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This paper presents a modelling study on the fate of CHBr3 and its product gases in the troposphere within the context of tropical deep convection. A cloud-scale case study was conducted along the west coast of Borneo, where several deep convective systems were triggered on the afternoon and early evening of 19 November 2011. These systems were sampled by the Falcon aircraft during the field campaign of the SHIVA project and analysed using a simulation with the cloud-resolving meteorological model C-CATT-BRAMS at 2x2 km resolution that represents the emissions, transport by large-scale flow, convection, photochemistry, and washout of CHBr3 and its product gases (PGs). We find that simulated CHBr3 mixing ratios and the observed values in the boundary layer and the outflow of the convective systems agree. However, the model underestimates the background CHBr3 mixing ratios in the upper troposphere, which suggests a missing source at the regional scale. An analysis of the simulated chemical speciation of bromine within and around each simulated convective system during the mature convective stage reveals that > 85% of the bromine derived from CHBr3 and its PGs is transported vertically to the point of convective detrainment in the form of CHBr3 and that the remaining small fraction is in the form of organic PGs, principally insoluble brominated carbonyls produced from the photo-oxidation of CHBr3. The model simulates that within the boundary layer and free troposphere, the inorganic PGs are only present in soluble forms, i.e. HBr, HOBr, and BrONO2, and, consequently, within the convective clouds, the inorganic PGs are almost entirely removed by wet scavenging. We find that HBr is the most abundant PG in background lower-tropospheric air and that this prevalence of HBr is a result of the relatively low background tropospheric ozone levels at the regional scale. Contrary to a previous study in a different environment, for the conditions in the simulation, the insoluble B

Halogenated very short-lived substances (VSLSs), such as bromoform (CHBr3), can be transported to the stratosphere and contribute to the halogen loading and ozone depletion. Given their highly variable emission rates and their short atmospheric lifetimes, the exact amount as well as the spatio-temporal variability of their contribution to the stratospheric halogen loading are still uncertain. We combine observational data sets with Lagrangian atmospheric modelling in order to analyse the spatial and temporal variability of the CHBr3 injection into the stratosphere for the time period 1979–2013. Regional maxima with mixing ratios of up to 0.4–0.5 ppt at 17 km altitude are diagnosed to be over Central America (1) and over the Maritime Continent–west Pacific (2), both of which are confirmed by high-altitude aircraft campaigns. The CHBr3 maximum over Central America is caused by the co-occurrence of convectively driven short transport timescales and strong regional sources, which in conjunction drive the seasonality of CHBr3 injection. Model results at a daily resolution reveal isolated, exceptionally high CHBr3 values in this region which are confirmed by aircraft measurements during the ACCENT campaign and do not occur in spatially or temporally averaged model fields. CHBr3 injection over the west Pacific is centred south of the Equator due to strong oceanic sources underneath prescribed by the here-applied bottom-up emission inventory. The globally largest CHBr3 mixing ratios at the cold point level of up to 0.6 ppt are diagnosed to occur over the region of India, Bay of Bengal, and Arabian Sea (3); however, no data from aircraft campaigns are available to confirm this finding. Inter-annual variability of stratospheric CHBr3 injection of 10 %–20 % is to a large part driven by the variability of coupled ocean–atmosphere circulation systems. Long-term changes, on the other hand, correlate with the regional sea surface temperature trends resulting in positive trends of

Oceanic very short-lived substances (VSLSs), such as bromoform (CHBr3), contribute to stratospheric halogen loading and, thus, to ozone depletion. However, the amount, timing, and region of bromine delivery to the stratosphere through one of the main entrance gates, the Indian summer monsoon circulation, are still uncertain. In this study, we created two bromoform emission inventories with monthly resolution for the tropical Indian Ocean and west Pacific based on new in situ bromoform measurements and novel ocean biogeochemistry modeling. The mass transport and atmospheric mixing ratios of bromoform were modeled for the year 2014 with the particle dispersion model FLEXPART driven by ERA-Interim reanalysis. We compare results between two emission scenarios: (1) monthly averaged and (2) annually averaged emissions. Both simulations reproduce the atmospheric distribution of bromoform from ship- and aircraft-based observations in the boundary layer and upper troposphere above the Indian Ocean reasonably well. Using monthly resolved emissions, the main oceanic source regions for the stratosphere include the Arabian Sea and Bay of Bengal in boreal summer and the tropical west Pacific Ocean in boreal winter. The main stratospheric injection in boreal summer occurs over the southern tip of India associated with the high local oceanic sources and strong convection of the summer monsoon. In boreal winter more bromoform is entrained over the west Pacific than over the Indian Ocean. The annually averaged stratospheric injection of bromoform is in the same range whether using monthly averaged or annually averaged emissions in our Lagrangian calculations. However, monthly averaged emissions result in the highest mixing ratios within the Asian monsoon anticyclone in boreal summer and above the central Indian Ocean in boreal winter, while annually averaged emissions display a maximum above the west Indian Ocean in boreal spring. In the Asian summer monsoon anticyclone bromoform atm

