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Short-lived bromo-, chloro- and iodocarbons from marine and anthropogenic sources contribute to the atmospheric halogen budgets and to ozone depletion in the troposphere and stratosphere. Their spatial variations are poorly known, given the sparse observations of marine and atmospheric concentrations. The distribution and air-sea fluxes of halocarbons need to be quantified in order to clarify the oceanic contributions to future tropospheric and stratospheric ozone chemistry.Here we present the first marine and atmospheric halocarbon dataset from the research cruise SO287-CONNECT (Pan-Atlantic connectivity of marine biogeochemical and ecological processes and the impact of anthropogenic pressures). The transit of RV SONNE from Las Palmas, Spain (departure: 11.12.2021) to Guayaquil, Ecuador (arrival: 11.01.2022) was conducted to decipher the coupling of biogeochemical and ecological processes and their influence on atmospheric chemistry along the transport pathway of water from the upwelling zones off Africa into the Sargasso Sea and further to the Caribbean and the equatorial Pacific. A comprehensive work program, which combined continuous underway and station work, marine and atmospheric measurements and sampling with incubation experiments was conducted.The distribution of short-lived halocarbons, e.g. bromoform (CHBr3), dibromomethane (CH2Br2), methyl iodide (CH3I), and trichloromethane (CHCl3) was highly dynamic in both ocean and atmosphere. We calculate the air-sea exchange of the compounds and relate physical and biological parameters to our observations. Among these are transport processes (e.g. long-range transport, eddies) and we show the varying composition of air and water masses and the potential sources of the compounds. For the first time, we estimate the contribution of the floating macroalgae Sargassum to halocarbon cycling around the North Atlantic gyre and in the Caribbean. The evaluation of the comprehensive data set collected during SO287-CONNECT improves our knowledge on the general role of the great Atlantic Sargassum belt and anthropogenic pollution in elemental biogeochemical cycles, as well as on trace gas exchange across the ocean-atmosphere interface.

Iron is an essential nutrient that limits primary productivity in up to 30% of the world’s ocean. Redox and complexation reactions control its solubility and therefore the fraction of dissolved and bioavailable iron. The iron (II) oxidation kinetic process was studied at 25 stations in coastal seawater of the Macaronesia region (around Cape Verde, the Canary Islands and Madeira). Laboratory experiments were carried out to study the pseudo-first-order oxidation rate constant (k’, min-1) over a range of pH (7.8-8.1) and temperature (T; 10-25ºC). Measured k’ varied from the calculated k’ (k'cal) at the same T, pH and salinity (S) at most stations. Measured iron (II) half-life times (t1/2=ln2/k’; min) at the 25 stations ranged from 1.8-3.5 min (mean 1.9±0.8 min) and for all but two stations were lower than the theoretically calculated t1/2 of 3.2±0.2 min. The biogeochemical context was considered by analysing nutrients and variables associated with the organic matter spectral properties (CDOM and FDOM). A multilinear regression model indicated that k’ can be described (R=0.921, SEE=0.064 for pH=8 and T=25ºC) from a linear combination of three organic variables.k’OM = k’cal -0.11* TDN + 29.9 * bDOM + 33.4 * C1humicwhere TDN is the total dissolved nitrogen, bDOM is the spectral peak obtained from coloured DOM analysis when protein-like or tyrosine-like components are present and C1humic is the component associated with humic-like compounds obtained from the parallel factor analysis (PARAFAC) of the fluorescent DOM. Experimentally, k’ and k’OM provide the net result between the compounds that accelerate the process and those that slow it down. Results show that compounds with nitrogen in their structures mainly explain the observed k’ increase for most of the samples, although other components could also present a relevant role.

Transport of air masses from the subtropics, enriched in trace gases from the oceans, coasts and islands, towards lower latitudes under the trade inversion and uplift to the stratosphere in tropical deep convection. The organic bromine compounds bromoform (CHBr 3 ) and dibromomethane (CH 2 Br 2 ) influence tropospheric chemistry and stratospheric ozone depletion. Their atmospheric abundance is generally related to a common marine source, which is not well characterized. A cruise between the three Macaroenesian Archipelagos of Cape Verde, the Canaries and Madeira revealed that anthropogenic sources increased oceanic CHBr 3 emissions significantly close to some islands, especially at the Canaries, while heterotrophic processes in the ocean increased the flux of CH 2 Br 2 from the sea to the atmosphere in the Cape Verde region. As anthropogenic disinfection processes, which release CHBr 3 in coastal areas increase, and as more CH 2 Br 2 may be produced from increased heterotrophy in a warming, deoxygenated ocean, both sources could supply higher fractions of stratospheric bromine in the future, with yet unknown consequences for stratospheric ozone.

