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Water-column data from seven cruises in 2007–2008 reveal pronounced temporal and spatial variations in the distribution of dissolved iron (DFe

Atmospheric deposition is an important pathway by which bioactive trace metals are delivered to the surface ocean. The proportions of total aerosol trace metals that dissolve in seawater, and thus become available to biota, are not well constrained and are therefore a key uncertainty when estimating atmospheric fluxes of these elements to surface waters. The aim of this study was to elucidate the main physico-chemical controls on the dissolution of the bioactive trace metals manganese (Mn), cobalt (Co), nickel (Ni) and lead (Pb). To this end, aerosol and surface seawater samples were collected in the Sargasso Sea and subsequently used in sequential seawater leach dissolution experiments to assess the role of aerosol source, seawater temperature, pH, and concentrations of dissolved oxygen and organic ligands, on aerosol trace metal dissolution. Results reveal that changes in key physico-chemical parameters in seawater leaches had little effect on the proportions of Mn, Co, Ni and Pb released from aerosols, although organic ligand amendments impacted the size distribution of aerosol-derived Mn in solution. Conversely, aerosol source and composition had the most significant effect on the dissolution of aerosol Co and Pb, with the most ‘anthropogenic’ aerosol samples displaying the highest fractional solubilities in seawater (up to 58% for Co and 112% for Pb). Fractional solubilities over the range of samples and conditions tested were in the range of 50–104% for Mn, 29–58% for Co, 40–85% for Ni and 67–112% for Pb. A large proportion (36–100%, median 89%) of the total dMn, dCo, dNi and dPb was mobilised rapidly during the first leaching step (5 min), with less dTM being released in leaches 2 through 4. Furthermore, investigation of the size distribution of the aerosol-derived trace metals in seawater showed that dissolved Pb was mostly colloidal (0.02–0.4 μm), dissolved Mn and Co were mostly soluble (

We report water column dissolved iron (dFe) and particulate iron (pFe) concentrations from fifty stations sampled across the Ross Sea during austral summer (January-February) of 2012. Concentrations of dFe and pFe were measured in each of the major Ross Sea water masses, including the Ice Shelf Water and off-shelf Circumpolar Deep Water. Despite significant lateral variations in hydrography, macronutrient depletion and primary productivity across several different regions on the continental shelf, dFe concentrations were consistently low (

Phytoplankton production in the Ross Sea is regulated by the availability of dissolved iron (dFe), a limiting micro-nutrient, whose sources include Circumpolar Deep Water, sea ice melt, glacial melt, and benthic sources (sediment efflux and remineralization). We employ a passive tracer dye to model the benthic dFe sources and track pathways from deep areas of the continental shelf to the surface mixed layer in simulations with and without tidal forcing, and at 5 and 1.5 km horizontal resolution. This, combined with dyes for each of the other dFe sources, provides an estimate of total dFe supply to surface waters. We find that tidal forcing increases the amount of benthic dye that covers the banks on the continental shelf. Calculations of mixed layer depth to define the surface ocean give similar average values over the shelf, but spatial patterns differ between simulations, particularly along the ice shelf front. Benthic dFe supply in simulations shows an increase with tidal forcing and a decrease with higher resolution. The changes in benthic dFe supply control the difference in total supply between simulations. Overall, the total dFe supply from simulations varies from 5.60 to 7.95 μmol m −2 year −1, with benthic supply comprising 32–50%, comparing well with recent data and model synthesis. We suggest that including tides and using high horizontal resolution is important, especially when considering spatial variability of iron supply on the Ross Sea shelf.

The Ross Sea is known for showing the greatest sea-ice increase, as observed globally, particularly from 1979 to 2015. However, corresponding changes in sea-ice thickness and production in the Ross Sea are not known, nor how these changes have impacted water masses, carbon fluxes, biogeochemical processes and availability of micronutrients. The PIPERS project sought to address these questions during an autumn ship campaign in 2017 and two spring airborne campaigns in 2016 and 2017. PIPERS used a multidisciplinary approach of manned and autonomous platforms to study the coupled air/ice/ocean/biogeochemical interactions during autumn and related those to spring conditions. Unexpectedly, the Ross Sea experienced record low sea ice in spring 2016 and autumn 2017. The delayed ice advance in 2017 contributed to (1) increased ice production and export in coastal polynyas, (2) thinner snow and ice cover in the central pack, (3) lower sea-ice Chl-a burdens and differences in sympagic communities, (4) sustained ocean heat flux delaying ice thickening and (5) a melting, anomalously southward ice edge persisting into winter. Despite these impacts, airborne observations in spring 2017 suggest that winter ice production over the continental shelf was likely not anomalous., SCOPUS: ar.j, info:eu-repo/semantics/published

