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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.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

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]

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]

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]

• δ56Fe values for dissolved Fe in hydrothermal plumes can be extremely low (−6.94 ‰). • Low δ56Fe values are accompanied by relatively high δ53Cr values for dissolved Cr. • The δ56Fe-δ53Cr mirroring is consistent with reduction of Cr(VI) by Fe(II). • High-temperature hydrothermal systems can be a net sink of Cr in the ocean. • Hydrothermal removal flux of Cr may change over glacial-interglacial cycles. Hydrothermal venting impacts the global-scale biogeochemical cycles of many trace metals and their isotopes. Processes in hydrothermal plumes regulate the dispersal of vent-derived metals and may vary in response to differences in the geologic setting of vent fields and/or the geochemistry of the overlying ocean water. Here we present results of analyses of dissolved Fe and Cr concentrations, and dissolved Fe isotope (δ56Fe) and Cr isotope (δ53Cr) distributions, in seawater samples collected from above TAG and Rainbow vent sites on the Mid-Atlantic Ridge during the GEOTRACES GA13 cruise. We show that profiles of dissolved Fe and Cr isotopes through the near-field hydrothermal plumes are the mirror image of each other. Oxidation of Fe(II) and precipitation of Fe-(oxyhydr)oxides account for the low δ56Fe values of dissolved Fe, as low as −1.83 ‰ at TAG and −6.94 ‰ at Rainbow. Plume samples with low δ56Fe values are associated with elevated δ53Cr values of dissolved Cr compared to background seawater (by up to +0.14 ‰ and +0.69 ‰ at TAG and Rainbow, respectively), while particulate Cr is characterised by relatively low δ53Cr values (−1.02 to −1.22 ‰). This striking result suggests that seawater Cr(VI) is reduced to Cr(III) and precipitates on the surface of Fe(III) particles within the hydrothermal plume. Reduction of Cr(VI) and scavenging of Cr(III) by plume Fe-(oxyhydr)oxide particles mean that high-temperature hydrothermal systems are likely a net sink for seawater Cr at Rainbow (and also at TAG). As the removal flux of Cr is related to the flux of hydrothermal Fe(II) and the rate of Fe(II) oxidation in the hydrothermal plume, it may (i) vary across vent sites at a global scale and (ii) change over glacial-interglacial cycles. [ABSTRACT FROM AUTHOR]

Abstract Copper (Cu) is both an essential micronutrient and toxic to photosynthesizing microorganisms at low concentrations. Its dissolved vertical distribution in the oceans is unusual, being neither a nutrient-type nor scavenged-type element. This distribution is attributed to biological uptake in the surface ocean with remineralisation at depth, combined with strong organic complexation by dissolved ligands, scavenging onto particles, and benthic sedimentary input. We present coupled dissolved and particulate phase Cu isotope data along the UK-GEOTRACES South Atlantic section, alongside higher resolution dissolved and particulate phase Cu concentration measurements. Our dissolved phase isotope data contribute to an emerging picture of homogeneous deep ocean δ65Cu, at about +0.65‰ (relative to NIST SRM 976). We identify two pools of Cu in the particulate phase: a refractory, lithogenic pool, at about 0‰, and a labile pool accessed via a weak acidic leach, at about +0.4‰. These two pools are comparable to those previously observed in sediments. We observe deviations towards lighter δ65Cu values in the dissolved phase associated with local enrichments in particulate Cu concentrations along the continental slopes, and in the surface ocean. Copper isotopes are thus a sensitive indicator of localised particle-associated benthic or estuarine Cu inputs. The measurement of Cu isotopes in seawater is analytically challenging, and we call for an intercalibration exercise to better evaluate the potential impacts of UV-irradiation, storage time, and different analytical procedures. [ABSTRACT FROM AUTHOR]

In the ocean, dissolved cobalt is affected by both nutrient cycling and scavenging onto manganese oxides. The latter process concentrates Co in pelagic sediments, resulting in a small deep water inventory. While the flux of scavenged cobalt to sediments appears steady on timescales > 100,000 years, its residence time in the water column is short, approximately 130 years. Using results from recent GEOTRACES expeditions, we show net removal of dissolved Co from the deep ocean on the order of 0.043 pM year − 1 , which corresponds to a turnover time of 980 years. Scavenging in deep ocean water masses is too slow to match cobalt accumulation rates in marine sediments, requiring most of the scavenging flux to derive from the mesopelagic ocean (< 1500 m depth) where nutrient cycling is active. Based on differences between the Co:P stoichiometry in particles sinking from the euphotic zone and dissolved Co:P remineralization ratios, we calculate areal scavenging rates in the North Atlantic and South Pacific basins on the order of 1.5 and 0.7 μmol m − 2 year − 1 , respectively, which agree with long-term accumulation rates in Atlantic and Pacific sediments. In both basins, over 50% of the scavenged flux of cobalt occurs in the upper 500 m, resulting in decadal turnover times in the mesopelagic. An assessment of sources suggests that the marine cobalt cycle is approximately in balance, but that this inventory may be sensitive to long term trends in the intensity of oxygen minimum zones, which account for ~ 25% of the annual cobalt source to the modern oceans. [ABSTRACT FROM AUTHOR]

• 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]

This study presents a water mass analysis along the JC150 section in the subtropical North Atlantic, based on hydrographic and nutrient data, by combining an extended optimum multiparameter analysis (OMPA) with a Lagrangian particle tracking experiment (LPTE). This combination, which was proposed for the first time, aided in better constraining the OMPA end-member choice and providing information about their trajectories. It also enabled tracing the water mass origins in surface layers, which cannot be achieved with an OMPA. The surface layers were occupied by a shallow type of Eastern South Atlantic Central Water (ESACW) with traces of the Amazon plume in the west. Western North Atlantic Central Water dominates from 100 to 500 m, while the 13 °C-ESACW contribution occurs marginally deeper (500–900 m). At approximately 700 m, Antarctic Intermediate Water (AAIW) dominates the west of the Mid-Atlantic Ridge (MAR), while Mediterranean Water dominates the east with a small but non-negligible contribution down to 3500 m. Below AAIW, Upper Circumpolar Deep Water (UCDW) is observed throughout section (900–1250 m). Labrador Sea Water (LSW) is found centered at 1500 m, where the LPTE highlights an eastern LSW route from the eastern North Atlantic to the eastern subtropical Atlantic, which was not previously reported. North East Atlantic Deep Water (encompassing a contribution of Iceland-Scotland Overflow Water) is centered at ~2500 m, while North West Atlantic Bottom Water (NWABW, encompassing a contribution of Denmark Strait Overflow Water) is principally localized in the west of the MAR in the range of 3500–5000 m. NWABW is also present in significant proportions (>25%) in the east of the MAR, suggesting a crossing of the MAR possibly through the Kane fracture zone. This feature has not been investigated so far. Finally, Antarctic Bottom Water is present in deep waters throughout the section, mainly in the west of the MAR. Source waters have been characterized from GEOTRACES sections, which enables estimations of trace elements and isotope transport within water masses in the subtropical North Atlantic. Image 1 • Optimum multiparameter analysis combined with a Lagrangian particle tracking experiment. • Impact of Amazon River plume identified as north as 22°N. • Mediterranean Water impact on North Atlantic Deep Water salinity as deep as 3500 m. • Un-previously described Labrador Sea Water route in the eastern North Atlantic. • North West Atlantic Bottom Water transport across the Mid-Atlantic Ridge. [ABSTRACT FROM AUTHOR]