ALBERT

Description: The spatial distribution, biogeochemical cycle and external sources of dissolved cobalt (DCo) were investigated in the southeastern Atlantic and the Southern Ocean between 33°58′S and 57°33′S along the Greenwich Meridian during the austral summer 2008 in the framework of the International Polar Year. DCo concentrations were measured by flow-injection analysis and chemiluminescence detection in filtered (0.2 μm), acidified and UV-digested samples at 12 deep stations in order to resolve the several biogeochemical provinces of the Antarctic Circumpolar Current and to assess the vertical and frontal structures in the Atlantic sector of the Southern Ocean. We measured DCo ranging from 5.73 ± 1.15 pM to 72.9 ± 4.51 pM. The distribution of DCo was nutrient-like in surface waters of the subtropical domain with low concentrations in the euphotic layer due to biological uptake. The biological utilization of dissolved cobalt was proportional to that of phosphate in the subtropical domain with a DCo:HPO42− depletion ratio of ~ 44 μM M−1. In deeper waters the distribution indicated remineralization of DCo and inputs from the margins of South Africa with lateral advection of enriched intermediate and deep waters to the southeastern Atlantic Ocean. In contrast the vertical distribution of DCo changed southward, from a nutrient-like distribution in the subtropical domain to scavenged-type behavior in the domain of the Antarctic Circumpolar Current and conservative distribution in the Weddell Gyre. There the cycle of DCo featured low biological removal by Antarctic diatoms with input to surface waters by snow, removal in oxygenated surface waters, and dissolution and stabilization in the low-oxygenated Upper Circumpolar Deep Waters. DCo distributions and physical hydro-dynamics features also suggest inputs from the Drake Passage and the southwestern Atlantic to the 0° meridian along the eastward flow of the Antarctic Circumpolar Current. Bottom enrichment of DCo in the Antarctic Bottom Waters was also evident, together with increasing water-mass pathway and aging, possibly due to sediment resuspension and/or mixing with North Atlantic Deep waters in the Cape Basin. Overall atmospheric input of soluble Co by dry aerosols to the surface waters was low but higher in the ACC domain than in the northern part of the section. At the highest latitudes, it is possible that snowfall could be a source of DCo to surface waters. Tentative budgets for DCo in the mixed layer of the subtropical and the ACC domains have been constructed for each biogeochemical region encountered during the cruise. The estimated DCo uptake flux was found to be the dominant cobalt flux along the section. This flux decreases southward, which is consistent with the observations that DCo shows a southward transition from nutrient-like towards conservative distribution in the mixed layer.

Description: The fraction of atmospherically deposited iron which dissolves in seawater, or becomes available to phytoplankton for growth, is a key determinant of primary productivity in many open ocean regions. As such this parameter plays an important part in the global oceanic cycles of iron and carbon, and yet the factors that control iron dissolution from aerosol are very poorly understood. In this manuscript we seek to synthesise the available knowledge of these factors, which operate in the atmosphere and in seawater. A conceptual model of the overall aerosol iron solubility is presented, in which we liken the various controls on iron solubility to sets of parallel electrical resistors. We also discuss experimental methods for the determination of iron solubility and make recommendations for future studies in this area.

Description: Atmospheric deposition fluxes of soluble nutrients (N, P, Si, Fe, Co, Zn) to the tropical North Atlantic were determined during cruise M55 of the German SOLAS programme. Nutrient fluxes were highest in the east of the section along 10°N, owing to the proximity of source regions in West Africa and Europe, and lowest in the west, for both dry and wet deposition modes. In common with other recent studies, atmospheric P and Si inputs during M55 were strongly depleted relative to the stoichiometry of phytoplankton Fe, N, P and Si requirements. Atmospheric N inputs were equivalent to 0.1–4.7% of observed primary productivity during the cruise. Atmospheric nutrient supply was also compared to observed nitrogen fixation rates during M55. While atmospheric Fe supply may have been sufficient to support N fixation (depending on the relationship between our simple Fe leaching experiment and aerosol Fe dissolution in seawater), atmospheric P supply was well below the required rate. The stable nitrogen isotope composition of nitrate–N in aerosol and rain was also determined. Results of a simple model indicate that atmospheric deposition and nitrogen fixation introduce similar amounts of isotopically light nitrogen into surface waters of the study region. This implies that nitrogen isotope-based methods would overestimate nitrogen fixation here by a factor of 2, if atmospheric inputs were not taken into account.

