Aerobic bacterial pyrite oxidation and acid rock drainage during the Great Oxidation Event
Abstract
The enrichment of redox-sensitive trace metals in ancient marine sedimentary rocks has been used to determine the timing of the oxidation of the Earth's land surface. Chromium (Cr) is among the emerging proxies for tracking the effects of atmospheric oxygenation on continental weathering; this is because its supply to the oceans is dominated by terrestrial processes that can be recorded in the Cr isotope composition of Precambrian iron formations. However, the factors controlling past and present seawater Cr isotope composition are poorly understood. Here we provide an independent and complementary record of marine Cr supply, in the form of Cr concentrations and authigenic enrichment in iron-rich sedimentary rocks. Our data suggest that Cr was largely immobile on land until around 2.48 Gyr ago, but within the 160 Myr that followed--and synchronous with independent evidence for oxygenation associated with the Great Oxidation Event (see, for example, refs 4-6)--marked excursions in Cr content and Cr/Ti ratios indicate that Cr was solubilized at a scale unrivalled in history. As Cr isotope fractionations at that time were muted, Cr must have been mobilized predominantly in reduced, Cr(III), form. We demonstrate that only the oxidation of an abundant and previously stable crustal pyrite reservoir by aerobic-respiring, chemolithoautotrophic bacteria could have generated the degree of acidity required to solubilize Cr(III) from ultramafic source rocks and residual soils. This profound shift in weathering regimes beginning at 2.48 Gyr ago constitutes the earliest known geochemical evidence for acidophilic aerobes and the resulting acid rock drainage, and accounts for independent evidence of an increased supply of dissolved sulphate and sulphide-hosted trace elements to the oceans around that time. Our model adds to amassing evidence that the Archaean-Palaeoproterozoic boundary was marked by a substantial shift in terrestrial geochemistry and biology.
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A significant increase in marine sulfate levels in this interval, widespread hematite-rich oolitic ironstone, and high enrichment of chromium in the middle part of the Timeball Hill Formation all suggest that a substantial rise in pO2 was at play.
“A significant increase in marine sulfate levels in this interval (see below), widespread hematite-rich oolitic ironstone, and a high enrichment of chromium in the middle part of the Timeball Hill Formation (16, 47) all suggest that a substantial rise in pO2 was at play.”
From Rapid oxygenation of Earth’s atmosphere 2.33 billion years ago (2016) · cites this paper as [16]
In the rock record, the GOE is manifested by changes including loss of detrital uraninite, pyrite, and siderite from fluvial siliciclastic sediments at ca. 2.4 Ga; loss of iron from palaeosols older than ca. 2.4 Ga; appearance of red beds after ca. 2.3 Ga; loss of S-MIF in sulfide and sulfate minerals after 2.3 Ga; and an increase in Cr and U contents in IF at 2.45 Ga.
“In the rock record, this event is manifested by a number of changes (see Farquhar et al., 2011, 2014, for reviews), including (1) loss of easily oxidisable detrital uraninite, pyrite, and siderite from fluvial siliciclastic sediments at ca. 2.4 Ga”
From Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history (2017) · cites this paper as Konhauser et al., 2011
The Weeli Wolli Formation displays a marked increase in Cr concentrations, interpreted by Konhauser et al. (2011) as a remnant signature of bacterial pyrite oxidation and associated acid rock drainage.
“The Weeli Wolli Formation displays a marked increase in Cr concentrations, interpreted by Konhauser et al. (2011) as a remnant signature of bacterial pyrite oxidation and associated acid rock drainage.”
From Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history (2017) · cites this paper as Konhauser et al. (2011)
This process continued perhaps for 150-200 m.y. (the crustal half-life) until the volume of easily oxidisable pyrite in the weathered crust was diminished.
“This process continued perhaps for 150-200 m.y. the crustal half-life (Garrels and Mackenzie, 1971) - until the volume of easily oxidisable pyrite in the weathered crust was diminished (Konhauser et al., 2011; Bekker and Holland, 2012).”
From Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history (2017) · cites this paper as Konhauser et al., 2011
The oolitic and pisolitic Timeball Hill Formation records the highest degree of Cr enrichment among Palaeoproterozoic IF.
“The oolitic and pisolitic Timeball Hill Formation records the highest degree of Cr enrichment among Palaeoproterozoic IF (Konhauser et al., 2011), which is not surprising considering its shallow-water depositional environment (pro-deltaic to offshore).”
From Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history (2017) · cites this paper as Konhauser et al., 2011
A moderate enrichment in Cr (molar Cr/Ti) beginning at 2.45 Ga in the Weeli Wolli Formation and similarly aged Cauê Iron Formation was followed by a spike in Cr enrichment in oolitic and pisolitic ironstone associated with the ca. 2.32 Ga Timeball Hill Formation.
“For instance, a moderate enrichment in Cr (as expressed by the molar Cr/Ti ratio) beginning at 2.45 Ga in the Weeli Wolli Formation, as well as the similarly aged Cauê Iron Formation in Brazil, was followed by a spike in Cr enrichment in oolitic and pisolitic ironstone associated with the ca. 2.32 Ga Timeball Hill Formation (Konhauser et al., 2011).”
From Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history (2017) · cites this paper as Konhauser et al., 2011
Cr enrichment with muted Cr isotope fractionation at this time points to a supply mechanism involving predominantly the reduced Cr(III) form.
