Abstract. A chemistry-transport model (CTM) intercomparison experiment (TransCom-CH4) has been designed to investigate the roles of surface emissions, transport and chemical loss in simulating the global methane distribution. Model simulations were conducted using twelve models and four model variants and results were archived for the period of 1990–2007. All but one model transports were driven by reanalysis products from 3 different meteorological agencies. The transport and removal of CH4 in six different emission scenarios were simulated, with net global emissions of 513 ± 9 and 514 ± 14 Tg CH4 yr−1 for the 1990s and 2000s, respectively. Additionally, sulfur hexafluoride (SF6) was simulated to check the interhemispheric transport, radon (222Rn) to check the subgrid scale transport, and methyl chloroform (CH3CCl3) to check the chemical removal by the tropospheric hydroxyl radical (OH). The results are compared to monthly or annual mean time series of CH4, SF6 and CH3CCl3 measurements from 8 selected background sites, and to satellite observations of CH4 in the upper troposphere and stratosphere. Most models adequately capture the vertical gradients in the stratosphere, the average long-term trends, seasonal cycles, interannual variations (IAVs) and interhemispheric (IH) gradients at the surface sites for SF6, CH3CCl3 and CH4. The vertical gradients of all tracers between the surface and the upper troposphere are consistent within the models, revealing vertical transport differences between models. An average IH exchange time of 1.39 ± 0.18 yr is derived from SF6 time series. Sensitivity simulations suggest that the estimated trends in exchange time, over the period of 1996–2007, are caused by a change of SF6 emissions towards the tropics. Using six sets of emission scenarios, we show that the decadal average CH4 growth rate likely reached equilibrium in the early 2000s due to the flattening of anthropogenic emission growth since the late 1990s. Up to 60% of the IAVs in the observed CH4 concentrations can be explained by accounting for the IAVs in emissions, from biomass burning and wetlands, as well as meteorology in the forward models. The modeled CH4 budget is shown to depend strongly on the troposphere-stratosphere exchange rate and thus on the model's vertical grid structure and circulation in the lower stratosphere. The 15-model median CH4 and CH3CCl3 atmospheric lifetimes are estimated to be 9.99 ± 0.08 and 4.61 ± 0.13 yr, respectively, with little IAV due to transport and temperature.

Abstract. Recent in situ and satellite measurements suggest a contribution of ∼5 pptv to stratospheric inorganic bromine from short-lived bromocarbons. We conduct a modeling study of the two most important short-lived bromocarbons, bromoform (CHBr 3 ) and dibromomethane (CH 2 Br 2 ), with the Goddard Earth Observing System Chemistry Climate Model (GEOS CCM) to account for this missing stratospheric bromine. We derive a "top-down" emission estimate of CHBr 3 and CH 2 Br 2 using airborne measurements in the Pacific and North American troposphere and lower stratosphere obtained during previous NASA aircraft campaigns. Our emission estimate suggests that to reproduce the observed concentrations in the free troposphere, a global oceanic emission of 425 Gg Br yr −1 for CHBr 3 and 57 Gg Br yr −1 for CH 2 Br 2 is needed, with 60% of emissions from open ocean and 40% from coastal regions. Although our simple emission scheme assumes no seasonal variations, the model reproduces the observed seasonal variations of the short-lived bromocarbons with high concentrations in winter and low concentrations in summer. This indicates that the seasonality of short-lived bromocarbons is largely due to seasonality in their chemical loss and transport. The inclusion Correspondence to: Q. Liang (qing.liang@nasa.gov) of CHBr 3 and CH 2 Br 2 contributes ∼5 pptv bromine throughout the stratosphere. Both the source gases and inorganic bromine produced from source gas degradation (Br VSLS y ) in the troposphere are transported into the stratosphere, and are equally important. Inorganic bromine accounts for half (2.5 pptv) of the bromine from the inclusion of CHBr 3 and CH 2 Br 2 near the tropical tropopause and its contribution rapidly increases to ∼100% as altitude increases. More than 85% of the wet scavenging of Br VSLS y occurs in large-scale precipitation below 500 hPa. Our sensitivity study with wet scavenging in convective updrafts switched off suggests that Br VSLS y in the stratosphere is not sensitive to convection. Convective scavenging only accounts for ∼0.2 pptv (4%) difference in inorganic bromine delivered to the stratosphere.

