Following the springtime polar sunrise, ozone concentrations in the lower troposphere episodically decline to near-zero levels 1 . These ozone depletion events are initiated by an increase in reactive bromine levels in the atmosphere 2-5 . Under these conditions, the oxidative capacity of the Arctic troposphere is altered, leading to the removal of numerous transported trace gas pollutants, including mercury 6 . However, the sources and mechanisms leading to increased atmospheric reactive bromine levels have remained uncertain, limiting simulations of Arctic atmospheric chemistry with the rapidly transforming sea-ice landscape 7,8 . Here, we examine the potential for molecular bromine production in various samples of saline snow and sea ice, in the presence and absence of sunlight and ozone, in an outdoor snow chamber in Alaska. Molecular bromine was detected only on exposure of surface snow (collected above tundra and first-year sea ice) to sunlight. This suggests that the oxidation of bromide is facilitated by a photochemical mechanism, which was most efficient for more acidic samples characterized by enhanced bromide to chloride ratios. Molecular bromine concentrations increased significantly when the snow was exposed to ozone, consistent with an interstitial air amplification mechanism. Aircraft-based observations confirm that bromine oxide levels were enhanced near the snow surface. We suggest that the photochemical production of molecular bromine in surface snow serves as a major source of reactive bromine, which leads to the episodic depletion of tropospheric ozone in the Arctic springtime.Proposed substrates for Arctic halogen activation include open water, frost flowers, sea ice, surface snow, blowing snow and aerosols 7 . To test the effectiveness of various snow and ice surfaces for bromine activation, ten outdoor snow chamber experiments were conducted during the March-April 2012 Bromine, Ozone and Mercury Experiment (BROMEX) in Barrow, Alaska. As listed in Table 1, locally obtained samples included first-year sea ice, brine icicles that drained through the base of uplifted sea-ice blocks, several different layers of snow located on first-year sea ice, and surface snow on the tundra. Real-time chemical ionization mass spectrometry was used to monitor Br 2 production 9 from the snow/ice samples in a perfluoroalkoxy-coated chamber, through which clean air, with and without ozone, was allowed to flow. Br 2 was observed only when snow samples were exposed to ambient sunlight, as shown in Fig. 1 and in the Supplementary Information. This indicates active snowpack photochemistry. On O 3 addition, chamber Br 2 concentrations increased, consistent with the autocatalytic bromine explosion mechanism, described below.Photochemical production of the hydroxyl radical (OH) in the snowpack condensed phase and the subsequent oxidation of bromide explains the initially observed Br 2 production. Photoactivated release of Br 2 into the atmosphere was previously proposed to explain boundary-layer ozone destruction beginn...

Abstract. Multiple axis differential absorption spectroscopy (MAX-DOAS) measurements of bromine monoxide (BrO) probed the vertical structure of halogen activation events during March–May 2012 at Barrow, Alaska. An analysis of the BrO averaging kernels and degrees of freedom obtained by optimal-estimation-based inversions from raw MAX-DOAS measurements reveals the information is best represented by reducing the retrieved BrO profile to two quantities: the integrated column from the surface through 200 m (VCD200 m), and the lower tropospheric vertical column density (LT-VCD), which represents the integrated column of BrO from the surface through 2 km. The percentage of lower tropospheric BrO in the lowest 200 m was found to be highly variable ranging from shallow layer events, where BrO is present primarily in the lowest 200 m, to distributed column events where BrO is observed at higher altitudes. The highest observed LT-VCD events occurred when BrO was distributed throughout the lower troposphere, rather than concentrated near the surface. Atmospheric stability in the lowest 200 m influenced the percentage of LT-VCD that is in the lowest 200 m, with inverted temperature structures having a first-to-third quartile range (Q1–Q3) of VCD200 m/LT-VCD from 15–39%, while near-neutral-temperature structures had a Q1–Q3 range of 7–13%. Data from this campaign show no clear influence of wind speed on either lower tropospheric bromine activation (LT-VCD) or the vertical distribution of BrO, while examination of seasonal trends and the temperature dependence of the vertical distribution supported the conclusion that the atmospheric stability affects the vertical distribution of BrO.

