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Highlights • Cu complexation was measured for the first time in the Fram Strait region. • Cu-binding ligand concentrations and binding strength varied longitudinally in the Fram Strait. • More than 99 % of dCu was organically complexed by strong ligands. • On the Greenland shelf the Transpolar Drift and the coastal processes were the main sources of Cu ligands. Abstract The Fram Strait represents the major gateway of Arctic Ocean waters towards the Nordic Seas and North Atlantic Ocean and is a key region to study the impact of climate change on biogeochemical cycles. In the region, information about trace metal speciation, such as copper, is scarce. This manuscript presents the concentrations and conditional stability constants of copper-binding ligands (LCu and log KcondCu2+L) in the water column of Fram Strait and the Greenland shelf (GEOTRACES cruise GN05). Cu-binding ligands were analysed by Competitive Ligand Exchange-Adsorptive Cathodic Stripping Voltammetry (CLE-ACSV) using salicylaldoxime (SA) as competitive ligand. Based on water masses and the hydrodynamic influences, three provinces were considered (coast, shelf, and Fram Strait) and differences were observed between regions and water masses. The strongest variability was observed in surface waters, with increasing LCu concentrations (mean values: Fram Strait = 2.6 ± 1.0 nM; shelf = 5.2 ± 1.3 nM; coast = 6.4 ± 0.8 nM) and decreasing log KcondCu2+L values (mean values: Fram Strait = 15.7 ± 0.3; shelf = 15.2 ± 0.3; coast = 14.8 ± 0.3) towards the west. The surface LCu concentrations obtained above the Greenland shelf indicate a supply from the coastal environment to the Polar Surface Water (PSW) which is an addition to the ligand exported from the central Arctic to Fram Strait. The significant differences (in terms of LCu and log KcondCu2+L) between shelf and coastal samples were explained considering the processes which modify ligand concentrations and binding strengths, such as biological activity in sea

The marine cyanobacterium Trichodesmium has the remarkable ability to interact with and utilize air‐borne dust as a nutrient source. However, dust may adversely affect Trichodesmium through buoyancy loss and exposure to toxic metals. Our study explored the effect of desert dust on buoyancy and mortality of natural Red Sea puff‐shaped Trichodesmium thiebautii . Sinking velocities and ability of individual colonies to stay afloat with increasing dust loads were studied in sedimentation chambers. Low dust loads of up to ∼400 ng per colony did not impact initial sinking velocity and colonies remained afloat in the chamber. Above this threshold, sinking velocity increased linearly with the colony dust load at a slope matching prediction based on Stoke's law. The potential toxicity of dust was assessed with regards to metal dissolution kinetics, differentiating between rapidly released metals, which may impact surface blooms, and gradually released metals that may impact dust‐centering colonies. Incubations with increasing dust concentrations revealed colony death, but the observed lethal dose far exceeded dust concentrations measured in coastal and open ocean systems. Removal of toxic particles as a mechanism to reduce toxicity was explored using SEM‐EDX imaging of colonies incubated with Cu‐minerals, yet observations did not support this pathway. Combining our current and former experiments, we suggest that in natural settings the nutritional benefits gained by Trichodesmium via dust collection outweigh the risks of buoyancy loss and toxicity. Our data and concepts feed into the growing recognition of the significance of dust for Trichodesmium 's ecology and subsequently to ocean productivity. Plain Language Summary Trichodesmium spp. are abundant cyanobacteria, forming extensive blooms in low latitude warm oceans, and contribute significantly to carbon (C) and nitrogen (N) fixation, recycling and export. Desert dust deposited on the ocean surface was shown to supply Tr

