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We report on a novel, medium-weight (∼ 25 kg) optical spectrometer coupled to an automated sun tracker for direct sun observations from azimuth-controlled balloon platforms weighing approximately 12 kg. It is designed to measure a suite of UV–Vis absorbing gases relevant in the context of stratospheric ozone depletion using the differential optical absorption spectroscopy (DOAS) method, i.e. O3, NO2, BrO, OClO, HONO, and IO. Here, we describe the design and major features of the instrument. Further, the instrument's performance during two stratospheric deployments from Esrange near Kiruna (Sweden) on 21 August 2021 and from Timmins (Ontario, Canada) on 23 August 2022 is discussed along with the first results concerning inferred mixing ratios of BrO above balloon float altitude. Using a photochemical correction for the partitioning of stratospheric bromine ([BrO]/[Bry]) obtained by chemical transport simulations, the inferred total stratospheric bromine load [Bry] amounts to (17.5 ± 2.2) ppt, with a purely statistical error amounting to 1.5 ppt in (5.5 ± 1.0)-year old air. The latter is inferred from simultaneous measurements of N2O by the GLORIA (Gimballed Limb Observer for Radiance Imaging of the Atmosphere) mid-IR instrument, resulting in a stratospheric entry of the investigated air mass in early 2017 ± 1 year.

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 on board NASA’s Global Hawk aircraft during the Airborne Tropical TRopopause Experiment (ATTREX), which took place in 2011, 2013, and 2014. The University of California Los Angeles and University of Heidelberg mini-differential optical absorption spectroscopy (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 of time. 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 represent a unique opportunity to test our approach and to infer properties of the ice particles, together with information on cirrus cloud radiative transfer.

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. The method is tested on data from two measurement campaigns that took place in the Allgäu region in 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 min resolution along with a non-linear photovoltaic module temperature model, global horizontal irradiance is extracted with a mean bias error compared to concurrent pyranometer measurements of 5.79 W m−2 (7.35 W m−2) under clear (cloudy) skies, averaged over the two campaigns, whereas for the retrieval using coarser 15 min power data with a linear temperature model the mean bias error is 5.88 and 41.87 W m−2 under clear and cloudy skies, respectively. During completely overcast periods the cloud optical depth is extracted from photovoltaic power using a lookup table method based on a 1D radiative transfer simulation, and the results are compared to both satellite retrievals and data from the Consortium for Small-scale Modelling (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 properly pre-screened to remove unwanted artefacts in the signal. Possible solutions to this problem are discussed in the context of future work.

In this study, airborne measurements of the sum of hydroperoxyl (HO2) and organic peroxy (RO2) radicals that react with nitrogen monoxide (NO) to produce nitrogen dioxide (NO2), 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. The 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 and Long Range Research Aircraft (HALO). The measurements of RO2∗ on HALO were made using the in situ instrument Peroxy Radical Chemical Enhancement and Absorption Spectrometer (PeRCEAS). RO2∗ is to a good approximation the sum of peroxy radicals reacting with NO to produce NO2. RO2∗ mixing ratios up to 120 pptv were observed in air masses of different origins and composition under different local actinometric conditions during seven HALO research flights in July 2017 over Europe. Radical production rates were estimated using knowledge of the photolysis frequencies and the RO2∗ precursor concentrations measured on board, as well as the relevant rate coefficients. Generally, high RO2∗ concentrations were measured in air masses with high production rates. In the air masses investigated, RO2∗ is primarily produced by the reaction of O1D with water vapour and the photolysis of nitrous acid (HONO) and of the oxygenated volatile organic compounds (OVOCs, e.g. formaldehyde (HCHO) and glyoxal (CHOCHO)). Due to their short lifetime in most environments, the RO2∗ concentrations are expected to be in a photostationary steady state (PSS), i.e. a balance between production and loss rates is assumed. The RO2∗ production and loss rates and the suitability of PSS assumptions to estimate the RO2∗ mixing ratios and variability during the airborne observations are discussed. The PSS assumption for RO2∗ is considered robust enough to calculate RO2∗ mixing ratios for most conditions encountered in the air masses measured. The similarities and discrepancies between measured and PSS calculated RO2∗ mixing ratios are discussed. The dominant terminating processes for RO2∗ in the pollution plumes measured up to 2000 m are the formation of nitrous acid, nitric acid, and organic nitrates. Above 2000 m, HO2–HO2 and HO2–RO2 reactions dominate the RO2∗ removal. RO2∗ calculations by the PSS analytical expression inside the pollution plumes probed often underestimated the measurements. The underestimation is attributed to the limitations of the PSS equation used for the analysis. In particular, this expression does not account for the yields of RO2∗ from the oxidation and photolysis of volatile organic compounds, VOCs, and OVOCs other than those measured during the EMeRGe research flights in Europe. In air masses with NO mixing ratios ≤50 pptv and low VOC/NO ratios, the RO2∗ measured is overestimated by the analytical expression. This may be caused by the formation of H2O and O2 from OH and HO2, being about 4 times faster than the rate of the OH oxidation reaction of the dominant OVOCs considered.

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.

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.

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.

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.

