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The international GEOTRACES program was developed to enhance knowledge about the distribution of trace elements and their isotopes (TEIs) in the ocean and to reduce the uncertainty about their sources, sinks, and internal cycling. Recognizing the importance of intercalibration from the outset, GEOTRACES implemented intercalibration efforts early in the program, and consensus materials were generated that included the full range of TEIs dissolved in seawater, in suspended particles, and from aerosols. The GEOTRACES section cruises include "crossover station(s)" that are occupied by two or more sections and whereby all aspects of sample collection, preservation, and processing can be compared and intercalibrated. Once data-sets are generated, an international intercalibration committee reviews intercalibration reports and works with the community to address issues and provide intercalibrated data for intermediate data products. This process has resulted in a highly cooperative community that shares advances in protocols to strengthen capacity building and GEOTRACES outcomes, including an unprecedented oceanic atlas of TEIs, with data quality that is state-of-the-art. This article outlines the development and implementation of the successful GEOTRACES intercalibration process. [ABSTRACT FROM AUTHOR]

Hydrothermal vents have emerged as an important source of iron to seawater, yet only a subset of iron is soluble and persists long enough to be available for surface biological uptake. The longevity and solubility of iron in seawater is governed by strong organic ligands, like siderophores, that are produced by marine microorganisms and are a part of the ocean's dissolved iron-binding ligand pool. These ligands have been hypothesized to aid in the persistence of dissolved iron in hydrothermal environments. To explore this hypothesis, we measured iron, iron-binding ligands, and siderophores from 11 geochemically distinct sites along a 1,700 km section of the Mid-Atlantic Ridge. Siderophores were found in hydrothermal plumes at all sites, with proximity to the vent playing an important role in dictating siderophore types and diversity. The notable presence of amphiphilic siderophores may point to microbial utilization of siderophores to access particulate hydrothermal iron, and the exchange of dissolved and particulate iron. The tight coupling between strong ligands and dissolved iron within neutrally buoyant plumes across six distinct hydrothermal environments, and the presence of dissolved siderophores with siderophore-producing microbial genera, suggests that biological production of siderophores exerts a key control on hydrothermal dissolved iron concentrations. [ABSTRACT FROM AUTHOR]

Supply of iron (Fe) to the surface ocean supports primary productivity, and while hydrothermal input of Fe to the deep ocean is known to be extensive it remains poorly constrained. Global estimates of hydrothermal Fe supply rely on using dissolved Fe (dFe) to excess He (xs3He) ratios to upscale fluxes, but observational constraints on dFe/xs3He may be sensitive to assumptions linked to sampling and interpolation. We examined the variability in dFe/xs3He using two methods of estimation, for four vent sites with different geochemistry along the Mid-Atlantic Ridge. At both Rainbow and TAG, the plume was sampled repeatedly and the range of dFe/xs3He was 4 to 63 and 4 to 87 nmol:fmol, respectively, primarily due to differences in plume age. To account for background xs3He and shifting plume position, we calibrated He values using contemporaneous dissolved Mn (dMn). Applying this approach more widely, we found dFe/xs3He ratios of 12, 4–8, 4–44, and 4–86 nmolfmol-1 for the Menez Gwen, Lucky Strike, Rainbow, and TAG hydrothermal vent sites, respectively. Differences in plume dFe/xs3He across sites were not simply related to the vent endmember Fe and He fluxes. Within 40 km of the vents, the dFe/xs3He ratios decreased to 3–38 nmolfmol-1 , due to the precipitation and subsequent settling of particulates. The ratio of colloidal Fe to dFe was consistently higher (0.67–0.97) than the deep N. Atlantic (0.5) throughout both the TAG and Rainbow plumes, indicative of Fe exchange between dissolved and particulate phases. Our comparison of TAG and Rainbow shows there is a limit to the amount of hydrothermal Fe released from vents that can form colloids in the rising plume. Higher particle loading will enhance the longevity of the Rainbow hydrothermal plume within the deep ocean assuming particles undergo continual dissolution/disaggregation. Future studies examining the length of plume pathways required to escape the ridge valley will be important in determining Fe supply from slow spreading mid-ocean ridges to the deep ocean, along with the frequency of ultramafic sites such as Rainbow. Resolving the ridge valley bathymetry and accounting for variability in vent sources in global biogeochemical models will be key to further constraining the hydrothermal Fe flux. [ABSTRACT FROM AUTHOR]

