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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]

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]

The ocean region along the latitude of 40°S in the South Atlantic, characterized by enhanced primary productivity, forms a transition zone between the nutrient replete but iron depleted Southern Ocean, and the nitrate and iron depleted Subtropical Gyre. Here, we present distributions of nutrient-type dissolved and particulate trace metals (dTMs and pTMs) including cadmium (Cd), nickel (Ni), copper (Cu), and zinc (Zn) in the South Atlantic from the GEOTRACES GA10 cruises. Phytoplankton uptake, riverine and atmospheric inputs shaped dTM and pTM concentrations in surface waters (dCd 27.8 ± 36.0 pmol kg−1, n = 222; dCu 0.732 ± 0.429 nmol kg−1, n = 222; dNi 3.38 ± 0.52 nmol kg−1, n = 219; dZn 0.332 ± 0.398 nmol kg−1, n = 214). Subsurface nutrients and dTMs (dCd 563 ± 184 pmol kg−1, n = 335; dCu 1.819 ± 0.773 nmol kg−1, n = 334; dNi 6.19 ± 1.06 nmol kg−1, n = 330; dZn 3.71 ± 2.10 nmol kg−1, n = 333) were controlled by the mixing of Antarctic origin waters and North Atlantic Deep Waters (NADW) with negligible contributions from local remineralization. Dissolved and particulate TMs in the Argentine Basin showed elevated concentrations towards the seafloor because of benthic inputs. Direct hydrothermal inputs of dTMs and pTMs to deep waters were not observed along the transect. The Cd-Cu-Zn-phosphate stoichiometries of Antarctic origin waters were set by a combination of dynamic physical circulation and preferential uptake of Cd, Cu, and Zn relative to phosphate in surface waters because of a dominance by diatoms in the Southern Ocean. Water mass mixing subsequently produced convoluted dCu-P and dZn-P relationships and apparent linear dCd-P and dNi-P relationships in the South Atlantic. More importantly, endmember characteristics of Antarctic waters and NADW are largely fixed in their formation regions in high latitude oceans. Therefore, the highly dynamic high latitude oceans are key regions that supply nutrients and TMs at specific ratios to low latitude oceans via the thermohaline circulation. Changes to processes in the high latitude oceans may have consequences for marine primary productivity downstream, and hence the global carbon cycle. [ABSTRACT FROM AUTHOR]

Abstract High quality observational data with a firm uncertainty assessment are essential for the proper validation of biogeochemical models for trace metals such as iron. Typically, concentrations of these metals are very low in oceanic waters (nM and sub nM) and ICP-MS is therefore a favoured technique for quantitative analysis. Uncertainties in the measurement step are generally well constrained, even at sub-nM concentrations. However, the measurement step is only part of the overall procedure. For the determination of trace metal solubilities from aerosols in the surface ocean, aerosol collection on a filter paper followed by a leaching procedure is likely to make a significant contribution to the overall uncertainty. This paper quantifies the uncertainties for key trace metals (cobalt, iron, lead and vanadium), together with aluminium as a reference element, for a controlled, flow through laboratory leaching procedure using filters collected from three different sampling sites (Tudor Hill (Bermuda), Heraklion (Crete) and Tel-Shikmona (Israel)) and water, glucuronic acid and desferrioxamine B as leachants. Relative expanded uncertainties were in the range of 12–29% for cobalt, 12–62% for iron, 13–45% for lead and 5–11% for vanadium. Fractional solubilities for iron ranged from 0.2 ± 0.1% to 16.9 ± 3.5%. Graphical abstract fx1 Highlights • Protocol for the leaching of aerosol filters for the determination of metals. • Aerosol samples from three different locations (Tudor Hill (Bermuda), Heraklion (Crete) and Tel-Shikmona (Israel). • Three contrasting leachants used (water, desferrioxamine B and glucuronic acid). • The relative expanded uncertainty for the total amount of each metal leached from a filter paper was 7% or better. • Sufficient replication essential to achieve acceptable relative expanded uncertainty. [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]

