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Photochemistry of Sulfur Dioxide and the Origin of Mass-Independent Isotope Fractionation in Earth's Atmosphere
Abstract
Archean sulfide and sulfate minerals commonly exhibit anomalous ratios among four stable sulfur isotopes,32 S,33 S,34 S, and 36 S. These anomalous relationships, referred to as sulfur mass-independent fractionation (S-MIF), provide strong evidence for an early anoxic atmosphere. Correlated variations among three isotope ratios (δ 33 S, δ 34 S, and δ 36 S) can be observed in rocks throughout the Archean and are a key clue toward identifying the source reaction of S-MIF. Studies to investigate the origin of Archean S-MIF so far have primarily focused on the photochemistry of sulfur dioxide (SO 2). Photolysis of SO 2 at wavelengths <220 nm and photoexcitation at 240–340 nm both yield large-magnitude S-MIF. Proposed mechanisms of S-MIF include isotopologue-dependent self-shielding, cross-sectional amplitudes, and vibronic coupling during intersystem crossing. This review discusses the emerging picture of the physical origins of S-MIF and their implications for the chemistry of the early Earth's atmosphere.
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“Photochemistry imparts S-MIF and produces elemental sulfur, starting with reactions that photolyze volcanic SO2 such as SO2 + hν (<217 nm) = SO + O and SO + hν (< 231 nm) = S + O (58, 59).”
From The Archean atmosphere (2020) · cites this paper as [59]
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Mass-independent fractionation processes in the atmosphere
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Atmospheric oxygen and methane on the early Earth
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Aerobic nitrogen cycle 100 My before permanent atmospheric oxygenation
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Metadata
- Authors
- Ono, S.
- Affiliations
- Massachusetts Institute of Technology (US)
- Corresponding author
- Ono, Shuhei
- ORCID
- Ono, Shuhei
- Venue
- Annual Review of Earth and Planetary Sciences
- Publisher
- Annual Reviews
- Published
- 2017-08-30
- Volume
- 45
- Issue
- 1
- Pages
- 301-329
- ISSN
- 0084-6597 (ISSN-L)
- 1545-4495
- OpenAlex
- W2620153389
- Cited by
- 119
- References
- 122
- Citations by year
- 2026: 8 · 2025: 11 · 2024: 15 · 2023: 14 · 2022: 12 · 2021: 13 · 2020: 22 · 2019: 13 · 2018: 9 · 2017: 2
- FWCI
- 1.58
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Annual Review of Earth and Planetary Sciences (publishedVersion)
- Funders
- National Science Foundation
- National Aeronautics and Space Administration
- Topics
- Physical Sciences › Earth and Planetary Sciences › Paleontology › Paleontology and Stratigraphy of Fossils
- Physical Sciences › Earth and Planetary Sciences › Atmospheric Science › Atmospheric chemistry and aerosols
- Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Geological and Geochemical Analysis
- Keywords
- sulfur dioxide, photochemistry, Archean atmosphere, early Earth atmosphere, anoxic atmosphere, sulfur isotopes, photolysis, photoexcitation, self-shielding, cross sections, vibronic coupling, intersystem crossing, sulfide minerals, sulfate minerals
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