Atmospheric acidity is increasingly determined by carbon dioxide and organic acids1–3. Among the latter, formic acid facilitates the nucleation of cloud droplets4 and contributes to the acidity of clouds and rainwater1,5. At present, chemistry–climate models greatly underestimate the atmospheric burden of formic acid, because key processes related to its sources and sinks remain poorly understood2,6–9. Here we present atmospheric chamber experiments that show that formaldehyde is efficiently converted to gaseous formic acid via a multiphase pathway that involves its hydrated form, methanediol. In warm cloud droplets, methanediol undergoes fast outgassing but slow dehydration. Using a chemistry–climate model, we estimate that the gas-phase oxidation of methanediol produces up to four times more formic acid than all other known chemical sources combined. Our findings reconcile model predictions and measurements of formic acid abundance. The additional formic acid burden increases atmospheric acidity by reducing the pH of clouds and rainwater by up to 0.3. The diol mechanism presented here probably applies to other aldehydes and may help to explain the high atmospheric levels of other organic acids that affect aerosol growth and cloud evolution.

Abstract. Theoretical, laboratory, and chamber studies have shown fast regeneration of the hydroxyl radical (OH) in the photochemistry of isoprene, largely due to unimolecular reactions which were previously thought not to be important under atmospheric conditions. Based on early field measurements, nearly complete regeneration was hypothesized for a wide range of tropospheric conditions, including areas such as the rainforest where slow regeneration of OH radicals is expected due to low concentrations of nitric oxide (NO). In this work the OH regeneration in isoprene oxidation is directly quantified for the first time through experiments covering a wide range of atmospherically relevant NO levels (between 0.15 and 2 ppbv – parts per billion by volume) in the atmospheric simulation chamber SAPHIR. These conditions cover remote areas partially influenced by anthropogenic NO emissions, giving a regeneration efficiency of OH close to 1, and areas like the Amazonian rainforest with very low NO, resulting in a surprisingly high regeneration efficiency of 0.5, i.e. a factor of 2 to 3 higher than explainable in the absence of unimolecular reactions. The measured radical concentrations were compared to model calculations, and the best agreement was observed when at least 50 % of the total loss of isoprene peroxy radicals conformers (weighted by their abundance) occurs via isomerization reactions for NO lower than 0.2 ppbv. For these levels of NO, up to 50 % of the OH radicals are regenerated from the products of the 1,6 α-hydroxy-hydrogen shift (1,6-H shift) of Z-δ-RO2 radicals through the photolysis of an unsaturated hydroperoxy aldehyde (HPALD) and/or through the fast aldehydic hydrogen shift (rate constant ∼10 s−1 at 300 K) in di-hydroperoxy carbonyl peroxy radicals (di-HPCARP-RO2), depending on their relative yield. The agreement between all measured and modelled trace gases (hydroxyl, hydroperoxy, and organic peroxy radicals, carbon monoxide, and the sum of methyl vinyl ketone, methacrolein, and hydroxyl hydroperoxides) is nearly independent of the adopted yield of HPALD and di-HPCARP-RO2 as both degrade relatively fast (<1 h), forming the OH radical and CO among other products. Taking into consideration this and earlier isoprene studies, considerable uncertainties remain on the distribution of oxygenated products, which affect radical levels and organic aerosol downwind of unpolluted isoprene-dominated regions.