This paper presents a modelling study on the fate of CHBr3 and its product gases in the troposphere within the context of tropical deep convection. A cloud-scale case study was conducted along the west coast of Borneo, where several deep convective systems were triggered on the afternoon and early evening of 19 November 2011. These systems were sampled by the Falcon aircraft during the field campaign of the SHIVA project and analysed using a simulation with the cloud-resolving meteorological model C-CATT-BRAMS at 2×2 km resolution that represents the emissions, transport by large-scale flow, convection, photochemistry, and washout of CHBr3 and its product gases (PGs). We find that simulated CHBr3 mixing ratios and the observed values in the boundary layer and the outflow of the convective systems agree. However, the model underestimates the background CHBr3 mixing ratios in the upper troposphere, which suggests a missing source at the regional scale. An analysis of the simulated chemical speciation of bromine within and around each simulated convective system during the mature convective stage reveals that >85 % of the bromine derived from CHBr3 and its PGs is transported vertically to the point of convective detrainment in the form of CHBr3 and that the remaining small fraction is in the form of organic PGs, principally insoluble brominated carbonyls produced from the photo-oxidation of CHBr3. The model simulates that within the boundary layer and free troposphere, the inorganic PGs are only present in soluble forms, i.e. HBr, HOBr, and BrONO2, and, consequently, within the convective clouds, the inorganic PGs are almost entirely removed by wet scavenging. We find that HBr is the most abundant PG in background lower-tropospheric air and that this prevalence of HBr is a result of the relatively low background tropospheric ozone levels at the regional scale. Contrary to a previous study in a different environment, for the conditions in the simulation, the insoluble Br2 species is hardly formed within the convective systems and therefore plays no significant role in the vertical transport of bromine. This likely results from the relatively small quantities of simulated inorganic bromine involved, the presence of HBr in large excess compared to HOBr and BrO, and the relatively efficient removal of soluble compounds within the convective column.

We report on measurements of total bromine (Brtot) in the upper troposphere and lower stratosphere taken during 15 flights with the German High Altitude and LOng range research aircraft (HALO). The research campaign WISE (Wave-driven ISentropic Exchange) included regions over the North Atlantic, Norwegian Sea, and northwestern Europe in fall 2017. Brtot is calculated from measured total organic bromine (Brorg) added to inorganic bromine (Bryinorg), evaluated from measured BrO and photochemical modeling. Combining these data, the weighted mean [Brtot] is 19.2±1.2 ppt in the northern hemispheric lower stratosphere (LS), in agreement with expectations for Brtot in the middle stratosphere (Engel and Rigby et al., 2018). The data reflect the expected variability in Brtot in the LS due to variable influx 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 and N2O) and an air mass lag time tracer (SF6), suggests that bromine-rich air masses persistently protruded into the lowermost stratosphere (LMS) in boreal summer, creating a high bromine region (HBrR). A subsection, HBrR∗, has a weighted average of [Brtot] = 20.9±0.8 ppt. The most probable source region is air recently transported from the tropical upper troposphere and tropopause layer (UT/TTL) with a weighted mean of [Brtot] = 21.6±0.7 ppt. CLaMS Lagrangian transport modeling shows that the HBrR air mass consists of 51.2 % from the tropical troposphere, 27.1 % from the stratospheric background, and 6.4 % from the midlatitude troposphere (as well as contributions from other domains). The majority of the surface air reaching the HBrR is from the Asian monsoon and its adjacent tropical regions, which greatly influences trace gas transport into the LMS in boreal summer and fall. Tropical cyclones from Central America in addition to air associated with the Asian monsoon region contribute to the elevated Brtot observed in the UT/TTL. TOMCAT global 3-D model simulations of a concurrent increase of Brtot show an associated O3 change of -2.6±0.7 % in the LS and -3.1±0.7 % near the tropopause. Our study of varying Brtot in the LS also emphasizes the need for more extensive monitoring of stratospheric Brtot globally and seasonally to fully understand its impact on LMS O3 and its radiative forcing of climate, as well as in aged air in the middle stratosphere to elucidate the stratospheric trend in bromine.

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 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.

We report on airborne measurements of tropospheric mixing ratios and vertical profiles of formaldehyde (CH2O), glyoxal (C2H2O2), methylglyoxal and higher carbonyls (C3H4O2*) (see below), and carbon monoxide (CO) over the Amazon Basin during the ACRIDICON-CHUVA campaign from the German High Altitude and Long-range research aircraft (HALO) in autumn 2014. The joint observation of in situ CO and remotely measured CH2O, C2H2O2, and C3H4O2*, together with visible imagery and air mass back-trajectory modelling using NOAA HYSPLIT (National Oceanic Atmospheric Administration, HYbrid Single-Particle Lagrangian Integrated Trajectory), allows us to discriminate between the probing of background tropical air, in which the concentration of the measured species results from the oxidation of biogenically emitted volatile organic compounds (VOCs, mostly isoprene), and measurements of moderately to strongly polluted air masses affected by biomass burning emissions or the city plume of Manaus. For 12 near-surface measurements of fresh biomass burning plumes, normalized excess mixing ratios of C2H2O2 and C3H4O2* with respect to CH2O are inferred and compared to recent studies. The mean glyoxal-to-formaldehyde ratio RGF=0.07 (range 0.02–0.11) is in good agreement with recent reports which suggest RGF to be significantly lower than previously assumed in global chemical transport models (CTMs). The mean methylglyoxal-to-formaldehyde ratio RMF=0.98 (range 0.09–1.50) varies significantly during the different observational settings but overall appears to be much larger (up to a factor of 5) than previous reports suggest even when applying a correction factor of 2.0±0.5 to account for the additional dicarbonyls included in the C3H4O2* measurements. Using recently reported emission factors of CH2O for tropical forests, our observations suggest emission factors of EFG=0.25 (range 0.11 to 0.52) g kg−1 for C2H2O2 and EFM = 4.7 (range 0.5 to 8.64) g kg−1 for C3H4O2*. While EFG agrees well with recent reports, EFM is (like RMF) slightly larger than reported in other studies, presumably due to the different plume ages or fuels studied. Our observations of these critical carbonyls and intermediate oxidation products may support future photochemical modelling of air pollution over tropical vegetation, as well as validate past and present space-borne observations of the respective species.

