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We report on airborne limb and nadir measurements of vertical profiles and total vertical column densities (VCDs) of glyoxal (C2H2O2) in the troposphere, which were performed aboard the German research aircraft HALO (High Altitude and LOng Range) in different regions and seasons around the globe between 2014 and 2019. The airborne nadir and integrated limb profiles agree excellently among each other. Our airborne observations are further compared to collocated glyoxal measurements of the TROPOspheric Monitoring Instrument (TROPOMI), with good agreement between both data sets for glyoxal observations in (1) pristine terrestrial, (2) pristine marine, (3) mixed polluted, and (4) biomass-burning-affected air masses with high glyoxal concentrations. Exceptions to the overall good agreement are observations of (1) faint and aged biomass burning plumes over the oceans and (2) of low-lying biomass burning or anthropogenic plumes in the terrestrial or marine boundary layer, both of which contain elevated glyoxal that is mostly not captured by TROPOMI. These differences in airborne and satellite-detected glyoxal are most likely caused by the overall small contribution of plumes of a limited extent to the total glyoxal absorption in the atmosphere and the difficulty in remotely detecting weak absorbers located close to low reflective surfaces (e.g. the ocean in the visible wavelength range) or within dense aerosol layers. Observations of glyoxal in aged biomass burning plumes (e.g. observed over the tropical Atlantic off the coast of West Africa in summer 2018, off the coast of Brazil by the end of the dry season 2019, and the East China Sea in spring 2018) could be traced back to related wildfires, such as a plume crossing over the Drake Passage that originated from the Australian bushfires in late 2019. Our observations of glyoxal in such aged biomass burning plumes confirm recent findings of enhanced glyoxal and presumably secondary organic aerosol (SOA) formation in aged wildfire plumes from yet-to-be-identified, longer-lived organic precursor molecules (e.g. aromatics, acetylene, or aliphatic compounds) co-emitted in the fires. Furthermore, elevated glyoxal (median 44 ppt – parts per trillion), as compared to other marine regions (median 10–19 ppt), is observed in the boundary layer over the tropical oceans, which is well in agreement with previous reports. The airborne data sets are further compared to glyoxal simulations performed with the global atmosphere chemistry model EMAC (ECHAM/MESSy Atmospheric Chemistry). When using an EMAC set up that resembles recent EMAC studies focusing on complex chemistry, reasonable agreement is found for pristine air masses (e.g. the unperturbed free and upper troposphere), but a notable glyoxal overestimation of the model exists for regions with high emissions of glyoxal and glyoxal-producing volatile organic compounds (VOCs) from the biosphere (e.g. the Amazon). In all other investigated regions, the model underpredicts glyoxal to varying degrees, in particular when probing mixed emissions from anthropogenic activities (e.g. over continental Europe, the Mediterranean, and East China Sea) and potentially from the sea (e.g. the tropical oceans). Also, the model tends to largely underpredict glyoxal in city plumes and aged biomass burning plumes. The potential causes for these differences are likely to be multifaceted, but they all point to missing glyoxal sources from the degradation of the mixture of potentially longer-chained organic compounds emitted from anthropogenic activities, biomass burning, and from the organic microlayer of the sea surface.

Tropical Tropopause Layer cirrus clouds and their radiative effects represent a major uncertainty in the evaluation of Earth’s energy budget. High altitude aircraft offer an opportunity to provide observations at cirrus cloud altitudes, most commonly using in-situ measurements of ice particle optical properties and composition. In particular, remote sensing of scattering properties and near-IR ice water absorption in the limb can provide unique insights into thin and sub-visible cirrus clouds. Here we present novel spectroscopic observations of path-averaged ice water absorptions onboard NASA’s Global Hawk aircraft, during the Airborne Tropical TRopopause Experiment, which took place in 2011, 2013, and 2014. The University of California Los Angeles and University of Heidelberg mini-DOAS instrument provided multi-angle limb-scanning observations of scattered solar radiation in the near-IR (900–1726 nm), allowing the identification of ice and liquid water, O2, CO2 and H2O. The VLIDORT-QS radiative transfer (RT) code was specifically developed for this study and used to simulate high altitude limb observations for varied cloud scenarios. We performed a comprehensive sensitivity study, developing a fundamental understanding of airborne near-IR limb observations of cirrus clouds. We identified two general distinct cases: a linear regime for optically thin clouds, where the ice absorption is proportional to ice water content (IWC), and a regime for optically thick cirrus clouds, where ice absorption is in saturation and independent of IWC. Results also demonstrate how molecular oxygen absorption can be used to infer information on optical properties of ice particles in the second regime only, with minimal information for thin cirrus clouds. We also explored the feasibility of retrieving IWC from mini-DOAS path-averaged ice water absorption (SIWP) measurements. This innovative interpolation-based approach requires a small number of RT calculations per observation to determine the sensitivity of SIWP to IWC. Spectral retrievals were applied for a particularly interesting case during Science Flight 2 over Guam in February 2014, during which the aircraft flew in circles in the same general area for an extended period. Retrieved IWC results are consistent with independent in situ measurements from other instruments on board. The measurements of ice particle scattering and absorption at different azimuths relative to the sun and at different altitudes represents a unique opportunity to test our approach and to infer properties of the ice particles, together with information on cirrus cloud radiative transfer.

As we observe and expect severe changes in the Earth’ climate, the analyses of past climate state transitions is of major value for improving our Earth system understanding. Under this objective, the last deglaciation (~ 21 ka to 9 ka before present), the transition from the Last Glacial Maximum (LGM) to the Holocene, is an ideal case study. During this transition, the orbital configuration gradually changed and greenhouse gases have risen, which caused a sharp decline in northern hemisphere ice sheets and an increase in the global mean surface temperature.We create an ensemble of deglaciation simulations with a modified version of the Planet Simulator, an Earth system model of intermediate complexity (EMIC). We produce single and combined forcing simulations for further investigation from a thermodynamic perspective. The response to the transiently changing radiative forcing is investigated in terms of energy and entropy budgets of the atmosphere. Here, we focus on the deglacial evolution of the material entropy production (MEP). Its contributions represent the strength of major climate features such as the kinetic energy generation rate, vertical and horizontal heat transport and the hydrological cycle. Preliminary results show an increase of the global mean MEP from the LGM to the Holocene because of a strengthening of the hydrological contribution. In contrast, the relative importance of kinetic energy dissipation and turbulent heat diffusion in the boundary layer decrease. Our work can provide the basis for investigating the MEP as a diagnostic quantity with other models and for other climate state transitions.

Discrepancies between expected and observed NO-NO2 ratios in the upper troposphere suggest the presence of an unknown NOX reservoir. We report on airborne remote sensing limb observations from the mini-DOAS instrument on board the HALO (High Altitude Long Range) aircraft during the CAFÉ-Africa (Chemistry of the Atmosphere Field Experiment) campaign in 2018. Nitrous acid (HONO) slant column densities in limb scattered sunlight in the ultraviolet wavelength range retrieved by DOAS (Differential Optical Absorption Spectroscopy) are converted to volume mixing ratios using the O3 / O4 scaling method. Over the tropical Atlantic Ocean, in the cold upper troposphere, HONO is found in excess of what may be expected from known gas phase formation mechanisms or is predicted by the ECHAM/MESSy Atmospheric Chemistry (EMAC) model. At these altitudes (10-15 km), heterogeneous sources of the excess HONO are inefficient and thus unlikely. Therefore, we investigate the possibility of a gas phase HONO source, namely the oxidation of peroxynitrous acid (HOONO) formed in the reactions NO + HO2 and OH + NO2. Since there are no reported atmospheric measurements of HOONO, we use complementary, simultaneous in situ measurements of OH, NO, HO2, NO2, O3 and photolysis frequencies from onboard HALO to make steady state arguments and quantify reaction rate coefficients for both formation pathways and destruction of HOONO by O3, OH, and NO, the last of which may form HONO and NO2.

Halogenated organic and inorganic compounds, in particular those containing chlorine, bromine and iodine are known to contribute to the global ozone depletion as well as directly and indirectly to climate forcing. As a result of the Montreal Protocol (1987), the chlorine and bromine loadings of the stratosphere are closely monitored, while the role of iodinated compounds to the stratospheric ozone photochemistry is still uncertain.To address the questions concerning bromine and iodine compounds, a compact solar occultation instrument (TotalBrO) has been specifically designed to measure BrO, IO (iodine oxide) and other UV/Vis absorbing gases by means of Differential Optical Absorption Spectroscopy (DOAS) from aboard a stratospheric balloon. The instrument (power consumption < 100 W) comprises of an active camera-based solar tracker (LxWxH ~ 0.40 m x 0.40 m x 0.50 m, weight ~ 12 kg) and a spectrometer unit (LxWxH ~ 0.45 m x 0.40 m x 0.40 m, weight ~ 25 kg). The spectrometer unit houses two grating spectrometers which operate in vacuum and under temperature stabilization by an ice-water bath.We discuss the performance of the TotalBrO instrument during the first two deployments on stratospheric balloons launched from Kiruna in August, 2021 and from Timmins in August, 2022 within the HEMERA program. Once the balloon gondola was azimuthally stabilized the solar tracker was able to follow the sun with a 1σ precision lower than 0.02° up to solar zenith angles (SZAs) of 95°. The spectral retrieval (of 46 spectra acquired at SZA between 84° and 90°) allowed us to infer the BrO mixing ratio above 32 km altitude. The total bromine in the middle stratosphere is inferred by accounting for the BrO/Bry partitioning derived from a photochemical model.