The iron(II) oxidation kinetic process was studied at 25 stations in coastal seawater of the Macaronesia region (9 around Cape Verde, 11 around the Canary Islands, and 5 around Madeira). In a physicochemical context, experiments were carried out to study the pseudo-first-order oxidation rate constant (k′, min–1) over a range of pH (7.8, 7.9, 8.0, and 8.1) and temperature (10, 15, 20, and 25 °C). Deviations from the calculated kcal′ at the same T, pH, and S were observed for most of the stations. The measured t1/2 (ln 2/k′, min) values at the 25 stations ranged from 1.82 to 3.47 min (mean 1.93 ± 0.76 min) and for all but two stations were lower than the calculated t1/2 of 3.21 ± 0.2 min. In a biogeochemical context, nutrients and variables associated with the organic matter spectral properties (CDOM and FDOM) were analyzed to explain the observed deviations. The application of a multilinear regression model indicated that k′ can be described (R = 0.921 and SEE = 0.064 for pH = 8 and T = 25 °C) from a linear combination of three organic variables, k′OM = kcal′ −0.11* TDN + 29.9*bDOM + 33.4*C1humic, where TDN is the total dissolved nitrogen, bDOM is the spectral peak obtained from colored dissolved organic matter (DOM) analysis when protein-like or tyrosine-like components are present, and C1humic is the component associated with humic-like compounds obtained from the parallel factor analysis of the fluorescent DOM. Results show that compounds with N in their structures mainly explain the observed k′ increase for most of the samples, although other components could also play a relevant role. Experimentally, k′ provides the net result between the compounds that accelerate the process and those that slow it down.

Reaction with iodide (I-) at the sea surface is an important sink for atmospheric ozone, and causes sea-air emission of reactive iodine which in turn drives further ozone destruction. To incorporate this process into chemical transport models, improved understanding of the factors controlling marine iodine speciation, and especially sea-surface iodide concentrations, is needed. The oxidation of I- to iodate (IO3-) is the main sink for oceanic I-, but the mechanism for this remains unknown. We demonstrate for the first time that marine nitrifying bacteria mediate I- oxidation to IO3-. A significant increase in IO3- concentrations compared to media-only controls was observed in cultures of the ammonia-oxidising bacteria Nitrosomonas sp. (Nm51) and Nitrosoccocus oceani (Nc10) supplied with 9-10 mM I-, indicating I- oxidation to IO3-. Cell-normalised production rates were 15.69 (+/- 4.71) fmol IO3- cell(-1) d(-1) for Nitrosomonas sp., and 11.96 (+/- 6.96) fmol IO3- cell(-1) d(-1) for Nitrosococcus oceani, and molar ratios of iodate-to-nitrite production were 9.2 +/- 4.1 and 1.88 +/- 0.91 respectively. Preliminary experiments on nitrite-oxidising bacteria showed no evidence of I- to IO3- oxidation. If the link between ammonia and I oxidation observed here is representative, our ocean iodine cycling model predicts that future changes in marine nitrification could alter global sea surface I fields with potential implications for atmospheric chemistry and air quality.