The dispersal of dissolved iron (DFe) from hydrothermal vents is poorly constrained. Combining field observations and a modeling hierarchy, we find the dispersal of DFe from the Trans‐Atlantic‐Geotraverse vent site occurs predominantly in the colloidal phase and is controlled by multiple physical processes. Enhanced mixing near the seafloor and transport through fracture zones at fine‐scales interacts with the wider ocean circulation to drive predominant westward DFe dispersal away from the Mid‐Atlantic ridge at the 100 km scale. In contrast, diapycnal mixing predominantly drives northward DFe transport within the ridge axial valley. The observed DFe dispersal is not reproduced by the coarse resolution ocean models typically used to assess ocean iron cycling due to their omission of local topography and mixing. Unless biogeochemical models account for fine‐scale physics and colloidal Fe, they will inaccurately represent DFe dispersal from axial valley ridge systems, which make up half of the global ocean ridge crest. Plain Language Summary: Hydrothermal venting along mid ocean ridges supplies large quantities of the trace metal iron to the ocean. Once it mixed with oxygenated seawater, precipitation leads to iron being lost from the dissolved phase to generate seafloor metal deposits. However, a small fraction of iron supplied escapes precipitation and remains in the dissolved phase. The processes that control the retention and ocean transport of hydrothermal dissolved iron is important as it has a disproportionate influence on the global carbon cycle. In this work, we examined the processes driving the dispersal of dissolved iron from a major site of hydrothermal venting on the northern mid Atlantic ridge. We found that the complex topography of the mid Atlantic ridge was crucial in steering the escape of dissolved iron in the colloidal size range out of the immediate mid ocean ridge system. This raises challenges for the large scale ocean models used to represent the global ocean iron cycle as they are typically not parameterized at sufficient spatial resolution. The use of multiple grids, with higher resolution nests, may offer a solution to the challenge of representing the interactions of tracer dispersal with complex topography. Key Points: Iron is dispersed from trans Atlantic geotraverse predominantly northward within the axial valley and westward off axis, dominated by the colloidal size fractionA combination of fine‐scale processes are necessary to explain the dispersal both within and outside the axial valleyCoarse resolution models are impaired in their ability to constrain the broader influence of iron supplied from axial valley ridge systems [ABSTRACT FROM AUTHOR]

Nano‐ and picophytoplankton are a major component of open‐ocean ecosystems and one of the main plankton functional types in biogeochemical models, yet little is known about their trace metal contents. In cultures of the picoeukaryote Ostreococcus lucimarinus, iron limitation reduced iron quotas by 68%, a fraction of the plasticity known in diatoms. In contrast, a commonly co‐occurring cyanobacterium, Prochlorococcus, showed variable iron contents with iron availability in culture. Synchrotron X‐ray fluorescence was used to measure single‐cell metal (Mn, Fe, Co, Ni, Zn) quotas of autotrophic flagellates (1.4–16.8‐μm diameter) collected from four ocean regions. Iron quotas were tightly constrained and showed little response to iron availability, similar to cultured Ostreococcus. Zinc quotas also did not vary with zinc availability but appeared to vary with phosphorus availability. These results suggest that macronutrient and metal availability may be equally important for controlling metal contents of small eukaryotic open‐ocean phytoplankton. [ABSTRACT FROM AUTHOR]

Supply of iron (Fe) to the surface ocean supports primary productivity and while hydrothermal input of Fe to the deep ocean is known to be extensive, it remains poorly constrained. Global estimates of hydrothermal Fe supply rely on using the dissolved Fe (dFe) to excess He (xs³ He) ratios to upscale fluxes, but observational constraints on dFe/xs³ He may be sensitive to assumptions linked to sampling and interpolation. We examined the variability in dFe/xs³ He using two methods of estimation, for four vent sites with different geochemistry along the Mid-Atlantic Ridge. At both Rainbow and TAG, the plume was sampled repeatedly and the range of dFe/xs3 He was 4 to 63 and 4 to 87 nmol/fmol, respectively, primarily due to differences in plume age. To account for background xs³ He and shifting plume position, we calibrated He values using contemporaneous dissolved Mn (dMn). Applying this approach more widely, we found dFe/xs³ He ratios of 12, 4-8, 4-44, 4-86 nmol/fmol for the Menez Gwen, Lucky Strike, Rainbow and TAG hydrothermal vent sites, respectively. Differences in plume dFe/xs3 He across sites were not simply related to the vent end member Fe and He fluxes. Within 40 km of the vents, the dFe/xs³ He ratios decreased to 3-38 nmol/fmol, due to the precipitation and subsequent settling of particulates. The ratio of colloidal Fe to dFe was consistently higher (0.67-0.97) than the deep N. Atlantic (0.5) throughout both the TAG and Rainbow plumes, indicative of Fe exchange between dissolved and particulate phases. Our comparison of TAG and Rainbow shows there is a limit to the amount of hydrothermal Fe released from vents that can form colloids in the rising plume. Higher particle loading will enhance the longevity of the Rainbow hydrothermal plume within the deep ocean assuming particles undergo continual dissolution/disaggregation. Future studies examining the length of plume pathways required to escape the ridge valley will be important in determining Fe supply from slow spreading mid-ocean ridges to the deep ocean, along with the frequency of ultramafic sites such as Rainbow. Resolving the ridge valley bathymetry and accounting for variability in vent sources in global biogeochemical models will be key to further constraining the hydrothermal Fe flux. [ABSTRACT FROM AUTHOR]