The Congo River supplies vast quantities of trace metals (TMs) to the South Atlantic Ocean, but TM budgets for the Congo plume derived using radium isotopes for GEOTRACES cruise GA08 suggest additional input other than the river outflow. Considering the tight correlations between most dissolved TMs and salinity in the plume and the high rainfall during the wet season over the Congo shelf, we hypothesized that wet atmospheric deposition is a TM source to the Congo plume. Observed TM concentrations in rainwaters across the Congo shelf were mostly comparable to values from previous work in the North Atlantic and Mediterranean Sea. Wet deposition contributed the equivalent of 43% dCd, 21% dCu, 20% dPb and 68% dZn of the Congo River fluxes. Our findings show an important role of wet deposition in supplying TMs to the South Atlantic overlapping with the region that receives substantial TM fluxes from the Congo River. Key Points The Congo River is an important source of trace metals (TMs) to the South Atlantic Ocean revealed by data from GEOTRACES cruise GA08 Wet deposition (rainfall) is identified as an additional TM source to the Congo plume by concurrently considering river and rain data Rainfall supplies anthropogenic dTMs (Cd, Cu, Pb and Zn) with fluxes equivalent to 20%–68% of those from the Congo River on the Congo shelf Plain Language Summary The Congo River has the second largest freshwater discharge volume globally and creates an extensive near-equatorial plume into the Atlantic Ocean. The Congo plume constitutes an important source of trace metals (TMs) to the ocean, which impacts biogeochemical cycles in the tropical and subtropical ocean. However, existing work suggests a discrepancy within the TM budgets in the Congo plume and points to unknown source other than the Congo River or shelf sediments. Most TM concentrations across the Congo plume remain tightly correlated with salinity, suggesting that any additional sources are likely also freshwater-derived or

We present high-resolution profiles of dissolved, labile and total particulate trace metals (TMs) on the Northeast Greenland shelf from GEOTRACES cruise GN05 in August 2016. Combined with radium isotopes, stable oxygen isotopes, and noble gas measurements, elemental distributions suggest that TM dynamics were mainly regulated by the mixing between North Atlantic-derived Intermediate Water, enriched in labile particulate TMs (LpTMs), and Arctic surface waters, enriched in Siberian shelf-derived dissolved TMs (dTMs; Co, Cu, Fe, Mn, and Ni) carried by the Transpolar Drift. These two distinct sources were delineated by salinity-dependent variations of dTM and LpTM concentrations and the proportion of dTMs relative to the total dissolved and labile particulate ratios. Locally produced meltwater from the Nioghalvfjerdsbræ (79NG) glacier cavity, distinguished from other freshwater sources using helium excess, contributed a large pool of dTMs to the shelf inventory. Localized peaks in labile and total particulate Cd, Co, Fe, Mn, Ni, Cu, Al, V, and Ti in the cavity outflow, however, were not directly contributed by submarine melting. Instead, these particulate TMs were mainly supplied by the re-suspension of cavity sediment particles. Currently, Arctic Ocean outflows are the most important source of dFe, dCu and dNi on the shelf, while LpTMs and up to 60% of dMn and dCo are mainly supplied by subglacial discharge from the 79NG cavity. Therefore, changes in the cavity-overturning dynamics of 79NG induced by glacial retreat, and alterations in the transport of Siberian shelf-derived materials with the Transport Drift may shift the shelf dTM-LpTM stoichiometry in the future. Key Points The overall dissolved and particulate trace metal dynamics were mainly regulated by the mixing with Arctic surface waters Resuspension of cavity sediments is a major localized source of labile and total particulate Cd, Co, Fe, Mn, Ni, Cu, Al, V, and Ti Whilst dissolved and particulate trace metal

Concentrations of the toxic element lead (Pb) are elevated in seawater due to historical emissions. While anthropogenic atmospheric emissions are the dominant source of dissolved Pb (dPb) to the Atlantic Ocean, evidence is emerging of a natural source associated with subglacial discharge into the ocean but this has yet to be constrained around Greenland. Here, we show subglacial discharge from the cavity underneath Nioghalvfjerdsbræ floating ice tongue, is a previously unrecognized source of dPb to the NE Greenland Shelf. Contrasting cavity-inflowing and cavity-outflowing waters, we constrain the associated net-dPb flux as 2.2 ± 1.4 Mg·yr−1, of which ∼90% originates from dissolution of glacial bedrock and cavity sediments. We propose that the retreat of the floating ice tongue, the ongoing retreat of many glaciers on Greenland, associated shifts in sediment dynamics, and enhanced meltwater discharges into shelf waters may result in pronounced changes, possibly increases, in net-dPb fluxes to coastal waters. Key Points - Helium and neon show strong evidence for a subglacial source of Pb discharging onto the NE Greenland Shelf - Contrasting inflowing and outflowing waters beneath the floating ice tongue of Nioghalvfjerdsbræ shows a 2-3-fold dPb enrichment - The dissolved Pb flux from Nioghalvfjerdsbræ (2.2 ± 1.4 Mg·yr−1) is comparable to small Arctic rivers, with ∼90% of a sedimentary origin