Abstract:The WeCare project (Utilizing Weather information for Climate efficient and eco efficient future aviation), an internal project of the German Aerospace Center (Deutsches Zentrum für Luft-und Raumfahrt, DLR), aimed at finding solutions for reducing the climate impact of aviation based on an improved understanding of the atmospheric impact from aviation by making use of measurements and modeling approaches. WeCare made some important contributions to advance the scientific understanding in the area of atmospheric and air transportation research. We characterize contrail properties, show that the aircraft type significantly influences these properties, and how contrail-cirrus interacts with natural cirrus. Aviation NO x emissions lead to ozone formation and we show that the strength of the ozone enhancement varies, depending on where within a weather pattern NO x is emitted. These results, in combination with results on the effects of aerosol emissions on low cloud properties, give a revised view on the total radiative forcing of aviation. The assessment of a fleet of strut-braced wing aircraft with an open rotor is investigated and reveals the potential to significantly reduce the climate impact. Intermediate stop operations have the potential to significantly reduce fuel consumption. However, we find that, if only optimized for fuel use, they will have an increased climate impact, since non-CO 2 effects compensate the reduced warming from CO 2 savings. Avoiding climate sensitive regions has a large potential in reducing climate impact at relatively low costs. Taking advantage of a full 3D optimization has a much better eco-efficiency than lateral re-routings, only. The implementation of such operational measures requires many more considerations. Non-CO 2 aviation effects are not considered in international agreements. We showed that climate-optimal routing could be achieved, if market-based measures were in place, which include these non-CO 2 effects. An alternative measure to foster climate-optimal routing is the closing of air spaces, which are very climate-sensitive. Although less effective than an unconstrained optimization with respect to climate, it still has a significant potential to reduce the climate impact of aviation. By combining atmospheric and air transportation research, we assess climate mitigation measures, aiming at providing information to aviation stakeholders and policy-makers to make aviation more climate compatible.

Abstract. Emissions of aviation include CO2, H2O, NOx, sulfur oxides, and soot. Many studies have investigated the annual mean climate impact of aviation emissions. While CO2 has a long atmospheric residence time and is almost uniformly distributed in the atmosphere, non-CO2 gases and particles and their products have short atmospheric residence times and are heterogeneously distributed. The climate impact of non-CO2 aviation emissions is known to vary with different meteorological background situations. The aim of this study is to systematically investigate the influence of characteristic weather situations on aviation climate effects over the North Atlantic region, to identify the most sensitive areas, and to potentially detect systematic weather-related similarities. If aircraft were re-routed to avoid climate-sensitive regions, the overall aviation climate impact might be reduced. Hence, the sensitivity of the atmosphere to local emissions provides a basis for the assessment of weather-related, climate-optimized flight trajectory planning. To determine the climate change contribution of an individual emission as a function of location, time, and weather situation, the radiative impact of local emissions of NOx and H2O to changes in O3, CH4, H2O and contrail cirrus was computed by means of the ECHAM5/MESSy Atmospheric Chemistry model. From this, 4-dimensional climate change functions (CCFs) were derived. Typical weather situations in the North Atlantic region were considered for winter and summer. Weather-related differences in O3, CH4, H2O, and contrail cirrus CCFs were investigated. The following characteristics were identified: enhanced climate impact of contrail cirrus was detected for emissions in areas with large-scale lifting, whereas low climate impact of contrail cirrus was found in the area of the jet stream. Northwards of 60∘ N, contrails usually cause climate warming in winter, independent of the weather situation. NOx emissions cause a high positive climate impact if released in the area of the jet stream or in high-pressure ridges, which induces a south- and downward transport of the emitted species, whereas NOx emissions at, or transported towards, high latitudes cause low or even negative climate impact. Independent of the weather situation, total NOx effects show a minimum at ∼250 hPa, increasing towards higher and lower altitudes, with generally higher positive impact in summer than in winter. H2O emissions induce a high climate impact when released in regions with lower tropopause height, whereas low climate impact occurs for emissions in areas with higher tropopause height. H2O CCFs generally increase with height and are larger in winter than in summer. The CCFs of all individual species can be combined, facilitating the assessment of total climate impact of aircraft trajectories considering CO2 and spatially and temporally varying non-CO2 effects. Furthermore, they allow for the optimization of aircraft trajectories with reduced overall climate impact. This also facilitates a fair evaluation of trade-offs between individual species. In most regions, NOx and contrail cirrus dominate the sensitivity to local aviation emissions. The findings of this study recommend considering weather-related differences for flight trajectory optimization in favour of reducing total climate impact.