We report the distributions and stoichiometry of dissolved zinc (dZn) and cobalt (dCo) in sub-tropical and sub-Antarctic waters of the south-eastern Atlantic Ocean during austral spring 2010 and summer 2011/2012. In sub-tropical surface waters, mixed-layer dZn and dCo concentrations during early spring were 1.60 ± 2.58 nM and 30 ± 11 pM, respectively, compared with summer values of 0.14 ± 0.08 nM and 24 ± 6 pM. The elevated spring dZn concentrations resulted from an apparent offshore transport of elevated dZn at depths between 20–55 m, derived from the Agulhas Bank. In contrast, open-ocean sub-Antarctic surface waters displayed largely consistent inter-seasonal mixed-layer dZn and dCo concentrations of 0.10 ± 0.07 nM and 11 ± 5 pM, respectively. Trace metal stoichiometry, calculated from concentration inventories, suggests a greater overall removal for dZn relative to dCo in the upper water column of the south-eastern Atlantic, with inter-seasonally decreasing dZn / dCo inventory ratios of 19–5 and 13–7 mol mol -1 for sub-tropical surface water and sub-Antarctic surface water, respectively. In this paper, we investigate how the seasonal influences of external input and phytoplankton succession may relate to the distribution of dZn and dCo and variation in dZn / dCo stoichiometry across these two distinct ecological regimes in the south-eastern Atlantic. [ABSTRACT FROM AUTHOR]

New dissolved aluminum (dAl) data from the 2017 GEOTRACES process study GApr08 along 22°N in the subtropical North Atlantic are presented. They show an east to west increase in dAl concentration in the surface waters. Simulation of these data with a 1D advection‐dust deposition revealed that, (a) advection and dust dissolution are equally important dAl sources, (b) scavenging plays a minor role compared to advection in dAl removal, and (c) in addition to dust dissolution, another dAl source is required at the westernmost stations to fully explain our observations. We attribute this additional source to the dissolution of erosion products delivered to the western subtropical North Atlantic by the Lesser Antilles. For waters deeper than ∼200–300 m, an optimum multi‐parameter analysis allowed to separate the component of the dAl signal derived from water mass transport from its biogeochemical component. This revealed, (a) a major role played by water mass transport, (b) a net dAl removal between 200 and 800 m, attributed to scavenging at the subtropical North Atlantic scale, and (c) internal dAl inputs between 800 m and the seafloor, attributed to reversible scavenging. While the dAl oceanic distribution is usually considered to be dominated by the atmospheric dust input and removal by particle scavenging, this study highlights the important role played by advection, and the need to explicitly take this into account in order to quantitatively reveal the impact of external sources and dissolved‐particulate interactions on the Al cycle in the North Atlantic Ocean. Key Points: Advection and dust deposition are the main processes driving the surface gradient of dissolved aluminum in the subtropical North AtlanticLesser Antilles erosion products are a possible source of dissolved aluminum to the western subtropical North AtlanticDissolved‐particle interactions play a major role in the dissolved aluminum distribution in the subtropical North Atlantic [ABSTRACT FROM AUTHOR]