We present labile (L-pTM) and refractory (R-pTM) particulate trace metal distributions of Fe, Mn, Al, Ti, Co, Zn, Cd, Ni, Pb, Cu, and P for a transect along the southwest African shelf and an off-shore section at 3°S of the GEOTRACES GA08 section cruise. Particle sources and biogeochemical cycling processes are inferred using particle-type proxies and elemental ratios. Enhanced concentrations of bio-essential L-pTMs (Zn, Cu, Ni, Cd, Co, and P) were observed in the Benguela upwelling region, attributed to enhanced primary production. Bio-essential pTM stoichiometric ratios (normalized to pP) were consistent with phytoplankton biomass across the transect, except for Fe and Mn, which included adsorbed and labile oxide phases. Low pP lability (∼41%) suggests a potential refractory biogenic source on the Benguela shelf. Variable labilities observed between stations along the transect indicated potentially different biogenic pP labilities among different plankton groups. Benthic resuspension was prevalent in (near-)bottom waters along the transect and formed an important source of Fe and Mn oxides. Lithogenic particles along the entire shelf were Mn deficient and particles on the Benguela shelf were enriched in Fe, consistent with regional sediment compositions. Enhanced available-Fe (dissolved + labile particulate Fe) concentrations (up to 39.6 nM) were observed in oxygen-deficient (near-)bottom waters of the Benguela shelf coinciding with low L-pMn. This was attributed to the faster oxidation kinetics of Fe, allowing Fe-oxide precipitation and retention on the shelf, while Mn oxidation was slower. Enhanced L-pFe in the Congo River plume, which comprised as much as 93% of the available-Fe pool, was attributed to increased scavenging and formation of Fe oxides. Increased scavenging of other particle-reactive trace metals (TMs) (Mn, Al, and Pb) was also apparent in Congo-influenced waters. However, particles did not play a significant role in transporting TMs off-shelf wit

The Arctic Ocean is considered a source of micronutrients to the Nordic Seas and the North Atlantic Ocean through the gateway of Fram Strait. However, there is a paucity of trace element data from across the Arctic Ocean gateways, and so it remains unclear how Arctic and North Atlantic exchange shapes micronutrient availability in the two ocean basins. In 2015 and 2016, GEOTRACES cruises sampled the Barents Sea Opening (GN04, 2015) and Fram Strait (GN05, 2016) for dissolved iron (dFe), manganese (dMn), cobalt (dCo), nickel (dNi), copper (dCu) and zinc (dZn). Together with the most recent synopsis of Arctic-Atlantic volume fluxes, the observed trace element distributions suggest that Fram Strait is the most important gateway for Arctic-Atlantic dissolved micronutrient exchange as a consequence of Intermediate and Deep Water transport. Combining fluxes from Fram Strait and the Barents Sea Opening with estimates for Davis Strait (GN02, 2015) suggests an annual net southward flux of 2.7 ± 2.4 Gg·a-1 dFe, 0.3 ± 0.3 Gg·a-1 dCo, 15.0 ± 12.5 Gg·a-1 dNi and 14.2 ± 6.9 Gg·a-1 dCu from the Arctic towards the North Atlantic Ocean. Arctic-Atlantic exchange of dMn and dZn were more balanced, with a net southbound flux of 2.8 ± 4.7 Gg·a-1 dMn and a net northbound flux of 3.0 ± 7.3 Gg·a-1 dZn. Our results suggest that ongoing changes to shelf inputs and sea ice dynamics in the Arctic, especially in Siberian shelf regions, affect micronutrient availability in Fram Strait and the high latitude North Atlantic Ocean.