Abstract. Sulphur dioxide emission rate measurements are an important tool for volcanic monitoring and eruption risk assessment. The SO2 camera technique remotely measures volcanic emissions by analysing the ultraviolet absorption of SO2 in a narrow spectral window between 300 and 320 nm using solar radiation scattered in the atmosphere. The SO2 absorption is selectively detected by mounting band-pass interference filters in front of a two-dimensional, UV-sensitive CCD detector. One important step for correct SO2 emission rate measurements that can be compared with other measurement techniques is a correct calibration. This requires conversion from the measured optical density to the desired SO2 column density (CD). The conversion factor is most commonly determined by inserting quartz cells (cuvettes) with known amounts of SO2 into the light path. Another calibration method uses an additional narrow field-of-view Differential Optical Absorption Spectroscopy system (NFOV-DOAS), which measures the column density simultaneously in a small area of the camera's field-of-view. This procedure combines the very good spatial and temporal resolution of the SO2 camera technique with the more accurate column densities obtainable from DOAS measurements. This work investigates the uncertainty of results gained through the two commonly used, but quite different, calibration methods (DOAS and calibration cells). Measurements with three different instruments, an SO2 camera, a NFOV-DOAS system and an Imaging DOAS (I-DOAS), are presented. We compare the calibration-cell approach with the calibration from the NFOV-DOAS system. The respective results are compared with measurements from an I-DOAS to verify the calibration curve over the spatial extent of the image. The results show that calibration cells, while working fine in some cases, can lead to an overestimation of the SO2 CD by up to 60% compared with CDs from the DOAS measurements. Besides these errors of calibration, radiative transfer effects (e.g. light dilution, multiple scattering) can significantly influence the results of both instrument types. The measurements presented in this work were taken at Popocatépetl, Mexico, between 1 March 2011 and 4 March 2011. Average SO2 emission rates between 4.00 and 14.34 kg s−1 were observed.

The return of sunlight in the polar spring leads to the production of reactive halogen species from the surface snowpack, significantly altering the chemical composition of the Arctic near-surface atmosphere and the fate of long-range transported pollutants, including mercury. Recent work has shown the initial production of reactive bromine at the Arctic surface snowpack; however, we have limited knowledge of the vertical extent of this chemistry, as well as the lifetime and possible transport of reactive bromine aloft. Here, we present bromine monoxide (BrO) and aerosol particle measurements obtained during the March 2012 BRomine Ozone Mercury EXperiment (BROMEX) near Utqiaġvik (Barrow), AK. The airborne differential optical absorption spectroscopy (DOAS) measurements provided an unprecedented level of spatial resolution, over 2 orders of magnitude greater than satellite observations and with vertical resolution unable to be achieved by satellite methods, for BrO in the Arctic. This novel method provided quantitative identification of a BrO plume, between 500 m and 1 km aloft, moving at the speed of the air mass. Concurrent aerosol particle measurements suggest that this lofted reactive bromine plume was transported and maintained at elevated levels through heterogeneous reactions on colocated supermicron aerosol particles, independent of surface snowpack bromine chemistry. This chemical transport mechanism explains the large spatial extents often observed for reactive bromine chemistry, which impacts atmospheric composition and pollutant fate across the Arctic region, beyond areas of initial snowpack halogen production. The possibility of BrO enhancements disconnected from the surface potentially contributes to sustaining BrO in the free troposphere and must also be considered in the interpretation of satellite BrO column observations, particularly in the context of the rapidly changing Arctic sea ice and snowpack

Abstract. Many relevant processes in tropospheric chemistry take place on rather small scales (e.g., tens to hundreds of meters) but often influence areas of several square kilometer. Thus, measurements of the involved trace gases with high spatial resolution are of great scientific interest. In order to identify individual sources and sinks and ultimately to improve chemical transport models, we developed a new airborne instrument, which is based on the well established Differential Optical Absorption Spectroscopy (DOAS) method. The Heidelberg Airborne Imaging DOAS Instrument (HAIDI) is a passive imaging DOAS spectrometer, which is capable of recording horizontal and vertical trace gas distributions with a resolution of better than 100 m. Observable species include NO 2 , HCHO, C 2 H 2 O 2 , H 2 O, O 3 , O 4 , SO 2 , IO, OClO and BrO.Here we give a technical description of the instrument including its custom-built spectrographs and CCD detectors. Also first results from measurements with the new instrument are presented. These comprise spatial resolved SO 2 and BrO in volcanic plumes, mapped at Mt. Etna (Sicily, Italy), NO 2 emissions in the metropolitan area of Indianapolis (Indiana, USA) as well as BrO and NO 2 distributions measured during arctic springtime in context of the BRomine, Ozone, and Mercury EXperiment (BROMEX) campaign, which was performed 2012 in Barrow (Alaska, USA).