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Institut für Physik der Atmosphäre and Erdsystem-Modellierung

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.

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.

The 13C isotopic ratio of methane, δ13C of CH4, provides additional constraints on the CH4 budget to complement the constraints from CH4 observations. The interpretation of δ13C observations is complicated, however, by uncertainties in the methane sink. The reaction of CH4 with Cl is highly fractionating, increasing the relative abundance of 13CH4, but there is currently no consensus on the strength of the tropospheric Cl sink. We use a set of GEOS global model simulations with different predicted Cl fields to test the sensitivity of the δ13C of CH4 to the diversity of Cl output from chemical transport models. We find that δ13C is highly sensitive to both the amount and geographic distribution of Cl. Simulatlons with Cl providing 0.28 % or 0.66 % of the total CH4 loss bracket the δ13C observations for a fixed set of emissions. Thus, even when Cl provides only a small fraction of the total CH4 loss and has a small impact on total CH4, it provides a strong lever on δ13C. The geographic distribution and seasonal cycle of Cl also impacts the hemispheric gradient and seasonal cycle of δ13C. The large effect of Cl on δ13C compared to total CH4 broadens the range of CH4 source mixtures that can be reconciled with δ13C observations. Stronger constraints on tropospheric Cl are necessary to improve estimates of CH4 sources from δ13C observations.

Chloroform (CHCl3), dichloromethane (CH2Cl2), perchloroethylene (C2Cl4) and 1,2-dichloroethane (C2H4Cl2) are chlorinated Very Short-Lived Substances (Cl-VSLS) with a range of commercial/industrial applications. Recent studies highlight the increasing influence of Cl-VSLS on the stratospheric chlorine budget and therefore their possible role in ozone depletion. Here, we evaluate the ozone depletion potential (ODP) of these Cl-VSLS using a three-dimensional chemical transport model and investigate sensitivity to emission location/season. The seasonal dependence of the ODPs is small but ODPs vary by a factor of 2-3 depending on the continent of emission: 0.0143-0.0264 (CHCl3), 0.0097-0.0208 (CH2Cl2), 0.0057-0.0198 (C2Cl4) and 0.0029-0.0119 (C2H4Cl2). Asian emissions produce the largest ODPs owing to proximity to the tropics and efficient troposphere-to-stratosphere transport of air originating from industrialised East Asia. The Cl-VSLS ODPs are generally small but the upper ends of the CHCl3 and CH2Cl2 ranges are comparable to the mean ODP of methyl chloride (0.02), a longer-lived ozone-depleting substance.