Atmospheric test of the J(BrONO₂)/<i>k</i>_BrO+NO₂ ratio: implications for total stratospheric Br_y and bromine-mediated ozone loss

Abstract

Abstract. We report on time-dependent O3, NO2 and BrO profile measurements taken in the stratosphere by limb observations of scattered skylight at high-latitudes during 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 indicates that, the measurements can be used to constrain the ratio J(BrONO2)/kBrO+NO2, for which overall a 1.69 &amp;pm; 0.04 larger ratio is found than indicated by the most recent JPL compilation (Sander et al., 2011). Sensitivity studies reveal the major reasons 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 J(BrONO2)/kBrO+NO2 ratio 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 brings estimates of total stratospheric bromine inferred from organic source gas measurements (i.e. CH3Br, the halons, CH2Br2, CHBr3, ...) 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) an overestimated Bry using the inorganic method would in return almost cancel out with the amount of reactive bromine calculated in the photochemical models.