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 since UV photochemical reactions generate MIF and non-zero Δ33S.
“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]
The strongest constraint on Archean atmospheric composition is that the ground-level mixing ratio of O2 was <10−6 PAL or <0.2 ppmv O2 for air of 1 bar, indicated by the presence of sulfur isotope MIF in Archean sedimentary minerals.
“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]
Production and preservation of non-mass-dependent sulfur isotope anomalies in Archean and earliest Paleoproterozoic sedimentary rocks indicate that atmospheric pO2 was maintained at extremely low values, likely below approximately 10^-7 PAL, for most of Archean time.
“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
Before ~2.45 billion years ago, Earth's atmosphere was essentially devoid of molecular oxygen.
“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]
Mass-independent fractionation of sulfur isotopes is thought to originate from photolysis and/or photoexcitation of volcanogenic SO2 by ultraviolet light in an anoxic atmosphere.
“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]
The authors accept ~10−5 PAL as the nominal threshold above which S-MIF is no longer preserved and apply it as a robust tool for tracing the first rise in pO2 to >10−5 PAL.
“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]
For simplicity, the model did not explicitly model different kinetics for different forms of sulfur that are likely present in the Archean oceans.
“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]
Atmospheric oxygen rose from <10−5 PAL at the Great Oxidation Event, as constrained by the disappearance of mass-independent fractionation of sulfur isotopes ∼2.45-2.32 Ga.
“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]
The lack of MIF-S after 2.32 Ga constrains pO2>10−5 PAL.
“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 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 Farquhar et al., 2000
S-MIF effectively disappeared from the sedimentary record between 2.45 and 2.32 Ga.
“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
Disappearance of S-MIF is perhaps the most accepted evidence for onset of widespread and permanent oxygenation of Earth's surface to levels above 10^-5 PAL.
“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
There was virtually no oxygen in the Archean eon (4.0 to 2.5 Ga).
“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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- 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 › Geophysics › 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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