Description: Anthropogenic emissions completely overwhelmed natural marine lead (Pb) sources during the past century, predominantly due to leaded petrol usage. Here, based on Pb isotope measurements, we reassess the importance of natural and anthropogenic Pb sources to the tropical North Atlantic following the nearly complete global cessation of leaded petrol use. Significant proportions of up to 30–50% of natural Pb, derived from mineral dust, are observed in Atlantic surface waters, reflecting the success of the global effort to reduce anthropogenic Pb emissions. The observation of mineral dust derived Pb in surface waters is governed by the elevated atmospheric mineral dust concentration of the North African dust plume and the dominance of dry deposition for the atmospheric aerosol flux to surface waters. Given these specific regional conditions, emissions from anthropogenic activities will remain the dominant global marine Pb source, even in the absence of leaded petrol combustion.

Description: The fractionation of silicon (Si) stable isotopes by biological activity in the surface ocean makes the stable isotope composition of silicon (δ30Si) dissolved in seawater a sensitive tracer of the oceanic biogeochemical Si cycle. We present a high-precision dataset that characterizes the δ30Si distribution in the deep Atlantic Ocean from Denmark Strait to Drake Passage, documenting strong meridional and smaller, but resolvable, vertical δ30Si gradients. We show that these gradients are related to the two sources of deep and bottom waters in the Atlantic Ocean: waters of North Atlantic and Nordic origin carry a high δ30Si signature of ≥+1.7‰ into the deep Atlantic, while Antarctic Bottom Water transports Si with a low δ30Si value of around +1.2‰. The deep Atlantic δ30Si distribution is thus governed by the quasi-conservative mixing of Si from these two isotopically distinct sources. This disparity in Si isotope composition between the North Atlantic and Southern Ocean is in marked contrast to the homogeneity of the stable nitrogen isotope composition of deep ocean nitrate (δ15N-NO3). We infer that the meridional δ30Si gradient derives from the transport of the high δ30Si signature of Southern Ocean intermediate/mode waters into the North Atlantic by the upper return path of the meridional overturning circulation (MOC). The basin-scale deep Atlantic δ30Si gradient thus owes its existence to the interaction of the physical circulation with biological nutrient uptake at high southern latitudes, which fractionates Si isotopes between the abyssal and intermediate/mode waters formed in the Southern Ocean. Key Points: - Deep Atlantic Ocean displays gradient in Si isotopic composition of silicic acid - The gradient is caused by quasi-conservative mixing of Si from NADW and AABW - Contrasting isotope signature of NADW and AABW due to interaction of biology and MOC

Description: Highlights: • GEOTRACES releases its first integrated and quality controlled Intermediate Data Product 2014 (IDP2014). • The IDP2014 digital data are available at http://www.bodc.ac.uk/geotraces/data/idp2014/ in 4 different formats. • The eGEOTRACES Electronic Atlas at http://egeotraces.org/ provides 329 section plots and 90 animated 3D tracer scenes. • The new 3D scenes provide geographical and bathymetric context crucial for tracer assessment and interpretation. Abstract: The GEOTRACES Intermediate Data Product 2014 (IDP2014) is the first publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2013. It consists of two parts: (1) a compilation of digital data for more than 200 trace elements and isotopes (TEIs) as well as classical hydrographic parameters, and (2) the eGEOTRACES Electronic Atlas providing a strongly inter-linked on-line atlas including more than 300 section plots and 90 animated 3D scenes. The IDP2014 covers the Atlantic, Arctic, and Indian oceans, exhibiting highest data density in the Atlantic. The TEI data in the IDP2014 are quality controlled by careful assessment of intercalibration results and multi-laboratory data comparisons at cross-over stations. The digital data are provided in several formats, including ASCII spreadsheet, Excel spreadsheet, netCDF, and Ocean Data View collection. In addition to the actual data values the IDP2014 also contains data quality flags and 1-σ data error values where available. Quality flags and error values are useful for data filtering. Metadata about data originators, analytical methods and original publications related to the data are linked to the data in an easily accessible way. The eGEOTRACES Electronic Atlas is the visual representation of the IDP2014 data providing section plots and a new kind of animated 3D scenes. The basin-wide 3D scenes allow for viewing of data from many cruises at the same time, thereby providing quick overviews of large-scale tracer distributions. In addition, the 3D scenes provide geographical and bathymetric context that is crucial for the interpretation and assessment of observed tracer plumes, as well as for making inferences about controlling processes.

