Global modeling of the isotopic analogues of N2O: Stratospheric distributions, budgets, and the 17O-18O mass-independent anomaly

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A three-dimensional chemical transport model (CTM) is used to study the stratospheric ditributions and global budgets of the five most abundant isotopic analogues of N2O: 14N14N16O, 14N15N16O, 15N14N16O, 14N14N18O, and 14N14N17O. Two different chemistry models are used to derive photolysis cross sections for the analogues of N2O: (1) the zero-point energy shift model, scaled by a factor of 2 to give better agreement with recent laboratory measurements and (2) the time-dependent Hermite propagator model. Overall, the CTM predicts stratospheric enrichments that are in good agreement with most measurements, with the latter model performing slightly better. Combining the CTM-calculated stratospheric losses for each N2O species with current estimates of tropospheric N2O sources defines a budget of flux-weighted enrichment factors for each. These N2O budgets are not in balance, and trends of -0.04 to -0.06 ‰/yr for the mean of 14N15N16O and 15N14N16O and -0.01 to -0.02 ‰/yr for 14N14N18O are predicted, although each has large uncertainties associated with the sources. The CTM also predicts that 14N14N17O and 14N14N18O will be fractionated by photolysis in a manner that produces a nonzero mass-independent anomaly. This effect can account for up to half of the observed anomaly in the stratosphere without invoking chemical sources. In addition, a simple one-dimensional model is used to investigate a number of chemical scenarios for the mass-independent composition of stratospheric N2O.

OriginalsprogEngelsk
TidsskriftJournal of Geophysical Research D: Atmospheres
Vol/bind108
Udgave nummer8
Sider (fra-til)ACH 1-1 - ACH 1-15
ISSN2169-8953
StatusUdgivet - 27 apr. 2003

ID: 236122124