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Funding: SL, AB and HP report financial support was provided by Natural Environment Research Council. Anthropogenic activities have significantly enhanced atmospheric metal inputs to the ocean, which has potentially important consequences for marine ecosystems. This study assesses the potential of Zn and Cu isotope compositions to distinguish between natural and anthropogenic atmospheric inputs of these metals to the surface ocean. To this end, the isotopic compositions of Zn and Cu in aerosols collected from the eastern tropical Atlantic Ocean on the GEOTRACES GA06 cruise are examined. Enrichment factors and fractional solubility measurements indicate the presence of a significant anthropogenic component in the aerosols collected furthest from the North African dust plume for both Zn and Cu. The mean δ65CuNIST SRM 976 for the fully digested aerosols is +0.07 ± 0.39 ‰ (n = 9, 2 SD), which is indistinguishable from the lithogenic value, and implies that Cu isotopes are not an effective tracer of aerosol sources in this region. The mean δ66ZnJMC-Lyon value for the aerosols that underwent a total digestion is +0.17 ± 0.22 ‰ (n = 11, 2 SD). The aerosols leached with ammonium acetate have similar Zn isotope compositions, with a mean of +0.15 ± 0.16 ‰ (n = 7, 2 SD). The aerosols were collected in a region with prevalent mineral dust but, despite this, exhibit isotopically lighter Zn than lithogenic Zn with δ66Zn ≈ +0.3 ‰. When coupled with the previously published Pb isotope data, the aerosols exhibit coupled Zn-Pb isotope systematics that are indicative of mixing between mineral dust (δ66Zn = +0.28 ‰ and 206Pb/207Pb = 1.205) and anthropogenic emissions (δ66Zn = −0.22 ‰ and 206Pb/207Pb = 1.129). This demonstrates the potential of Zn isotopes to trace atmospheric Zn inputs from anthropogenic sources to the surface ocean. Publisher PDF

We have compiled and analyzed a comprehensive dataset of field observations of iodine speciation in marine aerosol. The soluble iodine content of fine aerosol (PM1) is dominated by soluble organic ...

23 pags., 10 figs., 4 tabs., In this work, we describe the compilation and homogenization of an extensive data set of aerosol iodine field observations in the period between 1963 and 2018 and we discuss its spatial and temporal dependences by comparison with CAM-Chem model simulations. A close to linear relationship between soluble and total iodine in aerosol is found (∼80% aerosol iodine is soluble), which enables converting a large subset of measurements of soluble iodine into total iodine. The resulting data set shows a distinct latitudinal dependence, with an enhancement toward the Northern Hemisphere (NH) tropics and lower values toward the poles. This behavior, which has been predicted by atmospheric models to depend on the global distribution of the main oceanic iodine source (which in turn depends on the reaction of ozone with aqueous iodide on the sea water-air interface, generating gas-phase I2 and HOI), is confirmed here by field observations for the first time. Longitudinally, there is some indication of a waveone profile in the tropics, which peaks in the Atlantic and shows a minimum in the Pacific. New data from Antarctica show that the south polar seasonal variation of iodine in aerosol mirrors that observed previously in the Arctic, with two equinoctial maxima and the dominant maximum occurring in spring. While no clear seasonal variability is observed in NH middle latitudes, there is an indication of different seasonal cycles in the NH tropical Atlantic and Pacific. Long-term trends cannot be unambiguously established as a result of inhomogeneous time and spatial coverage and analytical methods, Juan Carlos Gómez Martín acknowledges financial support from the State Agency for Research of the Spanish MCIU through the “Center of Excellence Severo Ochoa” award to the Instituto de Astrofísica de Andalucía (SEV-2017-0709) and the Ramon y Cajal Program (RYC-2016-19,570). Alfonso Saiz-Lopez acknowledges financial support from the European Research Council Executive Agency under the European Union’s Horizon 2020 Research and Innovation program (Project “ERC-2016-COG 726349 CLIMAHAL”). Rafael P. Fernandez would like to thank financial support from ANPCyT (PICT 2015-0714), UNCuyo (SeCTyP M032/3853), and UTN (PID 4920-194/2018).

The speciation of soluble iodine and major-ion composition were determined in size-fractionated aerosols collected during the AMT21 cruise between Avonmouth, UK, and Punta Arenas, Chile, in September–November 2011. The proportions of iodine species (iodide, iodate and soluble organic iodine (SOI)) varied markedly between size fractions and with the extent to which the samples were influenced by pollutants. In general, fine mode aerosols (< 1 µm) contained higher proportions of both iodide and SOI, while iodate was the dominant component of coarse (< 1 µm) aerosols. The highest proportions of iodate were observed in aerosols that contained (alkaline) unpolluted sea spray or mineral dust. Fine mode samples with high concentrations of acidic species (e.g. non-sea-salt sulfate) contained very little iodate and elevated proportions of iodide and SOI. These results are in agreement with modelling studies that indicate that iodate can be reduced under acidic conditions and that the resulting hypoiodous acid (HOI) can react with organic matter to produce SOI and iodide. Further work that investigates the link between iodine speciation and aerosol pH directly, as well as studies on the formation and decay of organo-iodine compounds under aerosol conditions, will be necessary before the importance of this chemistry in regulating aerosol iodine speciation can be confirmed.

