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| Titel |
Photochemical self-shielding as a source of non-mass-dependent isotope fractionation |
| VerfasserIn |
James Lyons, Glenn Stark, Doug Blackie, Juliet Pickering, Alan Heays |
| Konferenz |
EGU General Assembly 2010
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| Medientyp |
Artikel
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| Sprache |
Englisch
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| Digitales Dokument |
PDF |
| Erschienen |
In: GRA - Volume 12 (2010) |
| Datensatznummer |
250043410
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| Zusammenfassung |
| Very large isotopic enrichments occur in the photolysis products of molecules that have line-type absorption spectra. Abundance-dependent line saturation, a process termed photochemical self-shielding, yields large non-mass-dependent (NMD) isotope effects, and has been proposed to have occurred in CO in the solar nebula (Clayton 2002) and SO2 in the early Earth atmosphere (Lyons 2007). The NMD signatures derived from photolysis of CO and SO2 are believed to be recorded in primitive meteorites inclusions (CAIs) and in Archean/Paleoproterozoic sulfur sediments, respectively. Comparison of theory and experiment can be used to distinguish self-shielding from other NMD processes.
Recent low-resolution (~10 cm^-1) measurements of isotopic SO2 cross sections (Danielache et al. 2008) exhibit NMD effects when included in photoechemical models (Ueno et al. 2009), but not as a result of self-shielding. Higher resolution measurements (1-0.2 cm^-1) of isotopic cross sections are in progress at Imperial College. Inclusion of preliminary 1 cm^-1 resolution cross sections in a photochemical model for Earth's early atmosphere clearly demonstrates that isotopic self-shielding is present, yielding d33S>0 and d34S>0 in photoproduct SO. However, uncertainties in the measured cross sections also introduce NMD signatures. We are presently working to remove these uncertainties.
Recent experiments on CO photodissociation at wavelengths ~91-108 nm show very large NMD effects in oxygen (Chakraborty et al. 2008). Because the measured NMD signatures are wavelength dependent, and differ in delta-values (i.e., d17O/d18O not equal unity), Chakraborty et al. claim that their experiments rule out CO self-shielding as the mechanism for the meteorite CAI slope-1 line. Here we show via model simulation of the experiments that the non-unity d17O/d18O values result primarily from self-shielding effects in both C16O and C18O. Also, model results indicate that the non-unity d17O/d18O values only arise for low CO dissociation fraction (<10 %). When a larger fraction of CO is dissociated (>10 %), d17O/d18O approaches unity. This is consistent with self-shielding models and with the CAI fractionation line. |
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