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.

We report on a novel six-channel optical spectrometer (further on called mini-DOAS instrument) for airborne nadir and limb measurements of atmospheric trace gases, liquid and solid water, and spectral radiances in the UV/vis and NIR spectral ranges. The spectrometer was developed for measurements from aboard the German High-Altitude and Long-Range (HALO) research aircraft during dedicated research missions. Here we report on the relevant instrumental details and the novel scaling method used to infer the mixing ratios of UV/vis absorbing trace gases from their absorption measured in limb geometry. The uncertainties of the scaling method are assessed in more detail than before for sample measurements of NO2 and BrO. Some first results are reported along with complementary measurements and comparisons with model predictions for a selected HALO research flight from Cape Town to Antarctica, which was performed during the research mission ESMVal on 13 September 2012.

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.

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.

Observations of atmospheric trace gases in the tropical upper troposphere (UT), tropical tropopause layer (TTL), and lower stratosphere (LS) require dedicated measurement platforms and instrumentation. Here we present a new limb-scanning Differential Optical Absorption Spectroscopy (DOAS) instrument developed for NASA's Global Hawk (GH) unmanned aerial system and deployed during the Airborne Tropical TRopopause EXperiment (ATTREX). The mini-DOAS system is designed for automatic operation under unpressurized and unheated conditions at 14–18 km altitude, collecting scattered sunlight in three wavelength windows: UV (301–387 nm), visible (410–525 nm), and near infrared (900–1700 nm). A telescope scanning unit allows selection of a viewing angle around the limb, as well as real-time correction of the aircraft pitch. Due to the high altitude, solar reference spectra are measured using diffusors and direct sunlight. The DOAS approach allows retrieval of slant column densities (SCDs) of O3, O4, NO2, and BrO with relative errors similar to other aircraft DOAS systems. Radiative transfer considerations show that the retrieval of trace gas mixing ratios from the observed SCD based on O4 observations, the most common approach for DOAS measurements, is inadequate for high-altitude observations. This is due to the frequent presence of low-altitude clouds, which shift the sensitivity of the O4 SCD into the lower atmosphere and make it highly dependent on cloud coverage. A newly developed technique that constrains the radiative transfer by comparing in situ and DOAS O3 observations overcomes this issue. Extensive sensitivity calculations show that the novel O3-scaling technique allows the retrieval of BrO and NO2 mixing ratios at high accuracies of 0.5 and 15 ppt, respectively. The BrO and NO2 mixing ratios and vertical profiles observed during ATTREX thus provide new insights into ozone and halogen chemistry in the UT, TTL, and LS.

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.

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 first concerted multi-model intercomparison of halogenated very short-lived substances (VSLS) has been performed, within the framework of the ongoing Atmospheric Tracer Transport Model Intercomparison Project (TransCom). Eleven global models or model variants participated (nine chemical transport models and two chemistry–climate models) by simulating the major natural bromine VSLS, bromoform (CHBr3) and dibromomethane (CH2Br2), over a 20-year period (1993–2012). Except for three model simulations, all others were driven offline by (or nudged to) reanalysed meteorology. The overarching goal of TransCom-VSLS was to provide a reconciled model estimate of the stratospheric source gas injection (SGI) of bromine from these gases, to constrain the current measurement-derived range, and to investigate inter-model differences due to emissions and transport processes. Models ran with standardised idealised chemistry, to isolate differences due to transport, and we investigated the sensitivity of results to a range of VSLS emission inventories. Models were tested in their ability to reproduce the observed seasonal and spatial distribution of VSLS at the surface, using measurements from NOAA's long-term global monitoring network, and in the tropical troposphere, using recent aircraft measurements – including high-altitude observations from the NASA Global Hawk platform. The models generally capture the observed seasonal cycle of surface CHBr3 and CH2Br2 well, with a strong model–measurement correlation (r ≥ 0.7) at most sites. In a given model, the absolute model–measurement agreement at the surface is highly sensitive to the choice of emissions. Large inter-model differences are apparent when using the same emission inventory, highlighting the challenges faced in evaluating such inventories at the global scale. Across the ensemble, most consistency is found within the tropics where most of the models (8 out of 11) achieve best agreement to surface CHBr3 observations using the lowest of the three CHBr3 emission inventories tested (similarly, 8 out of 11 models for CH2Br2). In general, the models reproduce observations of CHBr3 and CH2Br2 obtained in the tropical tropopause layer (TTL) at various locations throughout the Pacific well. Zonal variability in VSLS loading in the TTL is generally consistent among models, with CHBr3 (and to a lesser extent CH2Br2) most elevated over the tropical western Pacific during boreal winter. The models also indicate the Asian monsoon during boreal summer to be an important pathway for VSLS reaching the stratosphere, though the strength of this signal varies considerably among models. We derive an ensemble climatological mean estimate of the stratospheric bromine SGI from CHBr3 and CH2Br2 of 2.0 (1.2–2.5) ppt, ∼ 57 % larger than the best estimate from the most recent World Meteorological Organization (WMO) Ozone Assessment Report. We find no evidence for a long-term, transport-driven trend in the stratospheric SGI of bromine over the simulation period. The transport-driven interannual variability in the annual mean bromine SGI is of the order of ±5 %, with SGI exhibiting a strong positive correlation with the El Niño–Southern Oscillation (ENSO) in the eastern Pacific. Overall, our results do not show systematic differences between models specific to the choice of reanalysis meteorology, rather clear differences are seen related to differences in the implementation of transport processes in the models.