We present dissolved and total dissolvable trace elements for spring and summer cruises in 2010 in the high‐latitude North Atlantic. Surface and full depth data are provided for Al, Cd, Co, Cu, Mn, Ni, Pb, and Zn in the Iceland and Irminger Basins, and consequences of biological uptake and inputs by the spring Eyjafjallajökull volcanic eruption are assessed. Ash from Eyjafjallajökull resulted in pronounced increases in Al, Mn, and Zn in surface waters in close proximity to Iceland during the eruption, while 3 months later during the summer cruise levels had returned to more typical values for the region. The apparent seasonal removal ratios of surface trace elements were consistent with biological export. Assessment of supply of trace elements to the surface mixed layer for the region, excluding volcanic inputs, indicated that deep winter mixing was the dominant source, with diffusive mixing being a minor source (between 13.5% [dissolved Cd, DCd] and −2.43% [DZn] of deep winter flux), and atmospheric inputs being an important source only for DAl and DZn (DAl up to 42% and DZn up to 4.2% of deep winter + diffusive fluxes) and typically less than 1% for the other elements. Elemental supply ratios to the surface mixed layer through convection were comparable to apparent removal ratios we calculated between spring and summer. Given that deep mixing dominated nutrient and trace element supply to surface waters, predicted increases in water column stratification in this region may reduce supply, with potential consequences for primary production and the biological carbon pump., Key Points: Bio‐essential element concentrations in surface waters decreased from spring to summer with removal ratios reflecting biological uptake. Effects of volcanic inputs from Eyjafjallajökull in spring 2010 were pronounced for Al, Mn, and Zn but returned to typical levels in summer. Deep winter convection dominated trace element supply to surface waters with minor contributions from atmospheric and diffusive mixing., GEOMAR Helmholtz Centre for Ocean Research Kiel http://dx.doi.org/10.13039/501100003153, Natural Environment Research Council http://dx.doi.org/10.13039/501100000270

Changing atmospheric acidity alters the delivery of nutrients to the ocean and affects marine productivity and ecology., Anthropogenic emissions to the atmosphere have increased the flux of nutrients, especially nitrogen, to the ocean, but they have also altered the acidity of aerosol, cloud water, and precipitation over much of the marine atmosphere. For nitrogen, acidity-driven changes in chemical speciation result in altered partitioning between the gas and particulate phases that subsequently affect long-range transport. Other important nutrients, notably iron and phosphorus, are affected, because their soluble fractions increase upon exposure to acidic environments during atmospheric transport. These changes affect the magnitude, distribution, and deposition mode of individual nutrients supplied to the ocean, the extent to which nutrient deposition interacts with the sea surface microlayer during its passage into bulk seawater, and the relative abundances of soluble nutrients in atmospheric deposition. Atmospheric acidity change therefore affects ecosystem composition, in addition to overall marine productivity, and these effects will continue to evolve with changing anthropogenic emissions in the future.

The current poor understanding of soluble iron (Fe) yield in atmospheric aerosols leaves two observational facts having not yet been correctly simulated in numerical models: the high Fe solubility in aerosols with low Fe content and, hence, the wide range of observed Fe solubility. Our observation at Qingdao, a coastal city of China, revealed that soluble Fe was produced along with aerosol acidification much more efficiently in fog than under other weather conditions. The median Fe solubility in fog aerosols, 5.81%, was 3.3 times of that in haze aerosols, 5.2 times of that in clear days, and 21.5 times of that in dust aerosols. Involving fog processing in models may reduce the discrepancy in the atmospheric flux of soluble Fe to the ocean between numerical simulations and field observations.

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.