We report the distribution of cobalt (Co) in the Ross Sea polynya during austral summer 2005–2006 and the following austral spring 2006. The vertical distribution of total dissolved Co (dCo) was similar to soluble reactive phosphate (PO43−), with dCo and PO43− showing a significant correlation throughout the water column (r2 = 0.87, 164 samples). A strong seasonal signal for dCo was observed, with most spring samples having concentrations ranging from ~45–85 pM, whereas summer dCo values were depleted below these levels by biological activity. Surface transect data from the summer cruise revealed concentrations at the low range of this seasonal variability (~30 pM dCo), with concentrations as low as 20 pM observed in some regions where PO43− was depleted to ~0.1 μM. Both complexed Co, defined as the fraction of dCo bound by strong organic ligands, and labile Co, defined as the fraction of dCo not bound by these ligands, were typically observed in significant concentrations throughout the water column. This contrasts the depletion of labile Co observed in the euphotic zone of other ocean regions, suggesting a much higher bioavailability for Co in the Ross Sea. An ecological stoichiometry of 37.6 μmol Co:mol−1 PO43− calculated from dissolved concentrations was similar to values observed in the subarctic Pacific, but approximately tenfold lower than values in the Eastern Tropical Pacific and Equatorial Atlantic. The ecological stoichiometries for dissolved Co and Zn suggest a greater overall use of Zn relative to Co in the shallow waters of the Ross Sea, with a Co:PO43−/Zn:PO43− ratio of 1:17. Comparison of these observed stoichiometries with values estimated in culture studies suggests that Zn is a key micronutrient that likely influences phytoplankton diversity in the Ross Sea. In contrast, the observed ecological stoichiometries for Co were below values necessary for the growth of eukaryotic phytoplankton in laboratory culture experiments conducted in the absence of added zinc, implying the need for significant Zn nutrition in the Zn-Co cambialistic enzymes. The lack of an obvious kink in the dissolved Co:PO43− relationship was in contrast to Zn:PO43− and Cd:PO43− kinks previously observed in the Ross Sea. An excess uptake mechanism for kink formation is proposed as a major driver of Cd:PO43− kinks, where Zn and Cd uptake in excess of that needed for optimal growth occurs at the base of the euphotic zone, and no clear Co kink occurs because its abundances are too low for excess uptake. An unusual characteristic of Co geochemistry in the Ross Sea is an apparent lack of Co scavenging processes, as inferred from the absence of dCo removal below the euphotic zone. We hypothesize that this vertical distribution reflects a low rate of Co scavenging by Mn oxidizing bacteria, perhaps due to Mn scarcity, relative to the timescale of the annual deep winter mixing in the Ross Sea. Thus Co exhibits nutrient-like behavior in the Ross Sea, in contrast to its hybrid-type behavior in other ocean regions, with implications for the possibility of increased marine Co inventories and utility as a paleooceanographic proxy.

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)

International audience; Continental margins play a central role in the composition of seawater by being an important source of trace element essentials to the functioning of the ocean ecosystems. Here, we measured long-lived radium isotopes (Ra-226, Ra-228) along a zonal transect at 12 degrees S (US GEOTRACES GP16) in the eastern tropical South Pacific Ocean. We used Ra-228 to quantify the trace element and isotope (TEI) fluxes (DMn, DFe, and DCo) delivered from the Peruvian continental i) shelf and ii) slope. First, elevated Ra-228 activities were measured in surface water over the entire transect (similar to 8500 km), evidence that the continental shelf is an important source of sediment-derived TEIs not only to coastal areas, but to central Pacific Ocean waters. Modeled Ra-228 shelf fluxes combined with water column dissolved TEI/Ra-228 ratios were used to quantify the shelf-ocean input rates (normalized to shelf-area) for DMn (3.3 x 10(3) mu mol m(-2) y(-1)), DFe (1.5 x 10(3) mu mol m(-2) y(-1)), and DCo (1.0 x 10(2) mu mol m(-2) y(-1)). Second, co-occurring plumes of Ra-228, DFe, and DMn extended over 1800 km from the margin at 1000-2500 m depth, indicative of a continental slope sediment TEI input to the intermediate water column. The Ra-228 gradient allowed us to derive an effective horizontal eddy diffusion coefficient (K-h) of 46 m(2) s(-1), which in turn permitted the calculation of slope sediment DMn (6.4 mu mol m(-2) y(-1)) and DFe (5.9 x 10(2) mu mol m(-2) y(-1)) fluxes based on their offshore concentration gradients. On the scale of the South Pacific continental margin between 0-20 degrees S, the DMn shelf flux is approximately 2-3 orders of magnitude higher than the slope flux, while the DFe shelf/slope flux is similar to 3:1. Both shelf and slope sediment derived DMn was transported over a significant distance towards the ocean interior, while DFe concentration gradients were steep, consistent with longer water column residence time for DMn as compared to DFe in marine systems. These findings highlight the importance of considering the continental slope-ocean boundary in the oceanic budgets of biologically-important trace elements.

The Ross Sea sustains a rich ecosystem and is the most productive sector of the Southern Ocean. Most of this production occurs within a polynya during the November–February period, when the availability of dissolved iron (dFe) is thought to exert the major control on phytoplankton growth. Here we combine new data on the distribution of dFe, high-resolution model simulations of ice melt and regional circulation, and satellite-based estimates of primary production to quantify iron supply and demand over the Ross Sea continental shelf. Our analysis suggests that the largest sources of dFe to the euphotic zone are wintertime mixing and melting sea ice, with a lesser input from intrusions of Circumpolar Deep Water and a small amount from melting glacial ice. Together these sources are in approximate balance with the annual biological dFe demand inferred from satellite-based productivity algorithms, although both the supply and demand estimates have large uncertainties.

High-resolution dissolved Fe (dFe) and dissolved Mn (dMn) distributions were obtained using a trace metal clean rosette during the GEOTRACES GA03 zonal transect cruises (USGT10 and USGT11) across the North Atlantic Ocean. This manuscript provides a general overview of the dFe, as well as dMn and dissolved Al (dAl) distributions that reveal several Fe inputs at varying depths across the study region. Elevated dFe concentrations correlate with elevated dAl concentrations in the surface waters of the subtropical gyre, indicating a significant atmospheric source of Fe, in contrast there is no apparent significant dust source for Mn. In the subsurface waters, dFe maxima are a result of the remineralization process, as revealed by their correspondence with dissolved oxygen minima. Within the oxygen minimum, the ratio of dFe to apparent oxygen utilization (AOU) is lower than would be expected from the measured Fe content of surface water phytoplankton, suggesting that a significant amount of dFe that is remineralized at depth (~63–90%) is subsequently scavenged from the water column. The rate of remineralization, which is based on the slope of dFe:AOU plot, is similar across a wide area of the North Atlantic. In addition to the remineralization process, sedimentary inputs are apparent from elevated dMn signals in the eastern basin, particularly near the African coast. In the western basin, sedimentary input is also occurring along the advective flow path of the Upper Labrador Sea Water (ULSW), as ULSW transits along the North American continental shelf region. The largest dFe anomaly (~68 nM), which also corresponds to a dMn anomaly (up to ~33 nM) is seen in the neutrally buoyant hydrothermal plume sampled over the Mid-Atlantic Ridge, and that signal is visible for ~500 km to the west of the ridge.

