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We report on measurements of CH4, O3, NO2, BrO and some key brominated source gases within the subtropical lowermost stratosphere (LS), tropical upper troposphere (UT) and tropopause layer (TTL) (14-18.5 km). The measurements were performed within the framework of the NASA-ATTREX (National Aeronautics and Space Administration - Airborne Tropical Tropopause Experiment) project from aboard the Global Hawk (GH) during 6 deployments over the Eastern Pacific in early 2013. O3, NO2, and BrO were remotely monitored by analyzing limb scattered skylight in the UV and visible spectral ranges using the observations of the mini-DOAS (Differential Optical Absorption Spectroscopy) instrument (Stutz et al., 2016). CH4 was measured in-situ by the Harvard HUPCRS instrument and by the NOAA-UCATS instrument. O3 was recorded at high precision by the NOAA dual-beam UV photometer, and some key brominated source gases were analyzed in whole air samples of the GWAS (Global Hawk Whole Air Sampler) instrument. All of these measurements are used for comparison 10 with TOMCAT/SLIMCAT 3-D model simulations, aiming at improvements of our understanding of the bromine budget and photochemistry in the LS, UT, and TTL. Potential changes in local O3 (and NO2 and BrO) due to transport processes are separated from photochemical processes in inter-comparisons of measured and modeled CH4 and O3. After accounting for some minor deficiencies in the details of the modeled vertical transport, excellent agreement is achieved among measured and simulated CH4 and O3, indicating that in the subtropical LS and TTL O3 concentrations mostly vary due to dynamical rather than photochemical processes. The TOMCAT/SLIMCAT simulations are further used for the interpretation of the measured NO2 and BrO. In excellent agreement with the model predictions, NO2 concentrations are found to range between 70-170 ppt in the subtropical LS, and in the TTL they are close to, or below the detection limit of 15 ppt in daytime. The measured BrO concentrations range between 3-9 ppt in the subtropical LS, and in the TTL they reach 0.5 ± 0.5 ppt at the bottom of the TTL (150 hPa/355 K/14 km) and up to about 5 ppt at the top of the TTL (70 hPa/425 K/18.5 km, for the TTL definition see Fueglistaler et al. (2009)), in overall good agreement with the model simulation, and the expectation based on the destruction of brominated source gases. The TOMCAT/SLIMCAT simulations tend to slightly under-predict measured BrO depending on the photochemical regime studied, even when constrained to the measured O3 and NO2, and adjusted to match the observed concentrations of some key brominated source gases. The measured BrO and modeled BrO / Brinorgy ratio is further used to calculate inorganic bromine, Brinorgy. For the TTL (i.e. when [CH4] ± 1390 ppb), Brinorgy is found to increase from a mean of 2.63 ± 1.04 ppt for ± in the range of 350-360 K to 5.11 ± 1.57 ppt for θ = 390 to 400 K, whereas in the subtropical LS (i.e. when [CH4] ± 1390 ppb),it reaches 7.66 ± 2.95 ppt for theta in the range of 390-400 K. Finally, the TOMCAT/SLIMCAT simulations indicate a net destruction of ozone of -0.5 ppbv/day at the base of the TTL (θ = 355 K) and a net production of +1.8 ppbv/day at its top (θ = 383 K). [ABSTRACT FROM AUTHOR]

