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Tracing the stepwise oxygenation of the Proterozoic ocean
Open accessAbstract
Biogeochemical signatures preserved in ancient sedimentary rocks provide clues to the nature and timing of the oxygenation of the Earth's atmosphere. Geochemical data suggest that oxygenation proceeded in two broad steps near the beginning and end of the Proterozoic eon (2,500 to 542 million years ago). The oxidation state of the Proterozoic ocean between these two steps and the timing of deep-ocean oxygenation have important implications for the evolutionary course of life on Earth but remain poorly known. Here we present a new perspective on ocean oxygenation based on the authigenic accumulation of the redox-sensitive transition element molybdenum in sulphidic black shales. Accumulation of authigenic molybdenum from sea water is already seen in shales by 2,650 Myr ago; however, the small magnitudes of these enrichments reflect weak or transient sources of dissolved molybdenum before about 2,200 Myr ago, consistent with minimal oxidative weathering of the continents. Enrichments indicative of persistent and vigorous oxidative weathering appear in shales deposited at roughly 2,150 Myr ago, more than 200 million years after the initial rise in atmospheric oxygen. Subsequent expansion of sulphidic conditions after about 1,800 Myr ago (refs 8, 9) maintained a mid-Proterozoic molybdenum reservoir below 20 per cent of the modern inventory, which in turn may have acted as a nutrient feedback limiting the spatiotemporal distribution of euxinic (sulphidic) bottom waters and perhaps the evolutionary and ecological expansion of eukaryotic organisms. By 551 Myr ago, molybdenum contents reflect a greatly expanded oceanic reservoir due to oxygenation of the deep ocean and corresponding decrease in sulphidic conditions in the sediments and water column.
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“Furthermore, Archean marine sediments have low concentrations of elements that enter rivers during oxidative continental weathering (68–70).”
From The Archean atmosphere (2020) · cites this paper as [68]
In the citing paper
“Low concentrations of redox sensitive elements (e.g., Mo and V) and their low ratios with TOC of marine black shales have been observed throughout Earth history before the Ediacaran, and interpreted as the result of low oxygen concentration in ocean and atmosphere33,34.”
From Subtle Cr isotope signals track the variably anoxic Cryogenian interglacial period with voluminous manganese accumulation and decrease in biodiversity (2019) · cites this paper as [33]
In the citing paper
“The uranium isotope record indicates that the modeled oxygenation state of the early Cambrian oceans was neither steady nor monotonous (7–9, 47, 48), but rather oscillated dramatically in concert with changes to the global marine carbon cycle as indicated by the δ13C curve.”
From Atmosphere-ocean oxygen and productivity dynamics during early animal radiations (2019) · cites this paper as [47]
In the citing paper
“Based on the collective data for the boring billion (Arnold et al., 2004; Scott et al., 2008; Planavsky et al., 2011; Poulton and Canfield, 2011; Partin et al., 2013; Reinhard et al., 2013; as reviewed in Lyons et al., 2014), Fe-rich (ferruginous) waters must have dominated the deeper ocean.”
From Oxygenation, Life, and the Planetary System during Earth's Middle History: An Overview (2021) · cites this paper as Scott et al., 2008
In the citing paper
“Muted metal enrichments in euxinic shales support the possibility of low marine molybdenum (Mo) inventories during the boring billion due to high rates of sediment uptake within the anoxic and euxinic oceans (Scott et al., 2008)”
From Oxygenation, Life, and the Planetary System during Earth's Middle History: An Overview (2021) · cites this paper as Scott et al., 2008
In the citing paper
“The contrasting behaviors of molybdenum, chromium, uranium, and rhenium in organic-rich marginal sedimentary rocks deposited throughout the mid-Proterozoic qualitatively indicate widespread marine anoxia (Partin et al. 2013, Reinhard et al. 2013, Scott et al. 2008, Sheen et al. 2018)”
From The History of Ocean Oxygenation (2022) · cites this paper as Scott et al. 2008
In the citing paper
“All available data that constrain the marine landscape in the midProterozoic ocean are consistent with only locally developed euxinic conditions along productive continental margins (e.g., in oxygen-minimum zones) or within intracratonic basins”
From Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history (2017) · cites this paper as Scott et al., 2008
In the citing paper
“The emerging picture from black shales indicates that Precambrian seawater reservoirs of redox-sensitive elements were nowhere close to those of the Phanerozoic (e.g., Scott et al., 2008; Partin et al., 2013b; Reinhard et al., 2013).”
From Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history (2017) · cites this paper as Scott et al., 2008
In the citing paper
“Following increasing oxygenation in late Neoproterozoic (Canfield et al., 2007;Scott et al., 2008;Sahoo et al., 2012;Lyons et al., 2014a, Planavsky et al., 2014a;Sahoo et al., 2016), these sulfide complexes would have become less abundant, resulting in greater availability of Cd, Cu, and Zn.”
From Trace elements at the intersection of marine biological and geochemical evolution (2016) · cites this paper as Scott et al., 2008
In the citing paper
“the marine metal reservoir exerts a first order control on enrichments in euxinic and anoxic sediments (Algeo and Lyons, 2006;Lyons et al., 2009;Scott et al., 2008;Reinhard et al., 2013b).”
From Trace elements at the intersection of marine biological and geochemical evolution (2016) · cites this paper as Scott et al., 2008
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“…tools have come online to assess these events – especially various redox-sensitive metal tracers and their isotope systematics (Buick, 2007; Scott et al., 2008; Partin et al., 2013; Reinhard et al., 2013) and basin-scale reconstructions of redox state (Sperling et al., 2013a, b) that…”
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“(Fike et al. 2006; McFadden et al. 2008) or stepwise and protracted oxidation (e.g., Canfield et al. 2007; Scott et al. 2008)?”
BackgroundMethodTian, X., Luo, K., & Zuza, A. V. (2017) · Acta Geologica Sinica - English Edition · doi:10.1111/1755-6724.13445 · Cited by 9
Moore, E. K., Li, J., Zhang, A., Hao, J., Morrison, S. M., Hummer, D. R., & Yee, N. (2024) · Geochemistry Geophysics Geosystems · doi:10.1029/2023gc011267 · Cited by 8
“The time period of 0.65–0 Ga was chosen to focus on the increased mineralization and preservation of oxidized species that took place following the Proterozoic Oxidation Event (Sahoo et al., 2012; Scott et al., 2008).”
BackgroundInfluentialMolybdenum isotope behavior during subduction zone metamorphism
Stegner, C., Gaschnig, R. M., Marshall, S., Rader, S., Bebout, G. E., & Penniston‐Dorland, S. C. (2024) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2024.10.016 · Cited by 9
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Magnall, J. M., Gleeson, S. A., Hayward, N., & Oelze, M. (2021) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2021.12.001 · Cited by 8
“A decline in authigenic Mo enrichment during the mid-Proterozoic has been linked with low atmospheric O2 and a smaller oxidative weathering flux to the oceans (Scott et al., 2008), although samples from this time period are limited to a small number of localities.”
BackgroundSun, Y., Zhang, Y., Xi, A., Tang, Y. J., Zhou, R., Liu, D., & Chen, S. (2022) · Sedimentary Geology · doi:10.1016/j.sedgeo.2022.106296 · Cited by 8
Wang, X., Zhang, J., Shi, M., Pang, Y., Zhao, Y., & Xue, Y. (2023) · ACS Omega · doi:10.1021/acsomega.3c00174 · Cited by 8
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Chemical Speciation and Metallomics
de Jesus, J. R., da Costa, L. F., Lehmann, E. L., Galazzi, R. M., Madrid, K. C., & Arruda, M. A. Z. (2018) · Advances in experimental medicine and biology · doi:10.1007/978-3-319-90143-5_8 · Cited by 8
The global explosion of eukaryotic algae: The potential role of phosphorus?
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Precambrian and early Cambrian palaeobiology of India: Quo Vadis
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Earth: Atmospheric Evolution of a Habitable Planet
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“Indeed, several additional geochemical records suggest elevated atmospheric pO2 at this time (Scott et al 2008; Planavsky et al 2012; Partin et al 2013; Hardisty et al 2014).”