The bioavailability of iron influences the distribution, biomass and productivity of phytoplankton in the Ross Sea, one of the most productive regions in the Southern Ocean. We mapped the spatial and temporal extent and severity of iron-limitation of the native phytoplankton assemblage using long- (> 24 h) and short-term (24 h) iron-addition experiments along with physiological and molecular characterisations during a cruise to the Ross Sea in December–February 2012. Phytoplankton increased their photosynthetic efficiency in response to iron addition, suggesting proximal iron limitation throughout most of the Ross Sea during summer. Molecular and physiological data further indicate that as nitrate is removed from the surface ocean the phytoplankton community transitions to one displaying an iron-efficient photosynthetic strategy characterised by an increase in the size of photosystem II (PSII) photochemical cross section (σ PSII ) and a decrease in the chlorophyll-normalised PSII abundance. These results suggest that phytoplankton with the ability to reduce their photosynthetic iron requirements are selected as the growing season progresses, which may drive the well-documented progression from Phaeocystis antarctica- assemblages to diatom-dominated phytoplankton. Such a shift in the assemblage-level photosynthetic strategy potentially mediates further drawdown of nitrate following the development of iron deficient conditions in the Ross Sea.

Continental margin sediments provide a potentially large but poorly constrained source of dissolved iron (dFe) to the upper ocean. The Ross Sea continental shelf is one region where this benthic supply is thought to play a key role in regulating the magnitude of seasonal primary production. Here we present data collected during austral summer 2012 that reveal contrasting low surface (0.08 ± 0.07 nM) and elevated near-seafloor (0.74 ± 0.47 nM) dFe concentrations. Combining these observations with results from a high-resolution physical circulation model, we estimate dFe efflux of 5.8 × 107 mol yr−1 from the deeper portions (>400 m) of the Ross Sea continental shelf; more than sufficient to account for the inferred “winter reserve” dFe inventory at the onset of the growing season. In addition, elevated dFe concentrations observed over shallower bathymetry suggest that such features provide additional inputs of dFe to the euphotic zone throughout the year.

The proportion of aerosol iron (Fe) that dissolves in seawater varies greatly and is dependent on aerosol composition and the physicochemical conditions of seawater, which may change depending on location or be altered by global environmental change. Aerosol and surface seawater samples were collected in the Sargasso Sea and used to investigate the impact of these changing conditions on aerosol Fe dissolution in seawater. Our data show that seawater temperature, pH, and oxygen concentration, within the range of current and projected future values, had no significant effect on the dissolution of aerosol Fe. However, the source and composition of aerosols had the most significant effect on the aerosol Fe solubility, with the most anthropogenically influenced samples having the highest fractional solubility (up to 3.2%). The impact of ocean warming and acidification on aerosol Fe dissolution is therefore unlikely to be as important as changes in land usage and fossil fuel combustion. Our experimental results also reveal important changes in the size distribution of soluble aerosol Fe in solution, depending on the chemical conditions of seawater. Under typical conditions, the majority (77–100%) of Fe released from aerosols into ambient seawater existed in the colloidal (0.02–0.4 µm) size fraction. However, in the presence of a sufficient concentration of strong Fe-binding organic ligands (10 nM) most of the aerosol-derived colloidal Fe was converted to soluble Fe (

Marine dinitrogen (N2)-fixing cyanobacteria have large impacts on global biogeochemistry as they fix carbon dioxide (CO2) and fertilize oligotrophic ocean waters with new nitrogen. Iron (Fe) and phosphorus (P) are the two most important limiting nutrients for marine biological N2 fixation, and their availabilities vary between major ocean basins and regions. A long-standing question concerns the ability of two globally dominant N2-fixing cyanobacteria, unicellular Crocosphaera and filamentous Trichodesmium, to maintain relatively high N2-fixation rates in these regimes where both Fe and P are typically scarce. We show that under P-deficient conditions, cultures of these two cyanobacteria are able to grow and fix N2 faster when Fe deficient than when Fe replete. In addition, growth affinities relative to P increase while minimum concentrations of P that support growth decrease at low Fe concentrations. In Crocosphaera, this effect is accompanied by a reduction in cell sizes and elemental quotas. Relatively high growth rates of these two biogeochemically critical cyanobacteria in low-P, low-Fe environments such as those that characterize much of the oligotrophic ocean challenge the common assumption that low Fe levels can have only negative effects on marine primary producers. The closely interdependent influence of Fe and P on N2-fixing cyanobacteria suggests that even subtle shifts in their supply ratio in the past, present and future oceans could have large consequences for global carbon and nitrogen cycles.

Nearly all iron dissolved in the ocean is complexed by strong organic ligands of unknown composition. The effect of ligand composition on microbial iron acquisition is poorly understood, but amendment experiments using model ligands show they can facilitate or impede iron uptake depending on their identity. Here we show that siderophores, organic compounds synthesized by microbes to facilitate iron uptake, are a dynamic component of the marine ligand pool in the eastern tropical Pacific Ocean. Siderophore concentrations in iron-deficient waters averaged 9 pM, up to fivefold higher than in iron-rich coastal and nutrient-depleted oligotrophic waters, and were dominated by amphibactins, amphiphilic siderophores with cell membrane affinity. Phylogenetic analysis of amphibactin biosynthetic genes suggests that the ability to produce amphibactins has transferred horizontally across multiple Gammaproteobacteria, potentially driven by pressures to compete for iron. In coastal and oligotrophic regions of the eastern Pacific Ocean, amphibactins were replaced with lower concentrations (1–2 pM) of hydrophilic ferrioxamine siderophores. Our results suggest that organic ligand composition changes across the surface ocean in response to environmental pressures. Hydrophilic siderophores are predominantly found across regions of the ocean where iron is not expected to be the limiting nutrient for the microbial community at large. However, in regions with intense competition for iron, some microbes optimize iron acquisition by producing siderophores that minimize diffusive losses to the environment. These siderophores affect iron bioavailability and thus may be an important component of the marine iron cycle.