The first concerted multi-model intercomparison of halogenated very short-lived substances (VSLS) has been performed, within the framework of the ongoing Atmospheric Tracer Transport Model Intercomparison Project (TransCom). Eleven global models or model variants participated (nine chemical transport models and two chemistry- climate models) by simulating the major natural bromine VSLS, bromoform (CHBr3) and dibromomethane (CH2Br2), over a 20-year period (1993-2012). Except for three model simulations, all others were driven offline by (or nudged to) reanalysed meteorology. The overarching goal of TransCom- VSLS was to provide a reconciled model estimate of the stratospheric source gas injection (SGI) of bromine from these gases, to constrain the current measurement-derived range, and to investigate inter-model differences due to emissions and transport processes. Models ran with standardised idealised chemistry, to isolate differences due to transport, and we investigated the sensitivity of results to a range of VSLS emission inventories. Models were tested in their ability to reproduce the observed seasonal and spatial distribution of VSLS at the surface, using measurements from NOAA's long-term global monitoring network, and in the tropical troposphere, using recent aircraft measurements - including high-altitude observations from the NASA Global Hawk platform. The models generally capture the observed seasonal cycle of surface CHBr3 and CH2Br2 well, with a strong model-measurement correlation (r ≥0.7) at most sites. In a given model, the absolute model-measurement agreement at the surface is highly sensitive to the choice of emissions. Large inter-model differences are apparent when using the same emission inventory, highlighting the challenges faced in evaluating such inventories at the global scale. Across the ensemble, most consistency is found within the tropics where most of the models (8 out of 11) achieve best agreement to surface CHBr3 observations using the lowest of the three CHBr3 emission inventories tested (similarly, 8 out of 11 models for CH2Br2). In general, the models reproduce observations of CHBr3 and CH2Br2 obtained in the tropical tropopause layer (TTL) at various locations throughout the Pacific well. Zonal variability in VSLS loading in the TTL is generally consistent among models, with CHBr3 (and to a lesser extent CH2Br2) most elevated over the tropical western Pacific during boreal winter. The models also indicate the Asian monsoon during boreal summer to be an important pathway for VSLS reaching the stratosphere, though the strength of this signal varies considerably among models. We derive an ensemble climatological mean estimate of the stratospheric bromine SGI from CHBr3 and CH2Br2 of 2.0 (1.2-2.5) ppt, ~57% larger than the best estimate from the most recent World Meteorological Organization (WMO) Ozone Assessment Report. We find no evidence for a long-term, transport-driven trend in the stratospheric SGI of bromine over the simulation period. The transport-driven interannual variability in the annual mean bromine SGI is of the order of ±5%, with SGI exhibiting a strong positive correlation with the El Niño-Southern Oscillation (ENSO) in the eastern Pacific. Overall, our results do not show systematic differences between models specific to the choice of reanalysis meteorology, rather clear differences are seen related to differences in the implementation of transport processes in the models. [ABSTRACT FROM AUTHOR]

Marine-produced short-lived trace gases such as dibromomethane (CH2Br2/, bromoform (CHBr3/, methyliodide (CH3I) and dimethyl sulfide (DMS) significantly impact tropospheric and stratospheric chemistry. Describing their marine emissions in atmospheric chemistry models as accurately as possible is necessary to quantify their impact on ozone depletion and Earth's radiative budget. So far, marine emissions of trace gases have mainly been prescribed from emission climatologies, thus lacking the interaction between the actual state of the atmosphere and the ocean. Here we present simulations with the chemistry climate model EMAC (ECHAM5/MESSy Atmospheric Chemistry) with online calculation of emissions based on surface water concentrations, in contrast to directly prescribed emissions. Considering the actual state of the model atmosphere results in a concentration gradient consistent with model realtime conditions at the ocean surface and in the atmosphere, which determine the direction and magnitude of the computed flux. This method has a number of conceptual and practical benefits, as the modelled emission can respond consistently to changes in sea surface temperature, surface wind speed, sea ice cover and especially atmospheric mixing ratio. This online calculation could enhance, dampen or even invert the fluxes (i.e. deposition instead of emissions) of very short-lived substances (VSLS). We show that differences between prescribing emissions and prescribing concentrations (-28%for CH2Br2 to C11%for CHBr3/ result mainly from consideration of the actual, time-varying state of the atmosphere. The absolute magnitude of the differences depends mainly on the surface ocean saturation of each particular gas. Comparison to observations from aircraft, ships and ground stations reveals that computing the air-sea flux interactively leads in most of the cases to more accurate atmospheric mixing ratios in the model compared to the computation from prescribed emissions. Calculating emissions online also enables effective testing of different air-sea transfer velocity (k/ parameterizations, which was performed here for eight different parameterizations. The testing of these different k values is of special interest for DMS, as recently published parameterizations derived by direct flux measurements using eddy covariance measurements suggest decreasing k values at high wind speeds or a linear relationship with wind speed. [ABSTRACT FROM AUTHOR]