Atmospheric processing of iron in dust and combustion aerosols is simulated using an intermediate-complexity soluble iron mechanism designed for Earth system models. The solubilization mechanism includes both a dependence on aerosol water pH and in-cloud oxalic acid. The simulations of size-resolved total, soluble and fractional iron solubility indicate that this mechanism captures many but not all of the features seen from cruise observations of labile iron. The primary objective was to determine the extent to which our solubility scheme could adequately match observations of fractional iron solubility. We define a semi-quantitative metric as the model mean at points with observations divided by the observational mean (MMO). The model is in reasonable agreement with observations of fractional iron solubility with an MMO of 0.86. Several sensitivity studies are performed to ascertain the degree of complexity needed to match observations; including the oxalic acid enhancement is necessary, while different parameterizations for calculating model oxalate concentrations are less important. The percent change in soluble iron deposition between the reference case (REF) and the simulation with acidic processing alone is 63.8%, which is consistent with previous studies. Upon deposition to global oceans, global mean combustion iron solubility to total fractional iron solubility is 8.2%; however, the contribution of fractional iron solubility from combustion sources to ocean basins below 15°S is approximately 50%. We conclude that, in many remote ocean regions, sources of iron from combustion and dust aerosols are equally important. Our estimates of changes in deposition of soluble iron to the ocean since preindustrial climate conditions suggest roughly a doubling due to a combination of higher dust and combustion iron emissions along with more efficient atmospheric processing. We would like to acknowledge the support of DOE DE-SC0006735 and NSF 1049033. Carlos Pérez García-Pando acknowledges long-term support from the AXA Research Fund through the AXA Chair on Sand and Dust Storms, as well as the support received through the Ramón y Cajal program (grant RYC-2015-18690) of the Spanish Ministry of Economy and Competitiveness.

Metal dissolution from atmospheric aerosol deposition to the oceans is important in enhancing and inhibiting phytoplankton growth rates and modifying plankton community structure, thus impacting marine biogeochemistry. Here we review the current state of knowledge on the causes and effects of the leaching of multiple trace metals from natural and anthropogenic aerosols. Aerosol deposition is considered both on short timescales over which phytoplankton respond directly to aerosol metal inputs, as well as longer timescales over which biogeochemical cycles are affected by aerosols., Metal dissolution from atmospheric aerosol deposition plays an important role in enhancing and inhibiting phytoplankton growth and community structure. Here, the authors review the impacts of trace metal leaching from natural and anthropogenic aerosols on marine microorganisms over short and long timescales.

We briefly review the role of atmospheric deposition measurements within the Atlantic Meridional Transect (AMT) programme and then go on to present new data on the soluble concentrations of a range of trace metals (Fe, Al, Mn, Ti, Zn, V, Ni and Cu) and major ions in aerosols collected along the AMT transect. The results allow us to identify emission sources of the trace metals particularly in terms of the relative importance of anthropogenic versus crustal sources. We identify strong gradients in concentrations and deposition for both crustal and anthropogenically sourced metals with much higher inputs to the North Atlantic compared to the South Atlantic, reflecting stronger land based emission sources in the Northern Hemisphere. We suggest anthropogenic sources of Ni and V may include an important component from shipping. We consider the extent to which these gradients are reflected in surface water concentrations of these metals based on the GEOTRACES water column trace metal data. We find there is a clear difference in the concentrations of surface water dissolved Al and Fe between the north and south Atlantic gyres reflecting atmospheric inputs. However for Mn, V or Ni, higher inputs to the North Atlantic compared to the South Atlantic are not clearly reflected in their water column concentrations.

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 role ships play in atmospheric, oceanic, and biogeochemical observations is described with a focus on measurements made within 100 m of the ocean surface. Ships include merchant and research vessels, cruise liners and ferries, fishing vessels, coast guard, military, and other government-operated ships, yachts, and a growing fleet of automated surface vessels. The present capabilities of ships to measure essential climate/ocean variables and the requirements from a broad community to address operational, commercial, and scientific needs are described. Following the guidance from the OceanObs'19 organizing committee, the authors provide a vision to expand observations needed from ships to understand and forecast the exchanges across the ocean-atmosphere interface. The vision addresses (1) recruiting vessels to improve both spatial and temporal sampling, (2) conducting multi-variate sampling on ships, (3) raising technology readiness levels of automated shipboard sensors and ship-to-shore data communications, (4) advancing quality evaluation of observations, and (5) developing a unified data management approach for observations and metadata that meets the needs of a diverse user community. Recommendations are made focusing on integrating private and autonomous vessels into the observing system, investing in sensor and communications technology development, developing an integrated data management structure that includes all types of ships, and moving towards a quality evaluation process that will result in a subset of ships being defined as mobile reference ships that will support climate studies. We envision a future where commercial, research, and privately-owned vessels are making multivariate observations using a combination of automated and human-observed measurements. All data and metadata will be documented, tracked, evaluated, distributed, and archived to benefit users of marine data. This vision looks at ships as a holistic network, not a set of disparate commercial, research, and/or third-party activities working in isolation, to bring these communities together for the mutual benefit of all.

