Cu isotopes in marine black shales record the Great Oxidation Event
Open accessAbstract
Significance: Redox-sensitive transition metals and their isotopes provide some of the best lines of evidence for reconstructing early Earth’s oxygenation history, including permanent atmospheric oxygenation following the Great Oxidation Event (GOE), ∼2.45−2.32 Ga. We show a shift from dominantly negative to permanently positive copper isotope compositions in black shales spanning ∼2.66−2.08 Ga. We interpret the transition in marine δ 65 Cu values as reflecting some combination of waning banded iron formation deposition (which removes heavy Cu) and increased oxidative delivery of Cu from continental sulfides (which supplies heavy Cu). Both processes are ultimately related to increased oxidative weathering and a progressive increase in sulfate and sulfide availability accompanying the GOE. Our results provide insights into copper cycling and bioavailability coupled to Earth’s oxygenation history.
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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 [76]
Evidence for increased oxidative weathering of the continents is supported by a recent compilation of Cu isotopes in Precambrian marine sediments.
“Evidence for increased oxidative weathering of the continents is also supported by a recent compilation of Cu isotopes in Precambrian marine sediments.”
From Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history (2017) · cites this paper as Chi Fru et al., 2016
There is a clear trend in the stable isotope values of Cu.
“there is a clear trend in the stable isotopes values of Cu.”
From Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history (2017) · cites this paper as Chi Fru et al., 2016
The trend of heavier Cu isotopes following the GOE is attributed to secular changes in seawater composition due to waning IF deposition (which prior to the GOE preferentially removed 65Cu with Fe(III)-oxyhydroxides) and increased oxidative supply of 65Cu from continental weathering due to preferential leaching of the heavier Cu isotope.
“This trend has been attributed to secular changes in seawater composition, due to the combined effect of waning IF deposition, which prior to the GOE would have preferentially removed 65 Cu with Fe(III)-oxyhydroxides, and increased oxidative supply of 65 Cu derived from continental weathering due to preferential leaching of the heavier Cu isotope.”
From Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history (2017) · cites this paper as Chi Fru et al., 2016
The Cu concentration record for IFs and shales is relatively constant in abundance, reminiscent of the Zn record, raising the possibility of stabilisation of these trace metals by organic ligand complexation.
“Although the Cu concentration record presented by Chi Fru et al. (2016) for IFs and shales is relatively constant in terms of abundance reminiscent of the Zn record raising the possibility of stabilisation of these trace metals by organic ligand complexation (see Robbins et al., 2013; Scott et al., 2013) - there is a clear trend in the stable isotopes values of Cu.”
From Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history (2017) · cites this paper as Chi Fru et al., 2016
Following the GOE, Cu isotopes in black shales become progressively heavier.
“Following the GOE, Cu isotopes in black shales become progressively heavier.”
From Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history (2017) · cites this paper as Chi Fru et al., 2016
The results of Chi-Fru et al. (2016) seem to indicate that such a scenario was unlikely, considering the relatively static sedimentary Cu abundance record.
“The results of Chi-Fru et al. (2016) would seem to indicate that such a scenario was unlikely, considering the relatively static sedimentary Cu abundance record they present.”
From Trace elements at the intersection of marine biological and geochemical evolution (2016) · cites this paper as Chi-Fru et al. (2016)
Authigenic Cu enrichments in BIF and black shales, normalized to detrital input using Ti, are remarkably static throughout the Precambrian.
“recent examination of authigenic Cu enrichments in BIF and black shales, normalized to detrital input using Ti, are remarkably static throughout the Precambrian (Chi-Fru et al., 2016).”
From Trace elements at the intersection of marine biological and geochemical evolution (2016) · cites this paper as Chi-Fru et al., 2016
Black shale Cu isotope compositions vary significantly over time, apparently due to variations in Cu sinks and sources.
“Despite the static abundance record, there is significant variation in black shale Cu isotope compositions over time that appears to be due to variations in Cu sinks and sources (Chi-Fru et al., 2016).”
From Trace elements at the intersection of marine biological and geochemical evolution (2016) · cites this paper as Chi-Fru et al., 2016
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Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history
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Self-citationTrace elements at the intersection of marine biological and geochemical evolution
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Self-citation
- Authors
- Chi Fru, E., Rodríguez, N. P., Partin, C. A., Lalonde, S. V., Andersson, P., Weiss, D. J., El Albani, A., Rodushkin, I., & Konhauser, K. O.
- Affiliations
- Department of Geological Sciences and Bolin Centre for Climate Research, Stockholm University, SE-10691 Stockholm, Sweden;
- Stockholm University (SE)
- University of Saskatchewan (CA)
- Centre National de la Recherche Scientifique (FR)
- Swedish Museum of Natural History (SE)
- Imperial College London (GB)
- Institut de Chimie des Milieux et Matériaux de Poitiers, Université de Poitiers UMR 7285-CNRS, 86073 Poitiers, France;
- ALS Scandinavia AB, ALS Laboratory Group, S-977 75 Lulea, Sweden;
- University of Alberta (CA)
- ORCID
- Venue
- Proceedings of the National Academy of Sciences
- Publisher
- National Academy of Sciences
- Published
- 2016-04-18
- Volume
- 113
- Issue
- 18
- Pages
- 4941-4946
- ISSN
- 0027-8424 (ISSN-L)
- 1091-6490
- PMC
- PMC4983842
- OpenAlex
- W2335796111
- Cited by
- 123
- References
- 51
- Citations by year
- 2026: 6 · 2025: 10 · 2024: 13 · 2023: 13 · 2022: 9 · 2021: 16 · 2020: 14 · 2019: 19 · 2018: 8 · 2017: 13 · 2016: 2
- FWCI
- 11.64
- Type
- journal article
- Language
- en
- Open access
- green
- www.ncbi.nlm.nih.gov
- Locations
- Proceedings of the National Academy of Sciences (publishedVersion)
- PubMed Central (publishedVersion)
- PubMed (publishedVersion)
- HAL (submittedVersion)
- ORCA Online Research @Cardiff (Cardiff University) (submittedVersion)
- Spiral (Imperial College London) (submittedVersion)
- Funders
- EC | European Research Council (PIEF.GA-2010-276475; 336092)
- 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
- copper isotopes, Great Oxidation Event, atmospheric oxygenation, iron oxide, banded iron formations, marine sulfate, iron isotopes
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