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).

Emissions of halogenated very short-lived substances (VSLS) are poorly constrained. However, their inclusion in global models is required to simulate a realistic inorganic bromine (Bry) loading in both the troposphere, where bromine chemistry perturbs global oxidising capacity, and in the stratosphere, where it is a major sink for ozone (O3). We have performed simulations using a 3-D chemical transport model (CTM) including three top-down and a single bottom-up derived emission inventory of the major brominated VSLS bromoform (CHBr3) and dibromomethane (CH2Br2). We perform the first concerted evaluation of these inventories, comparing both the magnitude and spatial distribution of emissions. For a quantitative evaluation of each inventory, model output is compared with independent long-term observations at National Oceanic and Atmospheric Administration (NOAA) ground-based stations and with aircraft observations made during the NSF (National Science Foundation) HIAPER Pole-to-Pole Observations (HIPPO) project. For CHBr3, the mean absolute deviation between model and surface observation ranges from 0.22 (38%) to 0.78 (115%) parts per trillion (ppt) in the tropics, depending on emission inventory. For CH2Br2, the range is 0.17 (24%) to 1.25 (167%) ppt. We also use aircraft observations made during the 2011 Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere (SHIVA) campaign, in the tropical western Pacific. Here, the performance of the various inventories also varies significantly, but overall the CTM is able to reproduce observed CHBr3 well in the free troposphere using an inventory based on observed sea-to-air fluxes. Finally, we identify the range of uncertainty associated with these VSLS emission inventories on stratospheric bromine loading due to VSLS (BryVSLS). Our simulations show BryVSLS ranges from ~4.0 to 8.0 ppt depending on the inventory. We report an optimised estimate at the lower end of this range (~4 ppt) based on combining the CHBr3 and CH2Br2 inventories which give best agreement with the compilation of observations in the tropics.

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.

The international research project RECONCILE has addressed central questions regarding polar ozone depletion, with the objective to quantify some of the most relevant yet still uncertain physical and chemical processes and thereby improve prognostic modelling capabilities to realistically predict the response of the ozone layer to climate change. This overview paper outlines the scope and the general approach of RECONCILE, and it provides a summary of observations and modelling in 2010 and 2011 that have generated an in many respects unprecedented dataset to study processes in the Arctic winter stratosphere. Principally, it summarises important outcomes of RECONCILE including (i) better constraints and enhanced consistency on the set of parameters governing catalytic ozone destruction cycles, (ii) a better understanding of the role of cold binary aerosols in heterogeneous chlorine activation, (iii) an improved scheme of polar stratospheric cloud (PSC) processes that includes heterogeneous nucleation of nitric acid trihydrate (NAT) and ice on non-volatile background aerosol leading to better model parameterisations with respect to denitrification, and (iv) long transient simulations with a chemistry-climate model (CCM) updated based on the results of RECONCILE that better reproduce past ozone trends in Antarctica and are deemed to produce more reliable predictions of future ozone trends. The process studies and the global simulations conducted in RECONCILE show that in the Arctic, ozone depletion uncertainties in the chemical and microphysical processes are now clearly smaller than the sensitivity to dynamic variability.

We report on time-dependent O3, NO2 and BrO profiles measured by limb observations of scattered skylight in the stratosphere over Kiruna (67.9° N, 22.1° E) on 7 and 8 September 2009 during the autumn circulation turn-over. The observations are complemented by simultaneous direct solar occultation measurements around sunset and sunrise performed aboard the same stratospheric balloon payload. Supporting radiative transfer and photochemical modelling indicate that the measurements can be used to constrain the ratio J(BrONO2)/kBrO+NO2, for which at T = 220 ± 5 K an overall 1.7 (+0.4 −0.2) larger ratio is found than recommended by the most recent Jet Propulsion Laboratory (JPL) compilation (Sander et al., 2011). Sensitivity studies reveal the major reasons are likely to be (1) a larger BrONO2 absorption cross-section σBrONO2, primarily for wavelengths larger than 300 nm, and (2) a smaller kBrO+NO2 at 220 K than given by Sander et al. (2011). Other factors, e.g. the actinic flux and quantum yield for the dissociation of BrONO2, can be ruled out. The observations also have consequences for total inorganic stratospheric bromine (Bry) estimated from stratospheric BrO measurements at high NOx loadings, since the ratio J(BrONO2)/kBrO+NO2 largely determines the stratospheric BrO/Bry ratio during daylight. Using the revised J(BrONO2)/kBrO+NO2 ratio, total stratospheric Bry is likely to be 1.4 ppt smaller than previously estimated from BrO profile measurements at high NOx loadings. This would bring estimates of Bry inferred from organic source gas measurements (e.g. CH3Br, the halons, CH2Br2, CHBr3, etc.) into closer agreement with estimates based on BrO observations (inorganic method). The consequences for stratospheric ozone due to the revised J(BrONO2)/kBrO+NO2 ratio are small (maximum −0.8%), since at high NOx (for which most Bry assessments are made) the enhanced ozone loss by overestimating Bry is compensated for by the suppressed ozone loss due to the underestimation of BrO/Bry with a smaller J(BrONO2)/kBrO+NO2 ratio.