Abstract. Isocyanic acid (HNCO) is a chemical constituent suspected to be harmful to humans if ambient concentrations exceed ∼1 ppbv. HNCO is mainly emitted by combustion processes but is also inadvertently released by NOx mitigation measures in flue gas treatments. With increasing biomass burning and more widespread usage of catalytic converters in car engines, good prediction of HNCO atmospheric levels with global models is desirable. Little is known directly about the chemical loss processes of HNCO, which limits the implementation in global Earth system models. This study aims to close this knowledge gap by combining a theoretical kinetic study on the major oxidants reacting with HNCO with a global modelling study. The potential energy surfaces of the reactions of HNCO with OH and NO3 radicals, Cl atoms, and ozone were studied using high-level CCSD(T)/CBS(DTQ)//M06-2X/aug-cc-pVTZ quantum chemical methodologies, followed by transition state theory (TST) theoretical kinetic predictions of the rate coefficients at temperatures of 200–3000 K. It was found that the reactions are all slow in atmospheric conditions, with k(300K)≤7×10-16 cm3molecule-1s-1, and that product formation occurs predominantly by H abstraction; the predictions are in good agreement with earlier experimental work, where available. The reverse reactions of NCO radicals with H2O, HNO3, and HCl, of importance mostly in combustion, were also examined briefly. The findings are implemented into the atmospheric model EMAC (ECHAM/MESSy Atmospheric Chemistry) to estimate the importance of each chemical loss process on a global scale. The EMAC predictions confirm that the gas-phase chemical loss of HNCO is a negligible process, contributing less than 1 % and leaving heterogeneous losses as the major sinks. The removal of HNCO by clouds and precipitation contributes about 10 % of the total loss, while globally dry deposition is the main sink, accounting for ∼90 %. The global simulation also shows that due to its long chemical lifetime in the free troposphere, HNCO can be efficiently transported into the UTLS by deep convection events. Daily-average mixing ratios of ground-level HNCO are found to regularly exceed 1 ppbv in regions dominated by biomass burning events, but rarely exceed levels above 10 ppt in other areas of the troposphere, though locally instantaneous toxic levels are expected.

Abstract. The particularly strong dry season in Indonesia in 2015, caused by an exceptional strong El Niño, led to severe peatland fires resulting in high volatile organic compound (VOC) biomass burning emissions. At the same time, the developing Asian monsoon anticyclone (ASMA) and the general upward transport in the intertropical convergence zone (ITCZ) efficiently transported the resulting primary and secondary pollutants to the upper troposphere/lower stratosphere (UTLS). In this study, we assess the importance of these VOC emissions for the composition of the lower troposphere and the UTLS, and we investigate the effect of in-cloud oxygenated VOC (OVOC) oxidation during such a strong pollution event. This is achieved by performing multiple chemistry simulations using the global atmospheric model ECHAM/MESSy (EMAC). By comparing modelled columns of the biomass burning marker hydrogen cyanide (HCN) to spaceborne measurements from the Infrared Atmospheric Sounding Interferometer (IASI), we find that EMAC properly captures the exceptional strength of the Indonesian fires. In the lower troposphere, the increase in VOC levels is higher in Indonesia compared to other biomass burning regions. This has a direct impact on the oxidation capacity, resulting in the largest regional reduction in hydroxyl radicals (OH) and nitrogen oxides (NOx). Even though an increase in ozone (O3) is predicted close to the peatland fires, particular high concentrations of phenols lead to an O3 depletion in eastern Indonesia. By employing the detailed in-cloud OVOC oxidation scheme Jülich Aqueous-phase Mechanism of Organic Chemistry (JAMOC), we find that the predicted changes are dampened and that by ignoring these processes, global models tend to overestimate the impact of such extreme pollution events. In the ASMA and the ITCZ, the upward transport leads to elevated VOC concentrations in the UTLS region, which results in a depletion of lower stratospheric O3. We find that this is caused by a high destruction of O3 by phenoxy radicals and by the increased formation of NOx reservoir species, which dampen the chemical production of O3. The Indonesian peatland fires regularly occur during El Niño years and contribute to the depletion of O3. In the time period from 2001 to 2016, we find that the lower stratospheric O3 is reduced by about 0.38 DU and contributes to about 25 % to the lower stratospheric O3 reduction observed by remote sensing. By not considering these processes, global models might not be able to reproduce this variability in lower stratospheric O3.

