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We introduce the new Global Ozone Monitoring Experiment-2 (GOME-2) daily and monthly level-3 product of total column ozone (O3), total and tropospheric column nitrogen dioxide (NO2), total column water vapour, total column bromine oxide (BrO), total column formaldehyde (HCHO), and total column sulfur dioxide (SO2) (daily products 10.15770/EUM-SAF-AC-0048, ; monthly products 10.15770/EUM-SAF-AC-0049, ). The GOME-2 level-3 products aim to provide easily translatable and user-friendly data sets to the scientific community for scientific progress as well as to satisfy public interest. The purpose of this paper is to present the theoretical basis as well as the verification and validation of the GOME-2 daily and monthly level-3 products. The GOME-2 level-3 products are produced using the overlapping area-weighting method. Details of the gridding algorithm are presented. The spatial resolution of the GOME-2 level-3 products is selected based on the sensitivity study. The consistency of the resulting level-3 products among three GOME-2 sensors is investigated through time series of global averages, zonal averages, and bias. The accuracy of the products is validated by comparison to ground-based observations. The verification and validation results show that the GOME-2 level-3 products are consistent with the level-2 data. Small discrepancies are found among three GOME-2 sensors, which are mainly caused by the differences in the instrument characteristic and level-2 processor. The comparison of GOME-2 level-3 products to ground-based observations in general shows very good agreement, indicating that the products are consistent and fulfil the requirements to serve the scientific community and general public.

In September 2016, 36 spectrometers from 24 institutes measured a number of key atmospheric pollutants for a period of 17¿d during the Second Cabauw Intercomparison campaign for Nitrogen Dioxide measuring Instruments (CINDI-2) that took place at Cabauw, the Netherlands (51.97¿¿N, 4.93¿¿E). We report on the outcome of the formal semi-blind intercomparison exercise, which was held under the umbrella of the Network for the Detection of Atmospheric Composition Change (NDACC) and the European Space Agency (ESA). The three major goals of CINDI-2 were (1) to characterise and better understand the differences between a large number of multi-axis differential optical absorption spectroscopy (MAX-DOAS) and zenith-sky DOAS instruments and analysis methods, (2) to define a robust methodology for performance assessment of all participating instruments, and (3) to contribute to a harmonisation of the measurement settings and retrieval methods. This, in turn, creates the capability to produce consistent high-quality ground-based data sets, which are an essential requirement to generate reliable long-term measurement time series suitable for trend analysis and satellite data validation. The data products investigated during the semi-blind intercomparison are slant columns of nitrogen dioxide (NO2), the oxygen collision complex (O4) and ozone (O3) measured in the UV and visible wavelength region, formaldehyde (HCHO) in the UV spectral region, and NO2 in an additional (smaller) wavelength range in the visible region. The campaign design and implementation processes are discussed in detail including the measurement protocol, calibration procedures and slant column retrieval settings. Strong emphasis was put on the careful alignment and synchronisation of the measurement systems, resulting in a unique set of measurements made under highly comparable air mass conditions. The CINDI-2 data sets were investigated using a regression analysis of the slant columns measured by each instrument