Measurements of mixing ratio profiles of stratospheric bromine monoxide (BrO) were made using observations of BrO rotational line emission at 650.179 GHz by a balloon-borne SIS (superconductor-insulator-superconductor) submillimeterwave heterodyne limb sounder (SLS). The balloon was launched from Ft. Sumner, New Mexico (34° N) on 22 September 2011. Peak mid-day BrO abundance varied from 16 ± 2 ppt at 34 km to 6 ± 4 ppt at 16 km. Corresponding estimates of total inorganic bromine (Bry), derived from BrO vmr (volume mixing ratio) using a photochemical box model, were 21 ± 3 ppt and 11 ± 5 ppt, respectively. Inferred Bry abundance exceeds that attributable solely to decomposition of long-lived methyl bromide and other halons, and is consistent with a contribution from bromine-containing very short lived substances, BryVSLS, of 4 ppt to 8 ppt. These results for BrO and Bry were compared with, and found to be in good agreement with, those of other recent balloon-borne and satellite instruments.

A latitudinal cross-section and vertical profiles of iodine monoxide (IO) are reported from the marine boundary layer of the Western Pacific. The measurements were taken using Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) during the TransBrom cruise of the German research vessel Sonne, which led from Tomakomai, Japan (42° N, 141° E) through the Western Pacific to Townsville, Australia (19° S, 146° E) in October 2009. In the marine boundary layer within the tropics (between 20° N and 5° S), IO mixing ratios ranged between 1 and 2.2 ppt, whereas in the subtropics and at mid-latitudes typical IO mixing ratios were around 1 ppt in the daytime. The profile retrieval reveals that the bulk of the IO was located in the lower part of the marine boundary layer. Photochemical simulations indicate that the organic iodine precursors observed during the cruise (CH3I, CH2I2, CH2ClI, CH2BrI) are not sufficient to explain the measured IO mixing ratios. Reasonable agreement between measured and modelled IO can only be achieved if an additional sea-air flux of inorganic iodine (e.g., I2) is assumed in the model. Our observations add further evidence to previous studies that reactive iodine is an important oxidant in the marine boundary layer.

This study presents two scientific and one operational retrieval algorithms used to obtain vertical distributions of bromine monoxide (BrO) from observations of the scattered solar light performed by the SCIAMACHY instrument in limb viewing geometry. The study begins with a discussion of the theoretical basis of all algorithms followed by an investigation of the retrieval sensitivity. Simulations with three different radiative transfer models allow us to analyze influence of the forward model implementation upon the retrieval results. By means of synthetic retrievals we analyze major sources of uncertainties in the resulting BrO profiles such as different BrO cross sections, their temperature dependence, and stratospheric aerosols. Finally, the reliability of SCIAMACHY BrO profile retrievals is demonstrated comparing results from different algorithms to each other and to balloon-borne observations.

A novel limb scanning mini-DOAS spectrometer for the detection of UV/vis absorbing radicals (e.g., O3, BrO, IO, HONO) was deployed on the DLR-Falcon (Deutsches Zentrum für Luft- und Raumfahrt) aircraft and tested during the ASTAR 2007 campaign (Arctic Study of Tropospheric Aerosol, Clouds and Radiation) that took place at Svalbard (78° N) in spring 2007. Our main objectives during this campaign were to test the instrument, and to perform spectral and profile retrievals of tropospheric trace gases, with particular interest on investigating the distribution of halogen compounds (e.g., BrO) during the so-called ozone depletion events (ODEs). In the present work, a new method for the retrieval of vertical profiles of tropospheric trace gases from tropospheric DOAS limb observations is presented. Major challenges arise from modeling the radiative transfer in an aerosol and cloud particle loaded atmosphere, and from overcoming the lack of a priori knowledge of the targeted trace gas vertical distribution (e.g., unknown tropospheric BrO vertical distribution). Here, those challenges are tackled by a mathematical inversion of tropospheric trace gas profiles using a regularization approach constrained by a retrieved vertical profile of the aerosols extinction coefficient EM. The validity and limitations of the algorithm are tested with in situ measured EM, and with an absorber of known vertical profile (O4). The method is then used for retrieving vertical profiles of tropospheric BrO. Results indicate that, for aircraft ascent/descent observations, the limit for the BrO detection is roughly 1.5 pptv (pmol mol−1), and the BrO profiles inferred from the boundary layer up to the upper troposphere and lower stratosphere have around 10 degrees of freedom. For the ASTAR 2007 deployments during ODEs, the retrieved BrO vertical profiles consistently indicate high BrO mixing ratios (∼15 pptv) within the boundary layer, low BrO mixing ratios (≤1.5 pptv) in the free troposphere, occasionally enhanced BrO mixing ratios (∼1.5 pptv) in the upper troposphere, and increasing BrO mixing ratios with altitude in the lowermost stratosphere. These findings agree reasonably well with satellite and balloon-borne soundings of total and partial BrO atmospheric column densities.

