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  • 1
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    Oxygen isotope fractionation in stratospheric CO2 (1991)
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    Publication Date: 2011-08-19
    Description: A new cryogenic collection system has been flown on board a balloon gondola to obtain separate samples of ozone and carbon dioxide without entrapping major atmospheric gases. Precision laboratory isotopic analysis of CO2 samples collected between 26 and 35.5 km show a mass-independent enrichment in both O-17 and O-18 of about 11 per mil above tropospheric values. Ozone enrichment in its heavy isotopes was 9 to 16 percent in O3-50 and 8 to 11 percent in O3-49, respectively (Schueler et al., 1990). A mechanism to explain the isotope enrichment in CO2 has been recently proposed by Yung et al. (1991). The model is based on the isotope exchange between CO2 and O3 via O(1D), resulting in a transfer of the ozone isotope enrichment to carbon dioxide. Predicted enrichment and measured values agree well.
    Keywords: GEOPHYSICS
    Type: Geophysical Research Letters (ISSN 0094-8276); 18; 669-672
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  • 2
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    Laboratory studies of heavy ozone (1990)
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    Publication Date: 2011-08-19
    Description: Dissociation of ozone in the Chappuis bands has been used as an O atom source to study isotope effects occurring in the O(3P) + O2(3 Sigma g) recombination reaction. The ozone produced was found to be enriched in both of its heavy isotopes. The pressure dependence (5-1000 torr) and temperature dependence (127-360 K) of this isotope effect have been investigated. The enrichment is approximately constant from 5 torr to 100 torr and decreases at higher pressures. It increases with temperature, with O3-50 showing a slightly faster rate of increase than O3-45. The results of this experiment have clearly isolated the source of the isotope effect to the gas phase O(3P) + O2(3 Sigma g) recombination reaction.
    Keywords: INORGANIC AND PHYSICAL CHEMISTRY
    Type: Journal of Geophysical Research (ISSN 0148-0227); 95; 901-907
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  • 3
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    Measurement of isotopic abundances in collected stratospheric ozone samples (1990)
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    Publication Date: 2011-08-19
    Description: Enrichment of heavy O3 isotopes has been measured in collected stratospheric samples. A balloon-borne cryogenic sampler was used to gather six O3 samples between 26 and 35 km in three flights. Subsequent laboratory mass spectrometer analysis of rare O3 isotopes at both mass 49 and 50 has resulted in more precise measurements than have previously been reported with in situ and ground-based techniques. In one flight, (O-50)3 was enriched by 12-16 percent and (O-49)3 by 9-11 percent, both increasing with altitude. In the remaining two flights, the isotope enrichment was nearly mass-independent at 8-9 percent. The enrichments in O3 at mass 50 are less than the large 40 percent value observed in some stratospheric measurements but similar to (O-49)3 and (O-50)3 fractionations produced in laboratory-generated ozone.
    Keywords: GEOPHYSICS
    Type: Geophysical Research Letters (ISSN 0094-8276); 17; 1295-129
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  • 4
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    Multi-isotope study of ozone - Implications for the heavy ozone anomaly (1993)
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    Publication Date: 2019-08-14
    Description: Laboratory experiments have been performed with O and O2 in their ground electronic states to study the distribution of all possible ozone isotopes formed. Results show that with respect to (O-48)3, the two symmetric molecules O-17O-17O-17 and O-18O-18O-18 are depleted, in good agreement with standard recombination theory. An enrichment of about 18 percent is found in the asymmetric molecule O-16O-17O-18, while all others carry about 2/3 of that. A comparison with past laboratory and stratospheric ozone isotope measurements shows a standard enrichment which resides in asymmetric molecules only, and leads to an enrichment of stratospheric (O-49)3 and (O-50)3 of 8-9 percent; this has been observed in recent balloon experiments. The enrichments in the stratosphere can reach 40 percent at certain altitudes. Only when ozone was formed in an electric discharge process have larger enrichments been measured in laboratory experiments, affecting both symmetric and asymmetric molecules.
    Keywords: GEOPHYSICS
    Type: Geophysical Research Letters (ISSN 0094-8276); 20; 11; p. 1031-1034.
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