Marine produced short-lived trace gases such as dibromomethane (CH2Br2), bromoform (CHBr3), methyliodide (CH3I) and dimethylsulfide (DMS) significantly impact tropospheric and stratospheric chemistry. Describing their marine emissions in atmospheric chemistry models as accurately as possible is necessary to quantify their impact on ozone depletion and the Earth's radiative budget. So far, marine emissions of trace gases have mainly been prescribed from emission climatologies, thus lacking the interaction between the actual state of the atmosphere and the ocean. Here we present simulations with the chemistry climate model EMAC with online calculation of emissions based on surface water concentrations, in contrast to directly prescribed emissions. Considering the actual state of the model atmosphere results in a concentration gradient consistent with model real-time conditions at ocean surface and atmosphere, which determine the direction and magnitude of the computed flux. This method has a number of conceptual and practical benefits, as the modelled emission can respond consistently to changes in sea surface temperature, surface wind speed, sea ice cover and especially atmospheric mixing ratio. This online calculation could enhance, dampen or even invert the fluxes (i.e. deposition instead of emissions) of VSLS. We show that differences between prescribing emissions and prescribing concentrations (-28% for CH2Br2 to +11% for CHBr3) result mainly from consideration of the actual, time-varying state of the atmosphere. The absolute magnitude of the differences depends mainly on the surface ocean saturation of each particular gas. Comparison to observations from aircraft, ships and ground stations reveals that computing the air-sea flux interactively leads in most of the cases to more accurate atmospheric mixing ratios in the model compared to the computation from prescribed emissions. Calculating emissions online also enables effective testing of different air-sea transfer velocity parameterizations k, which was performed here for eight different parameterizations. The testing of these different k values is of special interest for DMS, as recently published parameterizations derived by direct flux measurements using eddy covariance measurements suggest decreasing k values at high wind speeds or a linear relationship with wind speed. Implementing these parameterizations reduces discrepancies in modelled DMS atmospheric mixing ratios and observations by a factor of 1.5 compared to parameterizations with a quadratic or cubic relationship to wind speed. [ABSTRACT FROM AUTHOR]

The absorption cross-section of N2O5, ...(λ, T), which is known from laboratory measurements with the uncertainty of a factor of 2 (Table 4-2 in JPL-2011, Sander et al., 2011), was investigated by balloon-borne observations of the relevant trace gases in the tropical mid-stratosphere. The method relies on the observation of the diurnal variation of NO2 supported by detailed photochemical modelling of NOy (NOx(= NO + NO2) + NO3 + 2N2O5 + ClONO2 + HO2NO2 +BrONO2 + HNO3) photochemistry. Simulations are initialised with O3 measured by direct sun observations, the NOy partitioning from MIPAS-B (Michelson Interferometer for Passive Atmospheric Sounding-Balloon) observations in similar air masses at nighttime, and all other relevant species from simulations of the SLIMCAT chemical transport model (CTM). Best agreement between the simulated and observed diurnal increase of NO2 is found if the ...(λ, T) is scaled by a factor of 1.6 ± 0.8 in the UV-C (200-260 nm) and by a factor of 0.9 ± 0.26 in the UV-B/A (260-350 nm), compared to current recommendations. In consequence, at 30 km altitude, the N2O5 lifetime against photolysis becomes a factor of 0.77 shorter at solar zenith angle (SZA) of 30° than using the recommended ... (λ, T), and stays more or less constant at SZAs of 60°. Our scaled N2O5 photolysis frequency slightly reduces the lifetime (0.2-0.6%) of ozone in the tropical mid- and upper stratosphere, but not to an extent to be important for global ozone. [ABSTRACT FROM AUTHOR]