Trace metals (TMs) manganese (Mn), cobalt (Co), and aluminium (Al) have important geochemical and biological roles in the ocean. Here, we present full depth profiles of dissolved (d) and particulate Al, Mn, and Co along the latitude of 40 °S in the South Atlantic Ocean from the GEOTRACES GA10 cruises that operated in austral spring 2010 and summer 2011. The region is characterized by enhanced primary productivity and forms a key transition zone between the Southern Ocean and South Atlantic Subtropical Gyre. The mean concentrations of dAl, dCo, and dMn (±standard deviation) were 3.36 ± 2.65 nmol kg−1, 35.3 ± 17.6 pmol kg−1, and 0.624 ± 1.08 nmol kg−1, respectively. Their distributions in surface waters were determined by external sources and complex internal biogeochemical processes. Specifically, surface ocean dCo was controlled by the interplay between phytoplankton uptake, remineralization and external inputs; dMn was likely determined by the formation and photoreduction of Mn-oxides; and dAl was supplied by atmospheric deposition and removed by scavenging onto particles. Fluvial and sedimentary inputs near the Rio de La Plata estuary and benthic sources from the Agulhas Bank resulted in elevated dTM concentrations in near-shore surface waters. These externally sourced dTMs were effectively delivered to the open ocean by offshore diffusion and/or advection, and potentially facilitated enhanced primary productivity along the transect. The distributions of dTMs at depth were predominantly controlled by the mixing of North Atlantic Deep Water (NADW) and waters of Antarctic origin (e.g., Upper Circumpolar Water (UCDW) and Antarctic Bottom Water (AABW)). The calculated endmember concentrations of dAl and dCo in NADW showed minor decreases in the SASTG following north–south transport, suggesting removal rates of 0.064 nM/year and 0.035–0.075 pM/year, respectively. The endmember concentration of dCo in AABW was maintained at ∼30 pmol kg−1 without evidence for scavenging removal in the Southern Ocean and SASTG (time frame >400 years). The concentrations of dMn in NADW and AABW were between 0.1 and 0.16 nmol kg−1, and any elevated dMn concentrations were ascribed to local external inputs (e.g., from sediments in the Argentine Basin and hydrothermal activity near the Mid-Atlantic Ridge). Hence, four controlling factors (sources, internal cycling, water mass mixing and time) need to be considered when assessing TM distributions in the global ocean, even for TMs that are vulnerable to scavenging removal processes. Because the deep waters formed in high latitude oceans are crucial components of the global thermohaline overturning system, any processes (e.g., glacier melting, upwelling and sinking, and biological activity) that impact the preformed dTM concentrations in high latitude oceans will determine the downstream dTM distributions. Therefore, the sources and sinks of TMs and associated biological activity in high latitude oceans could engender basin to global scale impacts on seawater distributions of Al, Co, and Mn and their stoichiometric relationships with macronutrients, and the global biogeochemical cycles of these scavenged-type TMs. [ABSTRACT FROM AUTHOR]

The Southern Ocean is the largest high nutrient low chlorophyll (HNLC) oceanic region, where iron limits phytoplankton growth and productivity and ultimately influences the Biological Carbon Pump (BCP). Natural exceptions to the HNLC regime occur where island wakes cause iron to be mixed into surface waters from sediments, enabling large, prolonged phytoplankton blooms and increased carbon drawdown. Interactions between iron and phytoplankton are reciprocal in blooms: with plankton regulating the (re)cycling of iron through cellular uptake and remineralisation. The depth of iron remineralisation then influences either re-supply to the surface mixed layer biota or sequestration into deeper waters. Water column trace metal observations and shipboard experiments, using bioassays and radioisotope (55Fe, 32Si, 14C) cycling, were undertaken to investigate surface mixed layer phytoplankton iron limitation, iron uptake, and mesopelagic iron remineralisation relative to carbon and silica within the November 2017 bloom downstream of South Georgia. Surface phytoplankton residing in the iron depleted mixed layer were iron limited throughout the four-week sampling period. Experiments designed to investigate particulate water column (re)cycling revealed limited iron remineralisation from freshly produced upper ocean particles. The main pathway of iron transfer from particulates into the dissolved phase was through rapid (<2 d) release of extra-cellular adsorbed iron, which, if occurring in situ , could contribute to observed higher sub-surface dissolved Fe concentrations. This was accompanied by a small loss of cellular carbon, likely through respiration of the fixed 14C, and limited dissolution of particulate 32Si to dissolved 32Si. Decoupling of the remineralisation length scales for Fe, C and Si, with Fe having the fastest turnover, is thus likely in the upper mesopelagic zone beneath the bloom. • Sinking diatom cells are viable in the upper mesopelagic, resisting remineralisation by microbial degradation. • Abiotic release of extracellular Fe, retention of bSiO 2 and respiration of C decouples the remineralisation length scales. • Abiotic release of extracellular Fe could be taken up to replenish cellular Fe or mixed to the surface to prolong a bloom. [ABSTRACT FROM AUTHOR]