Air pollution creates high Fe solubility in pyrogenic aerosols, raising the flux of biologically essential Fe to the oceans., Atmospheric deposition is a source of potentially bioavailable iron (Fe) and thus can partially control biological productivity in large parts of the ocean. However, the explanation of observed high aerosol Fe solubility compared to that in soil particles is still controversial, as several hypotheses have been proposed to explain this observation. Here, a statistical analysis of aerosol Fe solubility estimated from four models and observations compiled from multiple field campaigns suggests that pyrogenic aerosols are the main sources of aerosols with high Fe solubility at low concentration. Additionally, we find that field data over the Southern Ocean display a much wider range in aerosol Fe solubility compared to the models, which indicate an underestimation of labile Fe concentrations by a factor of 15. These findings suggest that pyrogenic Fe-containing aerosols are important sources of atmospheric bioavailable Fe to the open ocean and crucial for predicting anthropogenic perturbations to marine productivity.

The extraction into aqueous solution of total soluble iodine (TSI), iodide and iodate were examined as a function of extraction times between 5 and 60 min for two different extraction methods and from two types of commonly used aerosol collection substrates. The extraction methods tested were ultrasonic agitation and mechanical shaking, while the substrates were cellulose fibre (CF) and glass fibre (GF). Tests were carried on substrates spiked with known amounts of iodide and iodate and on a pair of ambient aerosol samples collected at the University of East Anglia on both substrates over the same time period. The combination of ultrasonic agitation and CF substrates (which has been used in many published studies of aerosol iodine speciation) was shown to lead to variable recovery of iodine species and changes in speciation over extraction time. Mechanical shaking of GF substrates gave good recoveries of iodide and iodate from spiked experiments and stable speciation with time for the ambient aerosol sample. This combination is recommended for future use in the determination of aerosol iodine speciation. Mechanical shaking also appeared to be preferable to ultrasonic agitation for samples that were collected on CF substrates. The optimised conditions (mechanical shaking of GF substrates for 30 min) were applied to the analysis of samples collected during the Stratospheric ozone: Halogen Impacts in a Varying Atmosphere (SHIVA) cruise in the South China and Sulu Seas in November 2011. The results obtained showed variable proportions of iodide, iodate and soluble organic iodine species in these samples, with iodide concentrations possibly related to airmass history and background chemistry. Keywords: Iodine speciation, Collection substrate, Aqueous extraction, Aerosol chemistry

The nature of atmospheric transport of aerosol particles from land to the ocean is described. The magnitude and significance for ocean biogeochemistry is then discussed for the atmospheric deposition of some particular components—nutrients (nitrogen, phosphorus, and iron), some trace metals, organic matter generally and then some specific organic compounds.

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’.

Iron, phosphate and nitrate are essential nutrients for phytoplankton growth and hence their supply into the surface ocean controls oceanic primary production. Here, we present a GEOTRACES zonal section (GP13; 30-33oS, 153oE-150oW) extending eastwards from Australia to the oligotrophic South Pacific Ocean gyre outlining the concentrations of these key nutrients. Surface dissolved iron concentrations are elevated at >0.4 nmol L-1 near continental Australia (west of 165°E) and decreased eastward to ≤0.2 nmol L-1 (170oW-150oW). The supply of dissolved iron into the upper ocean (

Current global inventories of ammonia emissions identify the ocean as the largest natural source. This source depends on seawater pH, temperature, and the concentration of total seawater ammonia (NHx(sw)), which reflects a balance between remineralization of organic matter, uptake by plankton, and nitrification. Here we compare [NHx(sw)] from two global ocean biogeochemical models (BEC and COBALT) against extensive ocean observations. Simulated [NHx(sw)] are generally biased high. Improved simulation can be achieved in COBALT by increasing the plankton affinity for NHx within observed ranges. The resulting global ocean emissions is 2.5 TgN a−1, much lower than current literature values (7–23 TgN a−1), including the widely used Global Emissions InitiAtive (GEIA) inventory (8 TgN a−1). Such a weak ocean source implies that continental sources contribute more than half of atmospheric NHx over most of the ocean in the Northern Hemisphere. Ammonia emitted from oceanic sources is insufficient to neutralize sulfate aerosol acidity, consistent with observations. There is evidence over the Equatorial Pacific for a missing source of atmospheric ammonia that could be due to photolysis of marine organic nitrogen at the ocean surface or in the atmosphere. Accommodating this possible missing source yields a global ocean emission of ammonia in the range 2–5 TgN a−1, comparable in magnitude to other natural sources from open fires and soils.

