Vibronic origin of sulfur mass-independent isotope effect in photoexcitation of SO 2 and the implications to the early earth’s atmosphere
Open accessAbstract
Signatures of mass-independent isotope fractionation (MIF) are found in the oxygen ((16)O,(17)O,(18)O) and sulfur ((32)S, (33)S, (34)S, (36)S) isotope systems and serve as important tracers of past and present atmospheric processes. These unique isotope signatures signify the breakdown of the traditional theory of isotope fractionation, but the physical chemistry of these isotope effects remains poorly understood. We report the production of large sulfur isotope MIF, with Δ(33)S up to 78‰ and Δ(36)S up to 110‰, from the broadband excitation of SO2 in the 250-350-nm absorption region. Acetylene is used to selectively trap the triplet-state SO2 ( (3)B1), which results from intersystem crossing from the excited singlet ( (1)A2/ (1)B1) states. The observed MIF signature differs considerably from that predicted by isotopologue-specific absorption cross-sections of SO2 and is insensitive to the wavelength region of excitation (above or below 300 nm), suggesting that the MIF originates not from the initial excitation of SO2 to the singlet states but from an isotope selective spin-orbit interaction between the singlet ( (1)A2/ (1)B1) and triplet ( (3)B1) manifolds. Calculations based on high-level potential energy surfaces of the multiple excited states show a considerable lifetime anomaly for (33)SO2 and (36)SO2 for the low vibrational levels of the (1)A2 state. These results demonstrate that the isotope selectivity of accidental near-resonance interactions between states is of critical importance in understanding the origin of MIF in photochemical systems.
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The high, spatially heterogeneous, and temporally variable Δ33S values and the large area of the Transvaal Basin suggest that photochemical products of SO2 in an anoxic atmosphere were the primary origin of these signals.
“The high, spatially heterogeneous, and temporally variable Δ33S values and the large area of the Transvaal Basin where these rocks were deposited suggest that the photochemical products of SO2 in an anoxic atmosphere were the primary origin of these signals.”
From Rapid oxygenation of Earth’s atmosphere 2.33 billion years ago (2016) · cites this paper as [22]
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 [22]
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“The large D(33)S valuesmight be due to some particular facet of the atmospheric chemistry at that time (22, 45).”
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Self-citationModeling the signature of sulfur mass-independent fractionation produced in the Archean atmosphere
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- Authors
- Whitehill, A. R., Xie, C., Hu, X., Xie, D., Guo, H., & Ono, S.
- Affiliations
- Massachusetts Institute of Technology (US)
- Nanjing University (CN)
- University of New Mexico (US)
- Venue
- Proceedings of the National Academy of Sciences
- Publisher
- National Academy of Sciences
- Published
- 2013-07-08
- Volume
- 110
- Issue
- 44
- Pages
- 17697-17702
- ISSN
- 0027-8424 (ISSN-L)
- 1091-6490
- PMC
- PMC3816475
- OpenAlex
- W2054316137
- Cited by
- 98
- References
- 72
- Citations by year
- 2026: 3 · 2025: 2 · 2024: 8 · 2023: 1 · 2022: 5 · 2021: 6 · 2020: 6 · 2019: 9 · 2018: 13 · 2017: 15 · 2016: 11 · 2015: 9 · 2014: 8 · 2013: 2
- FWCI
- 6.52
- Type
- journal article
- Language
- en
- Open access
- green
- www.ncbi.nlm.nih.gov
- Locations
- Proceedings of the National Academy of Sciences (publishedVersion)
- Europe PMC (PubMed Central) (publishedVersion)
- PubMed Central (publishedVersion)
- PubMed (publishedVersion)
- DSpace@MIT (Massachusetts Institute of Technology) (submittedVersion, cc-by-nc)
- Topics
- Physical Sciences › Earth and Planetary Sciences › Atmospheric Science › Atmospheric chemistry and aerosols
- Physical Sciences › Earth and Planetary Sciences › Paleontology › Paleontology and Stratigraphy of Fossils
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Advanced Chemical Physics Studies
- Keywords
- sulfur dioxide, photoexcitation, spin-orbit coupling, triplet state, intersystem crossing, isotope fractionation, early Earth atmosphere, oxygen isotopes, potential energy surface, excited state lifetime
- MeSH terms
- Acetylene, Atmosphere, Light, Models, Chemical, Photochemistry, Sulfur Dioxide, Sulfur Isotopes, Vibration, Evolution, Chemical
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