Dissolved (<0.2 μm) trace metals (dTMs) including iron (Fe), manganese (Mn), and cobalt (Co) are micronutrients that (co-) limit phytoplankton growth in many ocean regions. Here, we present the spatial and seasonal distributions of dFe, dMn, and dCo on the Northeast Atlantic continental margin (Celtic Sea), along a transect across the shelf and two off-shelf transects along a canyon and a spur. Waters on the continental shelf showed much higher dTM concentrations (dFe 0.07–6.50 nmol L−1, average 1.41 ± 0.96 nmol L−1, n = 138; dMn 0.868–14.8 nmol L−1, 2.75 ± 2.37 nmol L−1, n = 148; dCo 54.8–217 pmol L−1, 109 ± 32 pmol L−1, n = 144) than on the slope (dFe 0.03–1.90 nmol L−1, 0.65 ± 0.43 nmol L−1, n = 454; dMn 0.223–1.14 nmol L−1, 0.58 ± 0.20 nmol L−1, n = 458; dCo 27.3–122 pmol L−1, 71.7 ± 11.7 pmol L−1, n = 441), attributed to strong dTM contributions from a low-salinity endmember, i.e., riverine discharge. Benthic sedimentary input via reductive dissolution (especially for dFe and dMn), delineated by short-lived radium (Ra) isotopic activities (223Ra xs and 224Ra xs), was only prominent at a station (Site A) characterized by fine sediments. On the continental slope, dMn levels at depth were mainly determined by the formation of insoluble Mn oxides and the intrusion of Mediterranean Outflow Waters. In contrast, dFe and dCo concentrations at depth were balanced by the regeneration from remineralization of sinking organic particles and scavenging removal. In addition, bottom and intermediate nepheloid layers along the slope illustrated both elevated dTM concentrations and Ra isotopic activities. The presence of nepheloid layers is especially significant along the canyon transect relative to the spur transect, demonstrating the importance of slope topography on the off-shelf transport of dTMs into the Northeast Atlantic Ocean. As a seasonal stratified shelf sea, dTMs and nutrients showed synchronized seasonal variations on the shelf, indicating the influence of biological processes in addition to source effects. Surface dFe and dCo were depleted in summer due to enhanced biological uptake, while sub-surface dFe and dCo were elevated in summer and autumn ascribed to the remineralization of sinking organic particles. In contrast, surface dMn levels were predominantly controlled by the seasonal variations in photoreduction, while sub-surface dMn concentrations were relatively constant throughout the year. The combined effects of fluvial and benthic sources, topographical controls, and biological processes shape the seasonal variations of dTM distributions. Such seasonal variations in dTMs and biological activities can affect the biological carbon pump on the Northeast Atlantic continental margin, and may further influence the carbon cycle in the Atlantic Ocean via the dynamic dTM exchange between continental margins and the open ocean. [ABSTRACT FROM AUTHOR]

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 (< 0.02 μm), and dissolved Ni displayed a mixed size distribution. Good empirical relationships were observed between enrichment factors for aerosol antimony (Sb) and the fractional solubilities of aerosol Fe, Co and Pb, suggesting total aerosol Sb can be useful in estimating and modelling the fractional solubility of these metals using total aerosol trace metal concentrations from historical data. [ABSTRACT FROM AUTHOR]

