Sporenmetalen, de oceaan en een veranderende wereld:de kracht van de allerkleinsten

Leven in de oceaan, of leven in het algemeen, kan niet bestaan zonder metalen. Metalen in het milieu hebben meestal een slechte reputatie omdat ze giftig kunnen zijn en vaak in het milieu komen door vervuiling. Maar een heel aantal metalen hebben twee verschillende gezichten. Ze zijn inderdaad giftig bij hoge concentraties, maar te lage concentraties zijn ook schadelijk.  Omdat metalen veelal slecht oplosbaar zijn, komen ze in zeewater voor in extreem lage concentraties en zijn het dus met recht sporenmetalen. Lage beschikbaarheid van bio-essentiële sporenmetalen zoals ijzer of mangaan kan bepalend zijn voor de hoeveelheid leven in de oceaan. Hierbij spelen fytoplankton, eencellige algen die meestal niet met het blote oog te zien zijn, een belangrijke rol. Fytoplankton bedrijven fotosynthese (vastleggen van koolstofdioxide in biomassa) en vormen zo de basis van de voedselketen in zee en nemen veel koolstofdioxide op. Hierdoor wordt een grote hoeveelheid koolstof in de oceaan opgeslagen. Dit kunnen fytoplankton niet doen zonder bio-essentiële sporenmetalen en dus hebben veranderingen in de beschikbaarheid van sporenmetalen gevolgen voor het mariene ecosysteem, de productiviteit en koolstofopname van de oceaan. Mariene sporenmetalen zijn dus belangrijk voor het klimaat en de leefbaarheid van onze planeet. Voor een gezonde planeet is een gezonde oceaan cruciaal, maar de oceaan wordt sterk beïnvloed door klimaatverandering en staat onder toenemende druk door vervuiling en exploitatie. Dit heeft ook gevolgen voor de biogeochemische kringlopen van sporenmetalen en er is dus een sterke wisselwerking tussen sporenmetalen en de veranderende oceaan. Wat de gevolgen zullen zijn voor het functioneren van de oceaan is nog grotendeels onbekend. Een beter begrip van de oceaan is dus essentieel en hierbij mogen we sporenmetalen, ondanks hun lage concentraties, niet over het hoofd zien

The Distribution of Nickel in the West-Atlantic Ocean, Its Relationship With Phosphate and a Comparison to Cadmium and Zinc

Nickel (Ni) is a bio-essential element required for the growth of phytoplankton. It is the least studied bio-essential element, mainly because surface ocean Ni concentrations are never fully depleted and Ni is not generally considered to be a limiting factor. However, stimulation of growth after Ni addition has been observed in past experiments when seemingly ample ambient dissolved Ni was present, suggesting not all dissolved Ni is bio-available. This study details the distribution of Ni along the GEOTRACES GA02 Atlantic Meridional section. Concentrations of Ni were lowest in the surface ocean and the lowest observed concentration of 1.7 nmol kg(-1) was found in the northern hemisphere (NH). The generally lower surface concentrations in the NH subtropical gyre compared to the southern hemisphere (SH), might be related to a greater Ni uptake by nitrogen fixers that are stimulated by iron (Fe) deposition. The distribution of Ni resembles the distribution of cadmium (Cd) and also features a so called kink (change in the steepness of slope) in the Ni-PO4 relationship. Like for Cd, this is caused by the mixing of Nordic and Antarctic origin water masses. The overall distribution of Ni is driven by mixing with an influence of regional remineralization. This influence of remineralization is, with a maximum remineralization contribution of 13% of the highest observed concentration, smaller than for Cd (30%), but larger than for zinc (Zn; 6%). The uptake pattern in the formation regions of Antarctic origin water masses is suggested to be more similar to Zn than to Cd, however, the surface concentrations of Ni are never fully depleted. This results in a North Atlantic concentration distribution of Ni where the trends of increasing and decreasing concentrations between water masses are similar to those observed for Cd, but the actual concentrations as well as the uptake and remineralization patterns are different between these elements

Diapycnal mixing across the photic zone of the NE Atlantic

Variable physical conditions such as vertical turbulent exchange, internal wave, and mesoscale eddy action affect the availability of light and nutrients for phytoplankton (unicellular algae) growth. It is hypothesized that changes in ocean temperature may affect ocean vertical density stratification, which may hamper vertical exchange. In order to quantify variations in physical conditions in the northeast Atlantic Ocean, we sampled a latitudinal transect along 17 ± 5∘ W between 30 and 63∘ N in summer. A shipborne conductivity–temperature–depth (CTD) instrumented package was used with a custom-made modification of the pump inlet to minimize detrimental effects of ship motions on its data. Thorpe-scale analysis was used to establish turbulence values for the upper 500 m from three to six profiles obtained in a short CTD yo-yo, 3 to 5 h after local sunrise. From south to north, average temperature decreased together with stratification while turbulence values weakly increased or remained constant. Vertical turbulent nutrient fluxes did not vary significantly with stratification and latitude. This apparent lack of correspondence between turbulent mixing and temperature is likely due to internal waves breaking (increased stratification can support more internal waves), acting as a potential feedback mechanism. As this feedback mechanism mediates potential physical environment changes in temperature, global surface ocean warming may not affect the vertical nutrient fluxes to a large degree. We urge modellers to test this deduction as it could imply that the future summer phytoplankton productivity in stratified oligotrophic waters would experience little alterations in nutrient input from deeper waters