This study investigates the impact of halogens on atmospheric chemistry in the tropical troposphere and explores the sensitivity of this to uncertainties in the fluxes of halogens to the atmosphere and the chemical processing. To do this the regional chemistry transport model WRF-Chem has been extended, for the first time, to include halogen chemistry (bromine, chlorine and iodine chemistry), including heterogeneous recycling reactions involving sea-salt aerosol and other particles, reactions of Br with volatile organic compounds (VOCs), along with oceanic emissions of halocarbons, VOCs and inorganic iodine. The study focuses on the tropical East Pacific using field observations from the TORERO campaign (January–February 2012) to evaluate the model performance. Including all the new processes, the model does a reasonable job reproducing the observed mixing ratios of BrO and IO, albeit with some discrepancies, some of which can be attributed to difficulties in the model's ability to reproduce the observed halocarbons. This is somewhat expected given the large uncertainties in the air-sea fluxes of the halocarbons in a region where there are few observations of seawater concentrations. We see a considerable impact on the Bry partitioning when heterogeneous chemistry is included, with a greater proportion of the Bry in active forms such as BrO, HOBr and dihalogens. Including debromination of sea-salt increases BrO slightly throughout the free troposphere, but in the tropical marine boundary layer, where the sea-salt particles are plentiful and relatively acidic, debromination leads to overestimation of the observed BrO. However, it should be noted that the modelled BrO was extremely sensitive to the inclusion of reactions between Br and the VOCs, which convert Br to HBr, a far less reactive form of Bry. Excluding these reactions leads to modelled BrO mixing ratios greater than observed. The reactions between Br and aldehydes were found to be particularly important, despite the model underestimating the amount of aldehydes observed in the atmosphere. There are only small changes to Iy partitioning and IO when the heterogeneous reactions, primarly on sea-salt, are included. Our model results show that the tropospheric Ox loss due to halogens is 31 %. This loss is mostly due to I (16 %) and Br (14 %) and it is in good agreement with other estimates from state-of-the-art atmospheric chemistry models.

Iron (Fe) is an essential micronutrient for marine microbial organisms, and low supply controls productivity in large parts of the world’s ocean. The high latitude North Atlantic is seasonally Fe limited, but Fe distributions and source strengths are poorly constrained. Surface ocean dissolved Fe (DFe) concentrations were low in the study region (

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.

We report a new synthesis of best estimates of the inputs of fixed nitrogen to the world ocean via atmospheric deposition and compare this to fluvial inputs and dinitrogen fixation. We evaluate the scale of human perturbation of these fluxes. Fluvial inputs dominate inputs to the continental shelf, and we estimate that about 75% of this fluvial nitrogen escapes from the shelf to the open ocean. Biological dinitrogen fixation is the main external source of nitrogen to the open ocean, i.e., beyond the continental shelf. Atmospheric deposition is the primary mechanism by which land-based nitrogen inputs, and hence human perturbations of the nitrogen cycle, reach the open ocean. We estimate that anthropogenic inputs are currently leading to an increase in overall ocean carbon sequestration of ~0.4% (equivalent to an uptake of 0.15 Pg C yr−1 and less than the Duce et al. (2008) estimate). The resulting reduction in climate change forcing from this ocean CO2 uptake is offset to a small extent by an increase in ocean N2O emissions. We identify four important feedbacks in the ocean atmosphere nitrogen system that need to be better quantified to improve our understanding of the perturbation of ocean biogeochemistry by atmospheric nitrogen inputs. These feedbacks are recycling of (1) ammonia and (2) organic nitrogen from the ocean to the atmosphere and back, (3) the suppression of nitrogen fixation by increased nitrogen concentrations in surface waters from atmospheric deposition, and (4) increased loss of nitrogen from the ocean by denitrification due to increased productivity stimulated by atmospheric inputs.

A global assessment of precipitation chemistry and deposition has been carried out under the direction of the World Meteorological Organization (WMO) Global Atmosphere Watch (GAW) Scientific Advisory Group for Precipitation Chemistry (SAG-PC). The assessment addressed three questions: (1) what do measurements and model estimates of precipitation chemistry and wet, dry and total deposition of sulfur, nitrogen, sea salt, base cations, organic acids, acidity, and phosphorus show globally and regionally? (2) has the wet deposition of major ions changed since 2000 (and, where information and data are available, since 1990) and (3) what are the major gaps and uncertainties in our knowledge? To that end, regionally- representative measurements for two 3-year-averaging periods, 2000-2002 and 2005-2007, were compiled worldwide. Data from the 2000-2002 averaging period were combined with 2001 ensemble-mean modeling results from 21 global chemical transport models produced in Phase 1 of the Coordinated Model Studies Activities of the Task Force on Hemispheric Transport of Air Pollution (TF HTAP). The measurement data and modeling results were used to generate global and regional maps of concentrations in precipitation and deposition. A major product of the assessment is a database of quality assured ion concentration and wet deposition data gathered from regional and national monitoring networks. The database is available for download from the World Data Centre for Precipitation Chemisty http://wdcpc.org/). The assessment concludes that global concentrations and deposition of sulfur and nitrogen are reasonably well characterized with levels generally highest near emission sources and more than an order of magnitude lower in areas largely free of anthropogenic influences. In many parts of the world, wet deposition of reduced nitrogen exceeds that of oxidized nitrogen and is increasing. Sulfur and nitrogen concentrations and deposition in North America and Europe have declined significantly in line with emission reduction policies. Major regions of the world, including South America, the more remote areas of North America, much of Asia, Africa, Oceania, polar regions, and all of the oceans, are inadequately sampled for all of the major ions found in wet and dry deposition, and particularly so for phosphorus, organic forms of nitrogen, and weak acids including carbonates and organic acids. Measurement-based inferential estimates of dry deposition are limited to sulfur and some nitrogen in only a few regions of the world and methods are highly uncertain. The assessment concludes with recommendations to address major gaps and uncertainties in global ion concentration and deposition measurements., JRC.H.4-Monitoring Agricultural Resources