Iodine is a critical trace element involved in many diverse and important processes in the Earth system. The importance of iodine for human health has been known for over a century, with low iodine in the diet being linked to goitre, cretinism and neonatal death. Research over the last few decades has shown that iodine has significant impacts on tropospheric photochemistry, ultimately impacting climate by reducing the radiative forcing of ozone (O 3 ) and air quality by reducing extreme O 3 concentrations in polluted regions. Iodine is naturally present in the ocean, predominantly as aqueous iodide and iodate. The rapid reaction of sea-surface iodide with O 3 is believed to be the largest single source of gaseous iodine to the atmosphere. Due to increased anthropogenic O 3 , this release of iodine is believed to have increased dramatically over the twentieth century, by as much as a factor of 3. Uncertainties in the marine iodine distribution and global cycle are, however, major constraints in the effective prediction of how the emissions of iodine and its biogeochemical cycle may change in the future or have changed in the past. Here, we present a synthesis of recent results by our team and others which bring a fresh perspective to understanding the global iodine biogeochemical cycle. In particular, we suggest that future climate-induced oceanographic changes could result in a significant change in aqueous iodide concentrations in the surface ocean, with implications for atmospheric air quality and climate.

An ocean iodine cycling model is presented, which predicts upper ocean iodine speciation. The model comprises a three-layer advective and diffusive ocean circulation model of the upper ocean, and an iodine cycling model embedded within this circulation. The two primary reservoirs of iodine are represented, iodide and iodate. Iodate is reduced to iodide in the mixed layer in association with primary production, linked by an iodine to carbon (I:C) ratio. A satisfactory model fit with observations cannot be obtained with a globally constant I:C ratio, and the best fit is obtained when the I:C ratio is dependent on sea surface temperature, increasing at low temperatures. Comparisons with observed iodide distributions show that the best model fit is obtained when oxidation of iodide back to iodate is associated with mixed layer nitrification. Sensitivity tests, where model parameters and processes are perturbed, reveal that primary productivity, mixed layer depth, oxidation, advection, surface fresh water flux and the I:C ratio all have a role in determining surface iodide concentrations, and the timescale of iodide in the mixed layer is sufficiently long for non-local processes to be important. Comparisons of the modelled iodide surface field with parameterisations by other authors shows good agreement in regions where observations exist, but significant differences in regions without observations. This raises the question of whether the existing parameterisations are capturing the full range of processes involved in determining surface iodide, and shows the urgent need for observations in regions where there are currently none.

Reaction with iodide (I) at the sea surface is an important sink for atmospheric ozone, and causes sea-air emission of reactive iodine which in turn drives further ozone destruction. To incorporate...

The reaction between ozone and iodide at the sea surface is now known to be an important part of atmospheric ozone cycling, causing ozone deposition and the release of ozone-depleting reactive iodine to the atmosphere. The importance of this reaction is reflected by its inclusion in chemical transport models (CTMs). Such models depend on accurate sea surface iodide fields, but measurements are spatially and temporally limited. Hence, the ability to predict current and future sea surface iodide fields, i.e. sea surface iodide concentration on a narrow global grid, requires the development of process-based models. These models require a thorough understanding of the key processes that control sea surface iodide. The aim of this study was to explore if there are common features of iodate-to-iodide reduction amongst diverse marine phytoplankton in order to develop models that focus on sea surface iodine and iodine release to the troposphere. In order to achieve this, rates and patterns of changes in inorganic iodine speciation were determined in 10 phytoplankton cultures grown at ambient iodate concentrations. Where possible these data were analysed alongside results from previous studies. Iodate loss and some iodide production were observed in all cultures studied, confirming that this is a widespread feature amongst marine phytoplankton. We found no significant difference in log-phase, cell-normalised iodide production rates between key phytoplankton groups (diatoms, prymnesiophytes including coccolithophores and phaeocystales), suggesting that a phytoplankton functional type (PFT) approach would not be appropriate for building an ocean iodine cycling model. Iodate loss was greater than iodide formation in the majority of the cultures studied, indicating the presence of an as-yet-unidentified “missing iodine” fraction. Iodide yield at the end of the experiment was significantly greater in cultures that had reached a later senescence stage. This suggests that models should incorporate a lag between peak phytoplankton biomass and maximum iodide production and that cell mortality terms in biogeochemical models could be used to parameterise iodide production.