Trace elements (TEs) play important roles as micronutrients in modulating marine productivity in the global ocean. The South Atlantic around 40 ∘ S is a prominent region of high productivity and a transition zone between the nitrate-depleted subtropical gyre and the iron-limited Southern Ocean. However, the sources and fluxes of trace elements to this region remain unclear. In this study, the distribution of the naturally occurring radioisotope 228 Ra in the water column of the South Atlantic (Cape Basin and Argentine Basin) has been investigated along a 40 ∘ S zonal transect to estimate ocean mixing and trace element supply to the surface ocean. Ra-228 profiles have been used to determine the horizontal and vertical mixing rates in the near-surface open ocean. In the Argentine Basin, horizontal mixing from the continental shelf to the open ocean shows an eddy diffusion of Kx=1.8±1.4 (10 6 cm 2 s -1) and an integrated advection velocity w=0.6±0.3 cm s -1. In the Cape Basin, horizontal mixing is Kx=2.7±0.8 (10 7 cm 2 s -1) and vertical mixing Kz = 1.0–1.7 cm 2 s -1 in the upper 600 m layer. Three different approaches (228 Ra diffusion, 228 Ra advection, and 228Ra/TE ratio) have been applied to estimate the dissolved trace element fluxes from the shelf to the open ocean. These approaches bracket the possible range of off-shelf fluxes from the Argentine Basin margin to be 4–21 (×103) nmol Co m -2 d -1 , 8–19 (×104) nmol Fe m -2 d -1 and 2.7–6.3 (×104) nmol Zn m -2 d -1. Off-shelf fluxes from the Cape Basin margin are 4.3–6.2 (×103) nmol Co m -2 d -1 , 1.2–3.1 (×104) nmol Fe m -2 d -1 , and 0.9–1.2 (×104) nmol Zn m -2 d -1. On average, at 40 ∘ S in the Atlantic, vertical mixing supplies 0.1–1.2 nmol Co m -2 d -1 , 6–9 nmol Fe m -2 d -1 , and 5–7 nmol Zn m -2 d -1 to the euphotic zone. Compared with atmospheric dust and continental shelf inputs, vertical mixing is a more important source for supplying dissolved trace elements to the surface 40 ∘ S Atlantic transect. It is insufficient, however, to provide the trace elements removed by biological uptake, particularly for Fe. Other inputs (e.g. particulate or from winter deep mixing) are required to balance the trace element budgets in this region. [ABSTRACT FROM AUTHOR]

Trace elements play important roles as micronutrients in modulating marine productivity in the global ocean. The South Atlantic around 40°S is a prominent region of high productivity and a transition zone between the nitrate-depleted Subtropical Gyre and the iron-limited Southern Ocean. However, the sources and fluxes of trace elements to this region remain unclear. In this study, the distribution of the naturally occurring radioisotope 228Ra in the water column of the South Atlantic (Cape Basin and Argentine Basin) has been investigated along a 40°S zonal transect to estimate ocean mixing and trace element supply to the surface ocean. Ra-228 profiles have been used to determine the horizontal and vertical mixing rates in the near-surface open ocean. In the Argentine Basin, horizontal mixing from the continental shelf to the open ocean shows an eddy diffusion of Kx = 1.7 ± 1.4 (106 cm² s-1) and an integrated advection velocity w = 0.6 ± 0.3 cm s-1. In the Cape Basin, horizontal mixing is Kx = 2.7 ± 0.8 (107 cm² s-1) and vertical mixing Kz = 1.0 - 1.5 cm² s-1 in the upper 600 m layer. Three different approaches (228Ra-diffusion, 228Ra-advection and 228Ra/TE-ratio) have been applied to estimate the dissolved trace-element fluxes from shelf to open ocean. These approaches bracket the possible range of off-shelf fluxes from the Argentine margin to be: 3.8 - 22 (x10³) nmol Co m-2 d-1, 7.9 - 20 (x104) nmol Fe m-2 d-1 and 2.7 - 6.5 (x104) nmol Zn m-2 d-1. Off-shelf fluxes from the Cape margin are: 4.3 - 6.2 (x10³) nmol Co m-2 d-1, 1.2 - 3.1 (x104) nmol Fe m-2 d-1 and 0.9 - 1.2 (x104) nmol Zn m-2 d-1. On average, at 40°S in the Atlantic, vertical mixing supplies 0.4 - 1.2 nmol Co m-2 d-1, 3.6 - 11 nmol Fe m-2 d-1, and 13 - 16 nmol Zn m-2 d-1 to the euphotic zone. Compared with atmospheric dust and continental shelf inputs, vertical mixing is a more important source for supplying dissolved trace elements to the surface 40°S Atlantic. It is insufficient, however, to provide the trace elements removed by biological uptake. Other inputs (e.g. particulate, or from [ABSTRACT FROM AUTHOR]

