Contribution of isotopologue self-shielding to sulfur mass-independent fractionation during sulfur dioxide photolysis
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Author(s)
Lyons, J. R.
Ono, Shuhei
Whitehill, Andrew Richard
Date Issued
March 2013
Journal
Journal of Geophysical Research: Atmospheres
Citation
Ono, S., A. R. Whitehill, and J. R. Lyons. “Contribution of Isotopologue Self-Shielding to Sulfur Mass-Independent Fractionation During Sulfur Dioxide Photolysis.” Journal of Geophysical Research: Atmospheres 118, no. 5 (March 16, 2013): 2444–2454. Copyright © 2013 American Geophysical Union
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Final published version
Abstract
Signatures of sulfur mass-independent fractionation (S-MIF) are observed for sulfur minerals in Archean rocks, and for modern stratospheric sulfate aerosols (SSA) deposited in polar ice. Ultraviolet light photolysis of SO[subscript 2] is thought to be the most likely source for these S-MIF signatures, although several hypotheses have been proposed for the underlying mechanism(s) of S-MIF production. Laboratory SO[subscript 2] photolysis experiments are carried out with a flow-through photochemical reactor with a broadband (Xe arc lamp) light source at 0.1 to 5 mbar SO[subscript 2] in 0.25 to 1 bar N[subscript 2] bath gas, in order to test the effect of SO[subscript 2] pressure on the production of S-MIF. Elemental sulfur products yield high δ[superscript 34]S values up to 140 ‰, with δ[superscript 33]S/δ[superscript 34]S of 0.59 ± 0.04 and Δ[superscript 36]S/Δ[superscript 33]S ratios of −4.6 ± 1.3 with respect to initial SO[subscript 2]. The magnitude of the isotope effect strongly depends on SO[subscript 2] partial pressure, with larger fractionations at higher SO[subscript 2] pressures, but saturates at an SO[subscript 2] column density of 10[superscript 18] molecules cm[superscript −2]. The observed pressure dependence and δ[superscript 33]S/δ[superscript 34]S and Δ[superscript 36]S/Δ[superscript 33]S ratios are consistent with model calculations based on synthesized SO[subscript 2] isotopologue cross sections, suggesting a significant contribution of isotopologue self-shielding to S-MIF for high SO[subscript 2] pressure (>0.1 mbar) experiments. Results of dual-cell experiments further support this conclusion. The measured isotopic patterns, in particular the Δ[superscript 36]S/Δ[superscript 33]S relationships, closely match those measured for modern SSA from explosive volcanic eruptions. These isotope systematics could be used to trace the chemistry of SSA after large Plinian volcanic eruptions.
MIT Department
Massachusetts Institute of Technology. Department of Earth, Atmospheric, and Planetary Sciences
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DOI of Published Version
https://doi.org/10.1002/jgrd.50183