Solar photovoltaic power output is modulated by atmospheric aerosols and clouds and thus contains valuable information on the optical properties of the atmosphere. As a ground-based data source with high spatiotemporal resolution it has great potential to complement other ground-based solar irradiance measurements as well as those of weather models and satellites, thus leading to an improved characterisation of global horizontal irradiance. In this work several algorithms are presented that can retrieve global tilted and horizontal irradiance and atmospheric optical properties from solar photovoltaic data and/or pyranometer measurements. Specifically, the aerosol (cloud) optical depth is inferred during clear sky (completely overcast) conditions. The method is tested on data from two measurement campaigns that took place in Allgäu, Germany in autumn 2018 and summer 2019, and the results are compared with local pyranometer measurements as well as satellite and weather model data. Using power data measured at 1 Hz and averaged to 1 minute resolution, the hourly global horizontal irradiance is extracted with a mean bias error compared to concurrent pyranometer measurements of 11.45 W m−2, averaged over the two campaigns, whereas for the retrieval using coarser 15 minute power data the mean bias error is 16.39 W m−2. During completely overcast periods the cloud optical depth is extracted from photovoltaic power using a lookup table method based on a one-dimensional radiative transfer simulation, and the results are compared to both satellite retrievals as well as data from the COSMO weather model. Potential applications of this approach for extracting cloud optical properties are discussed, as well as certain limitations, such as the representation of 3D radiative effects that occur under broken cloud conditions. In principle this method could provide an unprecedented amount of ground-based data on both irradiance and optical properties of the atmosphere, as long as the required photovoltaic power data are available and are properly pre-screened to remove unwanted artefacts in the signal. Possible solutions to this problem are discussed in the context of future work.

The Indochina biomass burning (BB) season in springtime has a substantial environmental impact on the surrounding areas in Asia. In this study, we evaluated the environmental impact of a major long-range BB transport event on 19 March 2018 (a flight of the High Altitude and Long Range Research Aircraft (HALO; https://www.halo-spp.de, last access: 14 February 2023) research aircraft, flight F0319) preceded by a minor event on 17 March 2018 (flight F0317). Aircraft data obtained during the campaign in Asia of the Effect of Megacities on the transport and transformation of pollutants on the Regional to Global scales (EMeRGe) were available between 12 March and 7 April 2018. In F0319, results of 1 min mean carbon monoxide (CO), ozone (O3), acetone (ACE), acetonitrile (ACN), organic aerosol (OA), and black carbon aerosol (BC) concentrations were up to 312.0, 79.0, 3.0, and 0.6 ppb and 6.4 and 2.5 µg m−3, respectively, during the flight, which passed through the BB plume transport layer (BPTL) between the elevation of 2000–4000 m over the East China Sea (ECS). During F0319, the CO, O3, ACE, ACN, OA, and BC maximum of the 1 min average concentrations were higher in the BPTL by 109.0, 8.0, 1.0, and 0.3 ppb and 3.0 and 1.3 µg m−3 compared to flight F0317, respectively. Sulfate aerosol, rather than OA, showed the highest concentration at low altitudes ( m) in both flights F0317 and F0319 resulting from the continental outflow in the ECS. The transport of BB aerosols from Indochina and its impacts on the downstream area were evaluated using a Weather Research Forecasting with Chemistry (WRF-Chem) model. The modeling results tended to overestimate the concentration of the species, with examples being CO (64 ppb), OA (0.3 µg m−3), BC (0.2 µg m−3), and O3 (12.5 ppb) in the BPTL. Over the ECS, the simulated BB contribution demonstrated an increasing trend from the lowest values on 17 March 2018 to the highest values on 18 and 19 March 2018 for CO, fine particulate matter (PM2.5), OA, BC, hydroxyl radicals (OH), nitrogen oxides (NOx), total reactive nitrogen (NOy), and O3; by contrast, the variation of J(O1D) decreased as the BB plume's contribution increased over the ECS. In the lower boundary layer ( m), the BB plume's contribution to most species in the remote downstream areas was %. However, at the BPTL, the contribution of the long-range transported BB plume was as high as 30 %–80 % for most of the species (NOy, NOx, PM2.5, BC, OH, O3, and CO) over southern China (SC), Taiwan, and the ECS. BB aerosols were identified as a potential source of cloud condensation nuclei, and the simulation results indicated that the transported BB plume had an effect on cloud water formation over SC and the ECS on 19 March 2018. The combination of BB aerosol enhancement with cloud water resulted in a reduction of incoming shortwave radiation at the surface in SC and the ECS by 5 %–7 % and 2 %–4 %, respectively, which potentially has significant regional climate implications.

Nitrogen oxides ( NO x ≡ NO + NO 2 ) are centrally involved in the photochemical processes taking place in the Earth's atmosphere. Measurements of NO2 , particularly in remote areas where concentrations are of the order of parts per trillion by volume (pptv), are still a challenge and subject to extensive research. In this study, we present NO2 measurements via photolysis–chemiluminescence during the research aircraft campaign CAFE Africa (Chemistry of the Atmosphere – Field Experiment in Africa) 2018 around Cabo Verde and the results of laboratory experiments to characterize the photolytic converter used. We find the NO2 reservoir species MPN (methyl peroxy nitrate) to produce the only relevant thermal interference in the converter under the operating conditions during CAFE Africa. We identify a memory effect within the conventional photolytic converter (type 1) associated with high NO concentrations and rapidly changing water vapor concentrations, accompanying changes in altitude during aircraft measurements, which is due to the porous structure of the converter material. As a result, NO2 artifacts, which are amplified by low conversion efficiencies, and a varying instrumental background adversely affect the NO2 measurements. We test and characterize an alternative photolytic converter (type 2) made from quartz glass, which improves the reliability of NO2 measurements in laboratory and field studies.

The electricity grid of the future will be built on renewable energy sources, which are highly variable and dependent on atmospheric conditions. In power grids with an increasingly high penetration of solar photovoltaics (PV), an accurate knowledge of the incoming solar irradiance is indispensable for grid operation and planning, and reliable irradiance forecasts are thus invaluable for energy system operators. In order to better characterise shortwave solar radiation in time and space, data from PV systems themselves can be used, since the measured power provides information about both irradiance and the optical properties of the atmosphere, in particular the cloud optical depth (COD). Indeed, in the European context with highly variable cloud cover, the cloud fraction and COD are important parameters in determining the irradiance, whereas aerosol effects are only of secondary importance.Within the BMWK-funded MetPVNet project (Meilinger et al., 2021), inversion algorithms were developed in order to infer global, direct and diffuse irradiance as well as atmospheric optical properties from PV power measurements, with the goal of assimilating this information into numerical weather prediction (NWP) models. In this work, both the DISORT 1D and MYSTIC 3D radiative transfer schemes within libRadtran ⁠ are used to extract cloud properties and irradiance from pyranometer and PV power data, from two measurement campaigns in Allgäu, Germany and under different weather conditions. The DISORT-based algorithm is able to accurately retrieve COD, direct and diffuse irradiance components as long as the cloud fraction is high enough, whereas under broken cloud conditions the presence of 3D effects can lead to large errors. Horizontal photon transport results in radiation overshoots at the edges of clouds, and here these deviations are quantified using simulated cloud fields with known cloud microphysical properties, for different degrees of irradiance variability. In addition, global horizontal irradiance is derived directly from tilted irradiance measurements and/or PV data using a lookup table based on these same cloud fields and MYSTIC 3D simulations. This work will provide the basis for future investigations using a larger number of PV systems and/or irradiance sensors to evaluate the improvements to irradiance and power forecasts that could be achieved by the assimilation of inferred irradiance into an NWP model.References:Meilinger, S., Herman-Czezuch, A., Kimiaie, N., Schirrmeister, C., Yousif, R., Geiss, S., Scheck, L., Weissmann, M., Gödde, F., Mayer, B., Zinner, T., Barry, J., Pfeilsticker, K., Kraiczy, M., Winter, K., Altayara, A., Reise, C., Rivera, M., Deneke, H., Witthuhn, J., Betcke, J., Schroedter-Homscheidt, M., Hofbauer, P. and Rindt, B.: Development of innovative satellite-based methods for improved PV yield prediction on different time scales for distribution grid level applications (MetPVNet)., IZNE Working Paper Series, doi:10.18418/978-3-96043-094-0, 2021.