Continental margins are disproportionally important for global primary production, fisheries and CO2 uptake. However, across the Northeast Atlantic shelves, there has been an ongoing summertime decline of key biota—large diatoms, dinoflagellates and copepods—that traditionally fuel higher tropic levels such as fish, sea birds and marine mammals. Here, we combine multiple time series with in situ process studies to link these declines to summer nutrient stress and increasing proportions of picophytoplankton that can comprise up to 90% of the combined pico‐ and nanophytoplankton biomass in coastal areas. Among the pico‐fraction, it is the cyanobacterium Synechococcus that flourishes when iron and nitrogen resupply to surface waters are diminished. Our field data show how traits beyond small size give Synechococcus a competitive edge over pico‐ and nanoeukaryotes. Key is their ability to grow at low irradiances near the nutricline, which is aided by their superior light‐harvesting system and high affinity to iron. However, minute size and lack of essential biomolecules (e.g. omega‐3 polyunsaturated fatty acids and sterols) render Synechococcus poor primary producers to sustain shelf sea food webs efficiently. The combination of earlier spring blooms and lower summer food quantity and quality creates an increasing period of suboptimal feeding conditions for zooplankton at a time of year when their metabolic demand is highest. We suggest that this nutrition‐related mismatch has contributed to the widespread, ~50% decline in summer copepod abundance we observe over the last 60 years. With Synechococcus clades being prominent from the tropics to the Arctic and their abundances increasing worldwide, our study informs projections of future food web dynamics in coastal and shelf areas where droughts and stratification lead to increasing nutrient starvation of surface waters. [ABSTRACT FROM AUTHOR]

Trichodesmium is a globally important marine microbe that provides fixed nitrogen (N) to otherwise N-limited ecosystems. In nature, nitrogen fixation is likely regulated by iron or phosphate availability, but the extent and interaction of these controls are unclear. From metaproteomics analyses using established protein biomarkers for nutrient stress, we found that iron–phosphate co-stress is the norm rather than the exception for Trichodesmium colonies in the North Atlantic Ocean. Counterintuitively, the nitrogenase enzyme was more abundant under co-stress as opposed to single nutrient stress. This is consistent with the idea that Trichodesmium has a specific physiological state during nutrient co-stress. Organic nitrogen uptake was observed and occurred simultaneously with nitrogen fixation. The quantification of the phosphate ABC transporter PstA combined with a cellular model of nutrient uptake suggested that Trichodesmium is generally confronted by the biophysical limits of membrane space and diffusion rates for iron and phosphate acquisition in the field. Colony formation may benefit nutrient acquisition from particulate and organic sources, alleviating these pressures. The results highlight that to predict the behavior of Trichodesmium , both Fe and P stress must be evaluated simultaneously. [ABSTRACT FROM AUTHOR]

We report the distributions of dissolved zinc (dZn) and cobalt (dCo) in sub-tropical and sub-Antarctic waters of the Southeast Atlantic Ocean during austral spring 2010 and summer 2011/12. A strong seasonal signal was observed in sub-tropical surface waters with early spring mixed-layer dZn and dCo concentrations of 3.16 ± 1.35 nM and 39 ± 9 pM, respectively, compared with summer values depleted well below these levels by biological activity. The elevated spring mixed-layer dZn concentrations resulted from an apparent offshore transport of elevated dZn at depths between 20-50 m, derived from lithogenic inputs from the Agulhas Bank. In contrast, open-ocean sub-Antarctic surface waters displayed largely consistent inter-seasonal mixed-layer dZn and dCo concentrations of 0.11 ± 0.08 nM and 11 ± 5 pM, respectively. The vertical distributions of dZn and dCo in the upper water column were similar to that of phosphate (PO43-), with positive linear relationships during each of the seasons and across dynamic biogeochemical regimes, suggesting surface biological drawdown and shallow remineralisation of these metals in this region largely influences their distribution. The ecological stoichiometries for dZn and dCo, calculated from the linear regression with PO43-, suggest a greater overall use of dZn relative to dCo in the upper water column of the Southeast Atlantic with an inter-seasonal Zn:Co ratio ranging between 9 and 29. Sub-tropical surface water Zn:Co ratios were found to decrease between spring and summer indicating a preferential removal of dZn relative to dCo between seasons. In this paper we investigate how the seasonal influences of external input and phytoplankton succession may relate to the distribution of dZn and dCo, and variation in Zn:Co ecological stoichiometry, across two distinct ecological regimes in the Southeast Atlantic. [ABSTRACT FROM AUTHOR]