A new "Bayesian" minimization algorithm for the retrieval of the diurnal variation of UV/vis absorbing radicals (O3, NO2, BrO, OClO and HONO) from balloon-borne limb scattered skylight observations is discussed. The method evaluates spectroscopic measurements in combination with radiative transfer calculations to drive a mathematical inversion on a discrete time and height grid. Here, the proposed method is applied to data obtained during two deployments of the mini-DOAS instrument on different balloon payloads in northern Brazil in June 2005. The retrieval is tested by comparing the inferred profiles to in-situ ozone sounding data and to measurements of the ENVISAT/SCIAMACHY satellite instrument performed during a collocated overpass. The comparison demonstrates the strength and validity of our approach. In particular for time-varying radical concentrations, photochemical corrections due to temporal mismatch of the corresponding observations are rendered dispensable. Thus, limb scanning UV/vis spectrometry from balloon platforms offers a more direct and concise approach for satellite validation of radical measurements than solar occultation measurements. Furthermore, monitoring of the diurnal variation of stratospheric radicals allows us to constrain photochemical parameters which are critical for stratospheric ozone chemistry, such as the photolysis frequency of N2O5 by observations of the diurnal variation of NO2.

We report upper limits of IO and OIO in the tropical upper troposphere and stratosphere inferred from solar occultation spectra recorded by the LPMA/DOAS (Limb Profile Monitor of the Atmosphere/Differential Optical Absorption Spectroscopy) payload during two stratospheric balloon flights from a station in Northern Brazil (5.1° S, 42.9° W). In the tropical upper troposphere and lower stratosphere, upper limits for both, IO and OIO, are below 0.1 ppt. Photochemical modelling is used to estimate the compatible upper limits for the total gaseous inorganic iodine burden (Iy) amounting to 0.09 to 0.16 (+0.10/−0.04) ppt in the tropical lower stratosphere (21.0 km to 16.5 km) and 0.17 to 0.35 (+0.20/−0.08) ppt in the tropical upper troposphere (16.5 km to 13.5 km). In the middle stratosphere, upper limits increase with altitude as sampling sensitivity decreases. Our findings imply that the amount of gaseous iodine transported into the stratosphere through the tropical tropopause layer is small. Thus, iodine-mediated ozone loss plays a minor role for contemporary stratospheric photochemistry but might become significant in the future if source gas emissions or injection efficiency into the upper atmosphere are enhanced. However, photochemical modelling uncertainties are large and iodine might be transported into the stratosphere in particulate form.

A new climatology of stratospheric BrO profiles based on a parameterization using dynamical and chemical indicators has been developed, with the aim to apply it to the retrieval of tropospheric BrO columns from space nadir measurements. The adopted parameterization is based on three years of output data from the 3-D chemistry transport model BASCOE. The impact of the atmospheric dynamics on the stratospheric BrO distribution is treated by means of Bry/ozone correlations built from 3-D-CTM model results, while photochemical effects are taken into account using stratospheric NO2 columns as an indicator of the BrO/Bry ratio. The model simulations have been optimized for bromine chemistry and budget, and validated through comparisons using an extensive data set of ground-based, balloon-borne and satellite limb (SCIAMACHY) stratospheric BrO observations.

The first tropospheric and stratospheric (4 to 33 km) BrO profile is presented for the inner tropics derived from balloon-borne DOAS (Differential Optical Absorption Spectroscopy) measurements. In combination with photochemical modelling, total stratospheric inorganic bromine (Bry) is deduced to be (21.5±2.5) ppt in 4.5-year-old air, probed in 2005. We derive a total contribution of (5.2±2.5) ppt from brominated very short-lived substances and inorganic product gases to stratospheric Bry Tropospheric BrO was found to be y in the lower stratosphere. Bromine source gas measurements performed 10 days earlier Laube et al., 2008, indicate a lower Bry of (17.5±0.4) ppt. Potential reasons for this discrepancy are discussed.

A profiling algorithm based on the optimal estimation method is applied to ground-based zenith-sky UV-visible measurements from Harestua, Southern Norway (60° N, 11° E) in order to retrieve BrO vertical profiles. The sensitivity of the zenith-sky observations to the tropospheric BrO detection is increased by using for the spectral analysis a fixed reference spectrum corresponding to clear-sky noon summer conditions. The information content and retrieval errors are characterized and it is shown that the retrieved stratospheric profiles and total columns are consistent with correlative balloon and satellite observations, respectively. Tropospheric BrO columns are derived from profiles retrieved at 80° solar zenith angle during sunrise and sunset for the 2000–2006 period. They show a marked seasonality with mean column value ranging from 1.52±0.62×1013 molec/cm² in late winter/early spring to 0.92±0.38×1013 molec/cm² in summer, which corresponds to 1.0±0.4 and 0.6±0.2 pptv, respectively, if we assume that BrO is uniformly mixed in the troposphere. These column values are also consistent with previous estimates made from balloon, satellite, and other ground-based observations. Daytime (10:30 LT) tropospheric BrO columns are compared to the p-TOMCAT 3-D tropospheric chemical transport model (CTM) for the 2002–2003 period. p-TOMCAT shows a good agreement with the retrieved columns except in late winter/early spring where an underestimation by the model is obtained. This finding could be explained by the non-inclusion of sea-ice bromine sources in the current version of p-TOMCAT. Therefore the model cannot reproduce the possible transport of air-masses with enhanced BrO concentration due to bromine explosion events from the polar region to Harestua. The daytime stratospheric BrO columns are compared to the SLIMCAT stratospheric 3-D-CTM. The model run used in this study, which assumes 21.2 pptv for the Bry loading (15 pptv for long-lived bromine species and additional 6 pptv for very short-lived species (VSLS) added by a scaling of CH3Br), significantly underestimates the retrieved BrO columns. A sensitivity study shows that a good agreement can only be obtained if 6 to 8 pptv accounting for VSLS are added directly (and not by a scaling of CH3Br) to the SLIMCAT long-lived bromine species profile. This contribution of the VSLS to the total bromine loading is also consistent with recently published studies.

