Description: 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)i3−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.

Description: 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 (× 103) nmol Co m−2 d−1, 7.9–20 (× 104) nmol Fe m−2 d−1 and 2.7–6.5 (× 104) nmol Zn m−2 d−1. Off-shelf fluxes from the Cape 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 0.4–1.2 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 winter deep-mixing) are required to balance the trace element budgets in this region.

Description: 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 (223Raxs and 224Raxs), 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.

Description: We report the distributions and stoichiometry ofdissolved zinc (dZn) and cobalt (dCo) in sub-tropical andsub-Antarctic waters of the south-eastern Atlantic Oceanduring austral spring 2010 and summer 2011/2012. In sub-tropical surface waters, mixed-layer dZn and dCo con-centrations during early spring were 1.60±2.58 nM and30±11 pM, respectively, compared with summer values of0.14±0.08 nM and 24±6 pM. The elevated spring dZn con-centrations resulted from an apparent offshore transport ofelevated dZn at depths between 20–55 m, derived from theAgulhas Bank. In contrast, open-ocean sub-Antarctic surfacewaters displayed largely consistent inter-seasonal mixed-layer dZn and dCo concentrations of 0.10±0.07 nM and11±5 pM, respectively. Trace metal stoichiometry, calcu-lated from concentration inventories, suggests a greater over-all removal for dZn relative to dCo in the upper water columnof the south-eastern Atlantic, with inter-seasonally decreas-ing dZn/dCo inventory ratios of 19–5 and 13–7 mol mol−1for sub-tropical surface water and sub-Antarctic surface wa-ter, respectively. In this paper, we investigate how the sea-sonal influences of external input and phytoplankton succes-sion may relate to the distribution of dZn and dCo and varia-tion in dZn/dCo stoichiometry across these two distinct eco-logical regimes in the south-eastern Atlantic.

Description: 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.

Description: The ocean region along the latitude of 40oS 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.

Description: 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.