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Particulate nitrate ( pNO 3 − ) has long been considered a permanent sink for NO x (NO and NO 2 ), removing a gaseous pollutant that is central to air quality and that influences the global self-cleansing capacity of the atmosphere. Evidence is emerging that photolysis of pNO 3 − can recycle HONO and NO x back to the gas phase with potentially important implications for tropospheric ozone and OH budgets; however, there are substantial discrepancies in “renoxification” photolysis rate constants. Using aircraft and ground-based HONO observations in the remote Atlantic troposphere, we show evidence for renoxification occurring on mixed marine aerosols with an efficiency that increases with relative humidity and decreases with the concentration of pNO 3 − , thus largely reconciling the very large discrepancies in renoxification photolysis rate constants found across multiple laboratory and field studies. Active release of HONO from aerosol has important implications for atmospheric oxidants such as OH and O 3 in both polluted and clean environments.

The influence of organic compounds on iodine (I2) emissions from the O3 + I- reaction at the sea surface was investigated in laboratory and modeling studies using artificial solutions, natural subsurface seawater (SSW), and, for the first time, samples of the surface microlayer (SML). Gas-phase I2 was measured directly above the surface of liquid samples using broadband cavity enhanced absorption spectroscopy. I2 emissions were consistently lower for artificial seawater (AS) than buffered potassium iodide (KI) solutions. Natural seawater samples showed the strongest reduction of I2 emissions compared to artificial solutions with equivalent [I-], and the reduction was more pronounced over SML than SSW. Emissions of volatile organic iodine (VOI) were highest from SML samples but remained a negligible fraction (

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.

This study presents an overview of observations and modelling of reactive iodine chemistry in the marine boundary layer (MBL) of the Indian and Southern Ocean. Ship observations of iodine oxide (IO) from 2015 to 2017 show its ubiquitous presence with values up to 1 pptv (parts per trillion) in this region. To identify the source of iodine in this region, we computed inorganic fluxes of iodine using tropospheric ozone (O3), sea surface iodide concentration, and wind speed. The estimated fluxes of hypoiodous acid (HOI) and elemental iodine (I2) did not adequately explain the observed IO levels in the Indian and Southern Ocean region. However, a significant correlation of IO with chlorophyll-a indicates a possible biogenic control on iodine chemistry in the Indian Ocean MBL. To understand the role of organic and inorganic precursors in MBL iodine chemistry, we used the Weather Research and Forecast model coupled with Chemistry (WRF-Chem version 3.7.1) incorporating halogen (Br, Cl, and I) chemistry. The modelling study shows that including only organic sources of iodine underestimate the detected IO in the northern Indian Ocean MBL. This highlights the importance of inorganic emissions as a source of iodine over the ocean. However, the inorganic flux emissions in the model had to be reduced by 40% to match the detected IO levels in this region. The reduced emission produces an overall good match between the observed and modelled IO levels. This discrepancy with flux emissions and IO levels in both the modelled IO simulation and observation highlights that there may be uncertainties in estimating the fluxes or that the flux parameterisation does not perform well for the Indian and Southern Ocean region. The model results show that inclusion of iodine chemistry causes significant regional changes to O3 (up to 25%), nitrogen oxides (up to 50%), and hydroxyl radicals (up to 15%) affecting the chemical composition of open ocean MBL and coastal regions of the Indian sub-continent. Accurate estimation of iodine precursors in the MBL calls for an urgent need to improve the existing parameterisation of inorganic fluxes. Direct measurements of the HOI and I2 may prove useful in the accurate quantification of iodine precursors in the marine atmosphere.

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.