Megacities and other major population centres (MPCs) worldwide are major sources of air pollution, both locally as well as downwind. The overall assessment and prediction of the impact of MPC pollution on tropospheric chemistry are challenging. The present work provides an overview of the highlights of a major new contribution to the understanding of this issue based on the data and analysis of the EMeRGe (Effect of Megacities on the transport and transformation of pollutants on the Regional to Global scales) international project. EMeRGe focuses on atmospheric chemistry, dynamics, and transport of local and regional pollution originating in MPCs. Airborne measurements, taking advantage of the long range capabilities of the High Altitude and LOng Range Research Aircraft (HALO, https://www.halo-spp.de, last access: 22 March 2022), are a central part of the project. The synergistic use and consistent interpretation of observational data sets of different spatial and temporal resolution (e.g. from ground-based networks, airborne campaigns, and satellite measurements) supported by modelling within EMeRGe provide unique insight to test the current understanding of MPC pollution outflows. In order to obtain an adequate set of measurements at different spatial scales, two field experiments were positioned in time and space to contrast situations when the photochemical transformation of plumes emerging from MPCs is large. These experiments were conducted in summer 2017 over Europe and in the inter-monsoon period over Asia in spring 2018. The intensive observational periods (IOPs) involved HALO airborne measurements of ozone and its precursors, volatile organic compounds, aerosol particles, and related species as well as coordinated ground-based ancillary observations at different sites. Perfluorocarbon (PFC) tracer releases and model forecasts supported the flight planning, the identification of pollution plumes, and the analysis of chemical transformations during transport. This paper describes the experimental deployment and scientific questions of the IOP in Europe. The MPC targets - London (United Kingdom; UK), the Benelux/Ruhr area (Belgium, the Netherlands, Luxembourg and Germany), Paris (France), Rome and the Po Valley (Italy), and Madrid and Barcelona (Spain) - were investigated during seven HALO research flights with an aircraft base in Germany for a total of 53 flight hours. An in-flight comparison of HALO with the collaborating UK-airborne platform Facility for Airborne Atmospheric Measurements (FAAM) took place to assure accuracy and comparability of the instrumentation on board. Overall, EMeRGe unites measurements of near- and far-field emissions and hence deals with complex air masses of local and distant sources. Regional transport of several European MPC outflows was successfully identified and measured. Chemical processing of the MPC emissions was inferred from airborne observations of primary and secondary pollutants and the ratios between species having different chemical lifetimes. Photochemical processing of aerosol and secondary formation or organic acids was evident during the transport of MPC plumes. Urban plumes mix efficiently with natural sources as mineral dust and with biomass burning emissions from vegetation and forest fires. This confirms the importance of wildland fire emissions in Europe and indicates an important but discontinuous contribution to the European emission budget that might be of relevance in the design of efficient mitigation strategies. The present work provides an overview of the most salient results in the European context, with these being addressed in more detail within additional dedicated EMeRGe studies. The deployment and results obtained in Asia will be the subject of separate publications., The HALO deployment during EMeRGe was funded by a consortium comprising the German Research Foundation (DFG) Priority Program HALO-SPP 1294, the Institute of Atmospheric Physics of DLR, the Max Planck Society (MPG), and the Helmholtz Association. Flora Kluge, Benjamin Schreiner, and Klaus Pfeilsticker acknowledge the support given by the DFG through the project nos. PF 384-16, PF 384-17, and PG 385-19. Ralf Koppmann and Marc Krebsbach acknowledge DFG funding through project no. KR3861_1-1. Katja Bigge acknowledges additional funding from the Heidelberg Graduate School for Physics. Johannes Schneider, Katharina Kaiser, and Stephan Borrmann acknowledge funding through the DFG (project no. 316589531). Lisa Eirenschmalz and Hans Schlager acknowledge support by DFG through project MEPOLL (SCHL1857/4-1). Anna B. Kalisz Hedegaard would like to thank DAAD and DLR for a Research Fellowship. Hans Schlager acknowledge financial support by the DLR TraK (Transport and Climate) project. Michael Sicard acknowledges support from the EU (GA nos. 654109, 778349, 871115, and 101008004) and the Spanish Government (ref. nos. CGL2017-90884-REDT, PID2019-103886RB-I00, RTI2018-096548-B-I00, and MDM-2016-0600). Midhun George, Yangzhuoran Liu, M. Dolores Andrés Hernández, and John Phillip Burrows acknowledge financial support from the University of Bremen. FLEXPART simulations were performed on the HPC cluster Aether at the University of Bremen, financed by DFG within the scope of the Excellence Initiative. Anne-Marlene Blechschmidt was partly funded through the CAMS-84 project. Jennifer Wolf acknowledges support from the German Federal Ministry for Economic Affairs and Energy – BMWi (project Digitally optimized Engineering for Services – DoEfS; contract no. 20X1701B). Theresa Harlass thanks DLR VO-R for funding the young investigator research group “Greenhouse Gases”. Mariano Mertens, Patrick Jöckel, and Markus Kilian acknowledge resources of the Deutsches Klimarechenzentrum (DKRZ) granted by the WLA project ID bd0617 for the MECO(n) simulations and the financial support from the DLR projects TraK (Transport und Klima) and the Initiative and Networking Fund of the Helmholtz Association through the project “Advanced Earth System Modelling Capacity” (ESM). Bruna A. Holanda acknowledges the funding from Brazilian CNPq (process 200723/2015-4). The article processing charges for this open-access publication were covered by the University of Bremen.

Glyoxal (CHOCHO) is the simplest and one of the most abundant atmospheric α-dicarbonyls. In the atmosphere, it is mainly produced by the oxidation of other non-methane volatile organic compounds originating from natural and anthropogenic sources. Against photooxidation, it has a rather short lifetime of about 1 to 3 hours. Due to its high solubility, it quickly partitions into cloud droplets and deliquescent aerosols where it is known to form oligomers leading to secondary organic aerosols (SOA). In order to assess its significance for air pollution, it is thus necessary that global atmospheric chemistry models satisfactorily predict its abundance.On board of the Sentinel-5 Precursor satellite, the TROPOspheric Monitoring Instrument (TROPOMI) provides tropospheric glyoxal columns. These tropospheric columns are generated with an improved version of the BIRA-IASB scientific retrieval algorithm relying on the Differential Optical Absorption Spectroscopy (DOAS) approach. By combining these retrievals with glyoxal measurements obtained during multiple air-borne campaigns using the High Altitude and Long Range Research Aircraft (HALO), we evaluate the capabilities of the ECHAM/MESSy Atmospheric Chemistry (EMAC) model to reproduce the global distribution and abundance of glyoxal. In its standard configuration, EMAC uses the detailed Mainz Organic Mechanism (MOM) to represent gas-phase chemistry. Additionally, we use the Model of Emissions of Gases and Aerosols from Nature (MEGAN) and the Emissions Database for Global Atmospheric Research (EDGAR, v4.3.2) to represent natural and anthropogenic emissions, respectively. When analysing an EMAC simulation using this standard configuration, we find that EMAC tends to overestimate tropospheric glyoxal columns over continental regions close to strong natural (e.g., Amazon Basin) and anthropogenic emission sources (e.g., China). At the same time, EMAC tends to underestimate glyoxal columns over tropical oceanic regions.In this study, we perform a series of sensitivity simulations and demonstrate that the model bias over continental regions is mainly resolved by including detailed aqueous-phase chemistry from the Jülich Aqueous-phase Mechanism of Organic Chemistry (JAMOC) and by reducing biogenic emissions towards the latest estimates. In addition, by implementing additional glyoxal precursors from oceanic sources, we demonstrate that the model bias over the tropical ocean is reduced. Following the more realistic model representation of glyoxal levels, we present a revised tropospheric glyoxal budget.

This study presents glyoxal observations of the mini-DOAS instrument performed during seven different airborne campaigns (ACRIDICON-CHUVA (2014), OMO (2015), EMeRGe-EU (2017), EMeRGe-Asia (2018), CoMet (2018), CAFE (2018), and SouthTRAC (2019)) from the German HALO (High Altitude and LOng range) research aircraft. Geographic regions covered by the research missions include the southern tip of South America, the Weddell sea and the Western Antarctic Peninsula, the tropical and subtropical Atlantic, Europe, as well as the East China Sea, the Philippines, and Japan. The studied areas thus covered observations over (i) natural source regions of glyoxal and its precursors, (ii) local as well as regional pollution sources i.e. biomass burning and major anthropogenic activities, and (iii) the remote marine and terrestrial background atmosphere. Using simultaneous measurements of horizontally (Limb) and vertically (Nadir) aligned telescopes, atmospheric concentrations and vertical column densities (VCDs) of glyoxal along the flight tracks are inferred. For validation purposes, these air-borne measurements are compared to collocated observations of the TROPOspheric Monitoring Instrument (TROPOMI). Overall, a reasonable agreement among the two data sets is found. Finally, both measurements are compared to simulations of the global ECHAM/MESSy Atmospheric Chemistry (EMAC) model (*), which provide further insights into the different sources and sinks of glyoxal and its precursors as well as into its photochemistry.(*) See also the presentation of Rosanka et al., entitled ‘Improving the representation of glyoxal in the global EMAC model using TROPOMI retrievals and air-borne campaign data’.

During the SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere) campaign in Nov. and Dec. 2011, polluted air masses were observed in the marine and terrestrial boundary layer (0 – ~2 km) and in the free troposphere (~2 – 12 km) over Borneo/Malaysia. The measurements include CO, CO2, CH4, N2O, NO2, and SO2 as primary pollutants, O3 and HCHO as secondary pollutants, and meteorological parameters. This set of trace gases combined with a Lagrangian particle dispersion model (e.g., FLEXPART) and emission inventories are used to fingerprint different sources (e.g., biomass burning) of local and regional air pollution.The long-term trend and seasonal variation of biomass burning emissions in this region are first presented and discussed based on the FINN inventory the FLEXPART simulation. Results highlighted the recurrent influence of palm plantation fires near the Miri airport, allowing regular sampling of this fire at different age plumes. The study of the emission ratio compared to CO2 or CO can be used as a measure of combustion efficiency to help define the type of biomass burning. Additionally, the age of plume sampled by the aircraft measurement is determined by FLEXPART and compared with the ΔO3/ΔCO ratio measured in this study and bibliographic database in order to study the ozone production during the transport of biomass burning plumes and implement such database with palm fire data.

Spectroscopic remote sensing in solar occultation geometry offers an important tool for determining atmospheric trace gas concentrations in the middle atmosphere. Monitoring ozone-depleting substances such as halogen oxides is essential to watch the ozone layer throughout a changing climate. The new TotalBrO instrument consists of an active solar tracker (LxWxH ~ 0.40 x 0.40 x 0.50 m, weight ~ 12 kg) and a spectrometer unit (LxWxH ~ 0.45 x 0.40 x 0.40 m, weight ~ 25 kg) with two temperature-stabilized grating spectrometers for the UV/visible spectral range. The instrument is compact and designed to measure bromine and iodine monoxide (BrO and IO) in addition to other gases such as ozone (O3) and nitrogen dioxide (NO2) by means of Differential Optical Absorption Spectroscopy (DOAS). Sets of spectra collected during balloon ascent, sunset and sunrise allow for inferring vertical profiles of the gases.Here, we report on the first deployment of TotalBrO on a stratospheric balloon launched from Kiruna, Sweden, during the Klimat campaign in August 2021. The solar tracker was able to track the sun once the balloon gondola was azimuthally stabilized above altitudes of about 25 km. TotalBrO collected UV/visible absorption spectra throughout solar occultation during sunset and sunrise on August 21/22, 2021. For the solar occultation periods, the tracking deviation with respect to the center of the solar disk was in the targeted regime of < 0.05°, and the solar tracker was able to catch the sun down to solar zenith angles (SZA) of around 95°, corresponding to tangent heights of about 10 km. We show preliminary results for profile retrievals of O3 and NO2 and for DOAS analyses of BrO and IO. The latter currently suffer from an unexplained oscillatory spectral pattern, for which we report on extensive sensitivity studies.

