Beschreibung: The island of South Georgia is situated in the iron (Fe) depleted Antarctic Circumpolar Current of the Southern Ocean. Iron emanating from its shelf system fuels large phytoplankton blooms downstream of the island, but the actual supply mechanisms are unclear. To address this we present the first inventory of Fe, manganese (Mn) and aluminium (Al) in shelf sediments, pore waters and the water column in the vicinity of South Georgia, alongside data on zooplankton-mediated Fe cycling processes. The seafloor sediments were the main particulate Fe source to shelf bottom waters as indicated by Fe / Mn and Fe / Al ratios for shelf sediments and suspended particles in the water column. Less than 1 % of the total particulate Fe pool was leachable surface adsorbed (labile) Fe, and therefore potentially available to organisms. Pore waters formed the primary dissolved Fe (DFe) source to shelf bottom waters supplying 0.1–4 μmol DFe m−2 d−1. However, only 0.41 ± 0.26 μmol DFe m−2 d−1 was transferred to the surface mixed layer by vertical diffusive and advective mixing. Other trace metal sources to surface waters included glacial flour released by melting glaciers and zooplankton excretion processes. On average 6.5 ± 8.2 μmol m−2 d−1 of labile particulate Fe was supplied to the surface mixed layer via krill faecal pellets, with further DFe released by krill at around 1.1 ± 2.2 μmol m−2 d−1. The faecal pellets released by krill constituted of seafloor derived lithogenic material and settled algae debris, in addition to freshly ingested suspended phytoplankton specimen. The phytoplankton Fe requirement in the blooms ca. 1250 km downstream the island of South Georgia was 0.33 ± 0.11 μmol m−2 d−1, with the DFe supply by horizontal/vertical mixing, deep winter mixing and via aeolian dust estimated as ~ 0.12 μmol m−2 d−1. We suggest that additionally required DFe was provided through recycling of biogenically stored Fe following luxury Fe uptake by phytoplankton on the Fe rich shelf. This process would allow Fe to be retained in the surface mixed layer of waters downstream of South Georgia through continuous recycling and biological uptake, and facilitate the large scale blooms.

Beschreibung: The distribution of dissolved aluminium (dAl) in the water column of the North Atlantic and Labrador Sea was studied along GEOTRACES section GA01 to unravel the sources and sinks of this element. Surface water dAl concentrations were low (median of 2.5 nM) due to low aerosol deposition and removal by phytoplankton. However, surface water dAl concentrations were enhanced on the Iberian and Greenland shelves (up to 30.9 nM) due to continental inputs (rivers, glacial flour and ice melt). A negative correlation was observed between dAl in surface waters and primary production, phytoplankton community structure and biogenic opal production. The abundance of diatoms exerted a significant (p 〈 0.01) control on the surface particulate Al (pAl) to dAl ratios by decreasing dAl levels and increasing pAl levels. Dissolved Al concentrations generally increased with depth and correlated strongly with silicate (R2 〉 0.76) west of the Iberian Basin, suggesting net release of dAl at depth during remineralization of sinking biogenic opal containing particles. Enrichment of dAl at near-bottom depths was observed due to resuspension of sediments near the sediment-water interface. The highest dAl (up to 38.7 nM) concentrations were observed in Mediterranean Overflow Waters which act as a major source of dAl to mid depth waters of the eastern North Atlantic. This study clearly shows that the vertical and lateral distribution of dAl in the North Atlantic differs when compared to other regions of the North Atlantic and global ocean due to the large spatial differences both in the main source of Al, atmospheric deposition, and the main sink for Al, particle scavenging, between different oceanic regions.