Marine iodine speciation has emerged as a potential tracer of primary productivity, sedimentary inputs, and ocean oxygenation. The reaction of iodide with ozone at the sea surface has also been identified as the largest deposition sink for tropospheric ozone and the dominant source of iodine to the atmosphere. Accurate incorporation of these processes into atmospheric models requires improved understanding of iodide concentrations at the air-sea interface. Observations of sea surface iodide are relatively sparse and are particularly lacking in the Indian Ocean basin. Here we examine 127 new sea surface (≤10 m depth) iodide and iodate observations made during three cruises in the Indian Ocean and the Indian sector of the Southern Ocean. The observations span latitudes from ∼12°N to ∼70°S, and include three distinct hydrographic regimes: the South Indian subtropical gyre, the Southern Ocean and the northern Indian Ocean including the southern Bay of Bengal. Concentrations and spatial distribution of sea surface iodide follow the same general trends as in other ocean basins, with iodide concentrations tending to decrease with increasing latitude (and decreasing sea surface temperature). However, the gradient of this relationship was steeper in subtropical waters of the Indian Ocean than in the Atlantic or Pacific, suggesting that it might not be accurately represented by widely used parameterizations based on sea surface temperature. This difference in gradients between basins may arise from differences in phytoplankton community composition and/or iodide production rates. Iodide concentrations in the tropical northern Indian Ocean were higher and more variable than elsewhere. Two extremely high iodide concentrations (1241 and 949 nM) were encountered in the Bay of Bengal and are thought to be associated with sedimentary inputs under low oxygen conditions. Excluding these outliers, sea surface iodide concentrations ranged from 20 to 250 nM, with a median of 61 nM. Controls on sea surface iodide concentrations in the Indian Ocean were investigated using a state-of-the-art iodine cycling model. Multiple interacting factors were found to drive the iodide distribution. Dilution via vertical mixing and mixed layer depth shoaling are key controls, and both also modulate the impact of biogeochemical iodide formation and loss processes.

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...

Soluble and total trace metals were measured in four size fractionated aerosol samples collected over the tropical eastern Atlantic Ocean. In samples that were dominated by Saharan dust, the size distributions of total iron, aluminum, titanium, manganese, cobalt, and thorium were very similar to one another and to the size distributions of soluble manganese, cobalt, and thorium. Finer particle sizes (< ~3 μm) showed enhanced soluble concentrations of iron, aluminum, and titanium, possibly as a result of interactions with acidic sulfate aerosol during atmospheric transport. The difference in fine particle solubility between these two groups of elements might be related to the hyperbolic increase in the fractional solubility of iron, and a number of other elements, during the atmospheric transport of Saharan dust, which is not observed for manganese and its associated elements. In comparison to elements whose solubility varies during atmospheric transport, the stability of thorium fractional solubility should reduce uncertainties in the use of dissolved concentrations of this element in seawater as a proxy for dust deposition, although this topic requires further work.

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.

Iodine chemistry plays an essential role in controlling the radiation budget by changing various atmospheric parameters. Iodine in the atmosphere is known to cause depletion of ozone via catalytic reaction cycles. It alters the atmospheric oxidation capacity, and lead to ultrafine particle formation that acts as potential cloud condensation nuclei. The ocean is the primary source of iodine; it enters the atmosphere through fluxes of gaseous reactive iodine species. At the ocean surface, seawater iodide reacts with tropospheric ozone (gas) to form inorganic iodine species in gaseous form. These species namely, hypoiodous acid (HOI) and molecular iodine (I2) quickly photolyse to release reactive iodine (I) in the atmosphere. This process acts as a significant sink for tropospheric ozone contributing to ~16% ozone loss throughout the troposphere. Reactive iodine released in the atmosphere undergoes the formation of iodine monoxide (IO) or higher oxides of iodine (IxOx) via self-recombination reactions. It is known that inorganic iodine fluxes (HOI and I2) contribute to 75% of the detected IO over the Atlantic Ocean. However, we did not observe this from ship-based MAX-DOAS studies between 2014-2017. At present, there are no direct observations of inorganic iodine (HOI; few for I2) and are estimated via empirical methods derived from the interfacial kinetic model by Carpenter et al. in 2013. Based on the kinetic model, estimation of HOI and I2 fluxes depends on three parameters, namely, ozone concentration, surface iodide concentration, and the wind speed. This parameterisation for inorganic fluxes assumes a sea surface temperature (SST) of 293 K and has limiting wind speed conditions. Since the parameterisation conditions assumed SST of 293 K higher uncertainties due to errors in activation energy creeps in the estimation of HOI flux compared to I2 as the flux of HOI is ~20 times greater than that of I2. For three consecutive expeditions in the Indian and Southern Ocean, we detected ~1 pptv of IO in the marine boundary layer. These levels are not explained by the calculated inorganic fluxes by using observed and predicted sea surface iodide concentrations. This method of iodine flux estimation is currently used in all global models, along with the MacDonald et al. 2014 iodide estimation method. Model output using these parameterisations have not been able to match the observed IO levels in the Indian and Southern Ocean region. This discrepancy suggests that the process of efflux of iodine to the atmosphere may not be fully understood, and the current parametrisation does not do justice to the observations. It also highlights that the flux of organic iodine may also play a role in observed IO levels, especially in the Indian Ocean region. A correlation of 0.7 was achieved above the 99% confidence limit for chlorophyll-a with observed IO concentration in this region. There is a need to carry more observations to improve the estimation technique of iodine sea-air flux thus improving model predictions of IO in the atmosphere.