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, simulating the major natural bromine VSLS, bromoform (CHBr3) and dibromomethane (CH2Br2), over a 20-year period (1993-2012). 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 seasonal cycle of surface CHBr3 and CH2Br2 well, with a strong model-measurement correlation (r ≥ 0.7) and a low sensitivity to the choice of emission inventory, at most sites. In a given model, the absolute model-measurement agreement is highly sensitive to the choice of emissions and inter-model differences are also apparent, even when using the same 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 optimal agreement to surface CHBr3 observations using the lowest of the three CHBr3 emission inventories tested (similarly, 8 out of 11 models for CH2 Br2). In general, the models are able to rep

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 usin

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, simulating the major natural bromine VSLS, bromoform (CHBr3) and dibromomethane (CH2Br2), over a 20-year period (1993-2012). 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 seasonal cycle of surface CHBr3 and CH2Br2 well, with a strong model measurement correlation (r ≥0.7) and a low sensitivity to the choice of emission inventory, at most sites. In a given model, the absolute model-measurement agreement is highly sensitive to the choice of emissions and inter-model differences are also apparent, even when using the same 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 optimal 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 are able to repr

At present, anthropogenic halogens and oceanic emissions of Very Short-Lived Substances (VSLS) are responsible for stratospheric ozone destruction. Emissions of the, mostly long-lived, anthropogenic halogens have been reduced, and as a consequence, their atmospheric abundance has started to decline since the beginning of the 21st century. Emissions of VSLS are, on the other hand, expected to increase in the future. VSLS are known to have large natural sources; however increasing evidence arises that their oceanic production and emission is enhanced by anthropogenic activities. Here, we introduce a new approach of assessing the overall impact of all oceanic halogen emissions on stratospheric ozone by calculating Ozone Depletion Potential (ODP)-weighted emissions of VSLS. Seasonally and spatially dependent, global distributions are derived exemplary for CHBr3 for the period 1999–2006. At present, ODP-weighted emissions of CHBr3 amount up to 50% of ODP-weighted anthropogenic emissions of CFC-11 and to 9% of all long-lived ozone depleting substances. The ODP-weighted emissions are large where strong oceanic emissions coincide with high-reaching convective activity and show pronounced peaks at the equator and the coasts with largest contributions from the Maritime Continent and West Pacific. Variations of tropical convective activity lead to seasonal shifts in the spatial distribution of the ODP with the updraught mass flux explaining 71% of the variance of the ODP distribution. Future climate projections based on RCP8.5 scenario suggest a 31% increase of the ODP-weighted CHBr3 emissions until 2100 compared to present values. This increase is related to larger convective activity and increasing emissions in a future climate; however, is reduced at the same time by less effective bromine-related ozone depletion. The comparison of the ODP-weighted emissions of short and long-lived halocarbons provides a new concept for assessing the overall impact of oceanic bromine emissi

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 real-time 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 +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. Calculat