We present the inter-comparison of delta slant column densities (SCDs) and vertical profiles of nitrous acid (HONO) derived from measurements of different multiaxis differential optical absorption spectroscopy (MAXDOAS) instruments and using different inversion algorithms during the Second Cabauw Inter-comparison campaign for Nitrogen Dioxide measuring Instruments (CINDI- 2) in September 2016 at Cabauw, the Netherlands (51.97° N, 4.93° E). The HONO vertical profiles, vertical column densities (VCDs), and near-surface volume mixing ratios are compared between different MAX-DOAS instruments and profile inversion algorithms for the first time. Systematic and random discrepancies of the HONO results are derived from the comparisons of all data sets against their median values. Systematic discrepancies of HONO delta SCDs are observed in the range of ±0:3×1015 molec. cm2, which is half of the typical random discrepancy of 0:6× 1015 molec. cm2. For a typical high HONO delta SCD of 2×1015 molec. cm2, the relative systematic and random discrepancies are about 15% and 30 %, respectively. The inter-comparison of HONO profiles shows that both systematic and random discrepancies of HONO VCDs and nearsurface volume mixing ratios (VMRs) are mostly in the range of ∼ ±0:5×1014 molec. cm2 and ∼ ±0:1 ppb (typically ∼ 20 %). Further we find that the discrepancies of the retrieved HONO profiles are dominated by discrepancies of the HONO delta SCDs. The profile retrievals only contribute to the discrepancies of the HONO profiles by ∼ 5 %. However, some data sets with substantially larger discrepancies than the typical values indicate that inappropriate implementations of profile inversion algorithms and configurations of radiative transfer models in the profile retrievals can also be an important uncertainty source. In addition, estimations of measurement uncertainties of HONO dSCDs, which can significantly impact profile retrievals using the optimal estimation method, need to consider n

Multi-axis differential optical absorption spectroscopy (MAX-DOAS) and direct sun NO2 vertical column network data are used to investigate the accuracy of tropospheric NO2 column measurements of the GOME-2 instrument on the MetOp-A satellite platform and the OMI instrument on Aura. The study is based on 23 MAX-DOAS and 16 direct sun instruments at stations distributed worldwide. A method to quantify and correct for horizontal dilution effects in heterogeneous NO2 field conditions is proposed. After systematic application of this correction to urban sites, satellite measurements are found to present smaller biases compared to ground-based reference data in almost all cases. We investigate the seasonal dependence of the validation results as well as the impact of using different approaches to

In September 2016, 36 spectrometers from 24 institutes measured a number of key atmospheric pollutants for a period of 17 d during the Second Cabauw Intercomparison campaign for Nitrogen Dioxide measuring Instruments (CINDI-2) that took place at Cabauw, the Netherlands (51.97 degrees N, 4.93 degrees E). We report on the outcome of the formal semi-blind intercomparison exercise, which was held under the umbrella of the Network for the Detection of Atmospheric Composition Change (NDACC) and the European Space Agency (ESA). The three major goals of CINDI-2 were (1) to characterise and better understand the differences between a large number of multi-axis differential optical absorption spectroscopy (MAX-DOAS) and zenith-sky DOAS instruments and analysis methods, (2) to define a robust methodology for performance assessment of all participating instruments, and (3) to contribute to a harmonisation of the measurement settings and retrieval methods. This, in turn, creates the capability to produce consistent high-quality ground-based data sets, which are an essential requirement to generate reliable long-term measurement time series suitable for trend analysis and satellite data validation. The data products investigated during the semi-blind intercomparison are slant columns of nitrogen dioxide (NO2), the oxygen collision complex (O-4) and ozone (O-3) measured in the UV and visible wavelength region, formaldehyde (HCHO) in the UV spectral region, and NO2 in an additional (smaller) wavelength range in the visible region. The campaign design and implementation processes are discussed in detail including the measurement protocol, calibration procedures and slant column retrieval settings. Strong emphasis was put on the careful alignment and synchronisation of the measurement systems, resulting in a unique set of measurements made under highly comparable air mass conditions. The CINDI-2 data sets were investigated using a regression analysis of the slant columns measured by

In this study the consistency between MAX-DOAS measurements and radiative transfer simulations of the atmospheric O absorption is investigated on 2 mainly cloud-free days during the MAD-CAT campaign in Mainz, Germany, in summer 2013. In recent years several studies indicated that measurements and radiative transfer simulations of the atmospheric O absorption can only be brought into agreement if a so-called scaling factor (<1) is applied to the measured O absorption. However, many studies, including those based on direct sunlight measurements, came to the opposite conclusion, that there is no need for a scaling factor. Up to now, there is no broad consensus for an explanation of the observed discrepancies between measurements and simulations. Previous studies inferred the need for a scaling factor from the comparison of the aerosol optical depths derived from MAX-DOAS O measurements with that derived from coincident sun photometer measurements. In this study a different approach is chosen: the measured O absorption at 360nm is directly compared to the O absorption obtained from radiative transfer simulations. The atmospheric conditions used as input for the radiative transfer simulations were taken from independent data sets, in particular from sun photometer and ceilometer measurements at the measurement site. This study has three main goals: first all relevant error sources of the spectral analysis, the radiative transfer simulations and the extraction of the input parameters used for the radiative transfer simulations are quantified. One important result obtained from the analysis of synthetic spectra is that the O absorptions derived from the spectral analysis agree within 1% with the corresponding radiative transfer simulations at 360nm. Based on the results from sensitivity studies, recommendations for optimised settings for the spectral analysis and radiative transfer simulations are given. Second, the measured and simulated results are compared for 2 selecte