Nutrients and nutrient-like dissolved trace metals (dTMs) are essential for the functioning of marine organisms and therefore form an important part of ocean biogeochemical cycles. Here, we report on the seasonal distributions of dissolved zinc (dZn), nickel (dNi), copper (dCu), cadmium (dCd), aluminum (dAl), and nutrients on the Northeast Atlantic continental margin (Celtic Sea), which is representative for temperate shelf seas globally. Variations in surface water dTM and nutrient concentrations were mainly regulated by seasonal changes in biological processes. The stoichiometry of dTMs (especially for dCu and dZn) and nutrients on the continental shelf was additionally affected by fluvial inputs. Nutrients and dTMs at depth on the continental slope were determined by water mass mixing driven by ocean circulation, without an important role for local remineralization processes. The Mediterranean Outflow Waters are especially important for delivering Mediterranean-sourced dTMs to the Northeast Atlantic Ocean and drive dTM:nutrient kinks at a depth of ~1000 m. These results highlight the importance of riverine inputs, seasonality of primary production and ocean circulation on the distributions of nutrients and nutrient-like dTMs in temperate continental margin seas. Future climate related changes in the forcing factors may impact the availability of nutrients and dTMs to marine organisms in highly productive continental shelf regions and consequently the regional carbon cycle. • Biological processes and fluvial inputs drive seasonal variations in surface dissolved trace metals (TMs). • Dissolved trace metal concentrations and metal:P ratios at depth are controlled by water mass mixing. • Mediterranean Outflow Waters provide a strong imprint on TM concentrations and metal:P ratios in the Northeast Atlantic. [ABSTRACT FROM AUTHOR]

A flow injection manifold incorporating a solid phase chelating resin (Toyopearl AF-Chelate-650) is reported for the preconcentration of dissolved metals from seawater, with a focus on investigating the effect of the loading pH, wash solution composition and wash time. Cobalt, iron, lead and vanadium have been used as target analytes with contrasting oceanographic behaviour. Quadrupole ICP–MS has been used for detection to make the approach accessible to most laboratories and a collision/reaction cell has been incorporated to minimise polyatomic interferences. Results for the seawater CRM NASS-6 and two GEOTRACES reference materials were in good agreement with the certified/consensus values, demonstrating the suitability of the approach for the determination of trace metals in seawater. The experimental design used allowed a thorough investigation of the uncertainty contribution from each method parameter to the overall expanded uncertainty of the measurement. The results showed that the parameters making the largest contributions were the precision of the peak area measurement and the uncertainty associated with the slope of the calibration curve. Therefore, these are the critical parameters that should be targeted in order to reduce the overall measurement uncertainty. For iron, the wash blank also gave a measureable contribution. [ABSTRACT FROM AUTHOR]

We used a combined ion pairing - organic matter speciation model (NICA-Donnan) to predict the organic complexation of iron (Fe) at ambient pH and temperature in the Celtic Sea. We optimized our model by direct comparison with Fe speciation determined by Adsorptive Cathodic Stripping Voltammetry using the added Fe-binding ligand 1-nitroso-2-naphthol (HNN) in the presence and absence of natural organic matter. We compared determined Fe speciation with simulated titrations obtained via application of the NICA-Donnan model with four different NICA parameter sets representing a range of binding site strengths and heterogeneities. We tested the assumption that binding sites scale to dissolved organic carbon (DOC) concentrations in marine waters. We found that a constant low DOC concentration resulted in an improved fit of our titration data to the simulated titrations, suggesting that inputs of autochthonous marine DOM may not increase the heterogeneity or concentrations of Fe binding sites. Using the optimal parameter set, we calculated pFe(III)´ (−log(∑ Fe (OH) i 3− i )) and apparent Fe(III) solubility (SFe(III) app) at ambient pH and temperature in the water column of the Celtic Sea. SFe(III) app was defined as the sum of aqueous inorganic Fe(III) species and Fe(III) bound to DOM formed at a free Fe (Fe3+) concentration equal to the limiting solubility of Fe hydroxide (Fe(OH) 3 (s)). SFe(III) app was within range of the determined dissolved Fe concentrations observed after winter mixing on the shelf and in waters >1500 m depth at our most offshore stations. Our study supports the hypothesis that the ocean dissolved Fe inventory is controlled by the interplay between Fe solubility and Fe binding by organic matter, although the overall number of metal binding sites in the marine environment may not be directly scalable to DOC concentrations. • We determine iron speciation in samples collected from the North-West European Shelf region. • We optimize the NICA-Donnan model for iron binding to dissolved organic matter for the study region. • We predict apparent iron solubility as the sum of soluble inorganic and organic iron species. • Predicted apparent iron solubilities are within range of observed dissolved iron concentrations in waters >500 m deep. [ABSTRACT FROM AUTHOR]

