Abstract. Satellite observations from the SCIAMACHY, GOME-2 and OMI spectrometers have been used to retrieve atmospheric columns of glyoxal (CHOCHO) with the DOAS method. High CHOCHO levels were found over regions with large biogenic and pyrogenic emissions, and hot-spots have been identified over areas of anthropogenic activities.This study focuses on the development of an improved retrieval for CHOCHO from measurements by the OMI instrument. From sensitivity tests, a fitting window and a polynomial degree are determined. Two different approaches to reduce the interference of liquid water absorption over oceanic regions are evaluated, achieving significant reduction of the number of negative columns over clear water regions. The impact of using different absorption cross-sections for water vapour is evaluated and only small differences are found. Finally, a high-temperature (boundary layer ambient: 294 K) absorption cross-section of nitrogen dioxide (NO 2 ) is introduced in the DOAS retrieval to account for potential interferences of NO 2 over regions with large anthropogenic emissions, leading to improved fit quality over these areas. A comparison with vertical CHOCHO columns retrieved from GOME-2 and SCIAMACHY measurements over continental regions is performed, showing overall good consistency. However, SCIAMACHY CHOCHO columns are systematically higher than those obtained from the other instruments.Using the new OMI CHOCHO data set, the link between fires and glyoxal columns is investigated for two selected regions in Africa. In addition, mapped averages are computed for a fire event in Russia between mid-July and midAugust 2010. In both cases, enhanced CHOCHO levels are found in close spatial and temporal proximity to elevated levels of MODIS fire radiative power, demonstrating that pyrogenic emissions can be clearly identified in the new OMI CHOCHO product.

Abstract. Multi-axis differential optical absorption spectroscopy (MAX-DOAS) is a widely used measurement technique for the detection of a variety of atmospheric trace gases. Using inverse modelling, the observation of trace gas column densities along different lines of sight enables the retrieval of aerosol and trace gas vertical profiles in the atmospheric boundary layer using appropriate retrieval algorithms. In this study, the ability of eight profile retrieval algorithms to reconstruct vertical profiles is assessed on the basis of synthetic measurements. Five of the algorithms are based on the optimal estimation method, two on parametrised approaches, and one using an analytical approach without involving any radiative transfer modelling. The synthetic measurements consist of the median of simulated slant column densities of O4 at 360 and 477 nm, as well as of HCHO at 343 nm and NO2 at 477 nm, from seven datasets simulated by five different radiative transfer models. Simulations are performed for a combination of 10 trace gas and 11 aerosol profiles, as well as 11 elevation angles, three solar zenith, and three relative azimuth angles. Overall, the results from the different algorithms show moderate to good performance for the retrieval of vertical profiles, surface concentrations, and total columns. Except for some outliers, the root-mean-square difference between the true and retrieved state ranges between (0.05–0.1) km−1 for aerosol extinction and (2.5–5.0) ×1010 molec cm−3 for HCHO and NO2 concentrations.

Abstract. Long-range transport followed by deposition of black carbon on glaciers of Tibet is one of the key issues of climate research as it induces changes on radiative forcing and subsequently impacting the melting of glaciers. The transport mechanism, however, is not well understood. In this study, we use short-lived reactive aromatics as proxies to diagnose transport of pollutants to Tibet. In situ observations of short-lived reactive aromatics across the Tibetan Plateau are analyzed using a regional chemistry and transport model. The model performance using the current emission inventories over the region is poor due to problems in the inventories and model transport. Top-down emissions constrained by satellite observations of glyoxal are a factor of 2–6 higher than the a priori emissions over the industrialized Indo-Gangetic Plain. Using the top-down emissions, agreement between model simulations and surface observations of aromatics improves. We find enhancements of reactive aromatics over Tibet by a factor of 6 on average due to rapid transport from India and nearby regions during the presence of a high-altitude cut-off low system. Our results suggest that the cut-off low system is a major pathway for long-range transport of pollutants such as black carbon. The modeling analysis reveals that even the state-of-the-science high-resolution reanalysis cannot simulate this cut-off low system accurately, which probably explains in part the underestimation of black carbon deposition over Tibet in previous modeling studies. Another model deficiency of underestimating pollution transport from the south is due to the complexity of terrain, leading to enhanced transport. It is therefore challenging for coarse-resolution global climate models to properly represent the effects of long-range transport of pollutants on the Tibetan environment and the subsequent consequence for regional climate forcing.

