Airborne glyoxal measurements in different regions of the globe: Its atmospheric fate, comparison with TROPOMI observations and EMAC simulations, and inferred biomass burning emission factors for glyoxal and methylglyoxal

Tropospheric glyoxal mixing ratios and vertical column densities were measured during 72 research flights with the German research aircraft DLR HALO over different regions etween 2014 and 2019. Over the Amazon rainforest, the bservations are complemented by simultaneous formaldehyde and methylglyoxal measurements. The glyoxal measurements are confirmed by same-day observations of the TROPOMI satellite instrument and compared to simulations of the photochemical transport model EMAC. Deviations of air- and spaceborne glyoxal are found for spatially small pollution plumes and those located near the surface. This causes smaller satellite glyoxal measurements around urban centres. Unexplained glyoxal enhancements are detected repeatedly in aged biomass burning plumes and the tropical marine boundary layer. Over the rainforest, emission factors are estimated for tropical forest fires (0.11–0.52 gglyoxal kg−1 fuel, 0.50–8.64 gmethylglyoxal kg−1 fuel) and isoprene is identified as a potential glyoxal and methylglyoxal precursor above the boundary layer. The comparison to EMAC shows an underestimation of modelled glyoxal in most regions, especially in the boundary layer and pollution plumes. This is indicative of an underestimation of glyoxal and its precursors by EMAC, with consequences for the tropospheric oxidative capacity as well as the formation of ozone and secondary organic aerosols and hence for the radiative forcing

Airborne observations of peroxy radicals during the EMeRGe campaign in Europe

In this study, airborne measurements of the sum of hydroperoxyl (HO$_2$) and organic peroxy (RO$_2$) radicals that react with nitrogen monoxide (NO) to produce nitrogen dioxide (NO$_2$), 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 RO$^∗_2$ on HALO were made using the in situ instrument Peroxy Radical Chemical Enhancement and Absorption Spectrometer (PeRCEAS). RO$^∗_2$ is to a good approximation the sum of peroxy radicals reacting with NO to produce NO$_2$. RO$^∗_2$ 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 RO$^∗_2$ precursor concentrations measured on board, as well as the relevant rate coefficients. Generally, high RO$^∗_2$ concentrations were measured in air masses with high production rates. In the air masses investigated, RO$^∗_2$ is primarily produced by the reaction of O$^1$D 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 RO$^∗_2$ concentrations are expected to be in a photostationary steady state (PSS), i.e. a balance between production and loss rates is assumed. The RO$^∗_2$ production and loss rates and the suitability of PSS assumptions to estimate the RO$^∗_2$ mixing ratios and variability during the airborne observations are discussed. The PSS assumption for RO$^∗_2$ is considered robust enough to calculate RO$^∗_2$ mixing ratios for most conditions encountered in the air masses measured. The similarities and discrepancies between measured and PSS calculated RO$^∗_2$ mixing ratios are discussed. The dominant terminating processes for RO$^∗_2$ in the pollution plumes measured up to 2000 m are the formation of nitrous acid, nitric acid, and organic nitrates. Above2000 m, HO$_2$–HO$_2$ and HO$_2$–RO$_2$ reactions dominate the RO$^∗_2$ removal. RO$^∗_2$ 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 RO$^∗_2$ 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 RO$^∗_2$ measured is overestimated by the analytical expression. This may be caused by the formation of H$_2$O and O$_2$ from OH and HO$_2$, being about 4 times faster than the rate of the OH oxidation reaction of the dominant OVOCs considered

Overview: On the transport and transformation of pollutants in the outflow of major population centres – observational data from the EMeRGe European intensive operational period in summer 2017

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

Aircraft measurements of nitrous acid in excess of model predictions in the boundary layer and free troposphere

Middle and long-term &#160;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 (H&#252;neke 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 &#160;by the C-Tof-AMS instrument may reveal potential reaction mechanisms to explain the discrepancy.&#160;</p

Organic and inorganic bromine measurements around the extratropical tropopause and lowermost stratosphere (Ex-LMS): Insights into transport pathways and total bromine

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 &#177; 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&#730;N (high bromine filament &#8211; 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 &#177; 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.</p