Highlights • Cu speciation was investigated for the first time in the South-East Atlantic using CLE-AdCSV. • [Cu2+] were mostly below the putative biolimiting threshold of various marine microorganisms. • Cu speciation parameters showed a poor correlation with assessed biogeochemical parameters. • Spatial differences in Cu speciation parameters suggest that biogeochemical processes and sources strongly influence Cu speciation. Organic ligands play a key role in the marine biogeochemical cycle of copper (Cu), a bio-essential element, regulating its solubility and bioavailability. However, the sources, abundance, and distribution of these ligands are still poorly understood. In this study, we examined vertical Cu speciation profiles from the South-East Atlantic (GEOTRACES section GA08). Profiles were collected from a range of ocean conditions, including the Benguela upwelling region, the oligotrophic South Atlantic Gyre, and the Congo River outflow. In general, the lack of a significant correlation between most of the parameters assessed here with Cu speciation data obscures the provenance of Cu-binding ligands, suggesting that Cu speciation in the South-East Atlantic is influenced by a complex interplay between biotic and abiotic processes. Nevertheless, the total dissolved Cu (CuT) illustrated an allochthonous origin in the working area, while Cu-binding ligands showed both an allochthonous and a biogenic, autochthonous origin. Pigment concentrations showed that the phylogeography of different microorganisms influenced the spatial features of the Cu-binding ligand pool in the South-East Atlantic. Allochthonous Cu-binding ligand sources in the upper water column are likely associated with dissolved organic matter which originated from the Congo River and the Benguela upwelling system. Deep water ligand sources could include refractory dissolved organic carbon (DOC), resuspended benthic inputs, and lateral advected inputs from the shelf margin. The degradation of L1-t

Around the Greenlandic and Antarctic coastlines, sediment plumes associated with glaciers are significant sources of lithogenic material to the ocean. These plumes contain elevated concentrations of a range of trace metals, especially in particle bound phases, but it is not clear how these particles affect dissolved (<0.2 µm) metal distributions in the ocean. Here we show, using transects in 8 glacier fjords, trends in the distribution of dissolved iron, cobalt, nickel and copper (dFe, dCo, dNi, dCu). Following rapid dFe loss close to glacier outflows, dFe concentrations in particular showed strong similarities between different fjords. Similar dFe concentrations were also observed between seasons/years when Nuup Kangerlua (SW Greenland) was revisited in spring, mid- and late-summer. Dissolved Cu, dCo and dNi concentrations were more variable and showed different gradients with salinity depending on the fjord, season and year. The lack of consistent trends for dCu and dNi largely reflects less pronounced differences contrasting the concentration of inflowing shelf waters with fresher glacially-modified waters. Particles also made only small contributions to total dissolvable Cu (dCu constituted 83 ± 28% of total dissolvable Cu) and Ni (dNi constituted 86 ± 28% of total dissolvable Ni) within glacier plumes. For comparison, dFe was a lower fraction of total dissolvable Fe; 3.5 ± 4.8%. High concentrations of total dissolvable Fe in some inner-fjord environments, up to 77 µM in Ameralik (SW Greenland), may drive enhanced removal of scavenged type elements, such as Co. Further variability may have been driven by local bedrock mineralogy, which could explain high concentrations of dNi (25–29 nM) and dCo (6–7 nM) in one coastal region of west Greenland (Kangaatsiaq). Our results suggest that dissolved trace element distributions in glacier fjords are influenced by a range of factors including: freshwater concentrations, local geology, drawdown by scavenging and primary pr

