Abstract. We present novel measurements of five short-lived brominated source gases (CH2Br2, CHBr3, CH2ClBr, CHCl2Br and CHClBr2). These rather short-lived gases are an important source of bromine to the stratosphere, where they can lead to depletion of ozone. The measurements have been obtained using an in situ gas chromatography and mass spectrometry (GC–MS) system on board the High Altitude and Long Range Research Aircraft (HALO). The instrument is extremely sensitive due to the use of chemical ionization, allowing detection limits in the lower parts per quadrillion (ppq, 10−15) range. Data from three campaigns using HALO are presented, where the upper troposphere and lower stratosphere (UTLS) of the northern hemispheric mid-to-high latitudes were sampled during winter and during late summer to early fall. We show that an observed decrease with altitude in the stratosphere is consistent with the relative lifetimes of the different compounds. Distributions of the five source gases and total organic bromine just below the tropopause show an increase in mixing ratio with latitude, in particular during polar winter. This increase in mixing ratio is explained by increasing lifetimes at higher latitudes during winter. As the mixing ratios at the extratropical tropopause are generally higher than those derived for the tropical tropopause, extratropical troposphere-to-stratosphere transport will result in elevated levels of organic bromine in comparison to air transported over the tropical tropopause. The observations are compared to model estimates using different emission scenarios. A scenario with emissions mainly confined to low latitudes cannot reproduce the observed latitudinal distributions and will tend to overestimate organic bromine input through the tropical tropopause from CH2Br2 and CHBr3. Consequently, the scenario also overestimates the amount of brominated organic gases in the stratosphere. The two scenarios with the highest overall emissions of CH2Br2 tend to overestimate mixing ratios at the tropical tropopause, but they are in much better agreement with extratropical tropopause mixing ratios. This shows that not only total emissions but also latitudinal distributions in the emissions are of importance. While an increase in tropopause mixing ratios with latitude is reproduced with all emission scenarios during winter, the simulated extratropical tropopause mixing ratios are on average lower than the observations during late summer to fall. We show that a good knowledge of the latitudinal distribution of tropopause mixing ratios and of the fractional contributions of tropical and extratropical air is needed to derive stratospheric inorganic bromine in the lowermost stratosphere from observations. In a sensitivity study we find maximum differences of a factor 2 in inorganic bromine in the lowermost stratosphere from source gas injection derived from observations and model outputs. The discrepancies depend on the emission scenarios and the assumed contributions from different source regions. Using better emission scenarios and reasonable assumptions on fractional contribution from the different source regions, the differences in inorganic bromine from source gas injection between model and observations is usually on the order of 1 ppt or less. We conclude that a good representation of the contributions of different source regions is required in models for a robust assessment of the role of short-lived halogen source gases on ozone depletion in the UTLS.

During spring 2020, the COVID-19 pandemic caused massive reductions in emissions from industry, ground and airborne transportation. To explore the resulting atmospheric composition changes, we conducted the BLUESKY campaign with two research aircraft and measured trace gases, aerosols, and cloud properties from the boundary layer to the lower stratosphere. From 16 May to 9 June 2020, we performed 20 flights in the early COVID-19 lockdown phase over Europe and the Atlantic Ocean. We found up to 50% reductions in boundary layer nitrogen dioxide concentrations in urban areas from GOME-2B satellite data, along with carbon monoxide reductions in the pollution hot spots. We measured 20 to 70% reductions in total reactive nitrogen, carbon monoxide and fine mode aerosol concentration in profiles over German cities compared to a 10-year data set from passenger aircraft. The total aerosol mass was significantly reduced below 5 km altitude, and the organic aerosol fraction also aloft, indicative of decreased organic precursor gas emissions. The reduced aerosol optical thickness caused a perceptible shift in sky color towards the blue part of the spectrum (hence BLUESKY) and increased shortwave radiation at the surface. We find that the 80% decline in air traffic led to substantial reductions in nitrogen oxides at cruise altitudes, in contrail cover, and in resulting radiative forcing. The light extinction and depolarization by cirrus were also reduced in regions with substantially decreased air traffic. General circulation-chemistry model simulations indicate good agreement with the measurements when applying a reduced emission scenario. The comprehensive BLUESKY dataset documents the major impact of anthropogenic emissions on the atmospheric composition.