Description: Competitive ligand exchange – adsorptive cathodic stripping voltammetry (CLE-AdCSV) is a widely used technique to determine dissolved iron (Fe) speciation in seawater, and involves competition for Fe of a known added ligand (AL) with natural organic ligands. Three different ALs were used, 2-(2-thiazolylazo)-p-cresol (TAC), salicylaldoxime (SA) and 1-nitroso-2-napthol (NN). The total ligand concentrations ([L t ]) and conditional stability constants (log K ′ Fe’L ) obtained using the different ALs are compared. The comparison was done on seawater samples from Fram Strait and northeast Greenland shelf region, including the Norske Trough, Nioghalvfjerdsfjorden (79N) Glacier front and Westwind Trough. Data interpretation using a one-ligand model resulted in [L t ] SA (2.72 ± 0.99 nM eq Fe) > [L t ] TAC (1.77 ± 0.57 nM eq Fe) > [L t ] NN (1.57 ± 0.58 nM eq Fe); with the mean of log K ′ Fe’L being the highest for TAC (log ′ K Fe’L(TAC) = 12.8 ± 0.5), followed by SA (log K ′ Fe’L(SA) = 10.9 ± 0.4) and NN (log K ′ Fe’L(NN) = 10.1 ± 0.6). These differences are only partly explained by the detection windows employed, and are probably due to uncertainties propagated from the calibration and the heterogeneity of the natural organic ligands. An almost constant ratio of [L t ] TAC /[L t ] SA = 0.5 – 0.6 was obtained in samples over the shelf, potentially related to contributions of humic acid-type ligands. In contrast, in Fram Strait [L t ] TAC /[L t ] SA varied considerably from 0.6 to 1, indicating the influence of other ligand types, which seemed to be detected to a different extent by the TAC and SA methods. Our results show that even though the SA, TAC and NN methods have different detection windows, the results of the one ligand model captured a similar trend in [L t ], increasing from Fram Strait to the Norske Trough to the Westwind Trough. Application of a two-ligand model confirms a previous suggestion that in Polar Surface Water and in water masses over the shelf, two ligand groups existed, a relatively strong and relatively weak ligand group. The relatively weak ligand group contributed less to the total complexation capacity, hence it could only keep part of Fe released from the 79N Glacier in the dissolved phase.

Description: Competitive ligand exchange–adsorptive cathodic stripping voltammetry (CLE-AdCSV) is used to determine the conditional concentration ([L]) and the conditional binding strength (logKcond) of dissolved organic Fe-binding ligands, which together influence the solubility of Fe in seawater. Electrochemical applications of Fe speciation measurements vary predominantly in the choice of the added competing ligand. Although different applications show the same trends, [L] and logKcond differ between the applications. In this study, binding of two added ligands in three different common applications to three known types of natural binding ligands is compared. The applications are (1) salicylaldoxime (SA) at 25 µM (SA25) and short waiting time, (2) SA at 5 µM (SA5), and (3) 2-(2-thiazolylazo)-ρ-cresol (TAC) at 10 µM, the latter two with overnight equilibration. The three applications were calibrated under the same conditions, although having different pH values, resulting in the detection window centers (D) DTAC 〉 DSA25 ≥ SA5 (as logD values with respect to Fe3+: 12.3 〉 11.2 ≥ 11). For the model ligands, there is no common trend in the results of logKcond. The values have a considerable spread, which indicates that the error in logKcond is large. The ligand concentrations of the nonhumic model ligands are overestimated by SA25, which we attribute to the lack of equilibrium between Fe-SA species in the SA25 application. The application TAC more often underestimated the ligand concentrations and the application SA5 over- and underestimated the ligand concentration. The extent of overestimation and underestimation differed per model ligand, and the three applications showed the same trend between the nonhumic model ligands, especially for SA5 and SA25. The estimated ligand concentrations for the humic and fulvic acids differed approximately 2-fold between TAC and SA5 and another factor of 2 between SA5 and SA25. The use of SA above 5 µM suffers from the formation of the species Fe(SA)x (x〉1) that is not electro-active as already suggested by Abualhaija and van den Berg (2014). Moreover, we found that the reaction between the electro-active and non-electro-active species is probably irreversible. This undermines the assumption of the CLE principle, causes overestimation of [L] and could result in a false distinction into more than one ligand group. For future electrochemical work it is recommended to take the above limitations of the applications into account. Overall, the uncertainties arising from the CLE-AdCSV approach mean we need to search for new ways to determine the organic complexation of Fe in seawater.