Abstract. Aviation-attributed climate impact depends on a combination of composition changes in trace gases due to emissions of carbon dioxide (CO2) and non-CO2 species. Nitrogen oxides (NOx = NO + NO2) emissions induce an increase in ozone (O3) and a depletion of methane (CH4), leading to a climate warming and a cooling, respectively. In contrast to CO2, non-CO2 contributions to the atmospheric composition are short lived and are thus characterised by a high spatial and temporal variability. In this study, we investigate the influence of weather patterns and their related transport processes on composition changes caused by aviation-attributed NOx emissions. This is achieved by using the atmospheric chemistry model EMAC (ECHAM/MESSy). Representative weather situations were simulated in which unit NOx emissions are initialised in specific air parcels at typical flight altitudes over the North Atlantic flight sector. By explicitly calculating contributions to the O3 and CH4 concentrations induced by these emissions, interactions between trace gas composition changes and weather conditions along the trajectory of each air parcel are investigated. Previous studies showed a clear correlation between the prevailing weather situation at the time when the NOx emission occurs and the climate impact of the NOx emission. Here, we show that the aviation NOx contribution to ozone is characterised by the time and magnitude of its maximum and demonstrate that a high O3 maximum is only possible if the maximum occurs early after the emission. Early maxima occur only if the air parcel, in which the NOx emission occurred, is transported to lower altitudes, where the chemical activity is high. This downward transport is caused by subsidence in high-pressure systems. A high ozone magnitude only occurs if the air parcel is transported downward into a region in which the ozone production is efficient. This efficiency is limited by atmospheric NOx and HOx concentrations during summer and winter, respectively. We show that a large CH4 depletion is only possible if a strong formation of O3 occurs due to the NOx emission and if high atmospheric H2O concentrations are present along the air parcel's trajectory. Only air parcels, which are transported into tropical areas due to high-pressure systems, experience high concentrations of H2O and thus a large CH4 depletion. Avoiding climate-sensitive areas by rerouting aircraft flight tracks is currently computationally not feasible due to the long chemical simulations needed. The findings of this study form a basis of a better understanding of NOx climate-sensitive areas and through this will allow us to propose an alternative approach to estimate aviation's climate impact on a day-to-day basis, based on computationally cheaper meteorological simulations without computationally expensive chemistry. This comprises a step towards a climate impact assessment of individual flights, here with the contribution of aviation NOx emissions to climate change, ultimately enabling routings with a lower climate impact by avoiding climate-sensitive regions.

Abstract. The Jülich Aqueous-phase Mechanism of Organic Chemistry (JAMOC) is developed and implemented in the Module Efficiently Calculating the Chemistry of the Atmosphere (MECCA; version 4.5.0). JAMOC is an explicit in-cloud oxidation scheme for oxygenated volatile organic compounds (OVOCs), suitable for global model applications. It is based on a subset of the comprehensive Cloud Explicit Physico-chemical Scheme (CLEPS; version 1.0). The phase transfer of species containing up to 10 carbon atoms is included, and a selection of species containing up to 4 carbon atoms reacts in the aqueous phase. In addition, the following main advances are implemented: (1) simulating hydration and dehydration explicitly; (2) taking oligomerisation of formaldehyde, glyoxal, and methylglyoxal into account; (3) adding further photolysis reactions; and (4) considering gas-phase oxidation of new outgassed species. The implementation of JAMOC in MECCA makes a detailed in-cloud OVOC oxidation model readily available for box as well as for regional and global simulations that are affordable with modern supercomputing facilities. The new mechanism is tested inside the box model Chemistry As A Boxmodel Application (CAABA), yielding reduced gas-phase concentrations of most oxidants and OVOCs except for the nitrogen oxides.