Description: The Baltic Sea is a unique environment as the largest body of brackish water in the world. Acidification of the surface oceans due to absorption of anthropogenic CO2 emissions is an additional stressor facing the pelagic community of the already challenging Baltic Sea. To investigate its impact on trace gas biogeochemistry, a large-scale mesocosm experiment was performed off Tvärminne Research Station, Finland, in summer 2012. During the second half of the experiment, dimethylsulfide (DMS) concentrations in the highest-fCO2 mesocosms (1075–1333 µatm) were 34 % lower than at ambient CO2 (350 µatm). However, the net production (as measured by concentration change) of seven halocarbons analysed was not significantly affected by even the highest CO2 levels after 5 weeks' exposure. Methyl iodide (CH3I) and diiodomethane (CH2I2) showed 15 and 57 % increases in mean mesocosm concentration (3.8 ± 0.6 increasing to 4.3 ± 0.4 pmol L−1 and 87.4 ± 14.9 increasing to 134.4 ± 24.1 pmol L−1 respectively) during Phase II of the experiment, which were unrelated to CO2 and corresponded to 30 % lower Chl a concentrations compared to Phase I. No other iodocarbons increased or showed a peak, with mean chloroiodomethane (CH2ClI) concentrations measured at 5.3 (±0.9) pmol L−1 and iodoethane (C2H5I) at 0.5 (±0.1) pmol L−1. Of the concentrations of bromoform (CHBr3; mean 88.1 ± 13.2 pmol L−1), dibromomethane (CH2Br2; mean 5.3 ± 0.8 pmol L−1), and dibromochloromethane (CHBr2Cl, mean 3.0 ± 0.5 pmol L−1), only CH2Br2 showed a decrease of 17 % between Phases I and II, with CHBr3 and CHBr2Cl showing similar mean concentrations in both phases. Outside the mesocosms, an upwelling event was responsible for bringing colder, high-CO2, low-pH water to the surface starting on day t16 of the experiment; this variable CO2 system with frequent upwelling events implies that the community of the Baltic Sea is acclimated to regular significant declines in pH caused by up to 800 µatm fCO2. After this upwelling, DMS concentrations declined, but halocarbon concentrations remained similar or increased compared to measurements prior to the change in conditions. Based on our findings, with future acidification of Baltic Sea waters, biogenic halocarbon emissions are likely to remain at similar values to today; however, emissions of biogenic sulfur could significantly decrease in this region.

Description: The emission rates of eight volatile halogenated compounds by three tropical brown seaweed species collected from Cape Rachado, west coast Peninsular Malaysia, under different irradiances have been determined. A purge-and-trap sample preparation system with a gas chromatograph and mass-selective detector was used to measure a suite of halocarbons released by Sargassum binderi Sonder ex J. Agardh, Padina australis Hauck, and Turbinaria conoides (J. Agardh) Kützing. All species are widely distributed in Peninsular Malaysia, with S. binderi a dominant seaweed species at our survey site. Release of few halocarbons was found to be influenced by irradiance. Correlations were also observed between emission of certain halocarbons with photosynthetic activity, especially bromo-and iodinated compounds (0.6 〈 r 〈0.9; p 〈 0.01) suggesting that environmental factors such as light can affect the release of these volatile halogenated compounds by the seaweeds into the atmosphere. Compared with temperate and polar brown seaweeds, tropical species, such as T. conoides, may emit higher levels of bromoform, CHBr3, and other halocarbons. It is therefore important to investigate the contribution of tropical seaweeds towards the local atmospheric composition of halocarbons.

Description: The two-way exchange of trace gases between the ocean and the atmosphere is important for both the chemistry and physics of the atmosphere and the biogeochemistry of the oceans, including the global cycling of elements. Here we review these exchanges and their importance for a range of gases whose lifetimes are generally short compared to the main greenhouse gases and which are, in most cases, more reactive than them. Gases considered include sulphur and related compounds, organohalogens, non-methane hydrocarbons, ozone, ammonia and related compounds, hydrogen and carbon monoxide. Finally, we stress the interactivity of the system, the importance of process understanding for modeling, the need for more extensive field measurements and their better seasonal coverage, the importance of inter-calibration exercises and finally the need to show the importance of air-sea exchanges for global cycling and how the field fits into the broader context of Earth System Science.

Description: 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.

Description: 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.

Description: The marine iodine cycle has significant impacts on air quality and atmospheric chemistry. Specifically, the reaction of iodide with ozone in the top few micrometres of the surface ocean is an important sink for tropospheric ozone (a pollutant gas) and the dominant source of reactive iodine to the atmosphere. Sea surface iodide parameterisations are now being implemented in air quality models, but these are currently a major source of uncertainty. Relatively little observational data is available to estimate the global surface iodide concentrations, and this data has not hitherto been openly available in a collated, digital form. Here we present all available sea surface (〈20 m depth) iodide observations. The dataset includes values digitised from published manuscripts, published and unpublished data supplied directly by the originators, and data obtained from repositories. It contains 1342 data points, and spans latitudes from 70°S to 68°N, representing all major basins. The data may be used to model sea surface iodide concentrations or as a reference for future observations.

Description: 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 (O3) and air quality by reducing extreme O3 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 O3 is believed to be the largest single source of gaseous iodine to the atmosphere. Due to increased anthropogenic O3, 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.