In the past decade, several international efforts developed to address urgent societal issues have been identified through, for example, the United Nations 2030 Agenda for Sustainable Development and its associated 17 Sustainable Development Goals and the United Nations Decade of Ocean Science for Sustainable Development (2021-2030). These worthy efforts will bring ocean science research to bear on problems that need attention in the short term. Yet, there is also a continuing need at the international level to support fundamental ocean science and solve methodological issues over the long term. While knowledge needs to be created before it can be applied, national and international science strategy documents often do not mention the need to maintain the health of the basic science enterprise. We argue that international organizations designed to create knowledge must be maintained and strengthened to inform decisions on how to allocate funding for generating knowledge about the ocean versus solving ocean problems. We use the ocean iron cycle as an example of the benefits of using such a "bottom-up" approach to knowledge generation. [ABSTRACT FROM AUTHOR]

Trichodesmium is a globally important marine microbe that provides fixed nitrogen to otherwise N limited ecosystems. In nature, nitrogen fixation is likely regulated by iron or phosphate availability, but the extent and interaction of these controls is unclear. From metaproteomics analyses using established protein biomarkers for iron and phosphate stress, we found that co-stress is the norm rather than the exception for field Trichodesmium colonies. Counter-intuitively, the nitrogenase enzyme was most abundant under co-stress, consistent with the idea that Trichodesmium has a specific physiological state under nutrient co-stress. Organic nitrogen uptake was observed to occur simultaneously with nitrogen fixation. Quantification of the phosphate ABC transporter PstC combined with a cellular model of nutrient uptake suggested that Trichodesmium is confronted by the biophysical limits of membrane space and diffusion rates for iron and phosphate acquisition. Colony formation may benefit nutrient acquisition from particulate and organic nutrient sources, alleviating these pressures. The results indicate that to predict the behavior of Trichodesmium, we must consider multiple nutrients simultaneously across biogeochemical contexts. [ABSTRACT FROM AUTHOR]

Our study followed the seasonal cycling of soluble (SFe), colloidal (CFe), dissolved (DFe), total dissolvable (TDFe), labile particulate (LPFe), and total particulate (TPFe) iron in the Celtic Sea (NE Atlantic Ocean). Preferential uptake of SFe occurred during the spring bloom, preceding the removal of CFe. Uptake and export of Fe during the spring bloom, coupled with a reduction in vertical exchange, led to Fe deplete surface waters (<0.2 nM DFe; 0.11 nM LPFe, 0.45 nM TDFe, and 1.84 nM TPFe) during summer stratification. Below the seasonal thermocline, DFe concentrations increased from spring to autumn, mirroring NO3− and consistent with supply from remineralized sinking organic material, and cycled independently of particulate Fe over seasonal timescales. These results demonstrate that summer Fe availability is comparable to the seasonally Fe limited Ross Sea shelf and therefore is likely low enough to affect phytoplankton growth and species composition. [ABSTRACT FROM AUTHOR]

Continental shelves and shelf seas play a central role in the global carbon cycle. However, their importance with respect to trace element and isotope (TEI) inputs to ocean basins is less well understood. Here, we present major findings on shelf TEI biogeochemistry from the GEOTRACES programme as well as a proof of concept for a new method to estimate shelf TEI fluxes. The case studies focus on advances in our understanding of TEI cycling in the Arctic, transformations within a major river estuary (Amazon), shelf sediment micronutrient fluxes and basin-scale estimates of submarine groundwater discharge. The proposed shelf flux tracer is 228-radium (T1/2 =5.75 yr), which is continuously supplied to the shelf from coastal aquifers, sediment porewater exchange and rivers. Model-derived shelf 228Ra fluxes are combined with TEI/228Ra ratios to quantify ocean TEI fluxes from the western North Atlantic margin. The results from this new approach agree well with previous estimates for shelf Co, Fe, Mn and Zn inputs and exceed published estimates of atmospheric deposition by factors of approximately 3-23. Lastly, recommendations are made for additional GEOTRACES process studies and coastal margin-focused section cruises that will help refine the model and provide better insight on the mechanisms driving shelf-derived TEI fluxes to the ocean. [ABSTRACT FROM AUTHOR]