Abstract: Surface transects and vertical profiles of macronutrients, dissolved iron (D-Fe), and dissolved manganese (D-Mn) were investigated during August 2003 in the southeastern Bering Sea. We observed iron-limited, HNLC surface waters in the deep basin of the Bering Sea (15–20μmol/kg nitrate, ∼0.07nmol/kg D-Fe, and ⩽1.0nmol/kg D-Mn); nitrate-limited, iron-replete surface waters over the shelf (<0.1μmol/kg nitrate, 0.5–4nmol/kg D-Fe, and 2–33nmol/kg D-Mn); and high biomass at the shelf break (“Green Belt”), where diatoms appeared to have been stressed by low D-Fe concentrations (<0.3nmol/kg). Sources of nitrate and iron to the Green Belt were investigated. A mixture of Aleutian North Slope Current water (with elevated, but non-sufficient iron concentrations relative to its high nitrate concentrations) and surface waters from the vicinity of the Bering Canyon (with lower nitrate concentrations, but similar dissolved iron concentrations) was carried along the shelf break by the Bering Slope Current. This water mixture provided macro- and micronutrients at the southern end of the shelf break. The oceanic domain supplied additional macronutrients to Green Belt waters, while the bottom layer of the outer shelf domain supplied additional macro- and micronutrients through enhanced vertical mixing at the shelf break. Surface waters near the Pribilof Islands, where the highest surface D-Fe concentrations were observed (∼5–6nmol/kg), represent a potential source of additional iron to Green Belt waters. During summer, the subsurface water of the middle shelf domain is a potential source of nitrate to the nitrate depleted waters of the shelf. In this subsurface cool pool, we observed evidence of substantial denitrification with lower than expected nitrate concentrations. [Copyright &y& Elsevier]

• Ni and δ 60 Ni data depth profiles from South Atlantic Ocean transect. • Isotopically homogeneous deep ocean; fractionation to heavy values in the upper water column. • Phytoplankton mediated fractionation in the photic zone, but with small fractionation factor. • Ecologically controlled changes in Ni-nutrient systematics across Antarctic Polar Front. • Ni systematics provide another example of the biogeochemical divide in the Southern Ocean. Nickel (Ni) is important for a number of enzymes in oceanic phytoplankton. It has received less attention than some other bioactive metals because it is not reduced to extremely low dissolved concentrations in the photic zone. However, there are strong indications in previous studies that this residual pool is not bio-available. Oceanic Ni isotope data are still scarce, but have great potential for understanding this issue, as well as for understanding the Ni mass balance of the oceans now and in the past. Here, we present new concentration and isotope data for the UK GEOTRACES section at 40°S in the Atlantic (GA10). Nickel concentration data show typical nutrient-like profiles, slightly modified by variable pre-formed concentrations in sub-surface water masses, e.g. North Atlantic Deep Water. Nickel isotopes, in common with findings in previous studies, are homogeneous beneath 500 m, at about +1.3‰ in δ 60 Ni, in samples with Ni concentrations above 3-3.5 nM. The surface South Atlantic, however, has concentrations below 3 nM, and shows significantly higher δ 60 Ni, up to +1.74‰, that are closely anti-correlated with Ni concentrations. The data for the deep South Atlantic dissolved pool, with a δ 60 Ni = 1.31 ± 0.12‰ (average and 2SD) confirm the homogeneity of the global deep ocean, which previous data demonstrate extends all the way to the surface in the upwelling zone of the Southern Ocean south of the Polar Front. This Ni isotope composition is significantly heavier than known inputs to the oceanic dissolved pool. This mass balance requires an isotopically light sink that may be represented by sedimentary Mn-oxide associated Ni. The magnitude of the isotope fractionation implied by the upper ocean data is not consistent with plausible potential abiotic removal processes. Rather, these data are best explained by biological uptake. However, consideration of the detailed relationships between Ni concentrations and isotope compositions requires that a substantial portion of the oceanic dissolved Ni pool is not bio-available. The data are consistent either with a small preference for the light isotope during uptake (about 0.1‰) or two distinct pools of dissolved Ni, one bio-available and one strongly bound in organic complexes, with limited isotopic exchange between them. Patterns of co-variation in Ni concentrations and isotopes with the major nutrients point to strong contrasts across the Polar Front of the Southern Ocean, contrasts that exhibit both similarities and differences with those for the major nutrients and other trace metal micronutrients. South of the Polar Front, Ni is taken up in modest amounts by diatoms, without isotope fractionation. North of the Polar Front the data are most consistent with cyanobacteria as the dominant control on Ni uptake, leading to significant coupled abundance and isotope variation. [ABSTRACT FROM AUTHOR]