Halogenated very short-lived substances (VSLSs) are naturally produced in the ocean and emitted to the atmosphere. When transported to the stratosphere, these compounds can have a significant influence on the ozone layer and climate. During a research cruise on RV Sonne in the subtropical and tropical west Indian Ocean in July and August 2014, we measured the VSLSs, methyl iodide (CH3I) and for the first time bromoform (CHBr3) and dibromomethane (CH2Br2), in surface seawater and the marine atmosphere to derive their emission strengths. Using the Lagrangian particle dispersion model FLEXPART with ERA-Interim meteorological fields, we calculated the direct contribution of observed VSLS emissions to the stratospheric halogen burden during the Asian summer monsoon. Furthermore, we compare the in situ calculations with the interannual variability of transport from a larger area of the west Indian Ocean surface to the stratosphere for July 2000–2015. We found that the west Indian Ocean is a strong source for CHBr3 (910 pmol m−2 h−1), very strong source for CH2Br2 (930 pmol m−2 h−1), and an average source for CH3I (460 pmol m−2 h−1). The atmospheric transport from the tropical west Indian Ocean surface to the stratosphere experiences two main pathways. On very short timescales, especially relevant for the shortest-lived compound CH3I (3.5 days lifetime), convection above the Indian Ocean lifts oceanic air masses and VSLSs towards the tropopause. On a longer timescale, the Asian summer monsoon circulation transports oceanic VSLSs towards India and the Bay of Bengal, where they are lifted with the monsoon convection and reach stratospheric levels in the southeastern part of the Asian monsoon anticyclone. This transport pathway is more important for the longer-lived brominated compounds (17 and 150 days lifetime for CHBr3 and CH2Br2). The entrainment of CHBr3 and CH3I from the west Indian Ocean to the stratosphere during the Asian summer monsoon is lower than from previous cruises in the tropical west Pacific Ocean during boreal autumn and early winter but higher than from the tropical Atlantic during boreal summer. In contrast, the projected CH2Br2 entrainment was very high because of the high emissions during the west Indian Ocean cruise. The 16-year July time series shows highest interannual variability for the shortest-lived CH3I and lowest for the longest-lived CH2Br2. During this time period, a small increase in VSLS entrainment from the west Indian Ocean through the Asian monsoon to the stratosphere is found. Overall, this study confirms that the subtropical and tropical west Indian Ocean is an important source region of halogenated VSLSs, especially CH2Br2, to the troposphere and stratosphere during the Asian summer monsoon.

The reaction between ozone and iodide at the sea surface is now known to be an important part of atmospheric ozone cycling, causing ozone deposition and the release of ozone-depleting reactive iodine to the atmosphere. The importance of this reaction is reflected by its inclusion in chemical transport models (CTMs). Such models depend on accurate sea surface iodide fields but measurements are spatially and temporally limited. The ability to predict current and future sea surface iodide fields requires the development of process-based models which in turn require a thorough understanding of the key processes controlling inorganic iodine cycling. The aim of this study was to inform the development of ocean iodine cycling models by exploring if there are common features of iodate to iodide reduction amongst diverse marine phytoplankton. In order to achieve this, rates and patterns of changes in inorganic iodine speciation were determined in 10 phytoplankton cultures grown at ambient iodate concentrations. Where possible these data were analysed alongside results from previous studies. Iodate loss and some iodide production was observed in all cultures studied, confirming that this is a widespread feature amongst marine phytoplankton. We found no significant difference in log-phase, cell-normalised iodide production rates between key phytoplankton groups (diatoms, prymesiophytes including coccolithophores and phaeocystales) suggesting that a Phytoplankton Functional Type (PFT) approach would not be appropriate for building an ocean iodine cycling model. Iodate loss was greater than iodide formation in the majority of the cultures studied, indicating the presence of an as yet unidentified missing iodine fraction. Iodide yield at the end of the experiment was significantly greater in cultures that had reached a later senescence stage. This suggests that models should incorporate a lag between peak phytoplankton biomass and maximum iodide production, and that cell mortality terms in biogeochemical models could be used to parameterize iodide production.

