The DOI matches its Crossref record; 64 of the 65 references it cites were found in a registry or an index.
The loss of mass‐independent fractionation in sulfur due to a Palaeoproterozoic collapse of atmospheric methane
Abstract
We use a 1‐D numerical model to study the atmospheric photochemistry of oxygen, methane, and sulfur after the advent of oxygenic photosynthesis. We assume that mass‐independent fractionation (MIF) of sulfur isotopes – characteristic of the Archean – was best preserved in sediments when insoluble elemental sulfur (S 8) was an important product of atmospheric photochemistry. Efficient S 8 production requires three things: (i) very low levels of tropospheric O 2; (ii) a source of sulfur gases to the atmosphere at least as large as the volcanic SO 2 source today; and (iii) a sufficiently high abundance of methane or other reduced gas. All three requirements must be met. We suggest that the disappearance of a strong MIF sulfur signature at the beginning of the Proterozoic is better explained by the collapse of atmospheric methane, rather than by a failure of volcanism or the rise of oxygen. The photochemical models are consistent in demanding that methane decline before O 2 can rise (although they are silent as to how quickly), and the collapse of a methane greenhouse effect is consistent with the onset of major ice ages immediately following the disappearance of MIF sulfur. We attribute the decline of methane to the growth of the oceanic sulfate pool as indicated by the widening envelope of mass‐dependent sulfur fractionation through the Archean. We find that a given level of biological forcing can support either oxic or anoxic atmospheres, and that the transition between the anoxic state and the oxic state is inhibited by high levels of atmospheric methane. Transition from an oxygen‐poor to an oxygen‐rich atmosphere occurs most easily when methane levels are low, which suggests that the collapse of methane not only caused the end of MIF S and major ice ages, but it may also have enabled the rise of O 2. In this story the early Proterozoic ice ages were ended by the establishment of a stable oxic atmosphere, which protected a renewed methane greenhouse with an ozone shield.
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In the citing paper
“In anoxic air, sulfur ends up in insoluble S8 aerosols and water-soluble sulfate and SO2, unlike today’s atmospheric sulfur, which almost entirely oxidizes to sulfate (44, 45).”
From The Archean atmosphere (2020) · cites this paper as [44]
In the citing paper
“For a wide range of Archean atmospheric redox conditions, both types of aerosol should form and precipitate (44).”
From The Archean atmosphere (2020) · cites this paper as [44]
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 [44]
In the citing paper
“In the Archean, as well as anoxia, gases such as CH4 or H2 produced sufficiently reducing conditions that S, S2, S3, etc. gases persisted and polymerized into S8 (44, 60).”
From The Archean atmosphere (2020) · cites this paper as [44]
In the citing paper
“Permanent atmospheric oxygenation requires ~3 × 10−3 PAL O2 or more to prevent a destabilizing positive feedback of photochemical destruction of tropospheric O2 that otherwise occurs when an incipient ozone column is still transparent to far UV (44, 121, 122).”
From The Archean atmosphere (2020) · cites this paper as [44]
In the citing paper
“Second, Archean S-MIF requires >20-ppmv CH4 to generate particulate sulfur, S8 (Table 1).”
From The Archean atmosphere (2020) · cites this paper as [44]
In the citing paper
“Evidence points to high levels of Archean CH4 (Fig. 3B).”
From The Archean atmosphere (2020) · cites this paper as [44]
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 Zahnle et al. 2006
In the citing paper
“Photochemical models indicate that pO 2 must be above ∼10 -5 PAL to prevent the production and delivery of NMD-S anomalies near Earth's surface (Pavlov & Kasting 2002, Zahnle et al. 2006).”
From The History of Ocean Oxygenation (2022) · cites this paper as Zahnle et al. 2006
In the citing paper
“Such a relationship is consistent with biogeochemical modeling that suggests the collapse of a methane greenhouse (immediately followed by ice ages) before the rise of atmospheric O2 (32).”
From Rapid oxygenation of Earth’s atmosphere 2.33 billion years ago (2016) · cites this paper as [32]
In the citing paper
“a decreased flux of methane led to greater oxygen concentrations in the atmosphere even if the marine O2 flux to the atmosphere remained constant”
From Iron formations: A global record of Neoarchaean to Palaeoproterozoic environmental history (2017) · cites this paper as Zahnle et al., 2006
In the citing paper
“Extremely low Proterozoic oxygen, however, is difficult to reconcile with photochemical models that show that O2 levels between 10−6 PAL and 0.1% PAL are unstable against small perturbations in the O2 source flux (39), favoring Po2 closer to the upper boundary used for our maximum disequilibrium calculations.”
From Disequilibrium biosignatures over Earth history and implications for detecting exoplanet life (2018) · cites this paper as [39]
In the citing paper
“favoring Po2 closer to the upper boundary used for our maximum disequilibrium calculations.”
From Disequilibrium biosignatures over Earth history and implications for detecting exoplanet life (2018) · cites this paper as [39]
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Metadata
- Authors
- ZAHNLE, K., CLAIRE, M., & CATLING, D.
- Affiliations
- Ames Research Center (US)
- University of Washington (US)
- Corresponding author
- ZAHNLE, K.
- Venue
- Geobiology
- Publisher
- Wiley
- Published
- 2006-10-16
- Volume
- 4
- Issue
- 4
- Pages
- 271-283
- ISSN
- 1472-4669 (ISSN-L)
- 1472-4677
- OpenAlex
- W1999845220
- Cited by
- 315
- References
- 65
- Citations by year
- 2026: 10 · 2025: 23 · 2024: 13 · 2023: 21 · 2022: 17 · 2021: 26 · 2020: 24 · 2019: 14 · 2018: 28 · 2017: 20 · 2016: 13 · 2015: 8 · 2014: 12 · 2013: 19 · 2012: 15
- FWCI
- 8.90
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Geobiology (publishedVersion)
- Explore Bristol Research (publishedVersion)
- Bristol Research (University of Bristol) (submittedVersion)
- Funders
- National Aeronautics and Space Administration
- Topics
- Physical Sciences › Earth and Planetary Sciences › Paleontology › Paleontology and Stratigraphy of Fossils
- Physical Sciences › Environmental Science › Global and Planetary Change › Earth Systems and Cosmic Evolution
- Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Geological and Geochemical Analysis
- Keywords
- atmospheric photochemistry, oxygenic photosynthesis, sulfur cycling, elemental sulfur, atmospheric oxygen rise, Archean, volcanic SO2
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