In this study, airborne measurements of the sum of hydroperoxyl (HO2) and organic peroxy (RO2) radicals that react with NO to produce NO2, i.e. RO2*, coupled with actinometry and other key trace gases measurements, have been used to test the current understanding of the fast photochemistry in the outflow of major population centres (MPCs). All measurements were made during the airborne campaign of the EMeRGe (Effect of Megacities on the transport and transformation of pollutants on the Regional to Global scales) project in Europe on-board the High Altitude Long range research aircraft (HALO). The on-board measurements of RO2* were made using the in-situ instrument Peroxy Radical Chemical Enhancement and Absorption Spectrometer (PeRCEAS). RO2* mixing ratios up to 120 pptv were observed in air masses of different origins and composition under different local actinometrical conditions during seven HALO research flights in July 2017 over Europe. The range and variability of the RO2* measurements agree reasonably well with radical production rates estimated using photolysis frequencies and RO2* precursor concentrations measured on-board. RO2* is primarily produced following the photolysis of ozone (O3), formaldehyde (HCHO), glyoxal (CHOCHO), and nitrous acid (HONO) in the airmasses investigated. The suitability of photostationary steady-state (PSS) assumptions to estimate the mixing ratios and the variability of RO2* during the airborne observations is investigated. The PSS assumption is robust enough to calculate RO2* mixing rations for most conditions encountered in air masses measured. The similarities and discrepancies between measured and calculated RO2* mixing ratios are analysed stepwise. The parameters, which predominantly control the RO2* mixing ratios under different chemical and physical regimes, are identified during the analysis. The dominant removal processes of RO2* in the airmasses measured up to 2000 m are the loss of OH and RO through the reaction with NOx during the radical interconversion. Above 2000 m, HO2 – HO2 and HO2 – RO2 reactions dominate RO2* loss reactions. RO2* calculations underestimated (< 20 %) the measurements by the analytical expression inside the pollution plumes probed. The underestimation is attributed to the limitations of the PSS analysis to take into account the production of RO2* through oxidation and photolysis of the OVOCs not measured during EMeRGe.

The rapid increase in solar photovoltaic (PV) installations worldwide has resulted in the electricity grid becoming increasingly dependent on atmospheric conditions, thus requiring more accurate forecasts of incoming solar irradiance. In this context, measured data from PV systems are a valuable source of information about the optical properties of the atmosphere, in particular the cloud optical depth (COD). This work reports first results from an inversion algorithm developed to infer global, direct and diffuse irradiance as well as atmospheric optical properties from PV power measurements, with the goal of assimilating this information into numerical weather prediction (NWP) models. High resolution measurements from both PV systems and pyranometers were collected as part of the BMWi-funded MetPVNet project, in the Allgäu region during autumn 2018 and summer 2019. These data were then used together with a PV model and both the DISORT and MYSTIC radiative transfer schemes within libRadtran (Emde et al., 2016; Mayer and Kylling, 2005)⁠ to infer cloud optical depth as well as direct, diffuse and global irradiance under highly variable atmospheric conditions. Hourly averages of each of the retrieved quantities were compared with the corresponding predictions of the COSMO weather model as well as data from satellite retrievals, and periods with differing degrees of variability and different cloud types were analysed. The DISORT-based algorithm is able to accurately retrieve COD, direct and diffuse irradiance components as long as the cloud fraction is high enough, whereas under broken cloud conditions the presence of 3D effects can lead to large errors. In that case the global horizontal irradiance is derived from tilted irradiance measurements and/or PV data using a lookup table based on the MYSTIC 3D Monte Carlo radiative transfer solver (Mayer, 2009)⁠. This work will provide the basis for future investigations using a larger number of PV systems to evaluate the improvements to irradiance and power forecasts that could be achieved by the assimilation of inferred irradiance into an NWP model. References Emde, C., Buras-Schnell, R., Kylling, A., Mayer, B., Gasteiger, J., Hamann, U., Kylling, J., Richter, B., Pause, C., Dowling, T. and Bugliaro, L.: The libRadtran software package for radiative transfer calculations (version 2.0.1), Geosci. Model Dev., 9(5), 1647–1672, doi:10.5194/gmd-9-1647-2016, 2016. Mayer, B.: Radiative transfer in the cloudy atmosphere, EPJ Web Conf., 1, 75–99, doi:10.1140/epjconf/e2009-00912-1, 2009. Mayer, B. and Kylling, A.: Technical note: The libRadtran software package for radiative transfer calculations - description and examples of use, Atmos. Chem. Phys., 5(7), 1855–1877, doi:10.5194/acp-5-1855-2005, 2005.

Nitrous acid (HONO) is an important atmospheric gas given its contribution to the cycles of NOx and HOx, but its role in global atmospheric photochemistry is not fully understood. This study implemented three pathways of HONO formation in the chemistry–climate model CHASER (MIROC-ESM) to explore three physical phenomena: gas-phase kinetic reactions (GRs), direct emission (EM), and heterogeneous reactions on cloud and aerosol particles (HRs). We evaluated the simulations by the atmospheric aircraft-based measurements from EMeRGe-Asia-2018 (Effect of Megacities on the Transport and Transformation of Pollutants on the Regional to Global Scales), ATom-1 (atmospheric tomography), observations from the ship R/V Mirai, EANET (Acid Deposition Monitoring Network in eastern Asia)/EMEP (European Monitoring and Evaluation Programme) ground-based stationary observations, and the OMI (Ozone Monitoring Instrument). We showed that the inclusion of the HONO chemistry in the modelling process reduced the model bias against the measurements for PM2.5, NO3-/HNO3, NO2, OH, HO2, O3, and CO, especially in the lower troposphere and the North Pacific (NP) region. We found that the retrieved global abundance of tropospheric HONO was 1.4 TgN. Of the three source pathways, HRs and EM contributed 63 % and 26 % to the net HONO production, respectively. We also observed that reactions on the aerosol surfaces contributed larger amounts of HONO (51 %) than those on the cloud surfaces (12 %). The model exhibited significant negative biases for daytime HONO in the Asian off-the-coast region, compared with the airborne measurements by EMeRGe-Asia-2018, indicating the existence of unknown daytime HONO sources. Strengthening of aerosol uptake of NO2 near the surface and in the middle troposphere, cloud uptake, and direct HONO emission were all potential yet-unknown HONO sources. The most promising daytime source for HONO found in this study was the combination of enhanced aerosol uptake of NO2 and surface-catalysed HNO3 photolysis (maxST+JANO3-B case), which could also remedy the model bias for NO2 and O3 during EMeRGe. We also found that the simulated HONO abundance and its impact on NOx–O3 chemistry were sensitive to the yield of the heterogeneous conversion of NO2 to HONO (vs. HNO3). Inclusion of HONO reduced global tropospheric NOx (NO + NO2) levels by 20.4 %, thereby weakening the tropospheric oxidizing capacity (OH, O3) occurring for NOx-deficit environments (remote regions and upper altitudes), which in turn increased CH4 lifetime (13 %) and tropospheric CO abundance (8 %). The calculated reduction effect on the global ozone level reduced the model overestimates for tropospheric column ozone against OMI spaceborne observations for a large portion of the North Hemisphere. HRs on the surfaces of cloud particles, which have been neglected in previous modelling studies, were the main drivers of these impacts. This effect was particularly salient for the substantial reductions of levels of OH (40 %–67 %) and O3 (30 %–45 %) in the NP region during summer, given the significant reduction of the NOx level (50 %–95 %). In contrast, HRs on aerosol surfaces in China (Beijing) enhanced OH and O3 winter mean levels by 600 %–1700 % and 10 %–33 %, respectively, with regards to their minima in winter. Furthermore, sensitivity simulations revealed that the heterogeneous formation of HONO from NO2 and heterogenous photolysis of HNO3 coincided in the real atmosphere. Nevertheless, the global effects calculated in the combined case (enhancing aerosol uptakes of NO2 and implementing heterogeneous photolysis of HNO3), which most captured the measured daytime HONO level, still reduced the global tropospheric oxidizing capacity. Overall, our findings suggest that a global model that does not consider HONO heterogeneous mechanisms (especially photochemical heterogeneous formations) may erroneously predict the effect of HONO in remote areas and polluted regions.

Nitrogen oxides (NOx ≡ NO + NO2) are centrally involved in the photochemical processes taking place in the earth’s atmosphere. Measurements of NO2, particularly in remote areas where concentrations are of the order of pptv, are still a challenge and subject to extensive research. In this study, we present NO2 measurements via photolysis-chemiluminescence during the research aircraft campaign CAFE Africa (Chemistry of the Atmosphere – Field Experiment in Africa) 2018 around Cabo Verde as well as the results of laboratory experiments to characterize the photolytic converter used. We identify a memory effect within the conventional photolytic converter associated with high NO concentrations and rapidly changing water vapor concentrations, accompanying changes in altitude during aircraft measurements, which is due to the porous structure of the converter material. We test and characterize an alternative photolytic converter made from quartz glass which improves the reliability of NO2 measurements in laboratory and field studies.