MILAN was a multidisciplinary, international study examining how the diel variability of sea-surface microlayer biogeochemical properties potentially impacts ocean-atmosphere interaction, in order to improve our understanding of this globally important process. The sea-surface microlayer (SML) at the air-sea interface is < 1 mm deep but it is physically, chemically and biologically distinct from the underlying water and the atmosphere above. Wind-driven turbulence and solar radiation are important drivers of SML physical and biogeochemical properties. Given that the SML is involved in all ocean-atmosphere exchanges of mass and energy, its response to solar radiation, especially in relation to how it regulates the air-sea exchange of climate-relevant gases and aerosols, is surprisingly poorly characterised. MILAN (sea-surface MIcroLAyer at Night) was an international, multidisciplinary campaign designed to specifically address this issue. In spring 2017, we deployed diverse sampling platforms (research vessels, radio-controlled catamaran, free-drifting buoy) to study full diel cycles in the coastal North Sea SML and in underlying water, and installed a land-based aerosol sampler. We also carried out concurrent ex situ experiments using several microsensors, a laboratory gas exchange tank, a solar simulator, and a sea spray simulation chamber. In this paper we outline the diversity of approaches employed and some initial results obtained during MILAN. Our observations of diel SML variability, e.g. the influence of changing solar radiation on the quantity and quality of organic material, and diel changes in wind intensity primarily forcing air-sea CO2 exchange, underline the value and the need of multidisciplinary campaigns for integrating SML complexity into the context of air-sea interaction.

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 (, Measurement(s)iodideTechnology Type(s)digital curationFactor Type(s)sampling time and placeSample Characteristic - Environmentsea water • oceanSample Characteristic - LocationEarth (planet) Machine-accessible metadata file describing the reported data: 10.6084/m9.figshare.10130129

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.

Total and soluble trace metal concentrations were determined in atmospheric aerosol and rainwater samples collected during seven cruises in the south-east Atlantic. Back trajectories indicated that the samples all represented remote marine air masses, consistent with climatological expectations. Aerosol trace metal loadings were similar to previous measurements in clean, marine air masses. Median total Fe, Al, Mn, V, Co and Zn concentrations were 206, 346, 5, 3, 0.7 and 11 pmol m− 3 respectively. Solubility was operationally defined as the fraction extractable using a pH 4.7 ammonium acetate leach. Median soluble Fe, Al, Mn, V, Co, Zn, Cu, Ni, Cd and Pb concentrations were 6, 55, 1, 0.7, 0.06, 24, 2, 1, 0.05 and 0.3 pmol m− 3 respectively. Large ranges in fractional solubility were observed for all elements except Co; median solubility values for Fe, Al and Mn were below 20% while the median for Zn was 74%. Volume weighted mean rainwater concentrations were 704, 792, 32, 10, 3, 686, 25, 0.02, 0.3 and 10 nmol L− 1 for Fe, Al, Mn, V, Co, Zn, Cu, Ni, Cd and Pb respectively (n = 6). Wet deposition fluxes calculated from these values suggest that rain makes a significant contribution to total deposition in the study area for all elements except perhaps Ni.

