Description: We use isoprene and related field measurements from three different ocean data sets together with remotely sensed satellite data to model global marine isoprene emissions. We show that using monthly mean satellite-derived chl a concentrations to parameterize isoprene with a constant chl a normalized isoprene production rate underpredicts the measured oceanic isoprene concentration by a mean factor of 19 ± 12. Improving the model by using phytoplankton functional type dependent production values and by decreasing the bacterial degradation rate of isoprene in the water column results in only a slight underestimation (factor 1.7 ± 1.2). We calculate global isoprene emissions of 0.21 Tg C for 2014 using this improved model, which is twice the value calculated using the original model. Nonetheless, the sea-to-air fluxes have to be at least 1 order of magnitude higher to account for measured atmospheric isoprene mixing ratios. These findings suggest that there is at least one missing oceanic source of isoprene and, possibly, other unknown factors in the ocean or atmosphere influencing the atmospheric values. The discrepancy between calculated fluxes and atmospheric observations must be reconciled in order to fully understand the importance of marine-derived isoprene as a precursor to remote marine boundary layer particle formation.

Description: Natural, short-lived halocarbons play a role in the stratospheric ozone budget, besides the anthropogenic emitted long-lived chlorine- and bromine fluorocarbons. The tropical oceans are a known source of reactive iodine and bromine to the atmosphere in the form of iodinated and brominated methanes (VSLS), as methyl iodide (CH3I), dibromomethane (CH2Br2) and bromoform (CHBr3), which contributes to reactive bromine within the lower stratosphere. Elevated atmospheric concentrations above the oceans are related to oceanic super-saturations of the compounds, caused by photochemical and biological production. The tropical Western Pacific is of special interest since it is a largely uncharacterized region for the oceanic compounds and in certain regions a projected hot spot for their emissions and transport pathways into the stratosphere. Under the leadership of IFM-GEOMAR (Kiel, Germany) a cruise with RV Sonne was conducted from 9 to 25 October 2009 in the tropical western Pacific to investigate trace gas emissions on a 4030 nm (7,500 km) and 60 degrees latitude covering transit between Tomakomai (Japan, 42°35,4N/ 141°37,5E) and Townsville (Australia, 19°06,6S/ 146°50,5E). The ships cruise crossed various biogeochemical regimes of the northern and southern western Pacific Ocean, which differ in seawater properties, currents, productivity and atmospheric dynamics (e.g. Kuroshio Front, Northern Pacific Gyre, Pacific warm pool and Coral Seas). We will present highlights of the oceanic and atmospheric halocarbon measurements during the ships campaign, halocarbon emissions from the western Pacific Ocean, sources and transport calculations, including contributions to stratospheric bromine.

Description: 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 physical 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 and CH2Br2 from 1.0 to 42.4 pmol L−1 and to 9.4 pmol L−1, respectively were measured with maximum concentrations close to the Mauritanian coast. Atmospheric CH3I, CHBr3, and CH2Br2 of up to 3.3, 8.9, and 3.1 ppt, respectively were detected above the upwelling, as well as up to 1.8, 12.8, and 2.2 ppt at the Cape Verdean coast. While diel variability in CH3I emissions could be mainly ascribed to oceanic non-biological production, no main driver was identified for its emissions over the entire study region. In contrast, biological parameters showed the greatest influence on the regional distribution of sea-to-air fluxes of bromocarbons. 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) influenced halocarbon emissions via its influence on atmospheric mixing ratios. 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 explained by marine sources. This conclusion is in contrast to previous studies that hypothesized elevated atmospheric halocarbons above the eastern tropical Atlantic to be mainly originated from the West-African continent.

Description: 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 reproduce well observations of CHBr3 and CH2 Br2 obtained in the tropical tropopause layer (TTL) at various locations throughout the Pacific. Zonal variability in VSLS loading in the TTL is generally consistent among models, with CHBr3 (and to a lesser extent CH2 Br2) most elevated over the tropical West 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 CH2 Br2 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. However, transport-driven inter-annual variability in the annual mean bromine SGI is of the order of a ±5%, with SGI exhibiting a strong positive correlation with ENSO in the East Pacific.

Description: Sea surface and atmospheric measurements of dimethylsulphide (DMS) were performed during the TransBrom cruise in the western Pacific Ocean between Japan and Australia in October 2009. Air–sea DMS fluxes were computed between 0 and 30 μmol m−2 d−1, which are in agreement with those computed by the current climatology, and peak emissions of marine DMS into the atmosphere were found during the occurrence of tropical storm systems. Atmospheric variability in DMS, however, did not follow that of the computed fluxes and was more related to atmospheric transport processes. The computed emissions were used as input fields for the Lagrangian dispersion model FLEXPART, which was set up with actual meteorological fields from ERA-Interim data and different chemical lifetimes of DMS. A comparison with aircraft in situ data from the adjacent HIPPO2 campaign revealed an overall good agreement between modelled versus observed DMS profiles over the tropical western Pacific Ocean. Based on observed DMS emissions and meteorological fields along the cruise track, the model projected that up to 30 g S per month in the form of DMS, emitted from an area of 6 × 104 m2, can be transported above 17 km. This surprisingly large DMS entrainment into the stratosphere is disproportionate to the regional extent of the area of emissions and mainly due to the high convective activity in this region as simulated by the transport model. Thus, if DMS can cross the tropical tropopause layer (TTL), we suggest that the considerably larger area of the tropical western Pacific Ocean can be a source of sulphur to the stratosphere, which has not been considered as yet.

Description: 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 explained by marine sources. This conclusion is in contrast with previous studies that hypothesized the occurrence of elevated atmospheric halocarbons over the eastern tropical Atlantic mainly originating from the West-African continent.

Description: Oceanic emissions of halogenated very short-lived substances (VSLS) are expected to contribute significantly to the stratospheric halogen loading and therefore to ozone depletion. The amount of VSLS transported into the stratosphere is estimated based on in-situ observations around the tropical tropopause layer (TTL) and on modeling studies which mostly use prescribed global emission scenarios to reproduce observed atmospheric concentrations. In addition to upper-air VSLS measurements, direct observations of oceanic VSLS emissions are available along ship cruise tracks. Here we use such in-situ observations of VSLS emissions from the West Pacific and tropical Atlantic together with an atmospheric Lagrangian transport model to estimate the direct contribution of bromoform (CHBr3), and dibromomethane (CH2Br2) to the stratospheric bromine loading as well as their ozone depletion potential. Our emission-based estimates of VSLS profiles are compared to upper-air observations and thus link observed oceanic emissions and in situ TTL measurements. This comparison determines how VSLS emissions and transport in the cruise track regions contribute to global upper-air VSLS estimates. The West Pacific emission-based profiles and the global upper-air observations of CHBr3 show a relatively good agreement indicating that emissions from the West Pacific provide an average contribution to the global CHBr3 budget. The tropical Atlantic, although also being a CHBr3 source region, is of less importance for global upper-air CHBr3 estimates as revealed by the small emission-based abundances in the TTL. Western Pacific CH2Br2 emission-based estimates are considerably smaller than upper-air observations as a result of the relatively low sea-to-air flux found in the West Pacific. Together, CHBr3 and CH2Br2 emissions from the West Pacific are projected to contribute to the stratospheric bromine budget with 0.4 pptv Br on average and 2.3 pptv Br for cases of maximum emissions through product and source gas injection. These relatively low estimates reveal that the tropical West Pacific, although characterized by strong convective transport, might overall contribute less VSLS to the stratospheric bromine budget than other regions as a result of only low CH2Br2 and moderate CHBr3 oceanic emissions.