Stratospheric balloons are useful platforms for various research and technology needs. They allow to collect valuable data in many science fields, e.g. atmospheric science and astrophysics; they can be used for demonstrations in preparation of new space and Earth observation missions; they can be used to provide calibration/validation data for Earth observation space missions, or for dropping test objects from the stratosphere.Various types of balloons are available, corresponding to different missions: Zero Pressure Balloons (ZPB) for heavy payloads (100 kg to 3 tons) and short to medium duration (1 day to several days), Sounding Balloons (SB) for very light payloads (3 kg).Payloads can be flown at various altitudes between the ground surface up to 40 km, according the type of balloon and the kind of mission. Compared to satellites, stratospheric balloons can be operated at relatively low cost and with shorter lead times from the experiment idea to the flight.Mid-2017, a new Research Infrastructure called HEMERA has been selected by the European Commission within its programme Horizon 2020. The HEMERA objectives are to:Provide better and coordinated balloon access to the troposphere and stratosphere for scientific and technological research, in response to the scientific user needs. Attract new users to enlarge the community accessing the balloon infrastructure and foster scientific and technical collaboration. Enlarge the fields of science and technology research conducted with balloons. Improve the balloon service offered to scientific and technical users through innovative developments. Favour standardization, synergy, complementarities and industrialization through joint developments with greater cost-effectiveness. The project is coordinated by CNES and involves 13 partners in total, from various European entities and Canada. The project was kicked-off in late January 2018 and will be executed during 2018-2022.Six ZPB flights with a target payload mass of at least 150 kg are foreseen within HEMERA, offering free of charge access to users and scientists for various science measurements and/or for technology tests. In addition, several SB flights are foreseen. The launch sites will be Esrange in Sweden, Timmins in Canada, for the ZPB and Aire sur l'Adour in France for the SB. The selected experiments will fly on balloons during the years 2019-2022. Two Calls for Proposals were planned in the HEMERA project, the first was launched in 2018 and 39 answers from 12 countries have been received; 23 experiments have been selected. 31 answers have been received in the frame of the second call, from 10 countries. In total 39 experiments from 13 countries have been selected. The first HEMERA flights occurred in summer 2019 from Kiruna and Timmins.In addition, Open Access to balloon data will be organized in the frame of the Data Center, giving access to science data collected during the flights. Networking activities are planned in order to promote the Infrastructure in the European countries, and Joint Research activities are conducted in order to improve as far as possible the balloon offer in the view of the user needs.

We report on measurements of total bromine (Brtot) in the upper troposphere and lower stratosphere (UTLS) taken from the German High Altitude and LOng range research aircraft (HALO) over the North Atlantic, Norwegian Sea and north-western Europe in September/ October 2017 during the WISE (Wave-driven ISentropic Exchange) research campaign. Brtot is calculated from measured total organic bromine (Brorg) (i.e., the sum of bromine contained in CH3Br, the halons and the major very short-lived brominated substances) added to inorganic bromine (Bryinorg), evaluated from measured BrO and photochemical modelling. Combining these data, the weighted mean [Brtot] is 19.2 ± 1.2 ppt in the extratropical lower stratosphere (Ex-LS) of the northern hemisphere. The inferred average Brtot for the Ex-LS is slightly smaller than expected for the middle stratosphere in 2016 (~19.6 ppt (ranging from 19-20 ppt) as reported by the WMO/UNEP Assessment (2018)). However, it reflects the expected variability in Brtot in the Ex-LS due to influxes of shorter lived brominated source and product gases from different regions of entry. A closer look into Brorg and Bryinorg as well as simultaneously measured transport tracers (CO, N2O, ...) and an air mass lag-time tracer (SF6), suggests that a filament of air with elevated Brtot protruded into the extratropical lowermost stratosphere (Ex-LMS) from 350-385 K and between equivalent latitudes of 55-80˚N (high bromine filament – HBrF). Lagrangian transport modelling shows the multi-pathway contributions to Ex-LMS bromine. According to CLaMS air mass origin simulations, contributions to the HBrF consist of predominantly isentropic transport from the tropical troposphere (also with elevated [Brtot] = 21.6 ± 0.7 ppt) as well as a smaller contribution from an exchange across the extratropical tropopause which are mixed into the stratospheric background air. In contrast, the surrounding LS above and below the HBrF has less tropical tropospheric air, but instead additional stratospheric background air. Of the tropical tropospheric air in the HBrF, the majority is from the outflow of the Asian monsoon anticyclone and the adjacent tropical regions, which greatly influences concentrations of trace gases transported into the Ex-LMS in boreal summer and fall. The resulting increase of Brtot in the Ex-LMS and its consequences for ozone is investigated through the TOMCAT/SLIMCAT model simulations. However, more extensive monitoring of total stratospheric bromine in more aged air (i.e., in the middle stratosphere) as well as globally and seasonally is required in addition to model simulations to fully understand its impact on Ex-LMS ozone and the radiative forcing of climate.

Photovoltaic (PV) power data are a valuable but as yet under-utilised resource that could be used to characterise global irradiance with unprecedented spatio-temporal resolution. The resulting knowledge of atmospheric conditions can then be fed back into weather models and will ultimately serve to improve forecasts of PV power itself. This provides a data-driven alternative to statistical methods that use post-processing to overcome inconsistencies between ground-based irradiance measurements and the corresponding predictions of regional weather models (see for instance Frank et al., 2018). This work reports first results from an algorithm developed to infer global horizontal irradiance as well as atmospheric optical properties such as aerosol or cloud optical depth from PV power measurements.Building on previous work (Buchmann, 2018), an improved forward model of PV power as a function of atmospheric conditions was developed. As part of the BMWi-funded project MetPVNet, PV power data from twenty systems in the Allgäu region were made available, and the corresponding irradiance, temperature and wind speed were measured during two measurement campaigns in autumn 2018 and summer 2019. System calibration was performed using all available clear sky days; the corresponding irradiance was simulated using libRadtran (Emde et al., 2016). Particular attention was paid to describing the dynamic variations in PV module temperature in order to correctly take into account the heat capacity of the solar panels.PV power data from the calibrated systems were then used together with both the DISORT and MYSTIC radiative transfer codes (Emde et al., 2016) to infer aerosol optical depth, cloud optical depth and irradiance under all sky conditions. The results were compared to predictions from the COSMO weather model, and the accuracy of the inverted quantities was compared using both a simple and more complex forward model. The potential of the method to extract irradiance data over a larger area as well as the increase in information from combining neighbouring PV systems will be explored in future work.References Buchmann, T., 2018: Potenzial von Photovoltaikanlagen zur Ableitung raum-zeitlich hoch aufgelöster Globalstrahlungsdaten. Heidelberg University, http://archiv.ub.uni-heidelberg.de/volltextserver/24687/.Emde, C., and Coauthors, 2016: The libRadtran software package for radiative transfer calculations (version 2.0.1). Geosci. Model Dev., 9, 1647–1672, doi:10.5194/gmd-9-1647-2016. https://www.geosci-model-dev.net/9/1647/2016/.Frank, C. W., S. Wahl, J. D. Keller, B. Pospichal, A. Hense, and S. Crewell, 2018: Bias correction of a novel European reanalysis data set for solar energy applications. Sol. Energy, 164, 12–24, doi:10.1016/j.solener.2018.02.012. https://doi.org/10.1016/j.solener.2018.02.012.

Spectroscopic direct sun remote sensing of the atmosphere offers an essential tool for determining atmospheric trace gas concentrations. The monitoring of ozone-depleting substances, such as halogen oxides in the middle atmosphere, contributes to observing the progress in restoring the ozone layer.Here, we present a new compact solar occultation spectrometer for the UV/visible spectral range that can be mounted on stratospheric balloons such as deployed within the European HEMERA infrastructures. Due to its compactness, the instrument is suitable as a secondary payload.The instrument, consisting of a solar tracker providing direct sunlight for two grating spectrometers, is designed for deployment on a high altitude balloon to measure total bromine and iodine inventories using solar occultation and the DOAS method. All components of the setup have been chosen to withstand low temperatures (>-80°C) and low pressures (>5 mbar) as expected during the flight, and to have minimal power consumption while being compact, lightweight and only cooling radiatively. To perform solar occultation measurements, the device can track the sun down to 10° below its horizon.The solar tracker is based on a two-camera setup following the Camtracker [1]. One camera with a fish-eye lens (FoV 185°) that observes the sky gives the sun´s coarse position. The Alt-Azimuth mount projects direct sunlight onto a screen. When reaching this coarse position, the image of the second camera is used to center the solar image on the spectrometer entrance telescopes by adjusting both mirrors within a 100 Hz control loop.The tracker can reach a tracking precision of ≤0.05° for expected perturbations of smaller than 2° s-1. In lab experiments it was shown, that the tracker could handle even faster perturbations (larger than 3° s-1).The sunlight is coupled into the two spectrometers via a fiber-telescope setup.Two stabilized spectrometers (Ocean Optics QE Pro Series, resolution 0.5 nm) with a wavelength range for UV (305 to 385 nm) and vis (415 to 515 nm) are assembled within an evacuated box inside a water-ice bath. The vacuum avoids vapors condensing on the CCD an it ensures a constant refractive index within the spectrometers throughout the flight. At the same time the water-ice bath acts as a thermal buffer to stabilize the temperature of both spectrometers. Stable water-ice bath temperatures were achieved for >12 hours with deviations smaller than 0.5°C.Preliminary testing of the setup was conducted on a three-day stationary roof-based test campaign with nearly clear-sky conditions. We plan on further investigating the instrument´s performance under field conditions and finally deploy the instrument on a stratospheric balloon flight from Kiruna in summer 2021.[1] Gisi, M. et al.: Camtracker: a new camera controlled high precision solar tracker system for FTIR-spectrometers, Atmospheric Measurement Techniques, URL www.atmos-meas-tech.net/4/47/2011/, 2011.