The GEOTRACES Intermediate Data Product 2017 (IDP2017) is the second publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2016. The IDP2017 includes data from the Atlantic, Pacific, Arctic, Southern and Indian oceans, with about twice the data volume of the previous IDP2014. For the first time, the IDP2017 contains data for a large suite of biogeochemical parameters as well as aerosol and rain data characterising atmospheric trace element and isotope (TEI) sources. The TEI data in the IDP2017 are quality controlled by careful assessment of intercalibration results and multi-laboratory data comparisons at crossover stations. The IDP2017 consists of two parts: (1) a compilation of digital data for more than 450 TEIs as well as standard hydrographic parameters, and (2) the eGEOTRACES Electronic Atlas providing an on-line atlas that includes more than 590 section plots and 130 animated 3D scenes. The digital data are provided in several formats, including ASCII, Excel spreadsheet, netCDF, and Ocean Data View collection. Users can download the full data packages or make their own custom selections with a new on-line data extraction service. In addition to the actual data values, the IDP2017 also contains data quality flags and 1-σ data error values where available. Quality flags and error values are useful for data filtering and for statistical analysis. Metadata about data originators, analytical methods and original publications related to the data are linked in an easily accessible way. The eGEOTRACES Electronic Atlas is the visual representation of the IDP2017 as section plots and rotating 3D scenes. The basin-wide 3D scenes combine data from many cruises and provide quick overviews of large-scale tracer distributions. These 3D scenes provide geographical and bathymetric context that is crucial for the interpretation and assessment of tracer plumes near ocean margins or along ridges. The IDP2017 is the result of a truly international effort involving 326 researchers from 25 countries. This publication provides the critical reference for unpublished data, as well as for studies that make use of a large cross-section of data from the IDP2017. This article is part of a special issue entitled: Conway GEOTRACES - edited by Tim M. Conway, Tristan Horner, Yves Plancherel, and Aridane G. González., National Science Foundation (U.S.) (Grant OCE-0608600), National Science Foundation (U.S.) (Grant OCE0938349), National Science Foundation (U.S.) (Grant OCE-1243377), National Science Foundation (U.S.) (Grant OCE-1546580)

New production (New P, the rate of net primary production (NPP) supported by exogenously supplied limiting nutrients) and net community production (NCP, gross primary production not consumed by community respiration) are closely related but mechanistically distinct processes. They set the carbon balance in the upper ocean and define an upper limit for export from the system. The relationships, relative magnitudes and variability of New P (from 15 NO 3 – uptake), O 2 : argon-based NCP and sinking particle export (based on the 238 U : 234 Th disequilibrium) are increasingly well documented but still not clearly understood. This is especially true in remote regions such as polar marginal ice zones. Here we present a 3-year dataset of simultaneous measurements made at approximately 50 stations along the Western Antarctic Peninsula (WAP) continental shelf in midsummer (January) 2012–2014. Net seasonal-scale changes in water column inventories (0–150 m) of nitrate and iodide were also estimated at the same stations. The average daily rates based on inventory changes exceeded the shorter-term rate measurements. A major uncertainty in the relative magnitude of the inventory estimates is specifying the start of the growing season following sea-ice retreat. New P and NCP(O 2 ) did not differ significantly. New P and NCP(O 2 ) were significantly greater than sinking particle export from thorium-234. We suggest this is a persistent and systematic imbalance and that other processes such as vertical mixing and advection of suspended particles are important export pathways. This article is part of the theme issue ‘The marine system of the west Antarctic Peninsula: status and strategy for progress in a region of rapid change’.