The absorption cross-section of N2O5, σN2O5(λ, T), which is known from laboratory measurements with the uncertainty of a factor of 2 (Table 4-2 in JPL-2011, Sander et al., 2011), was investigated by balloon-borne observations of the relevant trace gases in the tropical mid-stratosphere. The method relies on the observation of the diurnal variation of NO2 supported by detailed photochemical modelling of NOy (NOx(= NO + NO2) + NO3 + 2N2O5 + ClONO2 + HO2NO2 +BrONO2 + HNO3) photochemistry. Simulations are initialised with O3 measured by direct sun observations, the NOy partitioning from MIPAS-B (Michelson Interferometer for Passive Atmospheric Sounding-Balloon) observations in similar air masses at nighttime, and all other relevant species from simulations of the SLIMCAT chemical transport model (CTM). Best agreement between the simulated and observed diurnal increase of NO2 is found if the sN2O5(λ, T) is scaled by a factor of 1.6 ± 0.8 in the UV-C (200-260 nm) and by a factor of 0.9 ± 0.26 in the UV-B/A (260-350 nm), compared to current recommendations. In consequence, at 30 km altitude, the N2O5 lifetime against photolysis becomes a factor of 0.77 shorter at solar zenith angle (SZA) of 30° than using the recommended σN2O5 (λ, T), and stays more or less constant at SZAs of 60°. Our scaled N2O5 photolysis frequency slightly reduces the lifetime (0.2-0.6%) of ozone in the tropical mid- and upper stratosphere, but not to an extent to be important for global ozone. [ABSTRACT FROM AUTHOR]

We investigate the contribution of oceanic methyl iodide (CH3I) to the stratospheric iodine budget. Based on CH3I measurements during three tropical ship campaigns and the Lagrangian transport model FLEXPART we provide a detailed analysis of CH3I transport from the ocean surface to the cold point in the upper tropical tropopause layer (TTL). While average oceanic emissions differ by less than 50% from campaign to campaign, the measurements show much stronger variations within each campaign. A positive correlation between the oceanic CH3I emissions and the efficiency of CH3I troposphere-stratosphere transport has been identified for some cruise sections. The mechanism of strong horizontal surface winds triggering large emissions on the one hand and being associated with tropical convective systems, such as developing typhoons, on the other hand, could explain the identified correlations. As a result of the simultaneous occurrence of large CH3I emissions and strong vertical uplift, localized maximum mixing ratios of 0.6 ppt CH3I at the cold point have been determined for observed peak emissions during the SHIVA-Sonne campaign in the coastal West Pacific. The other two campaigns give considerable smaller maxima of 0.1 ppt CH3I for the Trans Brom campaign in the open West Pacific and 0.03 ppt for emissions from the coastal East Atlantic during the DRIVE campaign. In order to assess the representativeness of the large local mixing ratios we use climatological emission scenarios to derive global upper air estimates of CH3I abundances. The model results are compared to available upper air measurements including data from the recent ATTREX and HIPPO2 aircraft campaigns. In the East Pacific region, the location of the available measurement campaigns in the upper TTL, the comparisons give a good agreement indicating that around 0.01 to 0.02 ppt of CH3I enter the stratosphere. However, other tropical regions, which are subject to stronger convective activity show larger CH3I entrainment, e.g., 0.08 ppt in the West Pacific. The strong variations in the geographical distribution of CH3I entrainment suggest that currently available upper air measurements are not representative of global estimates and further campaigns will be necessary in order to better understand the CH3I contribution to stratospheric iodine. [ABSTRACT FROM AUTHOR]

Emissions of halogenated very short-lived substances (VSLS) are poorly constrained. However, their inclusion in global models is required to simulate a realistic inorganic bromine (Bry) loading in both the troposphere, where bromine chemistry perturbs global oxidizing capacity, and in the stratosphere, where it is a major sink for ozone (O3). We have performed simulations using a 3-D chemical transport model (CTM) including three top-down and a single bottom-up derived emission inventory of the major brominated VSLS bromoform (CHBr3) and dibromomethane (CH2Br2). We perform the first concerted evaluation of these inventories, comparing both the magnitude and spatial distribution of emissions. For a quantitative evaluation of each inventory, model output is compared with independent long-term observations at National Oceanic and Atmospheric Administration (NOAA) ground-based stations and with aircraft observations made during the NSF HIAPER Pole-to-Pole Observations (HIPPO) project. For CHBr3, the mean absolute deviation between model and surface observation ranges from 0.22 (38%) to 0.78 (115%) parts per trillion (ppt) in the tropics, depending on emission inventory. For CH2Br2, the range is 0.17 (24%) to 1.25 (167%) ppt. We also use aircraft observations made during the 2011 "Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere" (SHIVA) campaign, in the tropical West Pacific. Here, the performance of the various inventories also varies significantly, but overall the CTM is able to reproduce observed CHBr3 well in the free troposphere using an inventory based on observed sea-to-air fluxes. Finally, we identify the range of uncertainty associated with these VSLS emission inventories on stratospheric bromine loading due to VSLS (BryVSLS). Our simulations show BryVSLS ranges from ~ 4.0 to 8.0 ppt depending on the inventory. We report an optimised estimate at the lower end of this range (~ 4 ppt) based on combining the CHBr3 and CH2Br2 inventories which give best agreement with the compilation of observations in the tropics. [ABSTRACT FROM AUTHOR]

