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Atmospheric Influence of Earth's Earliest Sulfur Cycle
Abstract
Mass-independent isotopic signatures for delta(33)S, delta(34)S, and delta(36)S from sulfide and sulfate in Precambrian rocks indicate that a change occurred in the sulfur cycle between 2090 and 2450 million years ago (Ma). Before 2450 Ma, the cycle was influenced by gas-phase atmospheric reactions. These atmospheric reactions also played a role in determining the oxidation state of sulfur, implying that atmospheric oxygen partial pressures were low and that the roles of oxidative weathering and of microbial oxidation and reduction of sulfur were minimal. Atmospheric fractionation processes should be considered in the use of sulfur isotopes to study the onset and consequences of microbial fractionation processes in Earth's early history.
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“Δ³³S isotopic values can be used to determine whether sulfate aerosol formation occurred in the stratosphere (i.e., above the ozone layer) since UV photochemical reactions generate MIF and non-zero Δ³³S 40,122-124 .”
From Decadal-to-centennial increases of volcanic aerosols from Iceland challenge the concept of a Medieval Quiet Period (2024) · cites this paper as [122]
In the citing paper
“The strongest constraint on Archean atmospheric composition is that the ground-level mixing ratio of O2 was <10−6 PAL (present atmospheric level) or <0.2–parts per million by volume (ppmv) O2 for air of 1 bar, indicated by the presence of sulfur isotope MIF (S-MIF) in Archean sedimentary minerals (Fig. 2A) (44, 47).”
From The Archean atmosphere (2020) · cites this paper as [47]
In the citing paper
“However, the production and preservation of non-mass-dependent sulfur isotope anomalies (NMD-S) in Archean and earliest Paleoproterozoic sedimentary rocks indicate that atmospheric pO 2 was maintained at extremely low values, likely below ∼10 -7 PAL, for most of Archean time (Farquhar et al. 2000, Pavlov & Kasting 2002, Zahnle et al. 2006) (Figure 3a).”
From The History of Ocean Oxygenation (2022) · cites this paper as Farquhar et al. 2000
In the citing paper
“whereas geologic and geochemical constraints suggest that before ~2.45 billion years ago (Ga), the atmosphere was essentially devoid of this gas (1–4).”
From Rapid oxygenation of Earth’s atmosphere 2.33 billion years ago (2016) · cites this paper as [1]
In the citing paper
“Mass-independent fractionation of sulfur isotopes (S-MIF) is thought to originate from the photolysis and/or photoexcitation of volcanogenic SO2 by ultraviolet light in an anoxic atmosphere (1, 20–23).”
From Rapid oxygenation of Earth’s atmosphere 2.33 billion years ago (2016) · cites this paper as [1]
In the citing paper
“By accepting the original value of ~10−5 PAL as the nominal threshold above which S-MIF is no longer preserved, we apply it here as a robust tool for tracing the first rise in pO2 to >10−5 PAL because of its potential for high stratigraphic resolution (1, 31, 33).”
From Rapid oxygenation of Earth’s atmosphere 2.33 billion years ago (2016) · cites this paper as [1]
In the citing paper
“For simplicity, we did not explicitly model different kinetics for different forms of sulfur (for example, thiosulfate, S8, or sulfate) that are likely present in the Archean oceans (1, 30).”
From Rapid oxygenation of Earth’s atmosphere 2.33 billion years ago (2016) · cites this paper as [1]
In the citing paper
“Atmospheric oxygen (pO2) rose from <10−5 present atmospheric level (PAL) at the Great Oxidation Event, as constrained by the disappearance of mass-independent fractionation of sulfur isotopes1 (MIF-S) ∼2.45–2.32 Ga.”
From Atmospheric oxygen regulation at low Proterozoic levels by incomplete oxidative weathering of sedimentary organic carbon (2017) · cites this paper as [1]
In the citing paper
“However, the lack of MIF-S1 after 2.32 Ga constrains pO2>10−5 PAL.”
From Atmospheric oxygen regulation at low Proterozoic levels by incomplete oxidative weathering of sedimentary organic carbon (2017) · cites this paper as [1]
In the citing paper
“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 Farquhar et al., 2000
In the citing paper
“that effectively disappeared from the sedimentary record between 2.45 and 2.32 Ga (e.g., Bekker et al., 2004;Farquhar et al., 2000;2011).”
From Trace elements at the intersection of marine biological and geochemical evolution (2016) · cites this paper as Farquhar et al., 2000
In the citing paper
“The disappearance of S-MIF is perhaps the most accepted evidence for the onset of widespread and permanent oxygenation of the Earth's surface to levels above 10 -5 times present atmospheric levels (PAL) (see Pavlov and Kasting, 2002;Bekker et al., 2004;Farquhar et al., 2000;2011).”
From Trace elements at the intersection of marine biological and geochemical evolution (2016) · cites this paper as Farquhar et al., 2000
In the citing paper
“There was virtually no oxygen in the Archean eon [4.0 to 2.5 billion years ago (Ga)] (12)”
From Disequilibrium biosignatures over Earth history and implications for detecting exoplanet life (2018) · cites this paper as [12]
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- Supported by grants from NSF NASA and Calspace. Samples used in this study were supplied and/or collected by J. W. Schopf B. Runnegar D. Lowe H. Baadsgaard and S. J. Mojzsis. The interpretations herein are our responsibility but they have benefited from interesting conversations and questions from R. N. Clayton K. Boering T. Chacko D. DePaolo H. D. Holland M. Humayun J. Kasting A. Knoll S. J. Mojzsis A. Payton G. Retallack and K. K. Turekian. We thank D. Canfield and J. Kasting for providing copies of in press and unpublished materials.
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“…33 S, one can assess Mass-independent Fractionation (MIF) by calculating Δ ³³S (de fi ned as, Δ ³³S isotopic values can be used to determine whether sulfate aerosol formationoccurredinthestratosphere(i.e.,abovetheozonelayer)sinceUV photochemicalreactionsgenerateMIFandnon-zero Δ ³³S 40,122 – 124 .”
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Metadata
- Authors
- Farquhar, J., Bao, H., & Thiemens, M.
- Affiliations
- University of California San Diego (US)
- Venue
- Science
- Published
- 2000-08-04
- Volume
- 289
- Issue
- 5480
- Pages
- 756-758
- ISSN
- 0036-8075 (ISSN-L)
- 1095-9203
- OpenAlex
- W2081383679
- Cited by
- 1,805
- References
- 25
- Citations by year
- 2026: 70 · 2025: 91 · 2024: 76 · 2023: 70 · 2022: 84 · 2021: 99 · 2020: 98 · 2019: 105 · 2018: 117 · 2017: 98 · 2016: 69 · 2015: 74 · 2014: 70 · 2013: 96 · 2012: 81
- FWCI
- 28.74
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Science (publishedVersion)
- PubMed (publishedVersion)
- Civil War Book Review (submittedVersion)
- Topics
- Physical Sciences › Earth and Planetary Sciences › Paleontology › Paleontology and Stratigraphy of Fossils
- Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Geological and Geochemical Analysis
- Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Geochemistry and Elemental Analysis
- Keywords
- sulfur cycling, sulfur isotopes, Precambrian, oxidative weathering, microbial sulfur cycling, sulfide, sulfate, early Earth atmosphere, Precambrian rocks
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