Trace metal micronutrients play key roles in photosynthesis by oceanic phytoplankton. Though they are required in much smaller amounts than the major nutrients (P, N, Si), their bioavailable forms are also present in the seawater solution at much lower levels. Relationships between the dissolved chemistry of the nutrient-type trace metals, their stable isotope variations, as well those of the major nutrients, have highlighted the importance of biological and physical processes in the Southern Ocean in controlling their oceanic biogeochemistry. However, the first-order Southern Ocean processes are overprinted by vertical cycling in other parts of the ocean, particularly upwelling regions remote from the Southern Ocean, with the North Pacific standing out in particular. Here we present new zinc (Zn) concentration and isotope, as well as major nutrient data for the NE Pacific, and couple these new data with a compilation of published data from across the region, with the objective of better understanding the impact of this important region on oceanic biogeochemical cycles. The new Zn isotope data for two stations along Line P (P04 and P26) show a large range in δ 66 Zn in the upper ocean (−0.4‰ up to >1‰), associated with a very small isotope fractionation but extreme depletion of the dissolved pool during photic zone biological uptake, and the regeneration of this cellular Zn at very shallow depths (50 m). Beneath this, the two profiles approach the δ 66 Zn value of +0.5‰, seen throughout the deep ocean, by about 500 m. The minimum δ 66 Zn resulting from regeneration is associated with very high Zn concentrations, particularly at the marginal P04 station where diatoms dominate the phytoplankton ecology. Combining the new data with published Zn and major nutrient concentrations from across the North Pacific emphasises the role of vertical biological cycling in controlling regional biogeochemistry in the North Pacific, resulting in the partial overprinting of biogeochemical signatures transported out of the Southern Ocean by the ocean circulation. Zinc isotope data document the uptake of this metal into diatoms and the co-regeneration of Zn with phosphate in the upper water column. Silica in contrast is regenerated at greater depth, resulting in a decoupling of the Zn–Si correlation that is set in the Southern Ocean and that dominates the Atlantic. Previous work has suggested that the decoupling of Zn and Si in the subarctic North Pacific results from removal of Zn (and other metals) to water column particulate sulphide. In our dataset, and in the compilation of data documenting relationships between Zn and the major nutrients across the North Pacific, this decoupling is clearly due to the different lengthscales of regeneration for organic matter (Zn and P) and diatom opal (Si). • We present new zinc concentration and isotope for the NE Pacific. • The rate and pattern of biological uptake and regeneration control Zn and its isotopes in the North Pacific. • The North Pacific, like the Southern Ocean, is an important site of metal export from the photic zone. • Vertical biological cycling overprints biogeochemical signatures transported out of the Southern Ocean. [ABSTRACT FROM AUTHOR]