This work assesses the components contributing to the combined uncertainty budget associated with the measurement of the Fe amount content by flow injection chemiluminescence (FI-CL) in<0.2 lm filtered and acidified seawater samples. Amounts of loaded standard solutions and samples were determined gravimetrically by differential weighing. Up to 5% variations in the loaded masses were observed during measurements, in contradiction to the usual assumptions made when operating under constant loading time conditions. Hence signal intensities (V) were normalised to the loaded mass and plots of average normalised intensities (in V kg-1) vs. values of the Fe amount content (in nmol kg-1) added to a "low level" iron seawater matrix were used to produce the calibration graphs. The measurement procedure implemented and the uncertainty estimation process developed were validated from the agreement obtained with consensus values for three SAFe and GEOTRACES reference materials (D2, GS, and GD). Relative expanded uncertainties for peak height and peak area based results were estimated to be around 12% and 10% (coverage factor k=2), respectively. The most important contributory factors were the uncertainty on the sensitivity coefficient (i.e., calibration slope) and the within-sequence-stability (i.e., the signal stability over several hours of operation; here 32 h). For GD, using peak height measurements, these factors contributed respectively 69.7% and 21.6% while the short-term repeatability accounted for only 7.9%. Therefore, an uncertainty estimation based on the intensity repeatability alone, as is often done in FI-CL studies, is not a realistic estimation of the overall uncertainty of the procedure. [ABSTRACT FROM AUTHOR]

The supply and bioavailability of dissolved iron sets the magnitude of surface productivity for ∼40% of the global ocean. The redox state, organic complexation, and phase (dissolved versus particulate) of iron are key determinants of iron bioavailability in the marine realm, although the mechanisms facilitating exchange between iron species (inorganic and organic) and phases are poorly constrained. Here we use the isotope fingerprint of dissolved and particulate iron to reveal distinct isotopic signatures for biological uptake of iron during a GEOTRACES process study focused on a temperate spring phytoplankton bloom in subtropical waters. At the onset of the bloom, dissolved iron within the mixed layer was isotopically light relative to particulate iron. The isotopically light dissolved iron pool likely results from the reduction of particulate iron via photochemical and (to a lesser extent) biologically mediated reduction processes. As the bloom develops, dissolved iron within the surface mixed layer becomes isotopically heavy, reflecting the dominance of biological processing of iron as it is removed from solution, while scavenging appears to play a minor role. As stable isotopes have shown for major elements like nitrogen, iron isotopes offer a new window into our understanding of the biogeochemical cycling of iron, thereby allowing us to disentangle a suite of concurrent biotic and abiotic transformations of this key biolimiting element. [ABSTRACT FROM AUTHOR]

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 n M) most of the aerosol-derived colloidal Fe was converted to soluble Fe (<0.02 µm). This finding highlights the potential importance of organic ligands in retaining aerosol Fe in a biologically available form in the surface ocean. [ABSTRACT FROM AUTHOR]

Inorganic nitrogen depletion restricts productivity in much of the low-latitude oceans, generating a selective advantage for diazotrophic organisms capable of fixing atmospheric dinitrogen (N2). However, the abundance and activity of diazotrophs can in turn be controlled by the availability of other potentially limiting nutrients, including phosphorus (P) and iron (Fe). Here we present high-resolution data (~0.3°) for dissolved iron, aluminum, and inorganic phosphorus that confirm the existence of a sharp north-south biogeochemical boundary in the surface nutrient concentrations of the (sub)tropical Atlantic Ocean. Combining satellite-based precipitation data with results from a previous study, we here demonstrate that wet deposition in the region of the intertropical convergence zone acts as the major dissolved iron source to surface waters. Moreover, corresponding observations of N2 fixation and the distribution of diazotrophic Trichodesmium spp. indicate that movement in the region of elevated dissolved iron as a result of the seasonal migration of the intertropical convergence zone drives a shift in the latitudinal distribution of diazotrophy and corresponding dissolved inorganic phosphorus depletion. These conclusions are consistent with the results of an idealized numerical model of the system. The boundary between the distinct biogeochemical systems of the (sub)tropical Atlantic thus appears to be defined by the diazotrophic response to spatial-temporal variability in external Fe inputs. Consequently, in addition to demonstrating a unique seasonal cycle forced by atmospheric nutrient inputs, we suggest that the underlying biogeochemical mechanisms would likely characterize the response of oligotrophic systems to altered environmental forcing over longer timescales. [ABSTRACT FROM AUTHOR]