The atmospheric deposition of both macronutrients and micronutrients plays an important role in driving primary productivity, particularly in the low-latitude ocean. We report aerosol major ion measurements for five ship-based sampling campaigns in the western Pacific from similar to 25 degrees N to 20 degrees S and compare the results with those from Atlantic meridional transects (similar to 50 degrees N to 50 degrees S) with aerosols collected and analyzed in the same laboratory, allowing full incomparability. We discuss sources of the main nutrient species (nitrogen (N), phosphorus (P), and iron (Fe)) in the aerosols and their stoichiometry. Striking north-south gradients are evident over both basins with the Northern Hemisphere more impacted by terrestrial dust sources and anthropogenic emissions and the North Atlantic apparently more impacted than the North Pacific. We estimate the atmospheric supply rates of these nutrients and the potential impact of the atmospheric deposition on the tropical western Pacific. Our results suggest that the atmospheric deposition is P deficient relative to the needs of the resident phytoplankton. These findings suggest that atmospheric supply of N, Fe, and P increases primary productivity utilizing some of the residual excess phosphorus (P*) in the surface waters to compensate for aerosol P deficiency. Regional primary productivity is further enhanced via the stimulation of nitrogen fixation fuelled by the residual atmospheric iron and P*. Our stoichiometric calculations reveal that a P* of 0.1 mu mol L-1 can offset the P deficiency in atmospheric supply for many months. This study suggests that atmospheric deposition may sustain similar to 10% of primary production in both the western tropical Pacific.

The role of solution composition and ageing of arsenite treated with single and mixed mineral systems of kaolinite, montmorillonite and goethite injected with iron sulfide under sulfidic- anoxic conditions have been investigate. Variability in arsenite sorption exists over the range of pH investigated. This variability in sorption may be attributed to the presence of thiol (≡S-H) functional group contained in solution under sulfidic-anoxic condition. Arsenite sorption exhibits a non-promotive Cp effect (i.e. sorption decreases as Cp increases for all mineral systems. the nature of ionic species formed in solution is affected by changes in the mineral/ solution ratio. All mineral systems but kaolinite-goethite exhibits a step up arsenite sorption up to 288 hours residence time and flattens g out over the remaining residence time of the reactions.

The reactivity and removal kinetics of arsenite treated with single and mixed mineral systems of kaolinite, montmorillonite and goethite injected with iron sulfide under sulfidic- anoxic conditions has been investigated. Using empirical models derived from Freundlich isotherm model, injection of sulfidic-anoxic solution of iron sulfide onto the mixed mineral systems enhanced proton coefficient of all single minerals. Differences in sorption kinetics between the single and mixed mineral phases may be attributed to different types of reactive sites on the single and mixed mineral systems Except for iron sulfide, kinetic studies demonstrated three phase reactions attributed to outer sphere complexation, inner sphere complexation and intra-particle diffusion. Injection of sulfidic-anoxic solution of iron sulfide could not change the three phase reaction trend.

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.