Abstract. Fires emit a substantial amount of non-methane organic gases (NMOGs), the atmospheric oxidation of which can contribute to ozone and secondary particulate matter formation. However, the abundance and reactivity of these fire NMOGs are uncertain and historically not well constrained. In this work, we expand the representation of fire NMOGs in a global chemical transport model, GEOS-Chem. We update emission factors to Andreae (2019) and the chemical mechanism to include recent aromatic and ethene and ethyne model improvements (Bates et al., 2021; Kwon et al., 2021). We expand the representation of NMOGs by adding lumped furans to the model (including their fire emission and oxidation chemistry) and by adding fire emissions of nine species already included in the model, prioritized for their reactivity using data from the Fire Influence on Regional to Global Environments (FIREX) laboratory studies. Based on quantified emissions factors, we estimate that our improved representation captures 72 % of emitted, identified NMOG carbon mass and 49 % of OH reactivity from savanna and temperate forest fires, a substantial increase from the standard model (49 % of mass, 28 % of OH reactivity). We evaluate fire NMOGs in our model with observations from the Amazon Tall Tower Observatory (ATTO) in Brazil, Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) and DC3 in the US, and Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) in boreal Canada. We show that NMOGs, including furan, are well simulated in the eastern US with some underestimates in the western US and that adding fire emissions improves our ability to simulate ethene in boreal Canada. We estimate that fires provide 15 % of annual mean simulated surface OH reactivity globally, as well as more than 75 % over fire source regions. Over continental regions about half of this simulated fire reactivity comes from NMOG species. We find that furans and ethene are important globally for reactivity, while phenol is more important at a local level in the boreal regions. This is the first global estimate of the impact of fire on atmospheric reactivity.

Abstract. The tropical forests are Earth's largest source of biogenic volatile organic compounds (BVOCs) and thus also the largest atmospheric sink region for the hydroxyl radical (OH). However, the OH sink above tropical forests is poorly understood, as past studies have revealed large unattributed fractions of total OH reactivity. We present the first total OH reactivity and volatile organic compound (VOC) measurements made at the Amazon Tall Tower Observatory (ATTO) at 80, 150, and 320 m above ground level, covering two dry seasons, one wet season, and one transition season in 2018–2019. By considering a wide range of previously unaccounted for VOCs, which we identified by proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS), the unattributed fraction was with an overall average of 19 % within the measurement uncertainty of ∼ 35 %. In terms of seasonal average OH reactivity, isoprene accounted for 23 %–43 % of the total and oxygenated VOCs (OVOCs) for 22 %–40 %, while monoterpenes, sesquiterpenes, and green leaf volatiles combined were responsible for 9 %–14 %. These findings show that OVOCs were until now an underestimated contributor to the OH sink above the Amazon forest. By day, total OH reactivity decreased towards higher altitudes with strongest vertical gradients observed around noon during the dry season (−0.026 s−1 m−1), while the gradient was inverted at night. Seasonal differences in total OH reactivity were observed, with the lowest daytime average and standard deviation of 19.9 ± 6.2 s−1 during a wet–dry transition season with frequent precipitation; 23.7 ± 6.5 s−1 during the wet season; and the highest average OH reactivities during two dry-season observation periods with 28.1 ± 7.9 s−1 and 29.1 ± 10.8 s−1, respectively. The effects of different environmental parameters on the OH sink were investigated, and quantified, where possible. Precipitation caused short-term spikes in total OH reactivity, which were followed by below-normal OH reactivity for several hours. Biomass burning increased total OH reactivity by 2.7 to 9.5 s−1. We present a temperature-dependent parameterization of OH reactivity that could be applied in future models of the OH sink to further reduce our knowledge gaps in tropical-forest OH chemistry.

In this study, the odour thresholds (OT) and atmospheric lifetimes (AL) were compared for a suite of volatile organic compounds. It was found that odour threshold, as determined by the triangle bag method, correlated surprisingly well with atmospheric lifetime for a given chemical family. Molecules with short atmospheric lifetimes with respect to the primary atmospheric oxidant OH tend to be more sensitively detected by the human nose. Overall the correlation of odour threshold with atmospheric lifetime was better than with mass and vapour pressure. Several outliers from the correlations for particular chemical families were examined in detail. For example, diacetyl was an outlier in the ketone dataset that fitted the trend when its more important photolysis lifetime was included; and similarly, the relatively low odour threshold of carbonyl sulfide (OCS) was interpreted in terms of uptake by vegetation. The OT/AL relationship suggests that OH rate constants can be used as a first-order estimate for odour thresholds (and vice versa ). We speculate that the nose's high sensitivity to chemicals that are reactive in the air is likely an evolved rather than a learned condition. This is based on the lack of dependence on ozone in the aliphatics, that the anthropogenically emitted aromatic compounds had the worst correlation, and that OCS had a much lower than predicted OT. Finally, we use the OT/AL relationships derived to predict odour thresholds and rate constants that have not yet been determined in order to provide a test to this hypothesis. This article is part of the Theo Murphy meeting issue ‘Olfactory communication in humans’.

Tobacco combustion products in deposited particles and bodily reservoirs enable persistent thirdhand smoke contamination and transport.