We have used an off-line three-dimensional (3-D) chemical transport model (CTM) to study long-term changes in stratospheric O3. The model was run from 1977–2004 and forced by ECMWF ERA-40 and operational analyses. Model runs were performed to examine the impact of increasing halogens and additional stratospheric bromine from short-lived source gases. The analyses capture much of the observed interannual variability in column ozone, but there are also unrealistic features. In particular the ERA-40 analyses cause a large positive anomaly in northern hemisphere (NH) column O3 in the late 1980s. Also, the change from ERA-40 to operational winds at the start of 2002 introduces abrupt changes in some model fields (e.g. temperature, ozone) which affect analysis of trends. The model reproduces the observed column increase in NH mid-latitudes from the mid 1990s. Analysis of a run with fixed halogens shows that this increase is not due to a significant decrease in halogen-induced loss, i.e. is not an indication of recovery. The model predicts only a small decrease in halogen-induced loss after 1999. In the upper stratosphere, despite the modelled turnover of chlorine around 1999, O3 does not increase because of the effects of increasing ECMWF temperatures, decreasing modelled CH4 at this altitude, and abrupt changes in the SH temperatures at the end of the ERA-40 period. The impact of an additional 5 pptv stratospheric bromine from short-lived species decreases mid-latitude column O3 by about 10 DU. However, the impact on the modelled relative O3 anomaly is generally small except during periods of large volcanic loading.

Stratospheric O3 and NO2 abundances measured by different remote sensing instruments are inter-compared: (1) Line-of-sight absorptions and vertical profiles inferred from solar spectra in the ultra-violet (UV), visible and infrared (IR) wavelength ranges measured by the LPMA/DOAS (Limb Profile Monitor of the Atmosphere/Differential Optical Absorption Spectroscopy) balloon payload during balloon ascent/descent and solar occultation are examined with respect to internal consistency. (2) The balloon borne stratospheric profiles of O3 and NO2 are compared to collocated space-borne skylight limb observations of the Envisat/SCIAMACHY satellite instrument. The trace gas profiles are retrieved from SCIAMACHY spectra using different algorithms developed at the Universities of Bremen and Heidelberg and at the Harvard-Smithsonian Center for Astrophysics. A comparison scheme is used that accounts for the spatial and temporal mismatch as well as differing photochemical conditions between the balloon and satellite borne measurements. It is found that the balloon borne measurements internally agree to within ±10% and ±20% for O3 and NO2, respectively, whereas the agreement with the satellite is ±20% for both gases in the 20 km to 30 km altitude range and in general worse below 20 km.

For the first time, results of four stratospheric BrO profiling instruments, are presented and compared with reference to the SLIMCAT 3-dimensional chemical transport model (3-D CTM). Model calculations are used to infer a BrO profile validation set, measured by 3 different balloon sensors, for the new Envisat/SCIAMACHY (ENVIronment SATellite/SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY) satellite instrument. The balloon observations include (a) balloon-borne in situ resonance fluorescence detection of BrO (Triple), (b) balloon-borne solar occultation DOAS measurements (Differential Optical Absorption Spectroscopy) of BrO in the UV, and (c) BrO profiling from the solar occultation SAOZ (Systeme d'Analyse par Observation Zenithale) balloon instrument. Since stratospheric BrO is subject to considerable diurnal variation and none of the measurements are performed close enough in time and space for a direct comparison, all balloon observations are considered with reference to outputs from the 3-D CTM. The referencing is performed by forward and backward air mass trajectory calculations to match the balloon with the satellite observations. The diurnal variation of BrO is considered by 1-D photochemical model calculation along the trajectories. The 1-D photochemical model is initialised with output data of the 3-D model with additional constraints on the vertical transport, the total amount and photochemistry of stratospheric bromine as given by the various balloon observations. Total [Bry]=(20.1±2.5) pptv obtained from DOAS BrO observations at mid-latitudes in 2003, serves as an upper limit of the comparison. Most of the balloon observations agree with the photochemical model predictions within their given error estimates. First retrieval exercises of BrO limb profiling from the SCIAMACHY satellite instrument on average agree to around 20% with the photochemically-corrected balloon observations of the remote sensing instruments (SAOZ and DOAS). An exception is the in situ Triple profile, in which the balloon and satellite data mostly does not agree within the given errors. In general, the satellite measurements show systematically higher values below 25 km than the balloon data and a change in profile shape above about 25 km.

On 21–22 August 2001, NO, NO2 and HNO3 mixing ratio profiles were measured at high latitudes during sunset and sunrise using the Limb Profile Monitor of the Atmosphere (LPMA) and the DOAS experiments under stratospheric balloon. Photochemical simulations using the chemistry module of the Reprobus Chemistry Transport Model (CTM) that are constrained by ozone and total NOy balloon observations reproduce well the partitioning of NOx and NOy when model results are calculated at the exact time and location of the measurement for each tangent altitude. Taking the recently recommended reaction rate coefficients for the NOy partitioning (JPL-2003) and using realistic aerosol surface area in order to initialise the model leads to an agreement between calculations and measurements better than 10% all over the covered altitude range.