Abstract. Glyoxal (CHOCHO) and formaldehyde (HCHO) are intermediate products in the tropospheric oxidation of the majority of volatile organic compounds (VOCs). CHOCHO is also a precursor of secondary organic aerosol (SOA) in the atmosphere. CHOCHO and HCHO are released from biogenic, anthropogenic, and pyrogenic sources. CHOCHO and HCHO tropospheric lifetimes are typically considered to be short during the daytime at mid-latitudes (e.g. several hours), as they are rapidly removed from the atmosphere by their photolysis, oxidation by OH, and uptake on particles or deposition. At night and at high latitudes, tropospheric lifetimes increase to many hours or even days. Previous studies demonstrated that CHOCHO and HCHO vertical column densities (VCDs) are well retrieved from space-borne observations using differential optical absorption spectroscopy (DOAS). In this study, we present CHOCHO and HCHO VCDs retrieved from measurements by TROPOMI (TROPOspheric Monitoring Instrument), launched on the Sentinel-5 Precursor (S5P) platform in October 2017. We observe strongly elevated amounts of CHOCHO and HCHO during the 2018 fire season in British Columbia, Canada, where a large number of fires occurred in August. CHOCHO and HCHO plumes from individual fire hot spots are observed in air masses travelling over distances of up to 1500 km, i.e. much longer than expected for the relatively short tropospheric lifetime expected for CHOCHO and HCHO. Comparison with simulations by the particle dispersion model FLEXPART (FLEXible PARTicle dispersion model) indicates that effective lifetimes of 20 h and more are needed to explain the observations of CHOCHO and HCHO if they decay in an effective first-order process. FLEXPART used in the study calculates accurately the transport. In addition an exponential decay, in our case assumed to be photochemical, of a species along the trajectory is added. We have used this simple approach to test our assumption that CHOCHO and HCHO are created in the fires and then decay at a constant rate in the plume as it is transported. This is clearly not the case and we infer that CHOCHO and HCHO are either efficiently recycled during transport or continuously formed from the oxidation of longer-lived precursors present in the plume, or possibly a mixture of both. We consider the best explanation of the observed CHOCHO and HCHO VCD in the plumes of the fire is that they are produced by oxidation of longer-lived precursors, which were also released by the fire and present in the plume.

Abstract. Spectral effects of liquid water are present in absorption (differential optical absorption spectroscopy -DOAS) measurements above the ocean and, if insufficiently removed, may interfere with trace gas absorptions, leading to wrong results. Currently available literature cross sections of liquid water absorption are provided in coarser resolution than DOAS applications require, and vibrational Raman scattering (VRS) is mostly not considered, or is compensated for using simulated pseudo cross sections from radiative transfer modeling.During the ship-based TransBrom campaign across the western Pacific in October 2009, MAX-DOAS (Multi-AXis differential optical absorption spectroscopy) measurements of light penetrating very clear natural waters were performed, achieving average underwater light paths of up to 50 m. From these measurements, the retrieval of a correction spectrum (H 2 O corr ) is presented, compensating simultaneously for insufficiencies in the liquid water absorption cross section and broad-banded VRS structures. Small-banded structures caused by VRS were found to be very efficiently compensated for by the intensity offset correction included in the DOAS fit. No interference between the H 2 O corr spectrum and phytoplankton absorption was found.In the MAX-DOAS tropospheric NO 2 retrieval, this method was able to compensate entirely for all liquid water effects that decrease the fit quality, and performed better than using a liquid water cross section in combination with a simulated VRS spectrum. The decrease in the residual root mean square (rms) of the DOAS fit depends on the measurement's contamination with liquid water structures, and ranges from ≈ 30 % for measurements slightly towards the water surface to several percent in small angles above the horizon. Furthermore, the H 2 O corr spectrum was found to prevent misfits of NO 2 slant columns, especially for very low NO 2 scenarios, and thus increases the reliability of the fit. In test fits on OMI satellite data, the H 2 O corr spectrum was found selectively above ocean surfaces, where it decreases the rms by up to ≈ 11 %.