The temperature of photovoltaic modules is modelled as a dynamic function of ambient temperature, shortwave and longwave irradiance and wind speed, in order to allow for a more accurate characterisation of their efficiency. A simple dynamic thermal model is developed by extending an existing parametric steady-state model using an exponential smoothing kernel to include the effect of the heat capacity of the system. The four parameters of the model are fitted to measured data from three photovoltaic systems in the Allgäu region in Germany using non-linear optimisation. The dynamic model reduces the root-mean-square error between measured and modelled module temperature to 1.58 K on average, compared to 3.03 K for the steady-state model, whereas the maximum instantaneous error is reduced from 20.02 to 6.58 K.

Installed onboard the German research aircraft HALO, the integrated-path differential-absorption (IPDA) lidar CHARM-F measures weighted vertical columns of both greenhouse gases (GHG) below the aircraft and along its flight track, aiming at high accuracy and precision. Results will be shown from the deployment during the CoMet field campaign that was carried out in spring 2018, with its main focus on one of the major European hot spots in methane emissions: the Upper Silesian Coal Basin (USCB) in Poland. First analyses reveal a measurement precision of below 0.5% for 20-km averages and also low bias, which was assessed by comparison with in-situ instruments. The measurements flights were designed to capture individual CH4 and CO2 plumes from e.g. coal mine venting and coal-fired power plants, respectively, but also to measure large and regional scale GHG gradients and to provide comparisons with the Total Carbon Column Observing Network (TCCON). Many other different instruments, both airborne and ground-based, complemented the lidar measurements to provide a comprehensive dataset for model analyses. CHARM-F also acts as the airborne demonstrator for MERLIN, the “Methane Remote Lidar Mission”, conducted by the German and French space agencies, DLR and CNES, with launch foreseen in ~ 2024. In this context, the airborne lidar data are likewise important for mission support such as for e.g. algorithm development and improvement and, moreover, the CoMet mission was also an important step for MERLIN validation preparation.

Bromine greatly influences the UT/LS ozone concentrations, however the transport of bromine across the tropical tropopause layer and in particular across the extratropical tropopause is not well quantified. Air-borne measurements of atmospheric trace gases such as organic and inorganic bromine along the tropopause are studied during the WISE (Wave-driven ISentropic Exchange) research campaign over the northern Atlantic and western Europe from September 13 - October 21, 2017. The remote sensing instrument mini-DOAS (Differential Optical Absorption Spectroscopy) is mounted on the HALO (High Altitude and LOng range) aircraft and measures BrO (O3, NO2 among other trace gases). The novel scaling method is applied to infer the target gas BrO mixing ratios from slant column densities using in-situ O3 measurements from the FAIRO instrument (operated by KIT) as the scaling gas. For each flight, the inferred mixing ratios are directly compared with CLaMS (Chemical Lagrangian Model of the Stratosphere) simulated curtains of the trace gases along the flight path. The partitioning coefficient of inorganic bromine from CLaMS and all relevant organic halogen species and air mass ages (SF6, CO2) from the GhOST-MS instrument (operated by UFra) are used to determine the total bromine budget along the UT/LS. A climatology of organic, inorganic and total bromine is constructed with respect to the extratropical tropopause as well as the air mass ages. This indicates the interplay of bromine transport across the extratropical tropopause and of the transport of air via the lower branch from the tropics as well as potential losses of inorganic bromine by uptake onto and sedimentation of ice particles.

Since peroxy radicals are closely involved in a number of tropospheric chemical processes like O3 budget, hydrocarbon oxidation and acid formation, the accurate measurement of these radicals can provide essential information to improve our understanding of processing and transformation of polluted outflows from megacities and Major Population Centres (MPCs).Airborne measurements of the total sum of peroxy radicals, RO2* = HO2 + ∑ RO2, where R is an organic group, were conducted in Europe in summer 2017 and in East Asia in spring 2018 within the EMeRGe (Effect of Megacities on the Transport and Transformation of Pollutants on the Regional to Global Scales) project by using the PeRCEAS instrument (Peroxy Radical Chemical Enhancement and Absorption Spectrometer), on board of the HALO research aircraft (www.halo.dlr.de).Over the course of both measurement campaigns different MPC outflows were investigated including among others, London, Rome, Manila and Taipei. Polluted air masses of different origin and composition were probed. Overall the peroxy radical mixing ratios were of the same order of magnitude in the air masses probed in Europe and in East Asia. The variations in the photochemical activity were studied by taking into account simultaneous observations of radical precursors and photolysis rates, while applying known oxidation mechanisms. Radical precursors, photolysis rates and aerosol load were generally higher in Asia, which might indicate higher radical loss reactions on the aerosol surface than in Europe. Moreover this study shows a clear deviation in the photostationary state for MPC outflows close to the emission sources. Based on this information, this presentation will focus on the actual understanding of the photochemical processing in the probed air masses.

Depletion of the stratospheric ozone layer by chlorine and bromine species has been a major environmental issue since the early 1970s. Following controls on the production of the long-lived halocarbons which transport chlorine and bromine to the stratosphere, the ozone layer is expected to recover over the course of this century. Decreases in the stratospheric loading of chlorine and bromine have been observed and there are signs of this resulting in an increase in ozone in the upper stratosphere and the Antarctic lower stratosphere. However, in contrast to this expectation of increasing stratospheric ozone, Ball et al. (ACP doi:10.5194/acp-18-1379-2018, 2018, ACP doi:10.5194/acp-19-12731-2019, 2019) have reported evidence for an ongoing decline in lower stratospheric ozone at extrapolar latitudes between 60°S and 60°N. Chipperfield et al. (GRL, doi:10.1029/2018GL078071, 2018) analysed these results using the TOMCAT 3-D chemical transport model (CTM). They reported that much of the observed ozone decrease could be explained by dynamical variability. Furthermore, they investigated the potential role for bromine and chlorine from very short-lived species (VSLS) but found only a small contribution.Very recently, Koenig et al. (PNAS, doi:10.1073/pnas.1916828117, 2020) have reported quantitative observations of almost 1 pptv iodine in the lower stratosphere. They show that this iodine is an important contribution to the local iodine loss budget and speculate that a trend in iodine could therefore explain the observed downward trend in ozone.Here we use an updated version of the TOMCAT CTM to investigate the impact of iodine on lower stratospheric ozone trends. We repeat the simulations of Chipperfield et al. (2018), using both ERA-Interim and ERA5 reanalyses (to compare the quantification of the dynamical contribution). We use assume trends in the stratospheric injection of iodine to quantify the possible impact of this on global ozone trends through both gas-phase chemistry and novel heterogeneous processes.

Middle and long-term photo-chemical effects of local and regional pollution are not well quantified and are an area of active study. NOx (here defined as NO, NO2, and HONO) is a regional pollutant, which influences atmospheric oxidation capacity and ozone formation. Airborne measurements of atmospheric trace gases from the HALO (High Altitude Long Range) aircraft, particularly of NO, NO2, and HONO were performed as part of the EMeRGe (Effect of Megacities on the Transport and Transformation of Pollutants on the Regional to Global Scales) campaign over continental Europe and southeast Asia in July 2017 and April 2018, respectively. NO (and NOY), O3, and the photolysis frequencies of NO2 and HONO were measured in-situ. NO2 and HONO were inferred from Limb measurements of the mini-DOAS (Differential Optical Absorption Spectroscopy) instrument, using the novel scaling method (Hüneke et al., 2017). These measurements were compared with simulations of the MECO/EMAC models. In relatively polluted air-masses in the boundary layer and free troposphere, HONO measured in excess of model predictions (and previous measurements) suggests an in-situ formation and a significant source of OH as well as a pathway for re-noxification. Aerosol composition simultaneously measured by the C-Tof-AMS instrument may reveal potential reaction mechanisms to explain the discrepancy.

At the industrial revolution (1750-1800), the population of the earth was around 1 Billion and less than 5% of population lived in urban areas. In 1950, when the population reached about 2.9 billion, there were two megacities New York/Newark and Tokyo. In 2020, the earth’s population is around 7.8 Billion, more than 50% live in urban areas and there are now approximately 38 around the world. Since 2007, more than 50% of the population live in urban areas and the earth’s population has now reached 7.8 Billion. Anthropogenic activity to sustain and feed MPC is now one of the most important sources of pollution, modifying atmospheric chemistry, air quality and climate. To assess the impact of MPC emissions locally and regionally requires knowledge of the transport and transformation of the MPC plumes. The EMeRGe project was proposed to address this need and investigate the transport and transformation of the chemical composition of MPC plumes. Secondary objectives include the improvement of our understanding of the impact of biomass burning, which mixes with the plumes from MPC. EMeRGe selected European and Asian MPC as targets, where the regulations on emissions are significantly different.EMeRGe assumes that the nature of the local emissions, the meteorology and photochemistry/chemistry determines the transport and transformation of the plumes from MPCs. To test this hypothesis, the following scientific questions are addressed: a) which transport and dispersion processes dominate the MPC outflows in Europe and Asia during the selected measurement periods;b) which oxidation or other processes determine the chemical transformation of MPC emissions;c) what are the regional impacts of the emission by the selected European and Asian MPCs;d) what is the relevance of emission from European and Asian MPCs for radiative forcing and climate change;e) do our chemical models adequately simulate of transport and transformation processes of European and Asian MPC outflows.An integrating focus of EMeRGe were the measurement campaigns exploiting the capabilities of the German HALO research were undertaken during EMeRGe, which investigated the outflow from: i) European MPCs in July 2017; ii) MPCs in East and South East Asia during March and April 2018. In addition to the HALO aircraft measurements, the EMeRGe International scientists contributed studies of the measurement from instrumentation from ground based, airborne and satellite platforms. For example in EMeRGe in Europe the UK NERC FAAM (https://nerc.ukri.org/research/sites/facilities/aircraft/) "ERA - CNR - ISAFOM" (https://www.eufar.net/aircrafts/44) were deployed to make measurements around London and Rome respectively. In EMeRGe in Asia, measurement were made ground based and Lidar measurements were made by EMeRGe partners from Taiwan, Japan, the Philippines, Thailand and China. EMeRGe benefited from the support by iCACGP (international Commission on Atmospheric Chemistry and Global Pollution). This presentation will provide an overview of the objectives, the planning, the measurements and some highlights from the EMeRGe HALO campaigns.

