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Glyoxal is an important intermediate species formed by the oxidation of common biogenic and anthropogenic volatile organic compounds such as isoprene, toluene, and acetylene. Although glyoxal has been shown to play an important role in urban and forested environments, its role in the open ocean environment is still not well understood, with only a few observations showing evidence for its presence in the open ocean marine boundary layer (MBL). In this study, we report observations of glyoxal from 10 field campaigns in different parts of the world's oceans. These observations together represent the largest database of glyoxal in the MBL. The measurements are made with similar instruments that have been used in the past, although the open ocean values reported here, average of about 25 parts per trillion by volume (pptv) with an upper limit of 40 pptv, are much lower than previously reported observations that were consistently higher than 40 pptv and had an upper limit of 140 pptv, highlighting the uncertainties in the differential optical absorption spectroscopy method for the retrieval of glyoxal. Despite retrieval uncertainties, the results reported in this work support previous suggestions that the currently known sources of glyoxal are insufficient to explain the average MBL concentrations. This suggests that there is an additional missing source, more than a magnitude larger than currently known sources, which is necessary to account for the observed atmospheric levels of glyoxal. Therefore, it could play a more important role in the MBL than previously considered.

[1] The behavior of lower atmospheric ozone and ozone exchanges at the snow surface were studied using a suite of platforms during the Ocean-Atmosphere-Sea Ice-Snow (OASIS) Spring 2009 experiment at an inland, coastal site east of Barrow, Alaska. A major objective was to investigate if and how much chemistry at the snow surface at the site contributes to springtime ozone depletion events (ODEs). Between March 8 and April 16, seven ODEs, with atmospheric ozone dropping below 1.0 ppbv, were observed. The depth of the ozone-depleted layer was variable, extending from the surface to ∼200–800 m. ODEs most commonly occurred during low wind speed conditions with flow coming from the Arctic Ocean. Two high-sensitivity ozone chemiluminescence instruments were used to accurately define the remaining sub-ppbv ozone levels during ODEs. These measurements showed variable residual ODE ozone levels ranging between 0.010 and 0.100 ppbv. During the most extended ODE, when ozone remained below 1.0 ppbv for over 78 h, these measurements showed a modest ozone recovery or production in the early afternoon hours, resulting in increases in the ozone mixing ratio of 0.100 to 0.800 ppbv. The comparison between high-sensitivity ozone measurements and BrO measured by longpath differential absorption spectroscopy (DOAS) during ODEs indicated that at low ozone levels formation of BrO is controlled by the amount of available ozone. Measurements of ozone in air drawn from below the snow surface showed depleted ozone in the snowpack, with levels consistently remaining

[1] Multi AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations of the oxygen dimer O4 which can serve as a new method for the determination of atmospheric aerosol properties are presented. Like established methods, e.g., Sun radiometer and LIDAR measurements, MAX-DOAS O4 observations determine optical properties of aerosol under atmospheric conditions (not dried). However, the novel technique has two major advantages: It utilizes differential O4 absorption structures and thus does not require absolute radiometric calibration. In addition, O4 observations using this method provide a new kind of information: since the atmospheric O4 profile depends strongly on altitude, they can yield information on the atmospheric light path distribution and in particular on the atmospheric aerosol profile. From O4 observations during clear days and from atmospheric radiative transfer modeling, we conclude that our new method is especially sensitive to the aerosol extinction close to the ground. In addition, O4 observations using this method yield information on the penetration depth of the incident direct solar radiation. O4 observations at different azimuth angles can also provide information on the aerosol scattering phase function. We found that MAX-DOAS O4 observations are a very sensitive method: even aerosol extinction below 0.001 could be detected. In addition to the O4 absorptions we also investigated the magnitude of the Ring effect and the (relative) intensity. Both quantities yield valuable further information on atmospheric aerosols. From the simultaneous analysis of the observed O4 absorption and the measured intensity, in particular, information on the absorbing properties of the aerosols might be derived. The aerosol information derived from MAX-DOAS observations can be used for the quantitative analysis of various trace gases also analyzed from the measured spectra.

[1] We investigate chemistry and dynamics of bromine explosion events during Antarctic spring of 1999 and 2000 using ground-based differential optical absorption spectroscopy (DOAS) observations of BrO, surface ozone, and ozone sounding measurements performed at the German research station Neumayer, located at the coast of the Antarctic continent (70°39′S, 8°15′W). BrO maps from the GOME satellite instrument show huge areas of elevated BrO above the sea ice around Antarctica, covering several thousand square kilometers. Although the Neumayer station is located at a distance of only 7 km to the coast, bromine-activated air masses are only detected by our ground-based DOAS instrument under particular meteorological conditions. We use trajectory calculations in high temporal and spatial resolution in combination with sea ice maps to determine the source of air masses arriving at Neumayer. A comparison of these model calculations with measurements is in very good agreement with the theory that reactive bromine is heterogeneously released by sea-salt surfaces: in the majority of cases, enhanced levels of BrO are observed whenever a part of the probed air masses was previously in contact with sea ice surfaces, while depletion of surface ozone occurs only if the air at ground comes from the ice covered ocean. After being uplifted by advection processes, bromine-activated and ozone-depleted air masses are sometimes observed at high altitudes (>4000 m). This vertical transport of reactive bromine may have an impact on the free tropospheric ozone budget and on local climate in the Antarctic coastal region during springtime. BrO enhancements are usually accompanied by strong increases in light path (as detected by O4) owing to multiple scattering on aerosols, supporting the assumption that sea-salt particles, on which BrO recycling can take place, are present at the observation site.