Beschreibung: Certification of trace metals in seawater certified reference materials (CRMs) NASS-7 and CASS-6 is described. At the National Research Council Canada (NRC), column separation was performed to remove the seawater matrix prior to the determination of Cd, Cr, Cu, Fe, Pb, Mn, Mo, Ni, U, V, and Zn, whereas As was directly measured in 10-fold diluted seawater samples, and B was directly measured in 200-fold diluted seawater samples. High-resolution inductively coupled plasma mass spectrometry (HR-ICPMS) was used for elemental analyses, with double isotope dilution for the accurate determination of B, Cd, Cr, Cu, Fe, Pb, Mo, Ni, U, and Zn in seawater NASS-7 and CASS-6, and standard addition calibration for As, Co, Mn, and V. In addition, all analytes were measured using standard addition calibration with triple quadrupole (QQQ)-ICPMS to provide a second set of data at NRC. Expert laboratories worldwide were invited to contribute data to the certification of trace metals in NASS-7 and CASS-6. Various analytical methods were employed by participants including column separation, co-precipitation, and simple dilution coupled to ICPMS detection or flow injection analysis coupled to chemiluminescence detection, with use of double isotope dilution calibration, matrix matching external calibration, and standard addition calibration. Results presented in this study show that majority of laboratories have demonstrated their measurement capabilities for the accurate determination of trace metals in seawater. As a result of this comparison, certified/reference values and associated uncertainties were assigned for 14 elements in seawater CRMs NASS-7 and CASS-6, suitable for the validation of methods used for seawater analysis.

Beschreibung: The GEOVIDE cruise, a collaborative project within the framework of the international GEOTRACES programme, was conducted along the French-led section in the North Atlantic Ocean (Section GA01), between 15 May and 30 June 2014. In this Special Issue, results from GEOVIDE, including physical oceanography and trace element and isotope cyclings, are presented among seventeen articles. Here, the scientific context, project objectives and scientific strategy of GEOVIDE are provided, along with an overview of the main results from the articles published in the special issue.

Beschreibung: Trace element deposition from desert dust has important impacts on ocean primary productivity, the quantification of which could be useful in determining the magnitude and sign of the biogeochemical feedback on radiative forcing. However, the impact of elemental deposition to remote ocean regions is not well understood and is not currently included in global climate models. In this study, emission inventories for eight elements primarily of soil origin, Mg, P, Ca, Mn, Fe, K, Al, and Si are determined based on a global mineral data set and a soil data set. The resulting elemental fractions are used to drive the desert dust model in the Community Earth System Model (CESM) in order to simulate the elemental concentrations of atmospheric dust. Spatial variability of mineral dust elemental fractions is evident on a global scale, particularly for Ca. Simulations of global variations in the Ca / Al ratio, which typically range from around 0.1 to 5.0 in soils, are consistent with observations, suggesting that this ratio is a good signature for dust source regions. The simulated variable fractions of chemical elements are sufficiently different; estimates of deposition should include elemental variations, especially for Ca, Al and Fe. The model results have been evaluated with observations of elemental aerosol concentrations from desert regions and dust events in non-dust regions, providing insights into uncertainties in the modeling approach. The ratios between modeled and observed elemental fractions range from 0.7 to 1.6, except for Mg and Mn (3.4 and 3.5, respectively). Using the soil database improves the correspondence of the spatial heterogeneity in the modeling of several elements (Ca, Al and Fe) compared to observations. Total and soluble dust element fluxes to different ocean basins and ice sheet regions have been estimated, based on the model results. The annual inputs of soluble Mg, P, Ca, Mn, Fe and K associated with dust using the mineral data set are 0.30 Tg, 16.89 Gg, 1.32 Tg, 22.84 Gg, 0.068 Tg, and 0.15 Tg to global oceans and ice sheets.

Beschreibung: Copper, Cd and Zn can be found at elevated concentrations in contaminated estuarine and coastal waters and have potential toxic effects on phytoplankton species. In this study, the effects of these metals on the intracellular production of the polypeptides phytochelatin and glutathione by the marine diatom Phaeodactylum tricornutum were examined in laboratory cultures. Single additions of Cu and Cd (0.4 μM Cu2 and 0.45 μM Cd2+) to the culture medium induced the production of short-chained phytochelatins ((γ-Glu-Cys) n -Gly where n = 2-5), whereas a single addition of Zn (2.2 μM Zn2+) did not stimulate phytochelatin production. Combination of Zn with Cu resulted in a similar phytochelatin production compared with a single Cu addition. The simultaneous exposure to Zn and Cd led to an antagonistic effect on phytochelatin production, which was probably caused by metal competition for cellular binding sites. Glutathione concentrations were affected only upon exposure to Cd (85 increase) or the combination of Cd with Zn (65 decrease), relative to the control experiment. Ratios of phytochelatins to glutathione indicated a pronounced metal stress in response to exposures to Cu or Cd combined with Zn. This study indicates that variabilities in phytochelatin and glutathione production in the field can be explained in part by metal competition for cellular binding sites. © Springer 2006.