Within the framework of the ENVISAT/-SCIAMACHY satellite validation, solar irradiance spectra are absolutely measured at moderate resolution in the UV/visible spectral range (in the UV from 316.7-418 nm and the visible from 400-652 nm at a full width half maximum resolution of 0.55 nm and 1.48 nm, respectively) from aboard the azimuth-controlled LPMA/DOAS balloon gondola at around 32 km balloon float altitude. After accounting for the atmospheric extinction due to Rayleigh scattering and gaseous absorption (O3 and NO2), the measured solar spectra are compared with previous observations. Our solar irradiance spectrum perfectly agrees within +0.03% with the re-calibrated Kurucz et al. (1984) solar spectrum (Fontenla et al., 1999, called MODTRAN 3.7) in the visible spectral range (415-650 nm), but it is +2.1% larger in the (370-415 nm) wavelength interval, and -4% smaller in the UV-A spectral range (316.7-370 nm), when the Kurucz spectrum is convolved to the spectral resolution of our instrument. Similar comparisons of the SOLSPEC (Thuillier et al., 1997, 1998a, b) and SORCE/SIM (Harder et al., 2000) solar spectra with MODTRAN 3.7 confirms our findings with the values being -0.5%, +2%, and -1.4% for SOLSPEC -0.33%, -0.47%, and -6.2% for SORCE/SIM, respectively. Comparison of the SCIAMACHY solar spectrum from channels 1 to 4 (- re-calibrated by the University of Bremen -) with MODTRAN 3.7 indicates an agreement within -0.4% in the visible spectral range (415-585 nm), -1.6% within the 370-415 nm, and -5.7% within 325-370 nm wavelength interval, in agreement with the results of the other sensors. In agreement with findings of Skupin et al. (2002) our study emphasizes that the present ESA SCIAMACHY level 1 calibration is systematically +15% larger in the considered wavelength intervals when compared to all available other solar irradiance measurements.

A novel light-weight, elevation scanning and absolutely calibrated UV/vis spectrometer and its application to balloon-borne limb radiance and trace gas profile measurements is described. Its performance and the novel method of balloon-borne UV/vis limb trace gas measurements has been tested against simultaneous observations of the same atmospheric parameters available from either (a) in-situ instrumentation (cf., by an electrochemical cell (ECC) ozone sonde also deployed aboard the gondola) or (b) trace gas profiles inferred from UV/vis/near IR solar occultation measurements performed on the same payload. The novel technique is also cross validated with radiative transfer modeling. Reasonable agreement is found (a) between measured and simulated limb radiances and (b) inferred limb O3, NO2, and BrO and correlative profile measurements when properly accounting for all relevant atmospheric parameters (temperature, pressure, aerosol extinction, and major absorbers).

A retrieval algorithm based on the Optimal Estimation Method (OEM) has been developed in order to provide vertical distributions of NO2 in the stratosphere from ground-based (GB) zenith-sky UV-visible observations. It has been applied to observational data sets from the NDSC (Network for Detection of Stratospheric Change) stations of Harestua (60° N, 10° E) and Andøya (69° N, 16° E) in Norway. The information content and retrieval errors have been analyzed following a formalism used for characterizing ozone profiles retrieved from solar infrared absorption spectra. In order to validate the technique, the retrieved NO2 vertical profiles and columns have been compared to correlative balloon and satellite observations. Such extensive validation of the profile and column retrievals was not reported in previously published work on the profiling from GB UV-visible measurements. A good agreement - generally better than 25% - has been found with the SAOZ (Système d'Analyse par Observations Zénithales) and DOAS (Differential Optical Absorption Spectroscopy) balloons. A similar agreement has been reached with correlative satellite data from the HALogen Occultation Experiment (HALOE) and Polar Ozone and Aerosol Measurement (POAM) III instruments above 25km of altitude. Below 25km, a systematic underestimation - by up to 40% in some cases - of both HALOE and POAM III profiles by our GB profile retrievals has been observed, pointing out more likely a limitation of both satellite instruments at these altitudes. We have concluded that our study strengthens our confidence in the reliability of the retrieval of vertical distribution information from GB UV-visible observations and offers new perspectives in the use of GB UV-visible network data for validation purposes.

This paper addresses the statistics underlying cloudy sky radiative transfer (RT) by inspection of the distribution of the path lengths of solar photons. Recent studies indicate that this approach is promising, since it might reveal characteristics about the diffusion process underlying atmospheric radiative transfer (Pfeilsticker, 1999). Moreover, it uses an observable that is directly related to the atmospheric absorption and, therefore, of climatic relevance. However, these studies are based largely on the accuracy of the measurement of the photon path length distribution (PPD). This paper presents a refined analysis method based on high resolution spectroscopy of the oxygen A-band. The method is validated by Monte Carlo simulation atmospheric spectra. Additionally, a new method to measure the effective optical thickness of cloud layers, based on fitting the measured differential transmissions with a 1-dimensional (discrete ordinate) RT model, is presented. These methods are applied to measurements conducted during the cloud radar inter-comparison campaign CLARE’98, which supplied detailed cloud structure information, required for the further analysis. For some exemplary cases, measured path length distributions and optical thicknesses are presented and backed by detailed RT model calculations. For all cases, reasonable PPDs can be retrieved and the effects of the vertical cloud structure are found. The inferred cloud optical thicknesses are in agreement with liquid water path measurements. Key words. Meteorology and atmospheric dynamics (radiative processes; instruments and techniques)

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)