Why a chapter on Perspectives and Integration in SOLAS Science in this book? SOLAS science by its nature deals with interactions that occur: across a wide spectrum of time and space scales, involve gases and particles, between the ocean and the atmosphere, across many disciplines including chemistry, biology, optics, physics, mathematics, computing, socio-economics and consequently interactions between many different scientists and across scientific generations. This chapter provides a guide through the remarkable diversity of cross-cutting approaches and tools in the gigantic puzzle of the SOLAS realm. Here we overview the existing prime components of atmospheric and oceanic observing systems, with the acquisition of ocean–atmosphere observables either from in situ or from satellites, the rich hierarchy of models to test our knowledge of Earth System functioning, and the tremendous efforts accomplished over the last decade within the COST Action 735 and SOLAS Integration project frameworks to understand, as best we can, the current physical and biogeochemical state of the atmosphere and ocean commons. A few SOLAS integrative studies illustrate the full meaning of interactions, paving the way for even tighter connections between thematic fields. Ultimately, SOLAS research will also develop with an enhanced consideration of societal demand while preserving fundamental research coherency. The exchange of energy, gases and particles across the air-sea interface is controlled by a variety of biological, chemical and physical processes that operate across broad spatial and temporal scales. These processes influence the composition, biogeochemical and chemical properties of both the oceanic and atmospheric boundary layers and ultimately shape the Earth system response to climate and environmental change, as detailed in the previous four chapters. In this cross-cutting chapter we present some of the SOLAS achievements over the last decade in terms of integration, upscaling

Why a chapter on Perspectives and Integration in SOLAS Science in this book? SOLAS science by its nature deals with interactions that occur: across a wide spectrum of time and space scales, involve gases and particles, between the ocean and the atmosphere, across many disciplines including chemistry, biology, optics, physics, mathematics, computing, socio-economics and consequently interactions between many different scientists and across scientific generations. This chapter provides a guide through the remarkable diversity of cross-cutting approaches and tools in the gigantic puzzle of the SOLAS realm. Here we overview the existing prime components of atmospheric and oceanic observing systems, with the acquisition of ocean–atmosphere observables either from in situ or from satellites, the rich hierarchy of models to test our knowledge of Earth System functioning, and the tremendous efforts accomplished over the last decade within the COST Action 735 and SOLAS Integration project frameworks to understand, as best we can, the current physical and biogeochemical state of the atmosphere and ocean commons. A few SOLAS integrative studies illustrate the full meaning of interactions, paving the way for even tighter connections between thematic fields. Ultimately, SOLAS research will also develop with an enhanced consideration of societal demand while preserving fundamental research coherency. The exchange of energy, gases and particles across the air-sea interface is controlled by a variety of biological, chemical and physical processes that operate across broad spatial and temporal scales. These processes influence the composition, biogeochemical and chemical properties of both the oceanic and atmospheric boundary layers and ultimately shape the Earth system response to climate and environmental change, as detailed in the previous four chapters. In this cross-cutting chapter we present some of the SOLAS achievements over the last decade in terms of integration, upscaling

Methyl iodide (CH3I}, bromoform (CHBr3) and dibromomethane (CH2Br2), which are produced naturally in the oceans, take part in ozone chemistry both in the troposphere and the stratosphere. The significance of oceanic upwelling regions for emissions of these trace gases in the global context is still uncertain although they have been identified as important source regions. To better quantify the role of upwelling areas in current and future climate, this paper analyzes major factors that influenced halocarbon emissions from the tropical North East Atlantic including the Mauritanian upwelling during the DRIVE expedition. Diel and regional variability of oceanic and atmospheric CH3I, CHBr3 and CH2Br2 was determined along with biological and meteorological parameters at six 24 h-stations. Low oceanic concentrations of CH3I from 0.1–5.4 pmol L-1 were equally distributed throughout the investigation area. CHBr3 of 1.0–42.4 pmol L-1 and CH2Br2 of 1.0–9.4 pmol L-1 were measured with maximum concentrations close to the Mauritanian coast. Atmospheric mixing rations of CH3I of up to 3.3, CHBr3 to 8.9 and CH2Br2 to 3.1 ppt above the upwelling and 1.8, 12.8, respectively 2.2 ppt at a Cape Verdean coast were detected during the campaign. While diel variability in CH3I emissions could be mainly ascribed to oceanic non-biological production, no main driver was identified for its emissions in the entire study region. In contrast, oceanic bromocarbons resulted from biogenic sources which were identified as regional drivers of their sea-to-air fluxes. The diel impact of wind speed on bromocarbon emissions increased with decreasing distance to the coast. The height of the marine atmospheric boundary layer (MABL) was determined as an additional factor influencing halocarbon emissions. Oceanic and atmospheric halocarbons correlated well in the study region and in combination with high oceanic CH3I, CHBr3 and CH2Br2 concentrations, local hot spots of atmospheric halocarbons could solely be