Iron zinc-enrichment experiments were carried out at Ocean Station Papa in the subarctic North Pacific. In iron-enriched treatments, phytoplankton chlorophyll a (Chl a) increased 20-fold (9.7 µg L-1) above the concentration on day zero. No stimulation of Chl a production or nitrate drawdown was observed on addition of zinc alone compared to the control. In the iron-enriched treatment, bioavailable zinc concentration decreased to 0.2 pmol L-1 lower than that which is known in culture experiments to limit some phytoplankton growth. Theoretical analyses suggest that this zinc concentration would cause diffusion-limited growth of large diatom cells present at the end of the incubation. Direct measurements of zinc-binding ligands indicate that the natural microbial planktonic assemblages have the ability to respond rapidly to conditions of high dissolved zinc concentrations. Rapid ligand production may be a mechanism by which certain phytoplankton reduce zinc toxicity or for maintaining zinc concentrations in the upper water column. Zinc-binding ligands were observed to be both produced and removed on the timescale of 1 d. We suggest that these zinc-binding ligands are produced to assist assimilation, particularly under iron-enriched conditions when concentrations of bioavailable zinc were extremely low, thereby alleviating the effects of zinc limitation. [ABSTRACT FROM AUTHOR]

The concentrations of Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn were measured in several soft-tissue types of the Antarctic soft-shelled clam, Laternula elliptica, which had been collected from Rothera Research Station, Adelaide Island, Antarctic Peninsula. Concentrations of Mn, Ni, Cr and Pb were significantly higher in the kidney than in any other soft tissue and highest concentrations of Cu were observed in the digestive gland. In general, the total tissue concentrations of heavy metals in L. elliptica were considered to be at baseline levels, except for Cu in organisms near the end of the runway. Copper concentrations were an order of magnitude greater (357 µg/g dry weight) than baseline levels, suggesting anthropogenic contamination or an unidentified natural source. However, there was no indication of anthropogenic metal contamination occurring close to the sewage outfall at Rothera, which is a significant metal source. The results indicate that L. elliptica is a useful long-term biomonitor of heavy metal contamination in Antarctic coastal waters. [ABSTRACT FROM AUTHOR]

In the northern Gulf of Alaska, mesoscale, anticyclonic eddies have been implicated as a mechanism of the cross-shelf exchange of iron (Fe)-replete coastal waters with Fe-deplete subarctic Alaskan gyre waters. Based on existing hydrography and macronutrient distributions, a Sitka eddy sampled during August 2007 is divided into a surface eddy core, a shallow subsurface eddy core, and a deeper subsurface eddy core. The distributions of aluminum (Al), manganese (Mn), and Fe in the eddy are examined and compared to distributions at shelf stations similar to where the eddy formed as well as basin stations representative of the Fe-limited subarctic Alaskan gyre. Relative to basin stations, dissolved and particulate Al and dissolved Mn were elevated in eddy core waters. Reactive Fe concentrations within the shallow subsurface eddy core were nearly seven times greater than reactive Fe concentrations at similar densities at the basin stations. This shallow subsurface eddy core is likely mixed into the euphotic zone during storm-induced mixing as well as mixing during isopycnal relaxation as an eddy dies out. The flux of reactive Fe to surface waters from the shallow subsurface core of eddies in the Gulf of Alaska is a significant source compared to both remote and local atmospheric dust deposition. It is hypothesized that Fe supply from eddies in the eastern Gulf of Alaska shifts the core of the high-nutrient, lower-than-expected chlorophyll water farther west in conjunction with an "eddy desert" in that same region. [ABSTRACT FROM AUTHOR]

Primary production in the Ross Sea, one of the most productive areas in the Southern Ocean, has previously been shown to be seasonally limited by iron. In two of three bottle incubation experiments conducted in the austral summer, significantly higher chlorophyll a (Chl a) concentrations were measured upon the addition of iron and B12, relative to iron additions alone. Initial bacterial abundances were significantly lower in the two experiments that showed phytoplankton stimulation upon addition of B12 and iron relative to the experiment that did not show this stimulation. This is consistent with the hypothesis that the bacteria and archaea in the upper water column are an important source of B12 to marine phytoplankton. The addition of iron alone increased the growth of Phaeocystis antarctica relative to diatoms, whereas in an experiment where iron and B12 stimulated total phytoplankton growth, the diatom Pseudonitzschia subcurvata went from comprising approximately 70% of the phytoplankton community to over 90%. Cobalt additions, with and without iron, did not alter Chl a biomass relative to controls and iron additions alone in the Ross Sea. Iron and vitamin B12 plus iron treatments caused reductions in the DMSP (dimethyl sulfoniopropionate) : Chl a ratio relative to the control and B12 treatments, consistent with the notion of an antioxidant function for DMSP. These results demonstrate the importance of a vitamin to phytoplankton growth and community composition in the marine environment. [ABSTRACT FROM AUTHOR]