The Ross Sea, the most productive region in the Antarctic, reaches farther south than any body of water in the world. While its food web is relatively intact, its oceanography, biogeochemistry, and sea ice coverage have been changing dramatically, and likely will continue to do so in the future. Sea ice cover and persistence have been increasing, in contrast to the Amundsen-Bellingshausen sector, which has resulted in reduced open water duration for its biota. Models predict that as the ozone hole recovers, ice cover will begin to diminish. Currents on the continental shelf will likely change in the coming century, with a projected intensification of flow leading to altered deep ocean ventilation. Such changes in ice and circulation will lead to altered plankton distributions and composition, but it is difficult at present to predict the nature of these changes. Iron and irradiance play central roles in regulating phytoplankton production in the Ross Sea, but the impacts of oceanographic changes on the biogeochemistry of iron are unclear. Unlike other Southern Ocean regions, where continental shelves are very narrow and Antarctic krill dominates the herbivorous fauna, the broad shelf of the Ross Sea is dominated by crystal krill and silverfish, which are the major prey items for higher trophic levels. At present, the Ross Sea is considered to be one of the most species-rich areas of the Southern Ocean and a biodiversity "hotspot" due to its heterogeneous habitats. Despite being among the best-studied regions in the entire Southern Ocean, accurate predictions of the impacts of climate change on the oceanography and ecology of the Ross Sea remain fraught with uncertainty.

Aerosol deposition provides a major input of the essential micronutrient iron to the open ocean. A critical parameter with respect to biological availability is the proportion of aerosol iron that enters the oceanic dissolved iron pool – the so-called fractional solubility of aerosol iron (%FeS). Here we present a global-scale compilation of total aerosol iron loading (FeT) and estimated %FeS values for ∼1100 samples collected over the open ocean, the coastal ocean, and some continental sites, including a new data set from the Atlantic Ocean. Despite the wide variety of methods that have been used to define ‘soluble’ aerosol iron, our global-scale compilation reveals a remarkably consistent trend in the fractional solubility of aerosol iron as a function of total aerosol iron loading, with the great bulk of the data defining an hyperbolic trend. The hyperbolic trends that we observe for both global- and regional-scale data are adequately described by a simple two-component mixing model, whereby the fractional solubility of iron in the bulk aerosol reflects the conservative mixing of ‘lithogenic’ mineral dust (high FeT and low %FeS) and non-lithogenic ‘combustion’ aerosols (low FeT and high %FeS). An increasing body of empirical and model-based evidence points to anthropogenic fuel combustion as the major source of these non-lithogenic ‘combustion’ aerosols, implying that human emissions are a major determinant of the fractional solubility of iron in marine aerosols. The robust global-scale relationship between %FeS and FeT provides a simple heuristic method for estimating aerosol iron solubility at the regional to global scale.

A sensitive flow-injection method with chemiluminescence detection (FI-CL) for the determination of dissolved cobalt in open ocean samples, suitable for shipboard use has been developed. To date, FI methods for dissolved cobalt have been used only in coastal and estuarine waters. Therefore, significant modifications to existing methods were required, including (1) the use of a commercially available iminodiacetate (IDA) resin (Toyopearl AF-chelate 650M) in place of resin immobilized 8-hydroxyquinoline for online preconcentration and matrix removal, (2) the introduction of acidified ammonium acetate (pH 4) as a column-conditioning step before sample loading and rinse steps, and most importantly, (3) UV irradiation of acidified seawater samples to determine total dissolved cobalt, rather than an operationally defined fraction. This method had a detection limit of 4.5 pM (3σ of the blank). The accuracy of the method was evaluated by determining total dissolved cobalt in acidified North Pacific deep seawater (1000 m) samples from the Sampling and Analysis of Iron (SAFe) program and NASS-5. The method yields a mean (± SD) value of 40.9 ± 2.6 pM (n = 9), which is in excellent agreement with the SAFe consensus value of 43 ± 4 pM, and 208 ± 30 pM for NASS-5 (certified value 187 ± 51 pM). This study demonstrates that UV irradiation is an essential step for the determination of total dissolved cobalt in seawater by FI-CL. The method was applied to vertical profiles from the Sargasso Sea, indicating that total dissolved cobalt is influenced by both biological and physical processes.

The quotas of P, S, Mn, Fe, Ni, and Zn in individual Synechococcus cells collected from the surface and deep chlorophyll maximum (DCM) layer of three mesoscale eddies in the Sargasso Sea were measured using synchrotron X-ray fluorescence microscopy. Cells in a mode-water eddy had significantly higher P (57 6 10 amol) and Mn (28 6 7 zmol) cell quotas than cells collected from a cyclone (22 6 2 amol and 10 6 1 zmol, respectively) or anticyclone (25 6 3 amol and 18 6 3 zmol, respectively). Conversely, Ni and Zn quotas were significantly higher in the cells from the anticyclone (92 6 19 and 561 6 150 zmol, respectively) than in cells from the cyclonic (25 6 4 and 35 6 7 zmol, respectively) or mode-water (30 6 9 and 21 6 8 zmol, respectively) eddies. These changes may reflect biochemical responses (e.g., production of urease and alkaline phosphatase) to gradients in inorganic N and P supplies. Cellular quotas of Fe (111 6 17 zmol in the cyclone) and S (52 6 6 amol in the cyclone) did not vary significantly among eddies despite two- to threefold higher dissolved and particulate Fe concentrations in the anticylone. Cells collected from 10-m depth contained approximately 80% more Ni and S than cells collected from the DCM, potentially reflecting cell responses to heightened oxidative stress. Depthrelated trends varied by eddy for the other elements. Cellular P and Zn varied significantly during repeated samplings of the cyclone, with quotas of both elements dropping as bulk chlorophyll biomass in the DCM increased. These data demonstrate the dynamic responses of phytoplankton elemental composition to physical and chemical environmental gradients. Transition metals play numerous critical roles in the metabolism of marine phytoplankton, and their availability can exert important controls on algal community structure, physiology, production, and the associated cycling of carbon and nutrient elements. Iron appears to play the most significant role as a limiting trace nutrient for oceanic phytoplankton, but other metals may also influence phytoplankton function in certain areas of the ocean. For example, Cu availability can affect species composition as both a toxin and a micronutrient (Mann