Halocarbons from oceanic sources contribute to halogens in the troposphere, and can be transported into the stratosphere where they take part in ozone depletion. This paper presents distribution and sources in the equatorial Atlantic from June and July 2011 of the four compounds bromoform (CHBr3), dibromomethane (CH2Br2), methyl iodide (CH3I) and diiodomethane (CH2I2). Enhanced biological production during the Atlantic Cold Tongue (ACT) season, indicated by phytoplankton pigment concentrations, led to elevated concentrations of CHBr3 of up to 44.7 and up to 9.2 pmol L−1 for CH2Br2 in surface water, which is comparable to other tropical upwelling systems. While both compounds correlated very well with each other in the surface water, CH2Br2 was often more elevated in greater depth than CHBr3, which showed maxima in the vicinity of the deep chlorophyll maximum. The deeper maximum of CH2Br2 indicates an additional source in comparison to CHBr3 or a slower degradation of CH2Br2. Concentrations of CH3I of up to 12.8 pmol L−1 in the surface water were measured. In contrary to expectations of a predominantly photochemical source in the tropical ocean, its distribution was mostly in agreement with biological parameters, indicating a biological source. CH2I2 was very low in the near surface water with maximum concentrations of only 3.7 pmol L−1. CH2I2 showed distinct maxima in deeper waters similar to CH2Br2. For the first time, diapycnal fluxes of the four halocarbons from the upper thermocline into and out of the mixed layer were determined. These fluxes were low in comparison to the halocarbon sea-to-air fluxes. This indicates that despite the observed maximum concentrations at depth, production in the surface mixed layer is the main oceanic source for all four compounds and one of the main driving factors of their emissions into the atmosphere in the ACT-region. The calculated production rates of the compounds in the mixed layer are 34 ± 65 pmol m−3 h−1 for CHBr3, 10 ± 12 pmol m−3 h−1 for CH2Br2, 21 ± 24 pmol m−3 h−1 for CH3I and 384 ± 318 pmol m−3 h−1 for CH2I2 determined from 13 depth profiles.

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 activity show larger CH3I entrainment, e.g., 0.08 ppt in the western Pacific. Overall our model results give a tropical contribution of 0.04 ppt CH3I to the stratospheric iodine budget. 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.

Methyl iodide (CH3I) is a volatile organic halogen compound that contributes significantly to the transport of iodine from the ocean to the atmosphere, where it plays an important role in tropospheric chemistry. CH3I is naturally produced and occurs in the global ocean. The processes involved in the formation of CH3I, however, are not fully understood. In fact, there is an ongoing debate whether production by phytoplankton or photochemical degradation of organic matter is the main source term. Here, both the biological and photochemical production mechanisms are considered in a biogeochemical module that is coupled to a one-dimensional water column model for the eastern tropical Atlantic. The model is able to reproduce observed subsurface maxima of CH3I concentrations. But, the dominating source process cannot be clearly identified as subsurface maxima can occur due to both direct biological and photochemical production. However, good agreement between the observed and simulated difference between surface and subsurface methyl iodide concentrations is achieved only when direct biological production is taken into account. Production rates for the biological CH3I source that were derived from published laboratory studies are shown to be inappropriate for explaining CH3I concentrations in the eastern tropical Atlantic.

Emissions of halogenated very short lived substances (VSLS) from the tropical oceans contribute to the atmospheric halogen budget and affect tropospheric and stratospheric ozone. Here we investigate the contribution of natural oceanic VSLS emissions to the Marine Atmospheric Boundary Layer (MABL) and their transport into the Free Troposphere (FT) over the tropical West Pacific. The study concentrates in particular on ship and aircraft measurements of the VSLS bromoform, dibromomethane and methyl iodide and meteorological parameters during the SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere) campaign in the South China and Sulu Seas in November 2011. Elevated oceanic concentrations of 19.9 (2.80–136.91) pmol L−1 for bromoform, 5.0 (2.43–21.82) pmol L−1 for dibromomethane and 3.8 (0.55–18.83) pmol L−1 for methyl iodide in particular close to Singapore and at the coast of Borneo with high corresponding oceanic emissions of 1486 ± 1718 pmol m−2 h−1 for bromoform, 405 ± 349 pmol m−2 h−1 for dibromomethane and 433 ± 482 pmol m−2 h−1 for methyl iodide characterize this tropical region as a strong source of these compounds. Unexpectedly atmospheric mixing ratios in the MABL were relatively low with 2.08 ± 2.08 ppt for bromoform, 1.17 ± 1.17 ppt for dibromomethane and 0.39 ± 0.09 ppt for methyl iodide. We use meteorological and chemical ship and aircraft observations, FLEXPART trajectory calculations and source-loss estimates to identify the oceanic VSLS contribution to the MABL and to the FT. Our results show that a convective, well-ventilated MABL and intense convection led to the low atmospheric mixing ratios in the MABL despite the high oceanic emissions in coastal areas of the South-China and Sulu Seas. While the accumulated bromoform in the FT above the region origins almost entirely from the local South China Sea area, dibromomethane is largely advected from distant source regions. The accumulated FT mixing ratio of methyl iodide is higher than can be explained with the local oceanic or MABL contributions. Possible reasons, uncertainties and consequences of our observations and model estimates are discussed.