Description: We present major element and PGE (platinum-group-element) abundances in addition to Re–Os isotope data for 11 spinel-facies whole rock peridotites from a single maar from the Middle Atlas Mountains, Morocco. Major element systematics of these xenoliths are generally correlated with indices of depletion. FeO–MgO systematics appear to suggest spinel-facies melting in the range of 5 to 25%. However, Al2O3 abundances in these xenoliths appear elevated relative to primitive mantle (Prima). The Al2O3 abundances in conjunction with other major elements require distinct re-enrichment of the Middle Atlas continental mantle root due to melt/rock reaction and precipitation of amphibole and/or clinopyroxene from passing silicate melts akin to MORB or OIB that evolved in reverse direction along the melting curves in e.g. FeO–MgO space. Sc and V confirm the range of apparent depletion and also indicate that the currently preserved fO2 in these peridotites is distinctly different from fO2 conditions observed in subduction zones. The majority of these xenoliths have low Os and Ir (I-PGEs) concentrations relative to Prima and modelled sulphide- and clinopyroxene-depleted residues of mantle melting under low fO2, mid-ocean ridge-like conditions. Moreover, Pt and Pd (P-PGE) abundances are elevated when compared to their expected abundances after substantial melt extraction. Importantly, the systematically low Ir abundances in the majority of samples show well-correlated trends with Al2O3, MgO and Cu that are inconsistent with established melting trends. Os isotopes in the Middle Atlas xenoliths range from 187Os/188Os = 0.11604 to 0.12664 although most samples are close to chondritic. The Os isotope ratios are decoupled from 187Re/188Os but, together with Re abundances, also exhibit a good correlation with Al2O3, MgO and Cu. The major element, I-PGE and Os isotope correlations suggest that the initial melt depletion led to the exhaustion of sulphide and clinopyroxene (20 to 30%) without significant stabilization of I-PGE-rich alloys. During later modal metasomatism of the refractory Middle Atlas continental mantle root with silicate melts akin to MORB or OIB the introduction of clinopyroxene/amphibole reduced the volume of the melt inducing sulphur saturation in these melts causing precipitation of secondary sulphides. This coupled crystallization of pyroxenes and sulphides (chalcopyrite) resulted in the two-component mixing systematics exhibited by I-PGEs, Os isotopes with major elements and Cu preserved in the Middle Atlas continental mantle root.

Description: The shift of lava geochemistry between volcanic front to rear-arc volcanoes in active subduction zones is a widespread phenomenon. It is somehow linked to an increase of the slab surface depth of the subducting oceanic lithosphere and increasing thickness of the mantle wedge and new constraints for its causes may improve our understanding of magma generation and element recycling in subduction zones in general. As a case study, this paper focuses on the geochemical composition of lavas from two adjacent volcanic centres from the volcanic front (VF) to rear-arc (RA) transition of the Southern Kamchatkan subduction zone, with the aim to examine whether the shift in lava geochemistry is associated with processes in the mantle wedge or in the subducted oceanic lithosphere or both. The trace element and O–Sr–Nd–Hf–Pb (double-spike)-isotopic composition of the mafic Mutnovsky (VF) and Gorely (RA) lavas in conjunction with geochemical modelling provides constraints for the degree of partial melting in the mantle wedge and the nature of their slab components. Degrees of partial melting are inferred to be significantly higher beneath Mutnovsky (∼18%) than Gorely (∼10%). The Mutnovsky (VF) slab component is dominated by hydrous fluids, derived from subducted sediments and altered oceanic crust, eventually containing minor but variable amounts of sediment melts. The composition of the Gorely slab component strongly points to a hydrous silicate melt, most likely mainly stemming from subducted sediments, although additional fluid-contribution from the underlying altered oceanic crust (AOC) is likely. Moreover, the Hf–Nd-isotope data combined with geochemical modelling suggest progressive break-down of accessory zircon in the melting metasediments. Therefore, the drastic VF to RA shift in basalt chemistry mainly arises from the transition of the nature of the slab component (from hydrous fluid to melt) in conjunction with decreasing degrees of partial melting within ∼15 km across-arc. Finally, systematic variations of key inter-element with high-precision Pb-isotope ratios provide geochemical evidence for a pollution of the Mutnovsky mantle source with Gorely melt components but not vice versa, most likely resulting from trench-ward mantle wedge corner flow. We also present a geodynamic model integrating the location of the Mutnovsky and Gorely volcanic centres and their lava geochemistry with the recently proposed thermal structure of the southern Kamchatkan arc and constraints about phase equilibria in subducted sediments and AOC. Herein, the slab surface hosting the subducted sediments suffers a transition from dehydration to melting above a continuously dehydrating layer of AOC. Wider implications of this study are that an onset of (flush-) sediment melting may ultimately be the main trigger for the VF to RA transition of lava geochemistry in subduction zones.