The atmospheric cycle of phosphorus (P) is parameterized here in a state-of-the-art global 3-D chemistry transport model, taking into account primary emissions of total P (TP) and soluble P (DP) associated with mineral dust, combustion particles from natural and anthropogenic sources, bioaerosols, sea spray and volcanic aerosols. For the present day, global TP emissions are calculated to be roughly 1.33 Tg-P yr−1, with the mineral sources contributing more than 80 % to these emissions. The P solubilization from mineral dust under acidic atmospheric conditions is also parameterized in the model and is calculated to contribute about one-third (0.14 Tg-P yr−1) of the global DP atmospheric source. To our knowledge, a unique aspect of our global study is the explicit modeling of the evolution of phosphorus speciation in the atmosphere. The simulated present-day global annual DP deposition flux is 0.45 Tg-P yr−1 (about 40 % over oceans), showing a strong spatial and temporal variability. Present-day simulations of atmospheric P aerosol concentrations and deposition fluxes are satisfactory compared with available observations, indicating however an underestimate of about 70 % on current knowledge of the sources that drive the P atmospheric cycle. Sensitivity simulations using preindustrial (year 1850) anthropogenic and biomass burning emission scenarios showed a present-day increase of 75 % in the P solubilization flux from mineral dust, i.e., the rate at which P is converted into soluble forms, compared to preindustrial times, due to increasing atmospheric acidity over the last 150 years. Future reductions in air pollutants due to the implementation of air-quality regulations are expected to decrease the P solubilization flux from mineral dust by about 30 % in the year 2100 compared to the present day. Considering, however, that all the P contained in bioaerosols is readily available for uptake by marine organisms, and also accounting for all other DP sources, a total bioavailable P flux of about 0.17 Tg-P yr−1 to the oceans is derived. Our calculations further show that in some regions more than half of the bioavailable P deposition flux to the ocean can originate from biological particles, while this contribution is found to maximize in summer when atmospheric deposition impact on the marine ecosystem is the highest due to ocean stratification. Thus, according to this global study, a largely unknown but potentially important role of terrestrial bioaerosols as suppliers of bioavailable P to the global ocean is also revealed. Overall, this work provides new insights to the atmospheric P cycle by demonstrating that biological materials are important carriers of bioavailable P, with very important implications for past and future responses of marine ecosystems to global change.

Dissolved iron (dFe) distributions and atmospheric and vertical subduction fluxes of dFe were determined in the upper water column for two meridional transects of the Atlantic Ocean. The data demonstrate the disparity between the iron biogeochemistry of the North and South Atlantic Ocean and show well-defined gradients of size fractionated iron species in surface waters between geographic provinces. The highest dFe and lowest mixed layer residence times (0.4–2.5 years) were found in the northern tropical and subtropical regions. In contrast, the South Atlantic Gyre had lower dFe concentrations ( 5 years), presumably due to lower atmospheric inputs and more efficient biological recycling of iron in this region. Vertical input fluxes of dFe to surface waters ranged from 20 to 170 nmol m–2 d–1 in the North Atlantic and tropical provinces, whereas average fluxes of 6–13 nmol m–2 d–1 were estimated for the South Atlantic. Our estimates showed that the variable dFe distribution over the surface Atlantic ( 50% of total vertical Fe flux to surface waters) rather than upwelling or vertical mixing. This demonstrates the strength of the connection between land-derived atmospheric Fe fluxes and the biological cycling of carbon and nitrogen in the Atlantic Ocean.

Accurate characterization of the stable isotope composition of Cu and Zn in major global mineral dust sources and in aerosols is central to the application of these isotope systems to the studies of global geochemical processes and cycles. We test here for the first time Cu and Zn isotope ratios within a well-defined source-receptor setting on the continent-ocean interface and determine the isotope composition of (i) bulk surface soil dust samples from the Sahel region, (ii) individual size fractions of surface dust samples from the Taklimakan Desert, and (iii) aerosols collected in the equatorial eastern North Atlantic region. This is achieved reducing the blank contribution during the ion exchange step using small resin and acid volumes and using a second ion exchange passage to purify the Cu fraction. We find no significant correlation between size fractions and isotope ratios in the two samples analyzed from the Taklimakan Desert. Mass balance calculations suggest that isotope ratios of bulk samples are within the analytical precision of the

Atmospheric inputs of mineral dust supply iron and other trace metals to the remote ocean and can influence the marine carbon cycle due to iron's role as a potentially limiting micronutrient. Dust generation, transport, and deposition are highly heterogeneous, and there are very few remote marine locations where dust concentrations and chemistry (e.g., iron solubility) are routinely monitored. Here we use aerosol and rainwater samples collected during 10 large-scale research cruises to estimate the atmospheric input of iron, aluminum, and manganese to four broad regions of the Atlantic Ocean over two 3month periods for the years 2001-2005. We estimate total inputs of these metals to our study regions to be 4.2, 17, and 0.27Gmol in April-June and 4.9, 14, and 0.19Gmol in September-November, respectively. Inputs were highest in regions of high rainfall (the intertropical convergence zone and South Atlantic storm track), and rainfall contributed higher proportions of total input to wetter regions. By combining input estimates for total and soluble metals for these time periods, we calculated overall percentage solubilities for each metal that account for the contributions from both wet and dry depositions and the relative contributions from different aerosol types. Calculated solubilities were in the range 2.4%-9.1% for iron, 6.1%-15% for aluminum, and 54%-73% for manganese. We discuss sources of uncertainty in our estimates and compare our results to some recent estimates of atmospheric iron input to the Atlantic.