Laboratory culture experiments were used to investigate the growth rate of colonial Phaeocystis antarctica as a function of irradiance and dissolved iron concentration. The experiments were conducted with a P. antarctica strain isolated from the southern Ross Sea, Antarctica, and made use of natural, low-iron (

Osmium is one of the rarer elements in seawater, with typical concentration of ≈10 × 10 −15 g g −1 (5.3 × 10 −14 mol kg −1 ). The osmium isotope composition ( 187 Os/ 188 Os ratio) of deep oceans is 1.05, reflecting a balance between inputs from continental crust (≈1.3) and mantle/cosmic dust (≈0.13). Here, we show that the 187 Os/ 188 Os ratios measured in rain and snow collected around the world range from 0.16 to 0.48, much lower than expected (>1), but similar to the isotope composition of ores (≈0.2) that are processed to extract platinum and other metals to be used primarily in automobile catalytic converters. Present-day surface seawater has a lower 187 Os/ 188 Os ratio (≈0.95) than deep waters, suggesting that human activities have altered the isotope composition of the world's oceans and impacted the global geochemical cycle of osmium. The contamination of the surface ocean is particularly remarkable given that osmium has few industrial uses. The pollution may increase with growing demand for platinum-based catalysts.

Interpretation of photosynthetic pigment data using iterative programs such as CHEMTAX are widely used to examine algal community structure in the surface ocean. The accuracy of such programs relies on understanding the effects of environmental parameters on the pigment composition of taxonomically diverse algal groups. Phaeocystis antarctica is an important contributor to total autotrophic production and the biogeochemical cycling of carbon and sulfur in the Southern Ocean. Here we report the results of a laboratory culture experiment in which we examined the effects of ambient dissolved iron concentration on the pigment composition of colonial P. antarctica, using a new P. antarctica strain isolated from the southern Ross Sea in December 2003. Low-iron ( 3) indicative of Fe stress. We also observed that the ratio of fucoxanthin to 19′-hexanoyloxyfucoxanthin (Fuco:Hex ratio) was highly correlated (r 2 = 0.82) with initial dissolved Fe concentration, with Fuco:Hex ratios

We have carried out field and laboratory experiments to examine the iron requirements of colonial Phaeocystis antarctica in the Ross Sea. In December 2003, we performed an iron/light-manipulation bioassay experiment in the Ross Sea polynya, using an algal assemblage dominated by colonial Phaeocystis antarctica, collected from surface waters with an ambient dissolved Fe concentration of ∼0.4 nM. Results from this experiment suggest that P. antarctica growth rates were enhanced at high irradiance (∼50% of incident surface irradiance) but were unaffected by iron addition, and that elevated irradiance mediated a significant decrease in cellular chlorophyll a content. We also conducted a laboratory iron dose–response bioassay experiment using a unialgal, non-axenic strain of colonial P. antarctica and low-iron (

The GEOTRACES Intermediate Data Product 2014 (IDP2014) is the first publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2013. It consists of two parts: (1) a compilation of digital data for more than 200 trace elements and isotopes (TEIs) as well as classical hydrographic parameters, and (2) the eGEOTRACES Electronic Atlas providing a strongly inter-linked on-line atlas including more than 300 section plots and 90 animated 3D scenes. The IDP2014 covers the Atlantic, Arctic, and Indian oceans, exhibiting highest data density in the Atlantic. The TEI data in the IDP2014 are quality controlled by careful assessment of intercalibration results and multi-laboratory data comparisons at cross-over stations. The digital data are provided in several formats, including ASCII spreadsheet, Excel spreadsheet, netCDF, and Ocean Data View collection. In addition to the actual data values the IDP2014 also contains data quality flags and 1-σ data error values where available. Quality flags and error values are useful for data filtering. Metadata about data originators, analytical methods and original publications related to the data are linked to the data in an easily accessible way. The eGEOTRACES Electronic Atlas is the visual representation of the IDP2014 data providing section plots and a new kind of animated 3D scenes. The basin-wide 3D scenes allow for viewing of data from many cruises at the same time, thereby providing quick overviews of large-scale tracer distributions. In addition, the 3D scenes provide geographical and bathymetric context that is crucial for the interpretation and assessment of observed tracer plumes, as well as for making inferences about controlling processes., National Science Foundation (U.S.) (OCE-0608600), National Science Foundation (U.S.) (OCE-0938349), National Science Foundation (U.S.) (OCE-1243377)

Hydrothermal venting along mid-ocean ridges exerts an important control on the chemical composition of sea water by serving as a major source or sink for a number of trace elements in the ocean(1-3). Of these, iron has received considerable attention because of its role as an essential and often limiting nutrient for primary production in regions of the ocean that are of critical importance for the global carbon cycle(4). It has been thought that most of the dissolved iron discharged by hydrothermal vents is lost from solution close to ridge-axis sources(2,5) and is thus of limited importance for ocean biogeochemistry(6). This long-standing view is challenged by recent studies which suggest that stabilization of hydrothermal dissolved iron may facilitate its longrange oceanic transport(7-10). Such transport has been subsequently inferred from spatially limited oceanographic observations(11-13). Here we report data from the US GEOTRACES Eastern Pacific Zonal Transect (EPZT) that demonstrate lateral transport of hydrothermal dissolved iron, manganese, and aluminium from the southern East Pacific Rise (SEPR) several thousand kilometres westward across the South Pacific Ocean. Dissolved iron exhibits nearly conservative (that is, no loss from solution during transport and mixing) behaviour in this hydrothermal plume, implying a greater longevity in the deep ocean than previously assumed(6,14). Based on our observations, we estimate a global hydrothermal dissolved iron input of three to four gigamoles per year to the ocean interior, which is more than fourfold higher than previous estimates(7,11,14). Complementary simulations with a global-scale ocean biogeochemical model suggest that the observed transport of hydrothermal dissolved iron requires some means of physicochemical stabilization and indicate that hydrothermally derived iron sustains a large fraction of Southern Ocean export production

A lab- and ship-based analytical intercomparison of two flow injection methods for the determination of iron in seawater was conducted, using three different sets of seawater samples collected from the Southern Ocean and South Atlantic. In one exercise, iron was determined in three different size-fractions ( 6 months) of acidified samples as a possible protocol for the determination of dissolved iron in seawater.