We report on time-dependent O3, NO2 and BrO profiles measured by limb observations of scattered skylight in the stratosphere over Kiruna (67.9° N, 22.1° E) on 7 and 8 September 2009 during the autumn circulation turn-over. The observations are complemented by simultaneous direct solar occultation measurements around sunset and sunrise performed aboard the same stratospheric balloon payload. Supporting radiative transfer and photochemical modelling indicate that the measurements can be used to constrain the ratio J(BrONO2)/kBrO+NO2, for which at T = 220±5K an overall 1.7(+0.4-0.2) larger ratio is found than recommended by the most recent Jet Propulsion Laboratory (JPL) compilation (Sander et al., 2011). Sensitivity studies reveal the major reasons are likely to be (1) a larger BrONO2 absorption cross-section σBrONO2, primarily for wavelengths larger than 300 nm, and (2) a smaller kBrO+NO2 at 220K than given by Sander et al. (2011). Other factors, e.g. the actinic flux and quantum yield for the dissociation of BrONO2, can be ruled out. The observations also have consequences for total inorganic stratospheric bromine (Bry) estimated from stratospheric BrO measurements at high NOx loadings, since the ratio J(BrONO2)/kBrO+NO2 largely determines the stratospheric BrO/Bry ratio during daylight. Using the revised J(BrONO2)/kBrO+NO2 ratio, total stratospheric Bry is likely to be 1.4 ppt smaller than previously estimated from BrO profile measurements at high NOx loadings. This would bring estimates of Bry inferred from organic source gas measurements (e.g. CH3Br, the halons, CH3Br3, CHBr3, etc.) into closer agreement with estimates based on BrO observations (inorganic method). The consequences for stratospheric ozone due to the revised J(BrONO2)/kBrO+NO2 ratio are small (maximum -0.8 %), since at high NOx (for which most Bry assessments are made) the enhanced ozone loss by overestimating Bry is compensated for by the suppressed ozone loss due to the underestimation of BrO/Bry with a smaller (BrONO2)/kBrO+NO2 ratio. [ABSTRACT FROM AUTHOR]

We investigate the contribution of oceanic methyl iodide (CH3I) to the stratospheric iodine budget. Based on CH3I measurements during three tropical ship campaigns and the Lagrangian transport model FLEXPART we provide a detailed analysis of CH3I transport from the ocean surface to the cold point in the upper tropical tropopause layer (TTL). While average oceanic emissions differ by less than 50% from campaign to campaign, the measurements show much stronger variations within each campaign. A positive correlation between the oceanic CH3I emissions and the efficiency of CH3I Troposphere--stratosphere transport has been identified for some cruise sections. The mechanism of strong horizontal surface winds triggering large emissions on the one hand and being associated with tropical convective systems, such as developing typhoons, on the other hand, could explain the identified correlations. As a result of the simultaneous occurrence of large CH3I emissions and strong vertical uplift, localized maximum mixing ratios of 0.6 ppt CH3I at the cold point have been determined for observed peak emissions during the SHIVA-Sonne campaign in the coastal West Pacific. The other two campaigns give considerable smaller maxima of 0.1 ppt CH3I for the TransBrom campaign in the open West Pacific and 0.03 ppt for emissions from the coastal East Atlantic during the DRIVE campaign. In order to assess the representativeness of the large local mixing ratios we use climatological emission scenarios to derive global upper air estimates of CH3I abundances. The model results are compared to available upper air measurements including data from the recent ATTREX and HIPPO2 aircraft campaigns. In the East Pacific region, the location of the available measurement campaigns in the upper TTL, the comparisons give a good agreement indicating that around 0.01 to 0.02 ppt of CH3I enter the stratosphere. However, other tropical re gions, which are subject to stronger convective activity show larger CH3I entrainment, e.g., 0.08 ppt in the West Pacific. The strong variations in the geographical distribution of CH3I entrainment suggest that currently available upper air measurements are not representative of global estimates and further campaigns will be necessary in order to better understand the CH3I contribution to stratospheric iodine. [ABSTRACT FROM AUTHOR]