Whole season net community production in the Weddell Sea

Abstract Depletions of total CO 2 , nitrate, phosphate and silicate in the surface layer were calculated for cruise ANT XXII/3 with FS Polarstern in March 2005 for estimating the annual net community production. East-west across the Weddell Sea the variation of all depletions is similar, but this holds to a lesser extent for silicate. Depletions in March 2005 are 2-3 times larger than those in January 1993 for the same transect. Very low N:P and C:P depletion ratios seem to point to dominance of diatoms, in the central Weddell Sea more than in the margin. Estimates of annual net community productions are about 1.8 and 3.5 mol C m ¡2 year ¡1 for the interior Weddell Sea and a near-margin region, respectively. The region does not comply with the classical view of a marginal ice zone with high productivity. Net community production is similar to annual export production, implying that remineralization in the ensuing winter be minor

Iron Speciation in Fram Strait and Over the Northeast Greenland Shelf: An Inter-Comparison Study of Voltammetric Methods

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 ([Lt]) 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 [Lt]SA (2.72 ± 0.99 nM eq Fe) > [Lt]TAC (1.77 ± 0.57 nM eq Fe) > [Lt]NN (1.57 ± 0.58 nM eq Fe); with the mean of log K′Fe'L being the highest for TAC (log ′KFe'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 [Lt]TAC/[Lt]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 [Lt]TAC/[Lt]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 [Lt], 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.This study was supported by Royal Netherland Institute for Sea Research. Collection and analysis of samples were further supported by GEOMAR Helmholtz Centre for Ocean Research (the Helmholtz Association and the German Research Foundation (DFG Award Number AC 217/1-1 to EA). IA was supported by a doctoral scholarship from Indonesia Endowment Fund for Education (LPDP), and KZ was supported by a scholarship from the China Scholarship Council

Aqueous copper bioavailability linked to shipwreck-contaminated reef sediments

Pollution from the grounding or sinking of ships can have long lasting effects on the recovery and dynamics of coastal ecosystems. Research on the impact of copper (Cu) pollution from the 2011 MV Rena shipwreck at the Astrolabe Reef (Otaiti), New Zealand, 5 years after the grounding, followed a multi-method and multi-disciplinary approach. Three independent measures of aqueous Cu using trace-element-clean-techniques substantiate the presence of high total, total dissolved (<2 µm) and elevated bioavailable Cu in the water column immediately above the aft section of the wreck where the highest sedimentary load of Cu was located. Intermittently elevated concentrations of strong Cu-binding ligands occurred in this location, and their binding strength was consistent with ligands actively produced by organisms in response to Cu induced stress. The recruitment of benthic invertebrates was modified at the high-Cu location. Taxonomic groups usually considered robust to pollution were restricted to this site (e.g. barnacles) or were the most abundant taxa present (e.g. foraminifera). Our results demonstrate that Cu-contaminated sediments can impose a persistent point source of Cu pollution in high-energy reef environments, with the potential to modify the composition and recovery of biological communities

A First Global Oceanic Compilation of Observational Dissolved Aluminum Data With Regional Statistical Data Treatment

Large national and international observational efforts over recent decades have provided extensive and invaluable datasets of a range of ocean variables. Compiled large datasets, structured, or unstructured, are a powerful tool that allow scientists to access and synthesize data collected over large spatial and temporal scales. The data treatment approaches for any element in the ocean could lead to new global perspectives of their distribution patterns and to a better understanding of large-scale oceanic processes and their impact on other biogeochemical cycles, which may not be evident otherwise. Ocean chemistry Big Data analysis may not just be limited to distribution patterns, but may be used to assess how sampling efforts and analytical methodologies can be improved. Furthermore, a systematic global scale assessment of data is important to evaluate the gaps in knowledge and to provide avenues for future research. In this context, here we provide an extensive compilation of oceanic aluminum (Al) concentration data from global ocean basins, including data available in the GEOTRACES Intermediate Data product (Schlitzer et al., 2018), but also thus far unpublished data

Trace Metal Dynamics in Shallow Hydrothermal Plumes at the Kermadec Arc

Hydrothermal vents are a source of many trace metals to the oceans. Compared to mid-ocean ridges, hydrothermal vent systems at arcs occur in shallower water depth and are much more diverse in fluid composition, resulting in highly variable water column trace metal concentrations. However, only few studies have focused on trace metal dynamics in hydrothermal plumes at volcanic arcs. During R/V Sonne cruise SO253 in 2016/2017, hydrothermal plumes from two hydrothermally active submarine volcanoes along the Kermadec arc in the Southwest Pacific Ocean were sampled: (1) Macauley, a magmatic dominated vent site located in water depths between 300 and 680 m, and (2) Brothers, located between 1,200 and 1,600 m water depth, where hydrothermalism influenced by water rock interactions and magmatically influenced vent sites occur near each other. Surface currents estimated from satellite-altimeter derived currents and direct measurements at the sites using lowered acoustic Doppler current profilers indicate the oceanic regime is dominated by mesoscale eddies. At both volcanoes, results indicated strong plumes of dissolved trace metals, notably Mn, Fe, Co, Ni, Cu, Zn, Cd, La, and Pb, some of which are essential micronutrients. Dissolved metal concentrations commonly decreased with distance from the vents, as to be expected, however, certain element/Fe ratios increased, suggesting a higher solubility of these elements and/or their stronger stabilization (e.g., for Zn compared to Fe). Our data indicate that at the magmatically influenced Macauley and Brothers cone sites, the transport of trace metals is strongly controlled by sulfide nanoparticles, while at the Brothers NW caldera wall site iron oxyhydroxides seem to dominate the trace metal transport over sulfides. Solution stabilization of trace metals by organic complexation appears to compete with particle adsorption processes. As well as extending the generally sparse data set for hydrothermal plumes at volcanic arc systems, our study presents the first data on several dissolved trace metals in the Macauley system, and extends the existing plume dataset of Brothers volcano. Our data further indicate that chemical signatures and processes at arc volcanoes are highly diverse, even on small scales