Toxic nitrogen oxides produced by high temperature combustion are prevalent in urban environments, contributing to a significant health burden. Nitrogen oxides such as NO2 and HONO in pollution are important for hydroxyl radical (OH) production and overall oxidative capacity in urban environments; however, current mechanisms cannot explain high daytime levels of HONO observed in many urban and rural locations around the world. Here we present HONO, NO2 and aerosol extinction vertical distributions retrieved from multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements in suburban Melbourne, which are the first MAX-DOAS results from the Australian continent. Using the optimal estimation algorithm HEIPRO we show that vertical profiles for NO2 and HONO can be calculated with a low dependence on the retrieval forward model and a priori parameters, despite a lack of independent co-located aerosol or trace gas measurements. Between December 2016 and April 2017 average peak NO2 values of 8±2ppb indicated moderate traffic pollution levels, and high daytime peak values of HONO were frequently detected, averaging 220±30ppt in the middle of the day. HONO levels measured in Melbourne were typically lower than those recorded in the morning in other places around the world, indicating minimal overnight accumulation, but peaked in the middle of the day to be commensurate with midday concentrations in locations with much higher NO2 pollution. Regular midday peaks in the diurnal cycle of HONO surface concentrations have only previously been reported in rural locations. The HONO measured implies a daytime source term 1ppbh−1 above the predicted photostationary state (PSS) concentration and represents an OH radical source up to 4 times stronger than from ozone photolysis alone in the lowest 500m of the troposphere. The dependence of the high midday HONO levels on soil moisture, combined with the observed diurnal and vertical profiles, provides evidence for a str

Toxic nitrogen oxides produced by high temperature combustion are prevalent in urban environments, contributing to a significant health burden. Nitrogen oxides such as NO2 and HONO in pollution are important for hydroxyl radical (OH) production and overall oxidative capacity in urban environments; however, current mechanisms cannot explain high daytime levels of HONO observed in many urban and rural locations around the world. Here we present HONO, NO2 and aerosol extinction vertical distributions retrieved from multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements in suburban Melbourne, which are the first MAX-DOAS results from the Australian continent. Using the optimal estimation algorithm HEIPRO we show that vertical profiles for NO2 and HONO can be calculated with a low dependence on the retrieval forward model and a priori parameters, despite a lack of independent co-located aerosol or trace gas measurements. Between December 2016 and April 2017 average peak NO2 values of 8±2ppb indicated moderate traffic pollution levels, and high daytime peak values of HONO were frequently detected, averaging 220±30ppt in the middle of the day. HONO levels measured in Melbourne were typically lower than those recorded in the morning in other places around the world, indicating minimal overnight accumulation, but peaked in the middle of the day to be commensurate with midday concentrations in locations with much higher NO2 pollution. Regular midday peaks in the diurnal cycle of HONO surface concentrations have only previously been reported in rural locations. The HONO measured implies a daytime source term 1ppbh−1 above the predicted photostationary state (PSS) concentration and represents an OH radical source up to 4 times stronger than from ozone photolysis alone in the lowest 500m of the troposphere. The dependence of the high midday HONO levels on soil moisture, combined with the observed diurnal and vertical profiles, provides evidence for a str