“Cr enrichment in the face of muted Cr isotope fractionation at this time (Planavsky et al., 2014b) points to a supply mechanism that involved predominately the reduced Cr(III) form (Konhauser et al., 2011).”
From Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history (2017) · cites this paper as Konhauser et al., 2011
The Cr enrichment beginning at ca. 2.45 Ga reflects Earth's first acidic continental rock drainage, whereby acidity was generated with rising O2 at unprecedented scales via oxidation of a previously untapped terrestrial pyrite reservoir.
“Accordingly, it has been suggested that the Cr enrichment beginning at ca. 2.45 Ga reflects Earth's first acidic continental rock drainage, whereby acidity was generated with rising O2 at unprecedented scales via the oxidation of a previously untapped terrestrial pyrite reservoir.”
From Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history (2017) · cites this paper as Konhauser et al., 2011
The ability of cyanobacteria in the ocean's photic zones to remotely facilitate their own nutrient supply via O2-enhanced chemical weathering may represent an unrecognised positive biological feedback.
“The ability of cyanobacteria in the ocean's photic zones to remotely facilitate their own nutrient supply via O2-enhanced chemical weathering may represent an unrecognised positive biological feedback (Konhauser et al., 2011).”
From Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history (2017) · cites this paper as Konhauser et al., 2011
Recent Cr and U trace element proxy studies pushed the onset of the GOE back to 2.48-2.47 Ga.
“Recent studies based on the trace element proxies of Cr and U, as indicators for continental oxidative weathering have pushed the onset of the GOE back to 2.48-2.47Ga (Konhauser et al. (2011) and Partin et al. (2013a), respectively.”
From Trace elements at the intersection of marine biological and geochemical evolution (2016) · cites this paper as Konhauser et al., 2011
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 Konhauser et al., 2011
Konhauser et al. examined temporal trends in the degree of Cr enrichment in iron formations and found a peak at 2.48-2.32 Ga.
“Subsequently, Konhauser et al. (2011) examined temporal trends in the degree of Cr enrichment in IF and found a peak at 2.48-2.32Ga”
From Trace elements at the intersection of marine biological and geochemical evolution (2016) · cites this paper as Konhauser et al., 2011
This peak was suggested to indicate the onset of acidic weathering triggered by microaerophilic iron-oxidizing bacteria, which accelerated pyrite weathering as soon as some atmospheric oxygen became available.
“This peak was suggested to indicate the onset of acidic weathering triggered by microaerophilic iron-oxidizing bacteria which accelerated the weathering of pyrite as soon as some atmospheric oxygen became available.”
From Trace elements at the intersection of marine biological and geochemical evolution (2016) · cites this paper as Konhauser et al., 2011
A peak in molar Cr/Ti ratios at 2.4 Ga has been interpreted to reflect acid mine drainage caused by massive oxidation of pyrite by aerobic bacteria on land around the GOE.
“Here a peak in molar Cr/Ti ratios is observed at 2.4 Ga and has been interpreted to reflect acid mine drainage cause by massive oxidation of pyrite by aerobic bacteria on land around the time of the GOE.”
From Trace elements at the intersection of marine biological and geochemical evolution (2016) · cites this paper as Konhauser et al. (2011)
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- Authors
- Konhauser, K. O., Lalonde, S. V., Planavsky, N. J., Pecoits, E., Lyons, T. W., Mojzsis, S. J., Rouxel, O. J., Barley, M. E., Rosìere, C., Fralick, P. W., Kump, L. R., & Bekker, A.
- Affiliations
- University of Alberta (CA)
- University of California, Riverside (US)
- University of Colorado Boulder (US)
- Ifremer (FR)
- The University of Western Australia (AU)
- Pennsylvania State University (US)
- University of Manitoba (CA)
- Corresponding author
- Konhauser, Kurt O.
- ORCID
- Venue
- Nature
- Published
- 2011-10
- Volume
- 478
- Issue
- 7369
- Pages
- 369-373
- ISSN
- 0028-0836 (ISSN-L)
- 1476-4687
- OpenAlex
- W2094485738
- Cited by
- 366
- References
- 39
- Citations by year
- 2026: 20 · 2025: 23 · 2024: 21 · 2023: 22 · 2022: 22 · 2021: 36 · 2020: 23 · 2019: 30 · 2018: 25 · 2017: 25 · 2016: 26 · 2015: 25 · 2014: 26 · 2013: 27 · 2012: 13
- FWCI
- 15.06
- Type
- journal article
- Language
- en
- Open access
- closed
- Licence
- www.springer.com/tdm (tdm)
- Locations
- Nature (publishedVersion)
- PubMed (publishedVersion)
- UWA Profiles and Research Repository (UWA) (submittedVersion)
- HAL (submittedVersion)
- RePEc: Research Papers in Economics (submittedVersion)
- 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 › Geophysics › Geological and Geochemical Analysis
- Keywords
- Great Oxidation Event, pyrite oxidation, acid mine drainage, atmospheric oxygenation, continental weathering, chemolithoautotrophic bacteria, Precambrian iron formations, ultramafic rocks
- MeSH terms
- Bacteria, Aerobic, Chromium, Hydrogen-Ion Concentration, Iron, Oxidation-Reduction, Seawater, Sulfides, Time Factors, Geologic Sediments, Rivers
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