The supply and bioavailability of iron (Fe) controls primary productivity and N2 fixation in large parts of the global ocean. An important, yet poorly quantified, source to the ocean is particulate Fe (pFe). Here we present the first combined dataset of particulate, labile-particulate (L-pFe), and dissolved Fe (dFe) from the (sub)tropical North Atlantic. We show a strong relationship between L-pFe and dFe, indicating a dynamic equilibrium between these two phases whereby particles “buffer” dFe and maintain the elevated concentrations observed. Moreover, L-pFe can increase the overall “available” (L-pFe + dFe) Fe pool by up to 55%. The lateral shelf flux of this available Fe was similar in magnitude to observed soluble aerosol-Fe deposition, a comparison that has not been previously considered. These findings demonstrate that L-pFe is integral to Fe cycling and hence plays a role in regulating carbon cycling, warranting its inclusion in Fe budgets and biogeochemical models.

Reactive iodine compounds play a significant role in the atmospheric chemistry of the oceanic boundary layer by influencing the oxidising capacity through catalytically removing O3 and altering the HOx and NOx balance. The sea-to-air flux of iodine over the open ocean is therefore an important quantity in assessing these impacts on a global scale. This paper examines the effect of a number of relevant environmental parameters, including water temperature, salinity and organic compounds, on the magnitude of the HOI and I2 fluxes produced from the uptake of O3 and its reaction with iodide ions in aqueous solution. The results of these laboratory experiments and those reported previously (Carpenter et al., 2013), along with sea surface iodide concentrations measured or inferred from measurements of dissolved total iodine and iodate reported in the literature, were then used to produce parameterised expressions for the HOI and I2 fluxes as a function of wind speed, sea-surface temperature and O3. These expressions were used in the Tropospheric HAlogen chemistry MOdel (THAMO) to compare with MAX-DOAS measurements of iodine monoxide (IO) performed during the HaloCAST-P cruise in the eastern Pacific ocean (Mahajan et al., 2012). The modelled IO agrees reasonably with the field observations, although significant discrepancies are found during a period of low wind speeds (< 3 m s−1), when the model overpredicts IO by up to a factor of 3. The inorganic iodine flux contributions to IO are found to be comparable to, or even greater than, the contribution of organo-iodine compounds and therefore its inclusion in atmospheric models is important to improve predictions of the influence of halogen chemistry in the marine boundary layer.©Author(s) 2014.

Recent studies have highlighted the impact of sea surface iodide concentrations on the deposition of ozone to the sea surface and the sea to air flux of reactive iodine. The use of models to predict this flux demands accurate, spatially distributed sea surface iodide concentrations, but to date, the observational data required to support this is sparse and mostly arises from independent studies conducted on small geographical and temporal scales. We have compiled the available measurements of sea surface iodide to produce a data set spanning latitudes from 69°S to 66°N, which reveals a coherent, large scale distribution pattern, with highest concentrations observed in tropical waters. Relationships between iodide concentration and more readily available parameters (chlorophyll, nitrate, sea surface temperature, salinity, mixed layer depth) are evaluated as tools to predict iodide concentration. Of the variables tested, sea surface temperature is the strongest predictor of iodide concentration. Nitrate was also strongly inversely associated with iodide concentration, but chlorophyll-a was not.

This paper reviews atmospheric inputs of trace elements and nutrients to the oceans in the context of the GEOTRACES programme and provides new data from two Atlantic GEOTRACES cruises. We consider the deposition of nitrogen to the oceans, which is now dominated by anthropogenic emissions, the deposition of mineral dust and related trace elements, and the deposition of other trace elements which have a mixture of anthropogenic and dust sources. We then consider the solubility (as a surrogate for bioavailability) of the various elements. We consider briefly the sources, atmospheric transport and transformations of these elements and how this results in strong spatial deposition gradients. Solubility of the trace elements also varies systematically between elements, reflecting their sources and cycling, and for some trace elements there are also systematic gradients in solubility related to dust loading. Together, these effects create strong spatial gradients in the inputs of bioavailable trace elements to the oceans, and we are only just beginning to understand how these affect ocean biogeochemistry. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’.