Halocarbons are produced naturally in the oceans by biological and chemical processes. They are emitted from surface seawater into the atmosphere, where they take part in numerous chemical processes such as ozone destruction and the oxidation of mercury and dimethyl sulfide. Here we present oceanic and atmospheric halocarbon data for the Peruvian upwelling zone obtained during the M91 cruise onboard the research vessel METEOR in December 2012. Surface waters during the cruise were characterized by moderate concentrations of bromoform (CHBr3) and dibromomethane (CH2Br2) correlating with diatom biomass derived from marker pigment concentrations, which suggests this phytoplankton group is a likely source. Concentrations measured for the iodinated compounds methyl iodide (CH3I) of up to 35.4 pmol L−1, chloroiodomethane (CH2ClI) of up to 58.1 pmol L−1 and diiodomethane (CH2I2) of up to 32.4 pmol L−1 in water samples were much higher than previously reported for the tropical Atlantic upwelling systems. Iodocarbons also correlated with the diatom biomass and even more significantly with dissolved organic matter (DOM) components measured in the surface water. Our results suggest a biological source of these compounds as a significant driving factor for the observed large iodocarbon concentrations. Elevated atmospheric mixing ratios of CH3I (up to 3.2 ppt), CH2ClI (up to 2.5 ppt) and CH2I2 (3.3 ppt) above the upwelling were correlated with seawater concentrations and high sea-to-air fluxes. During the first part of the cruise, the enhanced iodocarbon production in the Peruvian upwelling contributed significantly to tropospheric iodine levels, while this contribution was considerably smaller during the second part.

Halocarbons are produced naturally in the oceans by biological and chemical processes. They are emitted from surface seawater into the atmosphere, where they take part in numerous chemical processes such as ozone destruction and the oxidation of mercury and dimethyl sulfide. Here we present oceanic and atmospheric halocarbon data for the Peruvian upwelling zone obtained during the M91 cruise onboard the research vessel METEOR in December 2012. Surface waters during the cruise were characterized by moderate concentrations of bromoform (CHBr3) and dibromomethane (CH2Br2) correlating with diatom biomass derived from marker pigment concentrations, which suggests this phytoplankton group is a likely source. Concentrations measured for the iodinated compounds methyl iodide (CH3I) of up to 35.4 pmol L−1, chloroiodomethane (CH2ClI) of up to 58.1 pmol L−1 and diiodomethane (CH2I2) of up to 32.4 pmol L−1 in water samples were much higher than previously reported for the tropical Atlantic upwelling systems. Iodocarbons also correlated with the diatom biomass and even more significantly with dissolved organic matter (DOM) components measured in the surface water. Our results suggest a biological source of these compounds as a significant driving factor for the observed large iodocarbon concentrations. Elevated atmospheric mixing ratios of CH3I (up to 3.2 ppt), CH2ClI (up to 2.5 ppt) and CH2I2 (3.3 ppt) above the upwelling were correlated with seawater concentrations and high sea-to-air fluxes. During the first part of the cruise, the enhanced iodocarbon production in the Peruvian upwelling contributed significantly to tropospheric iodine levels, while this contribution was considerably smaller during the second part.

Multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements were performed in the urban environment of Madrid, Spain, from March to September 2015. The O4 absorption in the ultraviolet (UV) spectral region was used to retrieve the aerosol extinction profile using an inversion algorithm. The results show a good agreement between the hourly retrieved aerosol optical depth (AOD) and the correlative Aerosol Robotic Network (AERONET) product, with a correlation coefficient of R=0.87. Higher AODs are found in the summer season due to the more frequent occurrence of Saharan dust intrusions. The surface aerosol extinction coefficient as retrieved by the MAX-DOAS measurements was also compared to in situ PM2.5 concentrations. The level of agreement between both measurements indicates that the MAX-DOAS retrieval has the ability to characterize the extinction of aerosol particles near the surface. The retrieval algorithm was also used to study a case of severe dust intrusion on 12 May 2015. The capability of the MAX-DOAS retrieval to recognize the dust event including an elevated particle layer is investigated along with air mass back-trajectory analysis.