The Fram Strait is the only deep connection between the Arctic and Atlantic Oceans. The main water and mercury (Hg) fluxes between these oceans occur via the Fram Strait and Barents Sea Opening. Several Hg mass balance studies indicated a net Hg export from the Arctic to the Atlantic Ocean. However, in the absence of Hg measurements in the Fram Strait and Barents Sea Opening, these estimates were based on North Atlantic and central Arctic Ocean data alone. Here, we refine the Arctic total Hg (tHg) and methylated Hg (MeHg) mass budgets using new data acquired during the 2015 GEOTRACES (section GN04) TransArcII cruise in the Barents Sea Opening and the 2016 GEOTRACES (section GN05) GRIFF cruise, which covered the Fram Strait and Northeast Greenland Shelf. Total Hg increased westward along the Fram Strait transect, reaching the highest concentrations on the Northeast Greenland Shelf. Concentrations of tHg averaged 1.29 ± 0.43 pM in the East Greenland Current, while core waters of the West Spitsbergen Current had average values of 0.80 ± 0.26 pM. Using our new data, we estimate that 43 ± 9 Mg y-1 of tHg is transported to the Arctic Ocean in the core of the West Spitsbergen Current, while 54 ± 13 Mg y-1 of tHg is exported from the Arctic Ocean in the East Greenland Current and Recirculated Atlantic Water. This results in a net tHg export of 11 ± 8 Mg y-1 via the Fram Strait. We find a shallow MeHg maximum (at 150Â m depth) in the East Greenland Current, in agreement to what was reported for the central Arctic Ocean and Canadian Arctic Archipelago. The West Spitsbergen Current is characterized by lower MeHg concentrations and a deeper MeHg maximum, that is located at approximately 1000Â m depth. We estimate a net MeHg export of 6 ± 2 Mg y-1 from the Arctic Ocean via the Fram Strait, which is nearly half of the exported tHg. Most of the exported MeHg is in the form of DMHg (2:1 ratio of dimethylmercury to monomethylmercury). Previous studies reported lower MeHg proportions

Climate change has led to a ~ 40% reduction in summer Arctic sea-ice cover extent since the 1970s. Resultant increases in light availability may enhance phytoplankton production. Direct evidence for factors currently constraining summertime phytoplankton growth in the Arctic region is however lacking. GEOTRACES cruise GN05 conducted a Fram Strait transect from Svalbard to the NE Greenland Shelf in summer 2016, sampling for bioessential trace metals (Fe, Co, Zn, Mn) and macronutrients (N, Si, P) at ~ 79°N. Five bioassay experiments were conducted to establish phytoplankton responses to additions of Fe, N, Fe + N and volcanic dust. Ambient nutrient concentrations suggested N and Fe were deficient in surface seawater relative to typical phytoplankton requirements. A west-to-east trend in the relative deficiency of N and Fe was apparent, with N becoming more deficient towards Greenland and Fe more deficient towards Svalbard. This aligned with phytoplankton responses in bioassay experiments, which showed greatest chlorophyll-a increases in + N treatment near Greenland and + N + Fe near Svalbard. Collectively these results suggest primary N limitation of phytoplankton growth throughout the study region, with conditions potentially approaching secondary Fe limitation in the eastern Fram Strait. We suggest that the supply of Atlantic-derived N and Arctic-derived Fe exerts a strong control on summertime nutrient stoichiometry and resultant limitation patterns across the Fram Strait region.

Runoff from the Greenland Ice Sheet (GrIS) is thought to enhance marine productivity by adding bioessential iron and silicic acid to coastal waters. However, experimental data suggest nitrate is the main summertime growth-limiting resource in regions affected by meltwater around Greenland. While meltwater contains low nitrate concentrations, subglacial discharge plumes from marine-terminating glaciers entrain large quantities of nitrate from deep seawater. Here, we characterize the nitrate fluxes that arise from entrainment of seawater within these plumes using a subglacial discharge plume model. The upwelled flux from 12 marine-terminating glaciers is estimated to be >1000% of the total nitrate flux from GrIS discharge. This plume upwelling effect is highly sensitive to the glacier grounding line depth. For a majority of Greenland’s marine-terminating glaciers nitrate fluxes will diminish as they retreat. This decline occurs even if discharge volume increases, resulting in a negative impact on nitrate availability and thus summertime marine productivity.