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.