Halocarbons are produced naturally in the oceans by biological and chemical processes. They are emitted from surface seawater into the atmosphere, where they take part in numerous chemical processes such as ozone destruction and the oxidation of mercury and dimethyl sulfide. Here we present oceanic and atmospheric halocarbon data for the Peruvian upwelling zone obtained during the M91 cruise onboard the research vessel METEOR in December 2012. Surface waters during the cruise were characterized by moderate concentrations of bromoform (CHBr3) and dibromomethane (CH2Br2) correlating with diatom biomass derived from marker pigment concentrations, which suggests this phytoplankton group is a likely source. Concentrations measured for the iodinated compounds methyl iodide (CH3I) of up to 35.4 pmol L−1, chloroiodomethane (CH2ClI) of up to 58.1 pmol L−1 and diiodomethane (CH2I2) of up to 32.4 pmol L−1 in water samples were much higher than previously reported for the tropical Atlantic upwelling systems. Iodocarbons also correlated with the diatom biomass and even more significantly with dissolved organic matter (DOM) components measured in the surface water. Our results suggest a biological source of these compounds as a significant driving factor for the observed large iodocarbon concentrations. Elevated atmospheric mixing ratios of CH3I (up to 3.2 ppt), CH2ClI (up to 2.5 ppt) and CH2I2 (3.3 ppt) above the upwelling were correlated with seawater concentrations and high sea-to-air fluxes. During the first part of the cruise, the enhanced iodocarbon production in the Peruvian upwelling contributed significantly to tropospheric iodine levels, while this contribution was considerably smaller during the second part.

Multi-Axis Differential Optical Absorption Spectroscopy (MAXDOAS)is a widely used technique for the detection of atmospheric trace gases, e.g. NO2, SO2, but also for the oxygen collision complex O4, whose atmospheric distribution is well known. By comparing measured O4 differential slant column densities (dSCDs) with modelled ones, information on aerosol distributions and optical properties can be gained. In combination with a radiative transfer model, an inversion of measured dSCDs allows the retrieval of vertical aerosol extinction profiles and properties. Here the ability of MAX-DOAS observations to detect cloud altitude and cloud optical properties of different cloud covers will be discussed. An accurate retrieval of these parameters is crucial for an interpretation of trace gas dSCDs and a subsequent retrieval of vertical profiles from MAX-DOAS measurements under cloudy conditions. The ability of MAX-DOAS to retrieve cloud layer height and optical properties will be demonstrated with a comparison to co-located measurements of a commercial Ceilometer during several cruises of the German research vessel Polarstern. Advantages, limitations and possible applications of the technique will be discussed.

Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) is a widely used technique for the detection of atmospheric trace gases, e.g. NO2, SO2, BrO, HCHO, but also for the oxygen collision complex O4. The atmospheric distribution of the latter is proportional to the square of the molecular oxygen concentration and thus well known. By comparing measured O4 differential slant column densities (dSCDs) from MAX-DOAS measurements with modeled ones, information on aerosol distributions and optical properties, as well as on clouds can be obtained using an algorithm based on optimal estimation. Here the ability of MAX-DOAS observations to detect cloud altitude and cloud optical properties of different cloud covers based on measurements of O4 will be discussed. The analysis uses measurements made by a shipborne instrument on two cruises of the German research vessel Polarstern to the Antarctic Weddell Sea from June to October 2013. During this time a broad range of cloud and aerosol conditions was encountered, in particular persistent low cloud cover with a high optical thickness. Aerosol and particle extinction profiles were retrieved with temporal resolutions of up to 15 minutes. For clouds at altitudes up to 2000 m the results show a very good agreement with co-located measurements of a commercial ceilometer and pictures from a cloud camera. Unless visibility was very poor due to fog, even rapid changes in cloud altitude or cover could be detected by MAX-DOAS. These results indicate that under homogeneous cloud cover an accurate retrieval of trace gas vertical profiles can be possible despite the strong influence of clouds on atmospheric light paths. We will discuss advantages and limitations of cloud detection with MAX-DOAS, implications for the subsequent retrieval of trace gas profiles and the possible use of external (ceilometer) data as a priori information for the profile retrieval algorithm.

Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) is a widely used technique for the detection of atmospheric trace gases, e.g. NO2, SO2, BrO, HCHO, but also for the oxygen collision complex O4. The atmospheric distribution of the latter is proportional to the square of the molecular oxygen concentration and thus well known. By comparing measured O4 differential slant column densities (dSCDs) from MAX-DOAS measurements with modeled ones, information on aerosol distributions and optical properties, as well as on clouds can be obtained using an algorithm based on optimal estimation. Here the ability of MAX-DOAS observations to detect cloud altitude and cloud optical properties of different cloud covers based on measurements of O4 will be discussed. The analysis uses measurements made by a shipborne instrument on two cruises of the German research vessel Polarstern to the Antarctic Weddell Sea from June to October 2013. During this time a broad range of cloud and aerosol conditions was encountered, in particular persistent low cloud cover with a high optical thickness. Aerosol and particle extinction profiles were retrieved with temporal resolutions of up to 15 minutes. For clouds at altitudes up to 2000 m the results show a very good agreement with co-located measurements of a commercial ceilometer and pictures from a cloud camera. Unless visibility was very poor due to fog, even rapid changes in cloud altitude or cover could be detected by MAX-DOAS. These results indicate that under homogeneous cloud cover an accurate retrieval of trace gas vertical profiles can be possible despite the strong influence of clouds on atmospheric light paths. We will discuss advantages and limitations of cloud detection with MAX-DOAS, implications for the subsequent retrieval of trace gas profiles and the possible use of external (ceilometer) data as a priori information for the profile retrieval algorithm.

Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) is a widely used technique for the detection of atmospheric trace gases, e.g. NO2, SO2, BrO, HCHO, but also for the oxygen collision complex O4. The atmospheric distribution of the latter is proportional to the square of the molecular oxygen concentration and thus well known. By comparing measured O4 differential slant column densities (dSCDs) from MAX-DOAS measurements with modeled ones, information on aerosol distributions and optical properties, as well as on clouds can be obtained using an algorithm based on optimal estimation. Here the ability of MAX-DOAS observations to detect cloud altitude and cloud optical properties of different cloud covers based on measurements of O4 will be discussed. The analysis uses measurements made by a shipborne instrument on two cruises of the German research vessel Polarstern to the Antarctic Weddell Sea from June to October 2013. During this time a broad range of cloud and aerosol conditions was encountered, in particular persistent low cloud cover with a high optical thickness. Aerosol and particle extinction profiles were retrieved with temporal resolutions of up to 15 minutes. For clouds at altitudes up to 2000 m the results show a very good agreement with co-located measurements of a commercial ceilometer and pictures from a cloud camera. Unless visibility was very poor due to fog, even rapid changes in cloud altitude or cover could be detected by MAX-DOAS. These results indicate that under homogeneous cloud cover an accurate retrieval of trace gas vertical profiles can be possible despite the strong influence of clouds on atmospheric light paths. We will discuss advantages and limitations of cloud detection with MAX-DOAS, implications for the subsequent retrieval of trace gas profiles and the possible use of external (ceilometer) data as a priori information for the profile retrieval algorithm.

Multi-Axis Differential Optical Absorption Spectroscopy (MAXDOAS)is a widely used technique for the detection of atmospheric trace gases, e.g. NO2, SO2, but also for the oxygen collision complex O4, whose atmospheric distribution is well known. By comparing measured O4 differential slant column densities (dSCDs) with modelled ones, information on aerosol distributions and optical properties can be gained. In combination with a radiative transfer model, an inversion of measured dSCDs allows the retrieval of vertical aerosol extinction profiles and properties. Here the ability of MAX-DOAS observations to detect cloud altitude and cloud optical properties of different cloud covers will be discussed. An accurate retrieval of these parameters is crucial for an interpretation of trace gas dSCDs and a subsequent retrieval of vertical profiles from MAX-DOAS measurements under cloudy conditions. The ability of MAX-DOAS to retrieve cloud layer height and optical properties will be demonstrated with a comparison to co-located measurements of a commercial Ceilometer during several cruises of the German research vessel Polarstern. Advantages, limitations and possible applications of the technique will be discussed.