Description: Recent studies, including many from the GEOTRACES program, have expanded our knowledge of trace metals in the Arctic Ocean, an isolated ocean dominated by continental shelf and riverine inputs. Here, we report a unique, pan-Arctic linear relationship between dissolved copper (Cu) and nickel (Ni) present north of 60°N that is absent in other oceans. The correlation is driven primarily by high Cu and Ni concentrations in the low salinity, river-influenced surface Arctic and low, homogeneous concentrations in Arctic deep waters, opposing their typical global distributions. Rivers are a major source of both metals, which is most evident within the central Arctic's Transpolar Drift. Local decoupling of the linear Cu-Ni relationship along the Chukchi Shelf and within the Canada Basin upper halocline reveals that Ni is additionally modified by biological cycling and shelf sediment processes, while Cu is mostly sourced from riverine inputs and influenced by mixing. This observation highlights differences in their chemistries: Cu is more prone to complexation with organic ligands, stabilizing its riverine source fluxes into the Arctic, while Ni is more labile and is dominated by biological processes. Within the Canadian Arctic Archipelago, an important source of Arctic water to the Atlantic Ocean, contributions of Cu and Ni from meteoric waters and the halocline are attenuated during transit to the Atlantic. Additionally, Cu and Ni in deep waters diminish with age due to isolation from surface sources, with higher concentrations in the younger Eastern Arctic basins and lower concentrations in the older Western Arctic basins.

Description: An insufficient supply of the micronutrient iron (Fe) limits phytoplankton growth across large parts of the ocean. Ambient Fe speciation and solubility are largely dependent on seawater physico-chemical properties. We calculated the apparent Fe solubility (SFe(III)app) at equilibrium for ambient conditions, where SFe(III)app is defined as the sum of aqueous inorganic Fe(III) species and Fe(III) bound to organic matter formed at a free Fe3+ concentration equal to the solubility of Fe hydroxide. We compared the SFe(III)app to measured dissolved Fe (dFe) in the Atlantic and Pacific Oceans. The SFe(III)app was overall ∼2 to 4-fold higher than observed dFe at depths less than 1000 m, ∼2-fold higher than the dFe between 1000-4000 m and ∼3-fold higher than dFe below 4000 m. Within the range of used parameters, our results showed that there was a similar trend in the vertical distributions of horizontally averaged SFe(III)app and dFe. Our results suggest that vertical dFe distributions are underpinned by changes in SFe(III)app which are driven by relative changes in ambient pH and temperature. Since both pH and temperature are essential parameters controlling ambient Fe speciation, these should be accounted for in investigations of changing Fe dynamics, particularly in the context of ocean acidification and warming. Key Points Apparent iron solubility is driven by ambient pH, temperature (T) and dissolved organic carbon (DOC), and showed a 6-fold variation between surface (pH= 8.05 on the total scale, DOC= 71.8 µmol L-1, T= 20.4 °C) and deep oceanic waters (pH= 7.82, DOC= 38.6 µmol L-1, T= 1.1°C). Higher values of apparent iron solubility were determined for deep Atlantic and Pacific waters, with lower values in subtropical gyres. Calculated apparent iron solubility showed a similar trend in vertical distribution to dissolved iron, highlighting the importance of considering the impact of changes in ambient physico-chemical conditions on seawater iron chemistry.