Shipboard bottle incubation experiments were performed to investigate the effects of iron, light, and silicate on algal production of particulate dimethylsulfoniopropionate (DMSPp) in the Subantarctic Zone (SAZ) south of Tasmania during March 1998. Iron enrichment resulted in threefold to ninefold increases in DMSPp concentrations relative to control treatments, following 7 and 8-day incubation experiments. Additions of Fe and Si preferentially stimulated the growth of lightly-silicified pennate diatoms and siliceous haptophytes, respectively, to which we attribute the increased DMSPp production in the incubation bottles. Both of these algal groups were previously believed to be low DMSPp producers; however, our experimental data suggest that addition of iron and silicate to the low-silicate low-iron waters of the SAZ will result in increased production of DMSPp by lightly silicified diatoms and siliceous haptophytes, respectively. Increased irradiance enhanced DMSPp production in iron-amended treatments with both low (0.5 nM) and high (5 nM) concentrations of added iron. However, the role of light in stimulating DMSPp production was apparently of secondary importance compared to the effects of iron addition. The combination of high irradiance and high iron enrichment produced the highest DMSPp production in the experiments, suggesting that iron and light may have a synergistic effect in limiting algal DMSPp production in subantarctic waters.

The influence of irradiance and iron (Fe) supply on phytoplankton processes was investigated, north (47S, 142E) and south (54S, 142E) of the Subantarctic Front in austral autumn (March 1998). At both sites, resident cells exhibited nutrient stress (Fv/ Fm 0.3). Shipboard perturbation experiments examined two light (mean in situ and elevated) and two Fe (nominally 0.5 and 3 nM) treatments under silicic acid-replete conditions. Mean in situ light levels (derived from incident irradiances, mixed layer depths (MLDs), wind stress, and a published vertical mixing model) differed at the two sites, 25% of incident irradiance I 0 at 47S and 9% I 0 at 54S because of MLDs of 40 (47S) and 90 m (54S), when these stations were occupied. The greater MLD at 54S is reflected by tenfold higher cellular chlorophyll a levels in the resident phytoplankton. In the 47S experiment, chlorophyll a levels increased to 1 gL 1 only in the high-Fe treatments, regardless of irradiance levels, suggesting Fe limitation. This trend was also noted for cell abundances, silica production, and carbon fixation rates. In contrast, in the 54S experiment there were increases in chlorophyll a (to 2 gL 1 ), cell abundances, silica production, and carbon fixation only in the high-light treatments to which Fe had been added, suggesting that Fe and irradiance limit algal growth rates. Irradiance by altering algal Fe quotas is a key determinant of algal growth rate at 54S (when silicic acid levels are nonlimiting); however, because of the integral nature of Fe/light colimitation and the restricted nature of the current data set, it was not possible to ascertain the relative contributions of Fe and irradiance to the control of phytoplankton growth. On the basis of a climatology of summer mean MLD for subantarctic (SA) waters south of Australia the 47 and 54S sites appear to represent minimum and maximum MLDs, where Fe and Fe/ irradiance, respectively, may limit/colimit algal growth. The implications for changes in the factors limiting algal growth with season in SA waters are discussed.

Subantarctic Southern Ocean surface waters in the austral summer and autumn are characterized by high concentrations of nitrate and phosphate but low concentrations of dissolved iron (Fe, ∼0.05 nM) and silicic acid (Si

Oceanographic processes in the subantarctic region contribute crucially to the physical and biogeochemical aspects of the global climate system. To explore and quantify these contributions, the Antarctic Cooperative Research Centre (CRC) organized the SAZ Project, a multidisciplinary, multiship investigation carried out south of Australia in the austral summer of 1997–1998. Here we present a brief overview of the SAZ Project and some of its major results, as detailed in the 16 papers that follow in this special section.

To evaluate the deposition and solubility of aerosol iron in the Antarctic seasonal sea ice zone (SSIZ), iron was measured in snow samples collected from three areas in the SSIZ (Prydz Bay, Dumont d'Urville Sea and Ross Sea) and one continental area (Princess Elizabeth Land) of East Antarctica. Concentrations of total-dissolvable iron (that soluble at pH ∼2) ranged from 20–2950 pg g−1, with the lowest concentrations measured in snow from the Dumont d'Urville Sea. Using estimates of snow accumulation rates, we calculate atmospheric iron deposition fluxes of 0.017–0.11 mg m−2 yr−1 (0.30–2.0 µmol m−2 yr−1), which are generally lower than previously published estimates. Measurements of iron in filtered meltwaters of snow samples from Prydz Bay and Princess Elizabeth Land suggest that ∼10–90% of the total atmospheric iron is readily soluble. Assuming our results to be broadly representative of atmospheric deposition over seasonally ice-covered, high-nutrient Antarctic waters, we use our mean estimates of atmospheric iron deposition (1.1 µmol m−2 yr−1) and solubility (32%) to calculate that atmospheric iron potentially supports annual phytoplankton production of 1.1 × 1012 mole C in the Antarctic SSIZ, which is less than 5% of the estimated total annual primary production in this ocean region.