Beschreibung: Dissolved iron (DFe; 〈0.2 µm) and dissolved manganese (DMn; 〈0.2 µm) concentrations were determined in the water column of the Bay of Biscay (eastern North Atlantic Ocean) in March 2002. The samples were collected along a transect traversing from the European continental shelf over the continental slope. The highest DFe and DMn concentrations (2.39 nM and 6.10 nM, respectively) were observed in the bottom waters on the shelf at stations closest to the coast. The release of trace metal from resuspended particles and the diffusion from pore waters were probably at the origin of elevated DFe and DMn concentrations in the Bottom Boundary Layer (BBL). In the slope region, the highest total dissolvable iron (TDFe), DFe and DMn values (24.6 nM, 1.58 nM and 2.12 nM, respectively) were observed close to the bottom at depth of ca.~600–700 m. Internal wave activity and slope circulation are thought to be at the origin of this phenomenon. These processes were also very likely the cause of elevated concentrations (DFe: 1.27 nM, DMn: 2.34 nM) measured in surface waters of stations located in the same area. At stations off the continental slope, the vertical distribution of both metals were typical of open ocean conditions, indicating that inputs from the continental margin did not impact the metal distributions in the offshore waters.

Beschreibung: Coccolithophores are a key functional group in terms of the pelagic production of calcium carbonate (calcite), although their contribution to shelf sea biogeochemistry, and how this relates to environmental conditions, is poorly constrained. Measurements of calcite production (CP) and coccolithophore abundance were made on the north-west European shelf to examine trends in coccolithophore calcification along natural gradients of carbonate chemistry, macronutrient availability and plankton composition. Similar measurements were also made in three bioassay experiments where nutrient (nitrate, phosphate) and pCO2 levels were manipulated. Nanoflagellates (〈 10 μm) dominated chlorophyll biomass and primary production (PP) at all but one sampling site, with CP ranging from 0.6 to 9.6 mmol C m−2 d−1. High CP and coccolithophore abundance occurred in a diatom bloom in fully mixed waters off Heligoland, but not in two distinct coccolithophore blooms in the central North Sea and Western English Channel. Coccolithophore abundance and CP showed no correlation with nutrient concentrations or ratios, while significant (p 〈 0.01) correlations between CP, cell-specific calcification (cell-CF) and irradiance in the water column highlighted how light availability exerts a strong control on pelagic CP. In the experimental bioassays, Emiliania-huxleyi-dominated coccolithophore communities in shelf waters (northern North Sea, Norwegian Trench) showed a strong response in terms of CP to combined nitrate and phosphate addition, mediated by changes in cell-CF and growth rates. In contrast, an offshore diverse coccolithophore community (Bay of Biscay) showed no response to nutrient addition, while light availability or mortality may have been more important in controlling this community. Sharp decreases in pH and a rough halving of calcite saturation states in the bioassay experiments led to decreased CP in the Bay of Biscay and northern North Sea, but not the Norwegian Trench. These decreases in CP were related to slowed growth rates in the bioassays at elevated pCO2 (750 μatm) relative to those in the ambient treatments. The combined results from our study highlight the variable coccolithophore responses to irradiance, nutrients and carbonate chemistry in north-west European shelf waters, which are mediated by changes in growth rates, cell-CF and species composition.

Beschreibung: The thiol peptide phytochelatins (PC2; the polymer with n = 2) are efficient metal-chelating compounds produced by phytoplankton and higher plants. Both PC2 and their precursor glutathione (GSH) are related to detoxification mechanisms. GSH and PC2 were quantified using liquid chromatography with fluorescent detection and observed in the particulate phase along a salinity gradient of the Tamar Estuary (SW UK), a heavily metal impacted site, at concentrations up to 274 and 16.5 μmol (g chl a) -1, respectively. The peptides predominated within low (0-5) and mid-salinities (5-20). Down-estuary, at sites farther from metal sources and salinities higher than 20, PC2 showed a sharp decrease or were not detected. High PC2/GSH ratios indicated areas with augmented concentrations of bioavailable metals at the tidal limit, near Cu mines and the mid-estuary where resuspension of sediments occurs. By following typical partitioning patterns previously reported for dissolved Cu and Zn, the production of thiol peptides, notably PC2, reflected a rapid interaction between the particulate and dissolved phases. © 2011 Coastal and Estuarine Research Federation.