Abstract. The reactivity of NO3 plays an important role in modifying the fate of reactive nitrogen species at nighttime. High reactivity (e.g. towards unsaturated volatile organic compounds – VOCs) can lead to formation of organic nitrates and secondary organic aerosol, whereas low reactivity opens the possibility of heterogeneous NOx losses via the formation and uptake of N2O5 to particles. We present direct NO3 reactivity measurements (kNO3) that quantify the VOC-induced losses of NO3 during the TO2021 campaign at the summit of the Kleiner Feldberg mountain (825 m, Germany) in July 2021. kNO3 was on average ∼0.035 s−1 during the daytime, ∼0.015 s−1 for almost half of the nights and below the detection limit of 0.006 s−1 for the other half, which may be linked to sampling from above the nocturnal surface layer. NO3 reactivities derived from VOC measurements and the corresponding rate coefficient were in good agreement with kNO3, with monoterpenes representing 84 % of the total reactivity. The fractional contribution F of kNO3 to the overall NO3 loss rate (which includes an additional reaction of NO3 with NO and photolysis) were on average ∼16 % during the daytime and ∼50 %–60 % during the nighttime. The relatively low nighttime value of F is related to the presence of several tens of parts per trillion by volume (pptv) of NO on several nights. NO3 mixing ratios were not measured, but steady-state calculations resulted in nighttime values between <1 and 12 pptv. A comparison of results from TO2021 with direct measurements of NO3 during previous campaigns between 2008 and 2015 at this site revealed that NO3 loss rates were remarkably high during TO2021, while NO3 production rates were low. We observed NO mixing ratios of up to 80 pptv at night, which has implications for the cycling of reactive nitrogen at this site. With O3 present at levels of mostly 25 to 60 ppbv (parts per billion by volume), NO is oxidized to NO2 on a timescale of a few minutes. We find that maintaining NO mixing ratios of, e.g., 40 pptv requires a ground-level NO emission rate of 0.33 pptv s−1 (into a shallow surface layer of 10 m depth). This in turn requires a rapid deposition of NO2 to the surface (vdNO2∼0.15 cm s−1) to reduce nocturnal NO2 levels to match the observations.

&lt;p&gt;&lt;strong&gt;Abstract.&lt;/strong&gt; We present novel measurements of five short-lived brominated source gases (CH&lt;sub&gt;2&lt;/sub&gt;Br&lt;sub&gt;2&lt;/sub&gt;, CHBr&lt;sub&gt;3&lt;/sub&gt;, CH&lt;sub&gt;2&lt;/sub&gt;ClBr, CHCl&lt;sub&gt;2&lt;/sub&gt;Br and CHClBr&lt;sub&gt;2&lt;/sub&gt;) obtained using a gas chromatograph-mass spectrometer system on board the High Altitude and Long Range Research Aircraft (HALO). The instrument is extremely sensitive due to the use of chemical ionisation, allowing detection limits in the lower parts per quadrillion (10&lt;sup&gt;&amp;#8722;15&lt;/sup&gt;) range. Data from three campaigns using the HALO aircraft are presented, where the Upper Troposphere/Lower Stratosphere (UTLS) of the Northern Hemisphere mid to high latitudes were sampled during winter and during late summer to early fall. We show that an observed decrease with altitude in the stratosphere is consistent with the relative lifetimes of the different compounds. Distributions of the five source gases and total organic bromine just below the tropopause shows an increase in mixing ratio with latitude, in particular during polar winter. This increase in mixing ratio is explained by increasing lifetimes at higher latitudes during winter. As the mixing ratio at the extratropical tropopause are generally higher than those derived for the tropical tropopause, extratropical troposphere-to-stratosphere transport will result in elevated levels of organic bromine in comparison to air transported over the tropical tropopause. The observations are compared to model estimates using different emission scenarios. A scenario which has emissions most strongly concentrated to low latitudes cannot reproduce the observed latitudinal distributions and will tend to overestimate bromine input through the tropical tropopause from CH&lt;sub&gt;2&lt;/sub&gt;Br&lt;sub&gt;2&lt;/sub&gt; and CHBr&lt;sub&gt;3&lt;/sub&gt;. Consequently, the scenario also overestimates the amount of brominated organic gases in the stratosphere. The two scenarios with the highest overall emissions of CH&lt;sub&gt;2&lt;/sub&gt;Br&lt;sub&gt;2&lt;/sub&gt; tend to overestimate mixing ratios at the tropical tropopause but are in much better agreement with extratropical tropopause values, showing that not only total emissions but also latitudinal distributions in the emissions are of importance. While an increase in tropopause values with latitude is reproduced with all emission scenarios during winter, the simulated extratropical tropopause values are on average lower than the observations during late summer to fall. We show that a good knowledge of the latitudinal distribution of tropopause mixing ratios and of the fractional contributions of tropical and extratropical air is needed to derive stratospheric inorganic bromine in the lowermost stratosphere from observations. Depending on the underlying emission scenario, differences of a factor 2 in reactive bromine derived from observations and model outputs are found for the lowermost stratosphere, based on source gas injection. We conclude that a good representation of the contributions of different source regions is required in models for a robust assessment of the role of short-lived halogen source gases on ozone depletion in the UTLS.&lt;/p&gt;