Atmospheric deposition of trace elements and isotopes (TEI) is an important source of trace metals to the open ocean, impacting TEI budgets and distributions, stimulating oceanic primary productivity, and influenc ing biological community structure and function. Thus, accurate sampling of aerosol TEIs is a vital component of ongoing GEOTRACES cruises, and standardized aerosol TEI sampling and analysis procedures allow the com parison of data from different sites and investigators. Here, we report the results of an aerosol analysis intercal ibration study by seventeen laboratories for select GEOTRACES-relevant aerosol species (Al, Fe, Ti, V, Zn, Pb, Hg, NO 3 ‐ , and SO 4 2‐ ) for samples collected in September 2008. The collection equipment and filter substrates are appropriate for the GEOTRACES program, as evidenced by low blanks and detection limits relative to analyte concentrations. Analysis of bulk aerosol sample replicates were in better agreement when the processing proto col was constrained (± 9% RSD or better on replicate analyses by a single lab, n = 7) than when it was not (gen erally 20% RSD or worse among laboratories using different methodologies), suggesting that the observed vari ability was mainly due to methodological differences rather than sample heterogeneity. Much greater variabil ity was observed for fractional solubility of aerosol trace elements and major anions, due to differing extraction methods. Accuracy is difficult to establish without an SRM representative of aerosols, and we are developing an SRM for this purpose. Based on these findings, we provide recommendations for the GEOTRACES program to

This study investigates the reactivity and removal kinetics of arsenite on mixed mineral systems from aqueous solution related to contaminated waters. The sorbents used were kaolinite, montmorillonite, goethite, and their mixtures. The effects of, proton coefficient, and sorption kinetics were studied at room temperature (23 ± 2 ◦C). Reactivity studies demonstrate enhancement of proton coefficient and the acidity of reactive sites by mixed mineral systems except for kaolinite-montmorillonite, thus increasing mercury removal by proton exchange. Kinetic studies demonstrate two- phase reactions attributed to outer sphere complexation and inner sphere complexation. In the first-phase reaction, mineral mixing based on our empirical model decrease the mass transfer rates for kaolinite-montmorillonite and montmorillonite-goethite, not affecting kaolinite-goethite. For the second-phase reaction, mineral mixing did not change the mass transfer rates for the mixed mineral systems except for montmorillonite-goethite. The behaviors of the mixed mineral systems in mercury sorption suggest that different reactive sites were involved at the onset of sorption, with reactions and sorption ending with inner-sphere complexation. Differences between actual and theoretical % sorption progressed from negative to positive for all mixed minerals as contact time was increased. This means that increase in contact time during Hg-sorbent interaction could help increase mercury removal based on mineral mixing.

This study investigates Hg(II) removal onto binary mixed mineral sorbents from simulated mercury contaminated water, relevant to surface and groundwater impacted environment. However, sorption pattern appeared to be controlled by outer sphere complexation, inner sphere complexation and intra-particle diffusion for Hg (II) sorbed on goethite and mixed mineral system of goethite-montmorillonite with respect to pH. Decrease in Hg (II) sorption as Cp was increased may be attributed to increase in particle size and aggregation of the mineral suspensions. The Cp effect is also related to effective surface area, pressure, and force at the mineral/water interface The complex behavior of mineral systems over the range of residence time investigated may be attributed to increased hydroxylation of the mineral surface resulting in the formation of new reactive sites.

The results of fine mode ( 2 or methane sulphonic acid (MSA). Using our estimates of marine biogenic sulphate and measurements of MSA concentrations we confirm that the ratio of MSA/sulphate from DMS oxidation increases systematically from low to high latitudes, consistent with the laboratory measurements, inferences from field studies and modelling predictions of others.

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’.

WOS:000391139900018; International audience; The importance of the atmospheric deposition of biologically essential trace elements, especially iron, is widely recognized, as are the difficulties of accurately quantifying the rates of trace element wet and dry deposition and their fractional solubility. This paper summarizes some of the recent progress in this field, particularly that driven by the GEOTRACES, and other, international research programmes. The utility and limitations of models used to estimate atmospheric deposition flux, for example, from the surface ocean distribution of tracers such as dissolved aluminium, are discussed and a relatively new technique for quantifying atmospheric deposition using the short-lived radionuclide beryllium-7 is highlighted. It is proposed that this field will advance more rapidly by using a multi-tracer approach, and that aerosol deposition models should be ground-truthed against observed aerosol concentration data. It is also important to improve our understanding of the mechanisms and rates that control the fractional solubility of these tracers. Aerosol provenance and chemistry (humidity, acidity and organic ligand characteristics) play important roles in governing tracer solubility. Many of these factors are likely to be influenced by changes in atmospheric composition in the future. Intercalibration exercises for aerosol chemistry and fractional solubility are an essential component of the GEOTRACES programme. This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.