[1] The Antarctic ozone hole demonstrates large-scale, man-made affects on our atmosphere. Surface observations now show that human produced ozone-depleting substances (ODSs) are declining. The ozone hole should soon start to diminish because of this decline. We demonstrate a parametric model of ozone hole area that is based upon a new algorithm for estimating chlorine and bromine levels over Antarctica and late spring Antarctic stratospheric temperatures. This model explains 95% of the ozone hole area's variance. We then use future ODS levels to predict ozone hole recovery. Full recovery to 1980 levels will occur around 2068 and the area will very slowly decline between 2001 and 2017. Detection of a statistically significant decrease of area will not occur until about 2024. We further show that nominal Antarctic stratospheric greenhouse gas forced temperature change should have a small impact on the ozone hole.

[1] The ability to reliably estimate CO 2 fluxes from current in situ atmospheric CO 2 measurements and future satellite CO 2 measurements is dependent on transport model performance at synoptic and shorter timescales. The TransCom continuous experiment was designed to evaluate the performance of forward transport model simulations at hourly, daily, and synoptic timescales, and we focus on the latter two in this paper. Twenty-five transport models or model variants submitted hourly time series of nine predetermined tracers (seven for CO 2 ) at 280 locations. We extracted synoptic-scale variability from daily averaged CO 2 time series using a digital filter and analyzed the results by comparing them to atmospheric measurements at 35 locations. The correlations between modeled and observed synoptic CO 2 variabilities were almost always largest with zero time lag and statistically significant for most models and most locations. Generally, the model results using diurnally varying land fluxes were closer to the observations compared to those obtained using monthly mean or daily average fluxes, and winter was often better simulated than summer. Model results at higher spatial resolution compared better with observations, mostly because these models were able to sample closer to the measurement site location. The amplitude and correlation of model-data variability is strongly model and season dependent. Overall similarity in modeled synoptic CO 2 variability suggests that the first-order transport mechanisms are fairly well parameterized in the models, and no clear distinction was found between the meteorological analyses in capturing the synoptic-scale dynamics.

Particle size and volume measurements obtained with the forward scattering spectrometer probe (FSSP), model 300 during January and February 1989 in the Airborne Arctic Stratospheric Experiment are presented and used to study processes important in the formation and growth of polar stratospheric cloud (PSC) particles. Comparisons of the observations with expected sulfuric acid droplet deliquescence suggest that in the Arctic a major fraction of the sulfuric acid droplets remain liquid until temperatures at least as low as 193 K. Arguments are presented to suggest that homogeneous freezing of the sulfuric acid droplets might occur near 190 K and might play a role in the formation of PSCs. The first suggestion of nitric acid trihydrate (NAT) particles appears near saturation ratios of HNO3 with respect to NAT of 1 (about 195 K) as an enhancement, of the large particles on the tail of the sulfuric acid droplet size distribution. The major increases in number and volume indicative of the main body of the NAT cloud are not seen in these Arctic investigations until 191 to 192 K, which corresponds to an apparent saturation ratio of HNO3 with respect to NAT of about 10, unlike the Antarctic where clouds were encountered at saturation ratios near 1. A decrease in the number of particles was observed in regions in which the airmass was denitrified, i.e. NOy, the sum of all reactive nitrogen species, was reduced. This was especially true for the larger particles on the upper tail of the sulfate size distribution. The loss of these largest particles supports the idea that denitrification may be the result of the preferential nucleation and growth of NAT on only the largest sulfate particles, which then sediment out of the airmass.

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Reactive nitrogen (NOy) and O3 were measured simultaneously from a NASA ER‐2 aircraft during 1987 through 1989. These high resolution measurements cover a broad range of latitudes in the upper troposphere and lower stratosphere. The data show a striking positive correlation between NOy and O3 in the lower stratosphere at all scales sampled. The ratio NOy/O3 is nearly independent of altitude from the tropopause to above 20 km, with ratios in the stratosphere of 0.0015–0.002 in the tropics and 0.0025–0.004 elsewhere. The ratio is much more constant than either individual species, thus providing an excellent reference point for comparing limited data sets with models. Two‐dimensional models reproduce general features of the vertical profile of NOy/O3 but not the gradient in the lower stratosphere between tropics and mid‐latitudes. NOy and O3 are better correlated in the lower stratosphere than in the upper troposphere. The magnitude and variability of both NOy mixing ratios and NOy/O3 ratios indicate a source of NOy in the upper troposphere. The most plausible source in the tropics is lightning production of NOx. Condensation of NOy onto aerosol particles is often possible in the tropical upper troposphere and may play a role in determining the vertical distribution of NOy. In the mid‐latitude upper troposphere the data suggest long‐range transport of NOy. NOy mixing ratios in the tropical upper troposphere were usually between 150 and 600 pptv, enough so that upward transport can affect the NOy abundance in the tropical lower stratosphere.

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