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 ten 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 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 (DOAS) 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.

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. Key Points Largest database of glyoxal in the MBL Levels of glyoxal in the MBL are lower than previously reported Additional source of glyoxal needed to explain observations ©2014. American Geophysical Union. All Rights Reserved.

Reactive halogen species (RHS) exert various influences on the photochemistry of the marine boundary layer. They are formed in the marine atmosphere for example from precursors released from sea salt aerosols, through the degradation of organo-halogens emitted by certain algae, or from inorganic aqueous reactions. The halogen radicals (BrO and IO) can destroy ozone catalytically, oxidize dimethyl sulfide (DMS) or cause the formation of new aerosol particles. However, there are still open questions concerning the abundance and significance of RHS in the marine boundary layer over the open ocean. Therefore, measurements of BrO and IO abundances were carried out during two ship cruises in two different parts of the ocean, i.e. the Western Pacific and the Eastern Tropical North Atlantic. The measurements were performed with Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS). From the spectral analysis of spectra of scattered sunlight recorded at different elevation angles, information about the vertical distribution and the concentration of trace gases can be derived. During the "TransBrom-Sonne" cruise on the German research vessel “Sonne” in the Western Pacific from Tomakomai, Japan (42°N/ 141°E) to Townsville, Australia (19°S/ 146°E) during October 2009, BrO could be detected in very small amounts in the marine boundary layer (MBL) close to Micronesia and Papua New Guinea, with maximum BrO mixing ratios around 2 ppt and a detection limit of 0.8 ppt. During the whole cruise, tropospheric IO clearly exceeded the detection limit of 0.6 ppt. The bulk of the IO was located in the lower troposphere up to 1 km. In the tropics, the IO concentration reached maximum values between 1 and 2.5 ppt. IO was measured in the Western Pacific for the first time and was used as input for model calculations of tropospheric chemistry. Further measurements of BrO and IO were carried out during a campaign on the German research vessel “Poseidon” in June 2010 in the Eastern N

Reactive halogen species (RHS) exert various influences on the photochemistry of the marine boundary layer. They are formed in the marine atmosphere for example from precursors released from sea salt aerosols, through the degradation of organo-halogens emitted by certain algae, or from inorganic aqueous reactions. The halogen radicals (BrO and IO) can destroy ozone catalytically, oxidize dimethyl sulfide (DMS) or cause the formation of new aerosol particles. However, there are still open questions concerning the abundance and significance of RHS in the marine boundary layer over the open ocean. Therefore, measurements of BrO and IO abundances were carried out during two ship cruises in two different parts of the ocean, i.e. the Western Pacific and the Eastern Tropical North Atlantic. The measurements were performed with Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS). From the spectral analysis of spectra of scattered sunlight recorded at different elevation angles, information about the vertical distribution and the concentration of trace gases can be derived. During the "TransBrom-Sonne" cruise on the German research vessel “Sonne” in the Western Pacific from Tomakomai, Japan (42°N/ 141°E) to Townsville, Australia (19°S/ 146°E) during October 2009, BrO could be detected in very small amounts in the marine boundary layer (MBL) close to Micronesia and Papua New Guinea, with maximum BrO mixing ratios around 2 ppt and a detection limit of 0.8 ppt. During the whole cruise, tropospheric IO clearly exceeded the detection limit of 0.6 ppt. The bulk of the IO was located in the lower troposphere up to 1 km. In the tropics, the IO concentration reached maximum values between 1 and 2.5 ppt. IO was measured in the Western Pacific for the first time and was used as input for model calculations of tropospheric chemistry. Further measurements of BrO and IO were carried out during a campaign on the German research vessel “Poseidon” in June 2010 in the Eastern N