We report on time-dependent O3, NO2 and BrO profile measurements taken in the stratosphere by limb observations of scattered skylight at high-latitudes during autumn circulation turn-over. The observations are complemented by simultaneous direct solar occultation measurements around sunset and sunrise performed aboard the same stratospheric balloon payload. Supporting radiative transfer and photochemical modelling indicates that, the measurements can be used to constrain the ratio J(BrONO2)/kBrO+NO2 , for which overall a 1.69±0.04 larger ratio is found than indicated by the most recent JPL compilation (Sander et al., 2011). Sensitivity studies reveal the major reasons likely to be (1) a larger BrONO2 absorption cross-section σBrONO2, primarily for wavelengths larger than 300 nm, and (2) a smaller kBrO+NO2 at 220 K than given by Sander et al. (2011). Other factors, e.g. the actinic flux and quantum yield for the dissociation of BrONO2, can be ruled out. The observations also have consequences for total inorganic stratospheric bromine (Bry) estimated from stratospheric BrO measurements at high NOx loadings, since the J(BrONO2)/kBrO+NO2 ratio largely determines the stratospheric BrO/Bry ratio during daylight. Using the revised J(BrONO2)/kBrO+NO2 ratio, total stratospheric Bry is likely to be 1.4 ppt smaller than previously estimated from BrO profile measurements at high NOx loadings. This brings estimates of total stratospheric bromine inferred from organic source gas measurements (i.e. CH3Br, the halons, CH2Br2, CHBr3, ...) into closer agreement with estimates based on BrO observations (inorganic method). The consequences for stratospheric ozone due to the revised J(BrONO2)/kBrO+NO2 ratio are small (maximum -0.8%), since at high NOx (for which most Bry assessments are made) an overestimated Bry using the inorganic method would in return almost cancel out with the amount of reactive bromine calculated in the photochemical models. [ABSTRACT FROM AUTHOR]

We have used a global three-dimensional chemical transport model to quantify the impact of the very short-lived substances (VSLS) CHBr3, CH2Br2, CHBr2Cl, CHBrCl2, CH2BrCl and C2H5Br on the bromine budget of the stratosphere. Atmospheric observations of these gases allow constraints on surface mixing ratios that, when incorporated into our model, contribute ~4.9-5.2 parts per trillion (ppt) of inorganic bromine (Bry) to the stratosphere. Of this total, ~76% comes from naturally-emitted CHBr3 and CH2Br2. The remaining species individually contribute modest amounts. However, their accumulated total accounts for up to ~1.2 ppt of the supply and thus should not be ignored. We have compared modelled tropical profiles of a range of VSLS with observations from the recent 2009 NSF HIPPO-1 aircraft campaign. Modelled profiles agree reasonably well with observations from the surface to the lower tropical tropopause layer. We have also considered the poorly studied anthropogenic VSLS, C2H5Br, CH2BrCH2Br, n-C3H7Br and i-C3H7Br. We find the local atmospheric lifetime of these species in the tropical tropopause layer are ~183, 603, 39 and 49 days, respectively. These species, particularly C2H5Br and CH2BrCH2Br, would thus be important carriers of bromine to the stratosphere if emissions were to increase substantially. Our model shows ~70-73% and ~80-85% of bromine from these species in the tropical boundary layer can reach the lower stratosphere. [ABSTRACT FROM AUTHOR]

