Abstract
Abstract. We report on time-dependent O3, NO2 and BrO profiles measured by limb observations of scattered skylight in the stratosphere over Kiruna (67.9° N, 22.1° E) on 7 and 8 September 2009 during the autumn circulation turn-over. The observations are complemented by simultaneous direct solar occultation measurements around sunset and sunrise performed aboard the same stratospheric balloon payload. Supporting radiative transfer and photochemical modelling indicate that the measurements can be used to constrain the ratio J(BrONO2)/kBrO+NO2, for which at T = 220 ± 5 K an overall 1.7 (+0.4 −0.2) larger ratio is found than recommended by the most recent Jet Propulsion Laboratory (JPL) compilation (Sander et al., 2011). Sensitivity studies reveal the major reasons are likely to be (1) a larger BrONO2 absorption cross-section σBrONO2, primarily for wavelengths larger than 300 nm, and (2) a smaller kBrO+NO2 at 220 K than given by Sander et al. (2011). Other factors, e.g. the actinic flux and quantum yield for the dissociation of BrONO2, can be ruled out. The observations also have consequences for total inorganic stratospheric bromine (Bry) estimated from stratospheric BrO measurements at high NOx loadings, since the ratio J(BrONO2)/kBrO+NO2 largely determines the stratospheric BrO/Bry ratio during daylight. Using the revised J(BrONO2)/kBrO+NO2 ratio, total stratospheric Bry is likely to be 1.4 ppt smaller than previously estimated from BrO profile measurements at high NOx loadings. This would bring estimates of Bry inferred from organic source gas measurements (e.g. CH3Br, the halons, CH2Br2, CHBr3, etc.) into closer agreement with estimates based on BrO observations (inorganic method). The consequences for stratospheric ozone due to the revised J(BrONO2)/kBrO+NO2 ratio are small (maximum −0.8%), since at high NOx (for which most Bry assessments are made) the enhanced ozone loss by overestimating Bry is compensated for by the suppressed ozone loss due to the underestimation of BrO/Bry with a smaller J(BrONO2)/kBrO+NO2 ratio.
Highlights
The effect reactive bromine haSs ocniesntractoesspheric ozone is largely dominated by the Reactions (1), (2a), and (2b)(Spencer and Rowland, 1977): quantum yield for the dissociation of BrONO2, can be ruled out.The observations have consequences for total inorganic stratospheric bromine (Bry) estimated from stratospheric BrO measurements at high NOx loadings, since the ratio J(BrONO2)/kBrO+NO2 largely determines the stratospheric BrO/Bry ratio during daylight
This is in particular true for the large BrO slant column densities (SCDs), which are obtained for large negative elevation angles, where the bulk of BrO and BrONO2 resides
In order to investigate potential causes for the deviation of the measured versus modelled BrO SCDs, a sensitivity test for the magnitude of the parameters J(BrONO2), kBrO+NO2, and Bry is performed for limb and solar occultation measurements (Figs. 6 and 7)
Summary
The effect reactive bromine haSs ocniesntractoesspheric ozone is largely dominated by the Reactions (1), (2a), and (2b). The observations have consequences for total inorganic stratospheric bromine (Bry) estimated from stratospheric BrO measurements at high NOx loadings, since the ratio J(BrONO2)/kBrO+NO2 largely determines the stratospheric BrO/Bry ratio during daylight. Using the revised J(BrONO2)/kBrO+NO2 ratio, total stratospheric Bry is likely to be 1.4 ppt smaller than previously estimated from BrO. The brackets give the recommended quantum yields for λ > 300 nm. They determine StheoalmidouEntaorftrheactive bromine (BrO) and the bromine-mediated ozone loss in almost profile measurements at high NOx loadings. This would the whole global lower stratosphere during daytime, except
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Free) 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call