Geochemical records are presented for five sediment cores from basins on the continental shelf of Mac. Robertson Land, East Antarctica. The cores contain 2–4 m thick sequences of hemipelagic, siliceous mud and ooze (SMO) deposited under seasonally open marine conditions. The inner and middle shelf SMO sequences are massive dark olive green material, whereas the outer shelf SMO sequences are dark olive material interspersed with light olive green layers ∼1–10 cm thick. The biogenic material is dominated by marine diatoms including Fragilariopsis curta, Fragilariopsis cylindrus, and Chaetoceros spp. in the dark-colored SMO and Corethron criophilum in the light-colored layers. Radiocarbon dates suggest that the cores provide continuous accumulation records extending from < 1 kyr before present (B.P.) back as far as 4–15 kyr B.P., with estimated accumulation rates of 0.07–5 mm yr−1. The three core records from the middle and outer shelf suggest six episodes of increased accumulation of biogenic material at ∼5.5 kyr B.P. (all three cores), 1, 2, and 6.2 kyr B.P. (two of the three cores), and 3.8 and 10.8 kyr B.P. (one core), most of which coincide with Corethron layers. We interpret these features as the result of enhanced diatom production over the outer shelf, possibly related to climatic warm periods. The absence of such features in the inner shelf core records is thought to reflect a relatively constant level of seasonal diatom production in adjacent waters maintained by a coastal polynya.

Dissolved iron and manganese and total dissolvable iron were measured in water column samples collected from the polynya region of the southern Ross Sea during cruises in November–December 1994 (spring 1994) and December 1995 to January 1996 (summer 1995). Iron and manganese addition bottle incubation experiments were also performed during these cruises in order to assess the nutritional sufficiency of ambient iron and manganese concentrations for growth of the phytoplankton community. Generally high dissolved iron concentrations (>0.5 nM) and relatively complex iron and manganese vertical profiles were obtained during the spring 1994 cruise, compared with the summer 1995 data. Dissolved iron concentrations in the upper water column averaged 1.0 nM during spring 1994 and 0.23 nM in summer 1995, excluding two stations where concentrations exceeding 1 nM are attributed to inputs from melting sea ice. The observed differences in the distribution of iron and manganese between spring 1994 and summer 1995 are attributed to seasonal decreases in the up welling of bottom waters and melting of sea ice, which supply these metals into the upper water column, combined with the cumulative removal of iron and manganese from the water column throughout the spring and summer, due to biological uptake, vertical export and scavenging by suspended and sinking particles. Results of the metal addition bottle incubation experiments indicate that ambient dissolved iron concentrations are adequate for phytoplankton growth requirements during the spring and early summer, when algal production is highest and Phaeocystis antarctica dominates the algal community, whereas low dissolved iron concentrations limit algal community growth later in the summer, except in the stratified, iron-enriched waters near melting sea ice, where diatoms are able to bloom. Our observations and the inferred seasonal distributions of P. antarctica and diatoms in these waters suggest that iron availability and vertical mixing (i.e., irradiance) exert the primary controls on phytoplankton growth and community structure in the southern Ross Sea during the spring and summer.

In March 1998 we measured iron in the upper water column and conducted iron- and nutrient-enrichment bottle-incubation experiments in the open-ocean Subantarctic region southwest of Tasmania, Australia. In the Subtropical Convergence Zone (∼42°S, 142°E), silicic acid concentrations were low (< 1.5 µM) in the upper water column, whereas pronounced vertical gradients in dissolved iron concentration (0.12-0.84 nM) were observed, presumably reflecting the interleaving of Subtropical and Subantarctic waters, and mineral aerosol input. Results of a bottle-incubation experiment performed at this location indicate that phytoplankton growth rates were limited by iron deficiency within the iron-poor layer of the euphotic zone. In the Subantarctic water mass (∼46.8°S, 142°E), low concentrations of dissolved iron (0.05-0.11 nM) and silicic acid (< 1 µM) were measured throughout the upper water column, and our experimental results indicate that algal growth was limited by iron deficiency. These observations suggest that availability of dissolved iron is a primary factor limiting phytoplankton growth over much of the Subantarctic Southern Ocean in the late summer and autumn.

The isotopic composition of Pb and the concentrations of Pb, Ba and Bi wert- measured in selected ice-core samples from Law Dome, East Antarctica, to a depth of 1196 m. The range of concentrat ions found in decontaminated ice was 0.03-1.5 pgg−1 for Pb, 0.9-6.1 pgg−1 for Ba and 0.4 17 fgg −1 for Bi, excluding the deepest sample which contained ~1 pjpm of rock dust. The abundances of all four stable lead isotopes were measured and gave 206Pb/207Pb ratios up to ~1.23. Avalue of 208Pb/207Pb= 2.78 was measured in the deepest sample and is consistent with reported Pb isotope ratios of Antarctic gran-ulites. Although the element concentrations in some samples were lower than have been reported elsewhere, geochemkal and isotopic evidence indicated that a number of samples were contaminated with Pb not present in the original ice. However, it appears that the technical skills now available are approaching the level where careful sample selection, decontamination and analysis can yield accurate results for the concentration and isotopic composition of Pb in Earth's purest naturally occurring ice.

During summer 1995–96, we measured iron in the water column and conducted iron-enrichment bottle-incubation experiments at a station in the central Ross Sea (76°30′S, 170°40′W), first, in the presence of melting sea ice, and 17 days later, in ice-free conditions. We observed a striking temporal change in mixed-layer dissolved iron concentrations at this station, from 0.72–2.3 nM with sea ice present, to 0.16–0.17 nM in ice-free conditions. These changes were accompanied by a significant drawdown in macronutrients and an approximate doubling of algal (diatom) biomass. Our incubation experiments suggest that conditions were iron-replete in the presence of sea ice, and iron-deficient in the absence of sea ice. We surmise that bioavailable iron was released into seawater from the melting sea ice, stimulating phytoplankton production and the biological removal of dissolved iron from the mixed layer, until iron-limited conditions developed. These observations suggest that the episodic release of bioavailable iron from melting sea ice is an important factor regulating phytoplankton production, particularly ice-edge blooms, in seasonally ice-covered Antarctic waters.