We have used a global three-dimensional chemical transport model to quantify the impact of the very short-lived species (VSLS) CHBr3, CH2Br2, CHBr2Cl, CHBrCl2, CH2BrCl and C2H5Br on the bromine budget of the stratosphere. Atmospheric observations of these gases allow constraints on surface mixing ratios that, when incorporated into our model, contribute ~4.9-5.2 parts per trillion (ppt) of inorganic bromine (Bry) to the stratosphere. Of this total, ~76% comes from naturally-emitted CHBr3 and CH2Br2. The remaining species individually contribute modest amounts. However, their accumulated total accounts for up to ~1.2 ppt of the supply and thus should not be ignored. We have compared modelled tropical profiles of a range of VSLS with observations from the recent 2009 NSF HIPPO-1 aircraft campaign. Modelled profiles agree reasonably well with observations from the surface to the lower tropical tropopause layer. We have also considered the poorly studied anthropogenic VSLS, C2H5Br, CH2BrCH2Br, n-C3H7Br and i-C3H7Br. We find the local atmospheric lifetime of these species in the tropical tropopause layer are ~183, 603, 39 and 49 days, respectively. These species, particularly C2H5Br and CH2BrCH2Br, would thus be important carriers of bromine to the stratosphere if emissions were to increase substantially. Our model shows ~70-73% and ~80-85% of bromine from these species in the tropical boundary layer can reach the lower stratosphere. [ABSTRACT FROM AUTHOR]

Stratospheric bromine loading due to very short-lived substances is investigated with a three-dimensional chemical transport model over a period of 21 years using meteorological input data from the European Centre for Medium-Range Weather Forecasts ERA-Interim reanalysis from 1989 to the end of 2009. Within this framework we analyze the impact of dehydration and deep convection on the amount of stratospheric bromine using an idealized and a detailed full chemistry approach. We model the two most important brominated short-lived substances, bromoform (CHBr3) and dibromomethane (CH2Br2), assuming a uniform convective detrainment mixing ratio of 1 part per trillion by volume (pptv) for both species. The contribution of very short-lived substances to stratospheric bromine varies drastically with the applied dehydration mechanism and the associated scavenging of soluble species ranging from 3.4 pptv in the idealized setup up to 5 pptv using the full chemistry scheme. In the latter case virtually the entire amount of bromine originating from very short-lived source gases is able to reach the stratosphere thus rendering the impact of dehydration and scavenging on inorganic bromine in the tropopause insignificant. Furthermore, our long-term calculations show that the mixing ratios of very short-lived substances are strongly correlated to convective activity, i.e. intensified convection leads to higher amounts of very shortlived substances in the upper troposphere/lower stratosphere especially under extreme conditions like El Niño seasons. However, this does not apply to the inorganic brominated product gases whose concentrations are anti-correlated to convective activity mainly due to convective dilution and possible scavenging, depending on the applied approach. [ABSTRACT FROM AUTHOR]

Stratospheric bromine loading due to very short-lived substances is investigated with a three-dimensional chemical transport model over a period of 21 years using meteorological input data from the European Centre for Medium-Range Weather Forecasts ERA-Interim reanalysis from 1989 to the end of 2009. Within this framework we analyze the impact of dehydration and deep convection on the amount of stratospheric bromine using an idealized and a detailed full chemistry approach. We model the two most important brominated short-lived substances, bromoform (CHBr3) and dibromomethane (CH2Br2), assuming a uniform detrainment mixing ratio of 1 part per trillion by volume (pptv) for both species. The contribution of very short-lived substances to stratospheric bromine varies drastically with the applied dehydration mechanism and the associated scavenging of soluble species ranging from 3.4 pptv in the idealized setup up to 5 pptv using the full chemistry scheme. In the latter case virtually the entire amount of bromine originating from very short-lived source gases is able to reach the stratosphere thus rendering the impact of dehydration and scavenging on inorganic bromine in the tropopause insignificant. Furthermore, our long-term calculations show that the mixing ratios of very short-lived substances are strongly correlated to convective activity, i.e. intensified convection leads to higher amounts of very short-lived substances in the upper troposphere/lower stratosphere especially under extreme conditions like El Niño seasons. However, this does not apply to the inorganic brominated product gases whose concentrations are anti-correlated to convective activity mainly due to convective dilution and possible scavenging, depending on the applied approach. [ABSTRACT FROM AUTHOR]