Iodine compounds were measured above, below and within the sea ice of the Weddell Sea during a cruise in 2009, to make progress in elucidating the mechanism of local enhancement and volatilisation of iodine. I2 mixing ratios of up to 12.4 pptv were measured 10 m above the sea ice, and up to 31 pptv was observed above surface snow on the nearby Brunt Ice Shelf – large amounts. Atmospheric IO of up to 7 pptv was measured from the ship, and the average sum of HOI and ICl was 1.9 pptv. These measurements confirm the Weddell Sea as an iodine hotspot. Average atmospheric concentrations of CH3I, C2H5I, CH2ICl, 2-C3H7I, CH2IBr and 1-C3H7I were each 0.2 pptv or less. On the Brunt Ice Shelf, enhanced concentrations of CH3I and C2H5I (up to 0.5 and 1 pptv respectively) were observed in firn air, with a diurnal profile that suggests the snow may be a source. In the sea ice brine, iodocarbons concentrations were over 10 times those of the sea water below. The sum of iodide + iodate was depleted in sea ice samples, suggesting some missing iodine chemistry. Flux calculations suggest I2 dominates the iodine atom flux to the atmosphere, but models cannot reconcile the observations and suggest either a missing iodine source or other deficiencies in our understanding of iodine chemistry. The observation of new particle formation, consistent with the model predictions, strongly suggests an iodine source. This combined study of iodine compounds is the first of its kind in this unique region of sea ice rich in biology and rich in iodine chemistry.

Iodine has recently been of interest in atmospheric chemistry due to its role in tropospheric ozone depletion, modification of the HO/HO(2) ratio and aerosol nucleation. Gas-phase iodine chemistry is tightly coupled to the aerosol phase through heterogeneous reactions, which are dependent on iodine concentrations and speciation in the aerosol. To date, the only method available for total iodine determination in aerosols is collection on filters by impaction and quantification by neutron activation analysis (NAA). NAA is not widely available to all working groups and is costly to commission. Here, we present a method to determine total iodine concentrations in aerosol impact filter samples by combustion of filter sub-samples (approximately 5 cm(2)) at 1,000 degrees C, trapping in deionised water and quantification by UV/Vis spectroscopy. Both quartz and cellulose filters were analysed from four separate sampling campaigns. The method proved to be sensitive (3sigma = 6 ng absolute iodine approximately 3 pmol m(-3)) precise (RSD approximately 5%) and accurate, as determined by external and standard addition calibrations. Total iodine concentrations ranged from 10 pmol m(-3) over the Southern Ocean to 100 pmol m(-3) over the tropical Atlantic, in agreement with previous estimates. The soluble iodine concentration (extracted with water and measured by ICP-MS) was then subtracted from the total iodine to yield non-water-soluble iodine (NSI). The NSI fraction ranged from 20% to 53% of total iodine, and thus can be significant in some cases.

A number of field and laboratory studies on the impact of marine macroalgae on dissolved inorganic iodine speciation are presented. Within tidally isolated rock pools, the brown macroalga Fucus serratus was found to both release stored iodide and to facilitate the reduction of iodate to iodide. In contrast, no discernible changes in iodine speciation were observed in rock pools containing green macroalgae of the genus Ulva. Incubation experiments confirmed that the macroalgae Laminaria digitata, F. serratus and Kallymenia antarctica release iodide, though the rate of release varied between species and between specimens of the same species. Application of oxidative stress by treatment with cell wall derived oligoguluronate elicitors increased the efflux of iodide by L. digitata approximately 20-fold. The release of iodide by macroalgae may impact upon the formation of volatile iodine species (molecular iodine and iodocarbons) that are of importance in the coastal atmosphere.

