Abstract.Measurements from the GOME-2 satellite instrument have been analyzed for tropospheric BrO using a residual technique that combines measured BrO columns and estimates of the stratospheric BrO content from a climatological approach driven by O 3 and NO 2 observations. Comparisons between the GOME-2 results and BrO vertical columns derived from correlative ground-based and SCIAMACHY nadir observations, present a good level of consistency. We show that the adopted technique enables separation of stratospheric and tropospheric fractions of the measured total BrO columns and allows quantitative study of the BrO plumes in polar regions. While some satellite observed plumes of enhanced BrO can be explained by stratospheric descending air, we show that most BrO hotspots are of tropospheric origin, although they are often associated to regions with low tropopause heights as well. Elaborating on simulations using the p-TOMCAT tropospheric chemical transport model, this result is found to be consistent with the mechanism of bromine release through sea salt aerosols production during blowing snow events. No definitive conclusion can be drawn however on the importance of blowing snow sources in comparison to other bromine release mechanisms. Outside polar regions, evidence is provided for a global tropospheric BrO background with column of 1-3 × 10 13 molec cm −2 , consistent with previous estimates.

[1] The analysis for BrO using the technique of differential optical absorption spectroscopy as applied to spectra of light scattered from the zenith sky has historically presented something of a challenge, leading to uncertainty about the accuracy of measurements. This has largely been due to the large sensitivity of the measurement to many analysis parameters and due to the small size of the absorption features being measured. BrO differential slant columns have been measured by six different groups taking part in an intercomparison exercise at Observatoire de Haute-Provence in France from 23 to 27 June 1996. The data are analyzed in a collaborative attempt to improve the overall analysis for BrO through investigation of a series of sources of errors in the instrumentation, calibration, input to the analysis, and the spectral analysis itself. The study included comprehensive sensitivity tests performed using both actual measurements and synthetic data. The latter proved invaluable for assessing several aspects of the spectral analysis without the limitations of spectral quality and instrument variability. The most significant sources of error are identified as the wavelength calibration of several of the absorption cross sections fitted and of the measured spectra themselves, the wavelength region of the fitting, the temperature dependence of the O 3 absorption cross sections, failure to adequately account for the so-called I 0 effect, inadequate offset correction, and inadequate measurement of the individual instrument slit functions. Recommendations for optimal analysis settings are presented, and comparing the results from the analysis of the campaign data shows BrO differential slant column observations from the various groups to be in agreement to within 4% on average between 87°and 90°s olar zenith angle, with a scatter of 16%.

[1] Emission of bromine from sea-salt aerosol, frost flowers, ice leads, and snow results in the nearly complete removal of surface ozone during Arctic spring. Regions of enhanced total column BrO observed by satellites have traditionally been associated with these emissions. However, airborne measurements of BrO and O 3 within the convective boundary layer (CBL) during the ARCTAS and ARCPAC field campaigns at times bear little relation to enhanced column BrO. We show that the locations of numerous satellite BrO "hotspots" during Arctic spring are consistent with observations of total column ozone and tropopause height, suggesting a stratospheric origin to these regions of elevated BrO. Tropospheric enhancements of BrO large enough to affect the column abundance are also observed, with important contributions originating from above the CBL. Closure of the budget for total column BrO, albeit with significant uncertainty, is achieved by summing observed tropospheric partial columns with calculated stratospheric partial columns provided that natural, short-lived biogenic bromocarbons supply between 5 and 10 ppt of bromine to the Arctic lowermost stratosphere. Proper understanding of bromine and its effects on atmospheric composition requires accurate treatment of geographic variations in column BrO originating from both the stratosphere and troposphere.

Abstract. The importance of nitrogen dioxide in both the troposphere and the stratosphere has been known for some years, and since the early 1970s, spectroscopic determinations have played an important role in understanding NOx chemistry. Spectroscopic measurements of the atmosphere have improved in quality in recent years to the point that an accurate determination of the NO 2 absorption cross section is essential to accurate retrievals of not only NO 2 but also less abundant species in the troposphere and stratosphere. NO2 is such a large absorber (approximately 1% at large air mass) in the stratosphere at twilight or in the troposphere under even mildly polluted conditions, that if it is not properly removed from observed spectra, the spectra of the more subtle species are masked and cannot be measured at all. We present cross sections of NO2 in the spectral region 350-585 nm at four temperatures between 217 and 298 K and total pressures between 100 and 600 torr at a mixing ratio of 84.1 ppmv and at a spectral resolution sufficient for accurate convolution with instruments typically used to measure atmospheric NO 2. Data will be presented to demonstrate the presence of NO 2 pressure dependence in high resolution. A detailed comparison with commonly used literature cross sections is made to show how such instrument parameters as wavelength accuracy, resolution, spectrograph scattered light, and data sampling affect the usefulness of the observed cross section.

Abstract.Ground-based measurements of BrO slant column densities (SCDs) were performed using zenith sky DOAS (Differential Optical Absorption Spectroscopy) during autumn (February'to May) and spring (August to October) of 1995 at Arrival Heights (77.8øS, 166.7øE).In