VUV pressure-broadening in sulfur dioxide

James Lyons, H. Herde, G. Stark, D. S. Blackie, J. C. Pickering, N. de Oliveira

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

In the pre-oxygenated ancient Earth atmosphere, the lack of O3 absorption allowed ultraviolet photodissociation of numerous molecules in the troposphere and lower stratosphere. For molecules with narrow line-type absorption spectra, optically thick columns would have produced isotope fractionation due to self-shielding of the most abundant isotopologues. In the lower atmosphere pressure broadening would modify, and in some cases, eliminate these isotope signatures. Shielding is particularly important for quantifying or constraining photolysis-derived isotope effects, such as those believed to explain the sulfur mass-independent fractionation in Archean sedimentary rocks. Here, we report pressure broadening coefficients for natural abundance SO2 in theC˜1B2←X˜1A1band system at 215 nm. For gas bath pressures up to 750 mbar, we find broadening coefficients of 0.30 ± 0.03 cm 1 atm−1 and 0.40 ± 0.04 cm 1 atm−1 for N2 and CO2, respectively. These broadening coefficients are ∼30% larger than SO2 broadening coefficients previously measured in the B˜−X˜ bands at 308 nm. Because of the highly congested nature of the C˜−X˜ bands, pressure broadening in the early Earth troposphere will cause line profile overlap that will diminish the self-shielding-derived mass-independent isotope fractionation for optically thick SO2 columns. Thus, non-explosive volcanic eruptions may not have left a signature of SO2 self-shielding in the ancient sedimentary rock record.

Original languageEnglish (US)
Pages (from-to)156-164
Number of pages9
JournalJournal of Quantitative Spectroscopy and Radiative Transfer
Volume210
DOIs
StatePublished - May 1 2018

Fingerprint

Sulfur Dioxide
pressure broadening
sulfur dioxides
Isotopes
Shielding
shielding
Fractionation
fractionation
Sedimentary rocks
Troposphere
isotopes
sedimentary rocks
Distillation columns
coefficients
troposphere
Volcanic Eruptions
signatures
Photodissociation
lower atmosphere
Upper atmosphere

Keywords

  • Earth atmosphere
  • Mass-independent fractionation
  • Pressure broadening
  • Self-shielding
  • Sulfur dioxide
  • Sulfur isotopes

ASJC Scopus subject areas

  • Radiation
  • Atomic and Molecular Physics, and Optics
  • Spectroscopy

Cite this

Lyons, J., Herde, H., Stark, G., Blackie, D. S., Pickering, J. C., & de Oliveira, N. (2018). VUV pressure-broadening in sulfur dioxide. Journal of Quantitative Spectroscopy and Radiative Transfer, 210, 156-164. https://doi.org/10.1016/j.jqsrt.2018.02.013

VUV pressure-broadening in sulfur dioxide. / Lyons, James; Herde, H.; Stark, G.; Blackie, D. S.; Pickering, J. C.; de Oliveira, N.

In: Journal of Quantitative Spectroscopy and Radiative Transfer, Vol. 210, 01.05.2018, p. 156-164.

Research output: Contribution to journalArticle

Lyons, J, Herde, H, Stark, G, Blackie, DS, Pickering, JC & de Oliveira, N 2018, 'VUV pressure-broadening in sulfur dioxide', Journal of Quantitative Spectroscopy and Radiative Transfer, vol. 210, pp. 156-164. https://doi.org/10.1016/j.jqsrt.2018.02.013
Lyons, James ; Herde, H. ; Stark, G. ; Blackie, D. S. ; Pickering, J. C. ; de Oliveira, N. / VUV pressure-broadening in sulfur dioxide. In: Journal of Quantitative Spectroscopy and Radiative Transfer. 2018 ; Vol. 210. pp. 156-164.
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