Spectral radiance measurements collected in nadir and sideward viewing directions by two airborne passive solar remote sensing instruments, the Spectral Modular Airborne Radiation measurement sysTem (SMART) and the Differential Optical Absorption Spectrometer (mini-DOAS), are used to compare the remote sensing results of cirrus optical thickness τ. The comparison is based on a sensitivity study using radiative transfer simulations (RTS) and on data obtained during three airborne field campaigns: the North Atlantic Rainfall VALidation (NARVAL) mission, the Mid-Latitude Cirrus Experiment (ML-CIRRUS) and the Aerosol, Cloud, Precipitation, and Radiation Interactions and Dynamics of Convective Cloud Systems (ACRIDICON) campaign. Radiative transfer simulations are used to quantify the sensitivity of measured upward radiance I with respect to τ, ice crystal effective radius reff, viewing angle of the sensor θV, spectral surface albedo α, and ice crystal shape. From the calculations it is concluded that sideward viewing measurements are generally better suited than radiance data from the nadir direction to retrieve τ of optically thin cirrus, especially at wavelengths larger than λ = 900 nm. Using sideward instead of nadir-directed spectral radiance measurements significantly improves the sensitivity and accuracy in retrieving τ, in particular for optically thin cirrus of τ ≤ 2. The comparison of retrievals of τ based on nadir and sideward viewing radiance measurements from SMART, mini-DOAS and independent estimates of τ from an additional active remote sensing instrument, the Water Vapor Lidar Experiment in Space (WALES), shows general agreement within the range of measurement uncertainties. For the selected example a mean τ of 0.54 ± 0.2 is derived from SMART, and 0.49 ± 0.2 by mini-DOAS nadir channels, while WALES obtained a mean value of τ = 0.32 ± 0.02 at 532 nm wavelength, respectively. The mean of τ derived from the sideward viewing mini-DOAS channels is 0.26 ± 0.2. For the few simultaneous measurements, the mini-DOAS sideward channel measurements systematically underestimate (−17.6 %) the nadir observations from SMART and mini-DOAS. The agreement between mini-DOAS sideward viewing channels and WALES is better, showing the advantage of using sideward viewing measurements for cloud remote sensing for τ ≤ 1. Therefore, we suggest sideward viewing measurements for retrievals of τ of thin cirrus because of the significantly enhanced capability of sideward viewing compared to nadir measurements.

A new retrieval algorithm for OSIRIS (Optical Spectrograph and Infrared Imager System) nitrogen dioxide (NO2) profiles is described and validated. The algorithm relies on spectral fitting to obtain slant column densities of NO2, followed by inversion using an algebraic reconstruction technique and the SaskTran spherical radiative transfer model (RTM) to obtain vertical profiles of local number density. The validation covers different latitudes (tropical to polar), years (2002–2012), all seasons (winter, spring, summer, and autumn), different concentrations of nitrogen dioxide (from denoxified polar vortex to polar summer), a range of solar zenith angles (68.6–90.5°), and altitudes between 10.5 and 39 km, thereby covering the full retrieval range of a typical OSIRIS NO2 profile. The use of a larger spectral fitting window than used in previous retrievals reduces retrieval uncertainties and the scatter in the retrieved profiles due to noisy radiances. Improvements are also demonstrated through the validation in terms of bias reduction at 15–17 km relative to the OSIRIS operational v3.0 algorithm. The diurnal variation of NO2 along the line of sight is included in a fully spherical multiple scattering RTM for the first time. Using this forward model with built-in photochemistry, the scatter of the differences relative to the correlative balloon NO2 profile data is reduced.

The Midlatitude Cirrus experiment (ML-CIRRUS) deployed the High Altitude and Long Range Research Aircraft (HALO) to obtain new insights into nucleation, life cycle, and climate impact of natural cirrus and aircraft-induced contrail cirrus. Direct observations of cirrus properties and their variability are still incomplete, currently limiting our understanding of the clouds’ impact on climate. Also, dynamical effects on clouds and feedbacks are not adequately represented in today’s weather prediction models. Here, we present the rationale, objectives, and selected scientific highlights of ML-CIRRUS using the G-550 aircraft of the German atmospheric science community. The first combined in situ–remote sensing cloud mission with HALO united state-of-the-art cloud probes, a lidar and novel ice residual, aerosol, trace gas, and radiation instrumentation. The aircraft observations were accompanied by remote sensing from satellite and ground and by numerical simulations. In spring 2014, HALO performed 16 flights above Europe with a focus on anthropogenic contrail cirrus and midlatitude cirrus induced by frontal systems including warm conveyor belts and other dynamical regimes (jet streams, mountain waves, and convection). Highlights from ML-CIRRUS include 1) new observations of microphysical and radiative cirrus properties and their variability in meteorological regimes typical for midlatitudes, 2) insights into occurrence of in situ–formed and lifted liquid-origin cirrus, 3) validation of cloud forecasts and satellite products, 4) assessment of contrail predictability, and 5) direct observations of contrail cirrus and their distinction from natural cirrus. Hence, ML-CIRRUS provides a comprehensive dataset on cirrus in the densely populated European midlatitudes with the scope to enhance our understanding of cirrus clouds and their role for climate and weather.

We report measurements of CH4 (measured in situ by the Harvard University Picarro Cavity Ringdown Spectrometer (HUPCRS) and NOAA Unmanned Aircraft System Chromatograph for Atmospheric Trace Species (UCATS) instruments), O3 (measured in situ by the NOAA dual-beam ultraviolet (UV) photometer), NO2, BrO (remotely detected by spectroscopic UV–visible (UV–vis) limb observations; see the companion paper of Stutz et al., 2016), and of some key brominated source gases in whole-air samples of the Global Hawk Whole Air Sampler (GWAS) instrument within the subtropical lowermost stratosphere (LS) and the tropical upper troposphere (UT) and tropopause layer (TTL). The measurements were performed within the framework of the NASA-ATTREX (National Aeronautics and Space Administration – Airborne Tropical Tropopause Experiment) project from aboard the Global Hawk (GH) during six deployments over the eastern Pacific in early 2013. These measurements are compared with TOMCAT/SLIMCAT (Toulouse Off-line Model of Chemistry And Transport/Single Layer Isentropic Model of Chemistry And Transport) 3-D model simulations, aiming at improvements of our understanding of the bromine budget and photochemistry in the LS, UT, and TTL.Changes in local O3 (and NO2 and BrO) due to transport processes are separated from photochemical processes in intercomparisons of measured and modeled CH4 and O3. After excellent agreement is achieved among measured and simulated CH4 and O3, measured and modeled [NO2] are found to closely agree with ≤ 15 ppt in the TTL (which is the detection limit) and within a typical range of 70 to 170 ppt in the subtropical LS during the daytime. Measured [BrO] ranges between 3 and 9 ppt in the subtropical LS. In the TTL, [BrO] reaches 0.5 ± 0.5 ppt at the bottom (150 hPa∕355 K∕14 km) and up to about 5 ppt at the top (70 hPa∕425 K∕18.5 km; see Fueglistaler et al., 2009 for the definition of the TTL used), in overall good agreement with the model simulations. Depending on the photochemical regime, the TOMCAT∕SLIMCAT simulations tend to slightly underpredict measured BrO for large BrO concentrations, i.e., in the upper TTL and LS. The measured BrO and modeled BrO ∕ Bryinorg ratio is further used to calculate inorganic bromine, Bryinorg. For the TTL (i.e., when [CH4] ≥ 1790 ppb), [Bryinorg] is found to increase from a mean of 2.63 ± 1.04 ppt for potential temperatures (θ) in the range of 350–360 K to 5.11 ± 1.57 ppt for θ = 390 − 400 K, whereas in the subtropical LS (i.e., when [CH4] ≤ 1790 ppb), it reaches 7.66 ± 2.95 ppt for θ in the range of 390–400 K. Finally, for the eastern Pacific (170–90° W), the TOMCAT/SLIMCAT simulations indicate a net loss of ozone of −0.3 ppbv day−1 at the base of the TTL (θ = 355 K) and a net production of +1.8 ppbv day−1 in the upper part (θ = 383 K).

The February–March 2014 deployment of the National Aeronautics and Space Administration (NASA) Airborne Tropical Tropopause Experiment (ATTREX) provided unique in situ measurements in the western Pacific tropical tropopause layer (TTL). Six flights were conducted from Guam with the long-range, high-altitude, unmanned Global Hawk aircraft. The ATTREX Global Hawk payload provided measurements of water vapor, meteorological conditions, cloud properties, tracer and chemical radical concentrations, and radiative fluxes. The campaign was partially coincident with the Convective Transport of Active Species in the Tropics (CONTRAST) and the Coordinated Airborne Studies in the Tropics (CAST) airborne campaigns based in Guam using lower-altitude aircraft (see companion articles in this issue). The ATTREX dataset is being used for investigations of TTL cloud, transport, dynamical, and chemical processes, as well as for evaluation and improvement of global-model representations of TTL processes. The ATTREX data are publicly available online (at https://espoarchive.nasa.gov/).