We have developed a detailed chemical scheme for the degradation of the short-lived source gases bromoform (CHBr3) and dibromomethane (CH2Br2) and implemented it in the TOMCAT/SLIMCAT three-dimensional (3- D) chemical transport model (CTM). The CTM has been used to predict the distribution of the two source gases (SGs) and 11 of their organic product gases (PGs). These first global calculations of the organic PGs show that their abundance is small. The longest lived organic PGs are CBr2O and CHBrO, but their peak tropospheric abundance relative to the surface volume mixing ratio (vmr) of the SGs is less than 5%. We calculate their mean local tropospheric lifetimes in the tropics to be ~7 and ~2 days (due to photolysis), respectively. Therefore, the assumption in previous modelling studies that SG degradation leads immediately to inorganic bromine seems reasonable. We have compared observed tropical SG profiles from a number of aircraft campaigns with various model experiments. In the tropical tropopause layer (TTL) we find that the CTM run using p levels (TOMCAT) and vertical winds from analysed divergence overestimates the abundance of CH2Br2, and to a lesser extent CHBr3, although the data is sparse and comparisons are not conclusive. Better agreement in the TTL is obtained in the sensitivity run using θ-levels (SLIMCAT) and vertical motion from diabatic heating rates. Trajectory estimates of residence times in the two model versions show slower vertical transport in the SLIMCAT θ-level version. In the p-level model even when we switch off convection we still find significant amounts of the SGs considered may reach the cold point tropopause; the stratospheric source gas injection (SGI) is only reduced by ~16% for CHBr3 and ~2% for CH2Br2 without convection. Overall, the relative importance of the SG pathway and the PG pathway for transport of bromine to the stratospheric overworld (~>380 K) has been assessed. Assuming a 10-day washout lifetime of Bry in TOMCAT, we find the delivery of total Br from CHBr3 to be 0.72 pptv with ~53% of this coming from SGI. Similary, for CH2Br2 we find a total Br value of 1.69 pptv with ~94% coming from SGI. We infer that these species contribute ~2.4 pptv of inorganic bromine to the lower stratosphere with SGI being the dominant pathway. Slower transport to and through the TTL would decrease this estimate. [ABSTRACT FROM AUTHOR]

We have developed a detailed chemical scheme for the degradation of the short-lived source gases bromoform (CHBr3) and dibromomethane (CH2Br2) and implemented it in the TOMCAT/SLIMCAT three-dimensional (3-D) chemical transport model (CTM). The CTM has been used to predict the distribution of the two source gases (SGs) and 11 of their organic product gases (PGs). These first global calculations of the organic PGs show that their abundance is small. The longest lived organic PGs are CBr2O and CHBrO, but their peak tropospheric abundance relative to the surface vmr of the SGs is less than 5%. We calculate their mean local tropospheric lifetimes in the tropics to be ∼7 and ∼2 days (due to photolysis), respectively. Therefore, the assumption in previous modelling studies that SG degradation leads immediately to inorganic bromine seems reasonable. We have compared observed tropical SG profiles from a number of aircraft campaigns with various model experiments. In the tropical tropopause layer (TTL) we find that the CTM run using p levels and vertical winds from analysed divergence overestimates the abundance of CH2Br2, and to a lesser extent CHBr3, although the data is sparse and comparisons are not conclusive. Better agreement in the TTL is obtained in the run using θ levels and vertical motion from diabatic heating rates. Trajectory estimates of residence times in the two model versions confirm the more realistic transport in the θ-level version. In the θ-level model even when we switch off convection we still find significant amounts of the SGs considered may reach the cold point; the stratospheric source gas injection is only reduced by ∼16% for CHBr3 and ∼2% for CH2Br2 without convection. Overall, the relative importance of the SG pathway and the PG pathway for transport of bromine to the stratosphere has been assessed. Assuming a 10-day washout lifetime of Bry we find the delivery of total Br from CHBr3 to be 0.72 pptv with ∼53% of this coming from SGI. Similary, for CH2Br2 we find a total Br value of 1.69 pptv with ∼94% coming from SGI. We infer that these species contribute ∼2.4 pptv of inorganic bromine to the lower stratosphere with SGI being the dominant pathway. [ABSTRACT FROM AUTHOR]