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European Geosciences Union, Atmospheric Chemistry and Physics, 18(14), p. 9555-9566, 2014

DOI: 10.5194/acp-14-9555-2014

European Geosciences Union, Atmospheric Chemistry and Physics Discussions, 4(14), p. 4687-4721

DOI: 10.5194/acpd-14-4687-2014

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Constraining the N<sub>2</sub>O<sub>5</sub> UV absorption cross section from spectroscopic trace gas measurements in the tropical mid-stratosphere

This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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Abstract

The absorption cross section of N 2 O 5 , σ N 2 O 5 (λ, T ), which is known from laboratory measurements with the uncertainty of a factor of 2 (Table 4-2 in (Jet Propulsion Laboratory) JPL-2011; the spread in laboratory data, however, points to an uncertainty in the range of 25 to 30%, Sander et al., 2011), was investigated by balloon-borne observations of the relevant trace gases in the tropical mid-stratosphere. The method relies on the observation of the diurnal variation of NO 2 by limb scanning DOAS (differential optical absorption spectroscopy) measurements (Weidner et al., 2005; Kritten et al., 2010), supported by detailed photochemical modelling of NO y (NO x (= NO + NO 2 ) + NO 3 + 2N 2 O 5 + ClONO 2 + HO 2 NO 2 + BrONO 2 + HNO 3 ) photochemistry and a non-linear least square fitting of the model result to the NO 2 observations. Simulations are initialised with O 3 measured by direct sun observations, the NO y partitioning from MIPAS-B (Michelson Interferometer for Passive Atmospheric Sounding – Balloon-borne version) observations in similar air masses at night-time, and all other relevant species from simulations of the SLIMCAT (Single Layer Isentropic Model of Chemistry And Transport) chemical transport model (CTM). Best agreement between the simulated and observed diurnal increase of NO 2 is found if the σ N 2 O 5 (λ, T ) is scaled by a factor of 1.6 ± 0.8 in the UV-C (200–260 nm) and by a factor of 0.9 ± 0.26 in the UV-B/A (260–350 nm), compared to current recommendations. As a consequence, at 30 km altitude, the N 2 O 5 lifetime against photolysis becomes a factor of 0.77 shorter at solar zenith angle (SZA) of 30° than using the recommended σ N 2 O 5 (λ, T ), and stays more or less constant at SZAs of 60°. Our scaled N 2 O 5 photolysis frequency slightly reduces the lifetime (0.2–0.6%) of ozone in the tropical mid- and upper stratosphere, but not to an extent to be important for global ozone.