Halocarbons are produced naturally in the oceans by biological and chemical processes. They are emitted from surface seawater into the atmosphere, where they take part in numerous chemical processes such as ozone destruction and the oxidation of mercury and dimethyl sulfide. Here we present oceanic and atmospheric halocarbon data for the Peruvian upwelling zone obtained during the M91 cruise onboard the research vessel METEOR in December 2012. Surface waters during the cruise were characterized by moderate concentrations of bromoform (CHBr3) and dibromomethane (CH2Br2) correlating with diatom biomass derived from marker pigment concentrations, which suggests this phytoplankton group is a likely source. Concentrations measured for the iodinated compounds methyl iodide (CH3I) of up to 35.4 pmol L−1, chloroiodomethane (CH2ClI) of up to 58.1 pmol L−1 and diiodomethane (CH2I2) of up to 32.4 pmol L−1 in water samples were much higher than previously reported for the tropical Atlantic upwelling systems. Iodocarbons also correlated with the diatom biomass and even more significantly with dissolved organic matter (DOM) components measured in the surface water. Our results suggest a biological source of these compounds as a significant driving factor for the observed large iodocarbon concentrations. Elevated atmospheric mixing ratios of CH3I (up to 3.2 ppt), CH2ClI (up to 2.5 ppt) and CH2I2 (3.3 ppt) above the upwelling were correlated with seawater concentrations and high sea-to-air fluxes. During the first part of the cruise, the enhanced iodocarbon production in the Peruvian upwelling contributed significantly to tropospheric iodine levels, while this contribution was considerably smaller during the second part.

During a cruise of R/V METEOR in December 2012 the oceanic sources and emissions of various halogenated trace gases and their mixing ratios in the marine atmospheric boundary layer (MABL) were investigated above the Peruvian upwelling. This study presents novel observations of the three very short lived substances (VSLSs) – bromoform, dibromomethane and methyl iodide – together with high-resolution meteorological measurements, Lagrangian transport and source–loss calculations. Oceanic emissions of bromoform and dibromomethane were relatively low compared to other upwelling regions, while those for methyl iodide were very high. Radiosonde launches during the cruise revealed a low, stable MABL and a distinct trade inversion above acting as strong barriers for convection and vertical transport of trace gases in this region. Observed atmospheric VSLS abundances, sea surface temperature, relative humidity and MABL height correlated well during the cruise. We used a simple source–loss estimate to quantify the contribution of oceanic emissions along the cruise track to the observed atmospheric concentrations. This analysis showed that averaged, instantaneous emissions could not support the observed atmospheric mixing ratios of VSLSs and that the marine background abundances below the trade inversion were significantly influenced by advection of regional sources. Adding to this background, the observed maximum emissions of halocarbons in the coastal upwelling could explain the high atmospheric VSLS concentrations in combination with their accumulation under the distinct MABL and trade inversions. Stronger emissions along the nearshore coastline likely added to the elevated abundances under the steady atmospheric conditions. This study underscores the importance of oceanic upwelling and trade wind systems on the atmospheric distribution of marine VSLS emissions.

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.

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).

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 has been estimated from observations and modelling 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 (Halocarbons in the Ocean and Atmosphere) 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 sea-to-air 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 Br yr−1 for CH3I (robust fit/ordinary least squares regression techniques). Contrary to recent studies, negative fluxes occur in each sea-to-air flux climatology, mainly in the Arctic and Antarctic regions. "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 flux calculations for all three compounds. Compared to earlier studies, our global fluxes are at the lower end of estimates, especially for bromoform. An under-representation of coastal emissions and of extreme events in our estimate might explain the mismatch between our bottom-up emission estimate and top-down approaches.