We investigate the contribution of oceanic methyl iodide (CH3I) to the stratospheric iodine budget. Based on CH3I measurements from 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 (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere)-Sonne research vessel campaign in the coastal western Pacific. The other two campaigns give considerably smaller maxima of 0.1 ppt CH3I in the open western Pacific and 0.03 ppt in the coastal eastern Atlantic. 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 with available upper air measurements, including data from the recent ATTREX and HIPPO2 aircraft campaigns. In the eastern 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 that are subject to stronger convective acti

During the DRIVE (Diurnal and Regional Variability of Halogen Emissions) ship campaign we investigated the variability of the halogenated very short-lived substances (VSLS) bromoform (CHBr3), dibromomethane (CH2Br2) and methyl iodide (CH3I) in the marine atmospheric boundary layer in the eastern tropical and subtropical North Atlantic Ocean during May/June 2010. The highest VSLS mixing ratios were found near the Mauritanian coast and close to Lisbon (Portugal). With backward trajectories we identified predominantly air masses from the open North Atlantic with some coastal influence in the Mauritanian upwelling area, due to the prevailing NW winds. The maximum VSLS mixing ratios above the Mauritanian upwelling were 8.92 ppt for bromoform, 3.14 ppt for dibromomethane and 3.29 ppt for methyl iodide, with an observed maximum range of the daily mean up to 50% for bromoform, 26% for dibromomethane and 56% for methyl iodide. The influence of various meteorological parameters - such as wind, surface air pressure, surface air and surface water temperature, humidity and marine atmospheric boundary layer (MABL) height - on VSLS concentrations and fluxes was investigated. The strongest relationship was found between the MABL height and bromoform, dibromomethane and methyl iodide abundances. Lowest MABL heights above the Mauritanian upwelling area coincide with highest VSLS mixing ratios and vice versa above the open ocean. Significant high anti-correlations confirm this relationship for the whole cruise. We conclude that especially above oceanic upwelling systems, in addition to sea-air fluxes, MABL height variations can influence atmospheric VSLS mixing ratios, occasionally leading to elevated atmospheric abundances. This may add to the postulated missing VSLS sources in the Mauritanian upwelling region (Quack et al., 2007).

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

Volatile halogenated organic compounds containing bromine and iodine, which are naturally produced in the ocean, are involved in ozone depletion in both the troposphere and stratosphere. Three prominent compounds transporting large amounts of marine halogens into the atmosphere are bromoform (CHBr3), dibromomethane (CH2Br2) and methyl iodide (CH3I). The input of marine halogens to the stratosphere is based on observations and modeling studies using low resolution oceanic emission scenarios derived from top down approaches. In order to improve emission inventory estimates, we calculate data-based high resolution global sea-to-air flux estimates of these compounds from surface observations within the HalOcAt database (https://halocat.geomar.de/). Global maps of marine and atmospheric surface concentrations are derived from the data which are divided into coastal, shelf and open ocean regions. Considering physical and biogeochemical characteristics of ocean and atmosphere, the open ocean water and atmosphere data are classified into 21 regions. The available data are interpolated onto a 1° × 1° grid while missing grid values are interpolated with latitudinal and longitudinal dependent regression techniques reflecting the compounds' distributions. With the generated surface concentration climatologies for the ocean and atmosphere, global concentration gradients and sea-to-air fluxes are calculated. Based on these calculations we estimate a total global flux of 1.5/2.5 Gmol Br yr−1 for CHBr3, 0.78/0.98 Gmol Br yr−1 for CH2Br2 and 1.24/1.45 Gmol I yr−1 for CH3I (Robust Fit/Ordinary Least Square regression technique). Contrary to recent studies, negative fluxes occur in each sea-to-air flux climatology, mainly in the Arctic and Antarctic region. "Hot spots" for global polybromomethane emissions are located in the equatorial region, whereas methyl iodide emissions are enhanced in the subtropical gyre regions. Inter-annual and seasonal variation is contained within our calcu