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Bridger, P., Poulton, S., Zhou, Y., Li, C., Zhang, K., & Shields, G. (2021) · Geological Magazine · doi:10.1017/s0016756821000261 · Cited by 8
“Despite this, several studies provide evidence for global oceanic oxygenation during deposition of DST IV (Scott et al. 2008; Kendall et al. 2015; Chen et al. 2015; Och et al. 2016; Sahoo et al. 2016; Shi et al. 2018; Ostrander et al. 2019).”
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Moore, E. K., Diedolf, J., Morrison, S. M., & Hummer, D. R. (2024) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2024.05.024 · Cited by 7
Revised oceanic molybdenum isotope budget from deep-sea pelagic sediments
Wang, Z., Li, J., Hu, B., Zou, L., Ding, X., Zhang, L., Ma, J., & Wei, G. (2025) · Nature Communications · doi:10.1038/s41467-025-65006-5 · Cited by 9
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Rice N-biofertilization by inoculation with an engineered photosynthetic diazotroph
Zeng, Y., Wang, M. E., Yu, Y., et al. (2024) · World Journal of Microbiology and Biotechnology · doi:10.1007/s11274-024-03956-6 · Cited by 7
“Therefore, the application of Fe-only nitrogenase presents advantage over Mo nitrogenase in those environments with limited Mo-availability (Li and Wang 2019; Scott et al. 2008; Tallkvist and Oskarsson 2015).”
A billion years of geological drama – Boring or brilliant?
Mukherjee, I., Corkrey, R., Gregory, D. D., Large, R. R., & Poole, A. M. (2025) · Gondwana Research · doi:10.1016/j.gr.2025.02.018 · Cited by 8
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“enging by Mn (oxyhydr)oxides in oxygenated waters (Scott et al., 2008) and complexation with dissolved organic carbon (Tessin et al.”
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Redox heterogeneity of the Ediacaran ocean constrained by chromium isotopes
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Metadata
- Authors
- Scott, C., Lyons, T. W., Bekker, A., Shen, Y., Poulton, S. W., Chu, X., & Anbar, A. D.
- Affiliations
- University of California, Riverside (US)
- Carnegie Institution for Science (US)
- Université du Québec à Montréal (CA)
- Newcastle University (GB)
- Chinese Academy of Sciences (CN)
- Arizona State University (US)
- Corresponding author
- Scott, C.
- Venue
- Nature
- Published
- 2008-03
- Volume
- 452
- Issue
- 7186
- Pages
- 456-459
- ISSN
- 0028-0836 (ISSN-L)
- 1476-4687
- OpenAlex
- W2041762395
- Cited by
- 1,098
- References
- 32
- Citations by year
- 2026: 37 · 2025: 60 · 2024: 55 · 2023: 73 · 2022: 60 · 2021: 81 · 2020: 83 · 2019: 74 · 2018: 81 · 2017: 61 · 2016: 53 · 2015: 71 · 2014: 51 · 2013: 55 · 2012: 56
- FWCI
- 37.03
- 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)
- Newcastle University ePrints (Newcastle Univesity)
- Funders
- National Science Foundation
- Danmarks Grundforskningsfond
- NASA Astrobiology Institute
- Natural Sciences and Engineering Research Council of Canada
- Natural Environment Research Council (NE/C518465/2)
- Topics
- Physical Sciences › Earth and Planetary Sciences › Paleontology › Paleontology and Stratigraphy of Fossils
- Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Geochemistry and Elemental Analysis
- Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Geological and Geochemical Analysis
- Keywords
- molybdenum, black shales, oxidative weathering, total organic carbon, ocean redox state, atmospheric oxygenation, Neoproterozoic, Precambrian, sulfur cycling, early animal evolution, Precambrian stratigraphy
- MeSH terms
- Atmosphere, Molybdenum, Oceans and Seas, Oxygen, Seawater, Sulfides, Time Factors, Geologic Sediments, History, Ancient
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