Polar stratospheric clouds (PSCs) are often observed in the Kiruna region in northern Sweden, east of the Scandinavian mountain range, during wintertime. PSC occurrence can be detected by ground-based optical instruments. Most of these require clear tropospheric weather. By applying the zenith-sky colour index technique, which works under most weather conditions, the data availability can be extended. The observations suggest that PSC events, especially of type II (water PSCs) may indeed more common than predicted by synoptic models, which is expected because of the frequent presence of mountain-induced leewaves. However, it will be of importance to increase the density of independent observations.Key words. Atmospheric composition and structure (aerosols and particles · cloud physics and chemistry) · Meteorology and atmospheric dynamics (mesoscale meteorology)

In order to improve our current knowledge on the budgets of the two most important anthropogenic greenhouse gases, CO2 and CH4, a co-ordinated measurement campaign in the Central European region was successfully carried out in May/June 2018 with the German research aircraft HALO and two smaller Cessna aircraft as its main experimental platforms. The goal of CoMet is to combine a suite of state-of-the-art airborne active (lidar) and passive remote sensors (spectrometer) with in-situ instruments to provide regional-scale data about greenhouse gases (GHGs) which are urgently required for their accurate modelling.

We present a new retrieval of stratospheric BrO (bromine monoxide) from channel 2 SCIAMACHY (SCanning Imaging Absorption spectrometer for Atmospheric CHartographY) limb observations. Retrievals are shown to agree with independent balloon observations to within one standard deviation of the retrieval noise. We retrieve BrO profiles for all of April 2008, and apply simulated [BrO]/[Bry] (bromine monoxide : stratospheric inorganic bromine) ratios to estimate the stratospheric Bry loading. We find 23.5 ± 6 ppt Br, suggesting 7 ppt Br from short-lived bromocarbons to be at the high end of the current best estimate (3–8 ppt). The 6 ppt Br uncertainty estimate is dominated by the 21% uncertainty in the simulated [BrO] / [Bry] ratio due to propagation of errors from the underlying chemical kinetics.

A new technique to compute the transition operator for a single arbitrary shaped particle is presented, called Green׳s dyadic technique for transition matrix (GDT-matrix). It is based on the use of the volume integral equation (VIE) for electromagnetic scattering. By interpreting the transition matrix as a generalized potential in combination with the Discrete Dipole Approximation (DDA) method, it is possible to make a parallel use of the Lippmann–Schwinger and the Dyson equations to iteratively solve for the transition matrix and Green׳s function dyadic, respectively. Hence, there is no need to explicitly specify the boundary conditions and only an accurate spatial discretization of the particle is required, which is done by a sparse-octree volume discretization. Further no assumptions regarding the particle symmetry, homogeneity and isotropy need to be made. For the validation of the code, examples in 1D and 2D are investigated. Then, 3D results are compared with Mie theory for spherical particles. A cubic particle is also considered while for more complex shaped particles, a qualitative comparison against experimental results is provided for forward-scattering.

The major volcanic eruption of Mount Pinatubo in 1991 has been shown to have significant effects on stratospheric chemistry and ozone depletion even at midlatitudes. Since then, only moderate but recurrent volcanic eruptions have modulated the stratospheric aerosol loading and are assumed to be one cause for the reported increase in the global aerosol content over the past 15 years. This particularly enhanced aerosol context raises questions about the effects on stratospheric chemistry which depend on the latitude, altitude and season of injection. In this study, we focus on the midlatitude Sarychev volcano eruption in June 2009, which injected 0.9 Tg of sulfur dioxide (about 20 times less than Pinatubo) into a lower stratosphere mainly governed by high-stratospheric temperatures. Together with in situ measurements of aerosol amounts, we analyse high-resolution in situ and/or remote-sensing observations of NO2, HNO3 and BrO from balloon-borne infrared and UV–visible spectrometers launched in Sweden in August–September 2009. It is shown that differences between observations and three-dimensional (3-D) chemistry-transport model (CTM) outputs are not due to transport calculation issues but rather reflect the chemical impact of the volcanic plume below 19 km altitude. Good measurement–model agreement is obtained when the CTM is driven by volcanic aerosol loadings derived from in situ or space-borne data. As a result of enhanced N2O5 hydrolysis in the Sarychev volcanic aerosol conditions, the model calculates reductions of ∼ 45 % and increases of ∼ 11 % in NO2 and HNO3 amounts respectively over the August–September 2009 period. The decrease in NOx abundances is limited due to the expected saturation effect for high aerosol loadings. The links between the various chemical catalytic cycles involving chlorine, bromine, nitrogen and HOx compounds in the lower stratosphere are discussed. The increased BrO amounts (∼ 22 %) compare rather well with the balloon-borne observations when volcanic aerosol levels are accounted for in the CTM and appear to be mainly controlled by the coupling with nitrogen chemistry rather than by enhanced BrONO2 hydrolysis. We show that the chlorine partitioning is significantly controlled by enhanced BrONO2 hydrolysis. However, simulated effects of the Sarychev eruption on chlorine activation are very limited in the high-temperature conditions in the stratosphere in the period considered, inhibiting the effect of ClONO2 hydrolysis. As a consequence, the simulated chemical ozone loss due to the Sarychev aerosols is low with a reduction of −22 ppbv (−1.5 %) of the ozone budget around 16 km. This is at least 10 times lower than the maximum ozone depletion from chemical processes (up to −20 %) reported in the Northern Hemisphere lower stratosphere over the first year following the Pinatubo eruption. This study suggests that moderate volcanic eruptions have limited chemical effects when occurring at midlatitudes (restricted residence times) and outside winter periods (high-temperature conditions). However, it would be of interest to investigate longer-lasting tropical volcanic plumes or sulfur injections in the wintertime low-temperature conditions.

Novel airborne in situ measurements of inorganic chlorine, nitrogen oxide species, and ozone were performed inside the lower Antarctic polar vortex and at its edge in September 2012. We focus on one flight during the Transport and Composition of the LMS/Earth System Model Validation (TACTS/ESMVal) campaign with the German research aircraft HALO (High-Altitude LOng range research aircraft), reaching latitudes of 65°S and potential temperatures up to 405 K. Using the early winter correlations of reactive trace gases with N2O from the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS), we find high depletion of chlorine reservoir gases up to ∼40% (0.8 ppbv) at 12 km to 14 km altitude in the vortex and 0.4 ppbv at the edge in subsided stratospheric air with mean ages up to 4.5 years. We observe denitrification of up to 4 ppbv, while ozone was depleted by 1.2 ppmv at potential temperatures as low as 380 K. The advanced instrumentation aboard HALO enables high-resolution measurements with implications for the oxidation capacity of the lowermost stratosphere.

The absorption cross section of N2O5, σN2O5(λ, T), which is known from laboratory measurements with the uncertainty of a factor of 2 (Table 4-2 in (Jet Propulsion Laboratory) JPL-2011; the spread in laboratory data, however, points to an uncertainty in the range of 25 to 30%, Sander et al., 2011), was investigated by balloon-borne observations of the relevant trace gases in the tropical mid-stratosphere. The method relies on the observation of the diurnal variation of NO2 by limb scanning DOAS (differential optical absorption spectroscopy) measurements (Weidner et al., 2005; Kritten et al., 2010), supported by detailed photochemical modelling of NOy (NOx(= NO + NO2) + NO3 + 2N2O5 + ClONO2 + HO2NO2 + BrONO2 + HNO3) photochemistry and a non-linear least square fitting of the model result to the NO2 observations. Simulations are initialised with O3 measured by direct sun observations, the NOy partitioning from MIPAS-B (Michelson Interferometer for Passive Atmospheric Sounding – Balloon-borne version) observations in similar air masses at night-time, and all other relevant species from simulations of the SLIMCAT (Single Layer Isentropic Model of Chemistry And Transport) chemical transport model (CTM). Best agreement between the simulated and observed diurnal increase of NO2 is found if the σN2O5(λ, T) is scaled by a factor of 1.6 ± 0.8 in the UV-C (200–260 nm) and by a factor of 0.9 ± 0.26 in the UV-B/A (260–350 nm), compared to current recommendations. As a consequence, at 30 km altitude, the N2O5 lifetime against photolysis becomes a factor of 0.77 shorter at solar zenith angle (SZA) of 30° than using the recommended σN2O5(λ, T), and stays more or less constant at SZAs of 60°. Our scaled N2O5 photolysis frequency slightly reduces the lifetime (0.2–0.6%) of ozone in the tropical mid- and upper stratosphere, but not to an extent to be important for global ozone.

We use the NASA Goddard Earth Observing System (GEOS) Chemistry Climate Model (GEOSCCM) to quantify the contribution of the two most important brominated very short lived substances (VSLSs), bromoform (CHBr3) and dibromomethane (CH2Br2), to stratospheric bromine and its sensitivity to convection strength. Model simulations suggest that the most active transport of VSLSs from the marine boundary layer through the tropopause occurs over the tropical Indian Ocean, the tropical western Pacific, and off the Pacific coast of Mexico. Together, convective lofting of CHBr3 and CH2Br2 and their degradation products supplies ~8 ppt total bromine to the base of the tropical tropopause layer (TTL, ~150 hPa), similar to the amount of VSLS organic bromine available in the marine boundary layer (~7.8–8.4 ppt) in the active convective lofting regions mentioned above. Of the total ~8 ppt VSLS bromine that enters the base of the TTL at ~150 hPa, half is in the form of organic source gases and half in the form of inorganic product gases. Only a small portion (3 and CH2Br2 together contribute ~7.7 pptv to the present-day inorganic bromine in the stratosphere. However, varying model deep-convection strength between maximum (strongest) and minimum (weakest) convection conditions can introduce a ~2.6 pptv uncertainty in the contribution of VSLSs to inorganic bromine in the stratosphere (BryVSLS). Contrary to conventional wisdom, the minimum convection condition leads to a larger BryVSLS as the reduced scavenging in soluble product gases, and thus a significant increase in product gas injection (2–3 ppt), greatly exceeds the relatively minor decrease in source gas injection (a few 10ths ppt).