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

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'.

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

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

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

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

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