Dissolved cobalt (dCo), iron (dFe) and aluminum (dAl) were determined in water column samples along a meridional transect (?31°N to 24°N) south of Bermuda in June 2008. A general north-to-south increase in surface concentrations of dFe (0.3–1.6 nM) and dAl (14–42 nM) was observed, suggesting that aerosol deposition is a significant source of dFe and dAl, whereas no clear trend was observed for near-surface dCo concentrations. Shipboard aerosol samples indicate fractional solubility values of 8–100% for aerosol Co, which are significantly higher than corresponding estimates of the solubility of aerosol Fe (0.44–45%). Hydrographic observations and analysis of time series rain samples from Bermuda indicate that wet deposition accounts for most (>80%) of the total aeolian flux of Co, and hence a significant proportion of the atmospheric input of dCo to our study region. Our aerosol data imply that the atmospheric input of dCo to the Sargasso Sea is modest, although this flux may be more significant in late summer. The water column dCo profiles reveal a vertical distribution that predominantly reflects ‘nutrient-type’ behavior, versus scavenged-type behavior for dAl, and a hybrid of nutrient- and scavenged-type behavior for dFe. Mesoscale eddies also appear to impact on the vertical distribution of dCo. The effects of biological removal of dCo from the upper water column were apparent as pronounced sub-surface minima (21 ± 4 pM dCo), coincident with maxima in Prochlorococcus abundance. These observations imply that Prochlorococcus plays a major role in removing dCo from the euphotic zone, and that the availability of dCo may regulate Prochlorococcus growth in the Sargasso Sea.

[1] The Ross Sea polynya is among the most productive regions in the Southern Ocean and may constitute a significant oceanic CO2 sink. Based on results from several field studies, this region has been considered seasonally iron limited, whereby a “winter reserve” of dissolved iron (dFe) is progressively depleted during the growing season to low concentrations (∼0.1 nM) that limit phytoplankton growth in the austral summer (December–February). Here we report new iron data for the Ross Sea polynya during austral summer 2005–2006 (27 December–22 January) and the following austral spring 2006 (16 November–3 December). The summer 2005–2006 data show generally low dFe concentrations in polynya surface waters (0.10 ± 0.05 nM in upper 40 m, n = 175), consistent with previous observations. Surprisingly, our spring 2006 data reveal similar low surface dFe concentrations in the polynya (0.06 ± 0.04 nM in upper 40 m, n = 69), in association with relatively high rates of primary production (∼170–260 mmol C m−2 d−1). These results indicate that the winter reserve dFe may be consumed relatively early in the growing season, such that polynya surface waters can become “iron limited” as early as November; i.e., the seasonal depletion of dFe is not necessarily gradual. Satellite observations reveal significant biomass accumulation in the polynya during summer 2006–2007, implying significant sources of “new” dFe to surface waters during this period. Possible sources of this new dFe include episodic vertical exchange, lateral advection, aerosol input, and reductive dissolution of particulate iron.

[1] Paytan et al. (2009) argue that the atmospheric deposition of aerosols lead to copper concentrations that are potentially toxic to marine phytoplankton in a large area of tropical and subtropical North Atlantic Ocean. A key assumption in their model is that all marine aerosols (mineral dust and anthropogenic particles) have a high (40%) fractional solubility of copper. Our data show that the fractional solubility of copper for Saharan dust over the Sargasso Sea and Bermuda is significantly lower (1–7%). In contrast, anthropogenic aerosols with non-Saharan sources have significantly higher values (10–100%). Hence, the potential Cu toxicity in the tropical and subtropical North Atlantic should be re-estimated, given the low fractional solubility of Cu in the Saharan dust that dominates aerosol deposition to this region.

Hydrothermal plumes associated with nearshore lava flows from Kilauea Volcano, Hawaii were studied on five occasions during 1989–1990 to address the current lack of data on direct lava-seawater interactions. The following enrichments were found in the sea-surface hydrothermal plumes above the active underwater lava flows: H2, 15,000x ambient seawater concentrations; Mn, 250x; and Si, 20x. Water temperatures reached 46°C. Lower concentrations and temperatures were observed in the plumes with increasing distance from shore, with H2, Si, and Mn concentrations linearly related to seawater temperature. Unlike deep sea spreading center hydrothermal plumes, no CH4 enrichment was observed. The elevated H2 is likely to be from water-rock reactions, rather than from the release of magmatic gas. The plume mass/heat ratios presented here suggest that submarine flood basalts, although aerially large, should be relatively small immediate contributors to oceanic geochemical cycles compared to hydrothermal circulation through the crust.

[1] We report iron measurements for water column and aerosol samples collected in the Sargasso Sea during July-August 2003 (summer 2003) and April-May 2004 (spring 2004). Our data reveal a large seasonal change in the dissolved iron (dFe) concentration of surface waters in the Bermuda Atlantic Time-series Study region, from ∼1–2 nM in summer 2003, when aerosol iron concentrations were high (mean 10 nmol m−3), to ∼0.1–0.2 nM in spring 2004, when aerosol iron concentrations were low (mean 0.64 nmol m−3). During summer 2003, we observed an increase of ∼0.6 nM in surface water dFe concentrations over 13 days, presumably due to eolian iron input; an estimate of total iron deposition over this same period suggests an effective solubility of 3–30% for aerosol iron. Our summer 2003 water column profiles show potentially growth-limiting dFe concentrations (0.02–0.19 nM) coinciding with a deep chlorophyll maximum at 100–150 m depth, where phytoplankton biomass is typically dominated by Prochlorococcus during late summer.

Stratigraphic information concerning the retreat of the Antarctic ice sheet from the continental shelf after the Last Glacial Maximum is reviewed and compared with new results from a shelf valley off Mac. Robertson Land, East Antarctica. Radiocarbon dates and detailed lithostratigraphic logs indicate that the onset of open-marine conditions over shallow shelfbanks «200 m water depth) was achieved prior to 7000 yr BP and over deep (~l 000 m) middle to oliter shelf valleys, open-marine conditions were achieved prior to 5400 yr BP. Radiocarbon dating of bulk-organic carbon in some diatom oozes by the AMS method demonstrates problems of contamination. Jurassic pollen, spores and organic matter have been eroded and incorporated into Holocene diatom ooze, causing anomalously old 14C dates (e.g. one surface age of7084 ± 86 yr BP was determined). This problem may arise at other locations around East Antarctica where older strata outcrop on the seafloor.