr sequestration in iron formations prior to the Great Oxidation Event.
“For instance, small variations in Cr isotope composition in 2.8-2.6 Ga IF were first suggested to document brief pulses in atmospheric oxygen, which mobilized Cr via oxidative weathering and led to Cr sequestration in IF prior to the GOE”
From Trace elements at the intersection of marine biological and geochemical evolution (2016) · cites this paper as Frei et al., 2009
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- Authors
- Frei, R., Gaucher, C., Poulton, S. W., & Canfield, D. E.
- Affiliations
- University of Copenhagen (DK)
- Newcastle University (GB)
- Corresponding author
- Frei, Robert
- Venue
- Nature
- Published
- 2009-09
- Volume
- 461
- Issue
- 7261
- Pages
- 250-253
- ISSN
- 0028-0836 (ISSN-L)
- 1476-4687
- OpenAlex
- W2060563278
- Cited by
- 653
- References
- 37
- Citations by year
- 2026: 17 · 2025: 20 · 2024: 32 · 2023: 35 · 2022: 37 · 2021: 59 · 2020: 32 · 2019: 46 · 2018: 63 · 2017: 47 · 2016: 47 · 2015: 47 · 2014: 35 · 2013: 43 · 2012: 31
- FWCI
- 23.70
- Type
- journal article
- Language
- en
- Open access
- green
- doi.org
- Licence
- www.springer.com/tdm (tdm)
- Locations
- Nature (publishedVersion)
- PubMed (publishedVersion)
- RePEc: Research Papers in Economics (submittedVersion)
- Research at the University of Copenhagen (University of Copenhagen) (submittedVersion)
- University of Southern Denmark Research Portal (University of Southern Denmark) (submittedVersion)
- Newcastle University ePrints (Newcastle Univesity)
- Funders
- Danmarks Grundforskningsfond
- Topics
- Physical Sciences › Earth and Planetary Sciences › Paleontology › Paleontology and Stratigraphy of Fossils
- Physical Sciences › Earth and Planetary Sciences › Geophysics › Geological and Geochemical Analysis
- Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Geochemistry and Elemental Analysis
- Keywords
- Great Oxidation Event, chromium isotopes, banded iron formations, hexavalent chromium, oxidative weathering, Precambrian oceans, iron oxide, Precambrian
- MeSH terms
- Animals, Atmosphere, Chromium, Chromium Isotopes, Iron, Oceans and Seas, Oxidation-Reduction, Oxides, Oxygen, Seawater, Manganese Compounds, Biodiversity, History, Ancient
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