The presence of a surface iodide maximum in seawater is commonly attributed to biological activity, however laboratory studies on the influence of phytoplankton on inorganic iodine speciation have yielded somewhat contradictory results. Here, we report changes in the speciation of inorganic dissolved iodine in nutrient-enriched seawater during the growth of a variety of phytoplankton taxa, including the cold water pennate diatoms Nitzschia and Navicula. Unialgal batch cultures were grown under axenic conditions in f/20 media; iodate was kept at ambient seawater levels or raised to 10 μM. The ability of algal cultures to reduce iodate to iodide varied considerably between the different algal species studied. Nitzschia sp. cultures removed close to 100% of iodate from growth media and produced iodide at rates of 0.03 and 3 nmol I μg chl-a− 1 day− 1 at ambient and elevated iodate levels, respectively. At elevated iodate levels, iodate depletion in Nitzschia cultures was matched by iodide production such that applying a linear regression to the concentrations of the two iodine species gave slopes of − 1 with R2 values greater than 0.9. At ambient iodate levels, only 50 to 100 nM of iodide was produced in Nitzschia cultures despite more than 200 nM of iodate being consumed, suggesting production of some other iodine species. Additionally, iodide levels peaked at the end of the exponential growth phase suggesting that an iodide consuming mechanism began to operate in the stationary growth phase. Cultures of the cold water diatom Navicula sp. and the temperate phytoplankton Emiliania huxleyi, Thalassiosira pseudonana and Dunaliella tertiolecta also exhibited iodate uptake, although the extent of this was variable and always less than in the Nitzschia cultures. Navicula and E. huxleyi also showed iodide production at both ambient and elevated iodate levels, but T. pseudonana and D. tertiolecta did not. In both the cold water algal cultures 50% to 100% of the lost iodate appeared to have been converted to an organic or particulate form, or lost by volatilisation.

[1] Climate change and human activities are expected to have a major impact on the structure and functioning of marine ecosystems and the biogeochemical cycles they mediate in the coming years. Here we describe time series measurements of biogenic bromocarbons (CHBr3 and CH2Br2) collected in coastal waters of the western Antarctic Peninsula which is one of the world's most rapidly changing marine environments. Our measurements spanned a period of changing sea-ice dynamics and phytoplankton community structure driven by climatic forcing. Specifically, the occurrence of high chlorophylla concentrations (≥5 μg L−1) and dominance of the largest phytoplankton size fraction (≥20 μm) indicating diatom bloom conditions was reduced following winter periods with a relatively short winter sea-ice duration (

Sea-to-air emissions of bromocarbon gases are known to play an important role in atmospheric ozone depletion. In this study, seawater concentrations of bromoform (CHBr3) and dibromomethane (CH2Br2) were measured regularly between February 2005 and March 2007 at the Rothera Oceanographic and Biological Time Series (RaTS) site located in Marguerite Bay on the Antarctic Peninsula. Strong seasonality in CHBr3 and CH2Br2 concentrations was observed. The highest bromocarbon concentrations (up to 276.4 +/- 13.0 pmol CHBr3 L-1 and 30.0 +/- 0.4 pmol CH2Br2 L-1) were found to coincide with the annual microalgal bloom during the austral summer, with lower concentrations (up to 39.5 pmol CHBr3 L-1 and 9.6 +/- 0.6 pmol CH2Br2 L-1) measured under the winter fast ice. The timing of the initial increase in bromocarbon concentrations was related to the sea-ice retreat and onset of the microalgal bloom. Observed seasonal variability in CH2Br2/CHBr3 suggests that this relationship may be of use in resolving bromocarbon source regions. Mainly positive saturation anomalies calculated for both the 2005/2006 and 2006/2007 summers suggest that the bay was a source of CHBr3 and CH2Br2 to the atmosphere. Estimates of bromocarbon sea-to-air flux rates from Marguerite Bay during ice-free periods are 84 (-13 to 275) CHBr3 nmol m(-2) d(-1) and 21 (2 to 70) nmol CH2Br2 m(-2) d(-1). If these flux rates are representative of the seasonal ice edge zone bloom which occurs each year over large areas of the Southern Ocean during the austral summer, sea-to-air bromocarbon emissions could have an important impact on the chemistry of the Antarctic atmosphere.