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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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“Another study, using Mo content in organic-rich sulfidic shales as a proxy for ocean redox state (Scott et al. 2008), found that Mo content in shales increased at ca. 2.15 Ga, and again, more strongly during the Ediacaran Period (ca. 580 Ma).”
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“This is because the size of a given trace metal seawater reservoir is determined by the weathering flux from land and the relative influence of the sulfidic and oxic sinks (e.g., Algeo and Maynard, 2004; Scott et al., 2008).”
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“Mo abundances are low (< 6 ppm, Table 2) as 311 expected in older BIFs (Stern et al., 2013; Scott et al., 2008).”
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Self-citationThe oxic degradation of sedimentary organic matter 1400 Ma constrains atmospheric oxygen levels
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“Due to efficient abiotic scavenging from sulfidic water masses, molybdenum has been suggested as limiting nitrogen-fixation rates during periods of low oxygen (e.g., Anbar & Knoll, 2002; Reinhard et al., 2013; Scott et al., 2008).”
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“These assumptions are based on results from numerous studies suggesting that anoxic conditions dominated the global Mesoproterozoic deep ocean, both near and offshore (e.g., Canfield, 1998; Reinhard et al., 2013; Scott et al., 2008).”
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The Acheulean workshop of la Noira (France, 700 ka) in the European technological context
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“…and perhaps limited availability of trace- metal micronutrients such as molybdenum) can result in reduced availability of organic matter required to sustain anoxia via aerobic respiration and to support sulfide production via microbial sulfate reduction (Anbar & Knoll, 2002; Scott et al., 2008).”
BackgroundSelf-citationPetrographic carbon in ancient sediments constrains Proterozoic Era atmospheric oxygen levels
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Extensive primary production promoted the recovery of the Ediacaran Shuram excursion
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“Based on the abundance of Mo in Precambrian shale, the Mo concentration in the 543 Precambrian ocean is roughly estimated to be less than 10 nM before 800 Ma (Scott et al., 2008).”
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Geologic and Geochemical Constraints on Earth's Early Atmosphere
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Self-citationOceanic molybdenum drawdown by epeiric sea expansion in the Mesoproterozoic
Gilleaudeau, G. J., & Kah, L. C. (2013) · Chemical Geology · doi:10.1016/j.chemgeo.2013.07.004 · Cited by 59
Phillips, R., & Xu, J. (2021) · Earth-Science Reviews · doi:10.1016/j.earscirev.2021.103799 · Cited by 56
Flake modification in European Early and Early–Middle Pleistocene stone tool assemblages
Barsky, D., García, J., Martínez, K., Sala, R., Zaidner, Y., Carbonell, E., & Toro-Moyano, I. (2013) · Quaternary International · doi:10.1016/j.quaint.2013.05.024 · Cited by 55
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Wang, Y., Lu, W., Costa, K. M., & Nielsen, S. G. (2022) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2022.07.022 · Cited by 53
Dynamic changes in sulfate sulfur isotopes preceding the Ediacaran Shuram Excursion
Osburn, M. R., Owens, J. D., Bergmann, K., Lyons, T. W., & Grotzinger, J. P. (2015) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2015.07.039 · Cited by 53
“…the onset of early animal evolution, and likely at least episodic oxygenation of the deep ocean (Hurtgen et al., 2004; Xiao, 2004; Fike et al., 2006; Canfield et al., 2007; Scott et al., 2008; Shen et al., 2008b; Maloof et al., 2010; Erwin et al., 2011; Sahoo et al., 2012; Lenton et al., 2014).”
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Li, C., Wang, F., Hao, X., et al. (2011) · International Geology Review · doi:10.1080/00206814.2011.623039 · Cited by 52
“These are probably the two main processes that can concentrate Mo. Molybdenum concentrations in anoxic sediments are up to several hundred times higher than in the continental crust (Rimmer 2004; Scott et al. 2008).”
BackgroundA transient swing to higher oxygen levels in the atmosphere and oceans at ~1.4 Ga
Wei, W., Frei, R., Klaebe, R., Tang, D., Wei, G., Li, D., Tian, L., Huang, F., & Ling, H. (2020) · Precambrian Research · doi:10.1016/j.precamres.2020.106058 · Cited by 52
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“, [59]).”
Isotopic Fingerprints of Anthropogenic Molybdenum in Lake Sediments
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Self-citationMarine redox stratification on the earliest Cambrian (ca. 542–529 Ma) Yangtze Platform
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Selenium isotopes trace anoxic and ferruginous seawater conditions in the Early Cambrian
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Oceanic anoxic events, subduction style and molybdenum mineralization
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Highly heterogeneous “poikiloredox” conditions in the early Ediacaran Yangtze Sea
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The impact of ionic strength on the proton reactivity of clay minerals
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Microbial feedbacks optimize ocean iron availability
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“It has been argued that nutrients were limiting due to several intertwined factors including slow remineralization in the absence of oxygen (80, 81), phosphate scavenging by abundant Fe(II) ions (78, 82), and suppression of nitrogen supply due to scavenging of molybdenum (83, 84), an essential nitrogen cycle cofactor,…”
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A 450‐Million‐Year History of Fire
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An integrated view of precambrian eumetazoan evolution
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“Other isotopic evidence, however, suggests that the oxidation may have occurred somewhat earlier, perhaps ~600 mya (Canfield et al. 2008; Scott et al. 2008; Shen et al. 2008), and it is quite possible that the oceanic oxidation did not happen synchronously around the world, but instead in a staggered and regionally va…”
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“…high δ 98 Mo points to widespread ocean oxygenation since mass balance constraints dictate that only this redox state permits both a large global oceanic Mo reservoir and high seawater δ 98 Mo (Scott et al., 2008; Dahl et al., 2010b; Reinhard et al., 2013; Chen et al., 2015; Kendall et al., 2015).”
BackgroundSwanner, E. D., Bayer, T., Wu, W., Hao, L., Obst, M., Sundman, A., Byrne, J. M., Michel, F. M., Kleinhanns, I. C., Kappler, A. A., et al. (2017) · Environmental Science & Technology · doi:10.1021/acs.est.6b05833 · Cited by 51
Mid-Proterozoic redox evolution and the possibility of transient oxygenation events
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“In this study, we describe the draft genome sequence of Geitlerinema sp. PCC 9228, formerly Oscillatoria limnetica ‘Solar Lake’, a mat-forming diazotrophic cyanobacterium that can switch between oxygenic photosynthesis and sulfide-based anoxygenic photosynthesis (AP).”
Method
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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