Description: A sensitive method using Competitive Ligand Exchange-Adsorptive Cathodic Stripping Voltammetry (CLE-ACSV) has been developed to determine for the first time iron (Fe) organic speciation in rainwater over the typical natural range of pH. We have adapted techniques previously developed in other natural waters to rainwater samples, using the competing ligand 1-nitroso-2-naphthol (NN). The blank was equal to 0.17 +/- 0.05 nM (n = 14) and the detection limit (DL) for labile Fe was 0.15 nM which is 10-70 times lower than that of previously published methods. The conditional stability constant for NN under rainwater conditions was calibrated over the pH range 5.52-6.20 through competition with ethylenediaminetetraacetic acid (EDTA). The calculated value of the logarithm of beta'(FE3+(NN)3) increased linearly with increasing pH according to log beta'(FE3+(NN)3) = 2.4 +/- 0.6 x pH + 11.9 +/- 3.5 (salinity =2.9, T= 20 degrees C). The validation of the method was carried out using desferrioxamine mesylate B (DFOB) as a natural model ligand for Fe. Adequate detection windows were defined to detect this class of ligands in rainwater with 40 mu M of NN from pH 5.52 to 6.20. The concentration of Fe-complexing natural ligands was determined for the first time in three unfiltered and one filtered rainwater samples. Organic Fe-complexing ligand concentrations varied from 104.2 +/- 4.1 nM equivalent of Fe(III) to 336.2 +/- 19.0 nM equivalent of Fe(III) and the logarithm of the conditional stability constants, with respect to Fe3+, varied from 21.1 +/- 0.2 to 22.8 +/- 0.3. This method will provide important data for improving our understanding of the role of wet deposition in the biogeochemical cycling of iron.

Description: The water column imprint of the hydrothermal plume observed at the Nibelungen field (8 18'S 13 degrees 30'W) is highly variable in space and time. The off-axis location of the site, along the southern boundary of a non-transform ridge offset at the joint between two segments of the southern Mid-Atlantic Ridge, is characterized by complex, rugged topography, and thus favorable for the generation of internal tides, subsequent internal wave breaking, and associated vertical mixing in the water column. We have used towed transects and vertical profiles of stratification, turbidity, and direct current measurements to investigate the strength of turbulent mixing in the vicinity of the vent site and the adjacent rift valley, and its temporal and spatial variability in relation to the plume dispersal. Turbulent diffusivities K(rho) were calculated from temperature inversions via Thorpe scales. Heightened mixing (compared to open ocean values) was observed in the whole rift valley within an order of K(rho) around 10(-3) m(2) s(-1). The mixing close to the vent site was even more elevated, with an average of K(rho) = 4 x 10(-2) m(2) s(-1). The mixing, as well as the flow field, exhibited a strong tidal cycle, with strong currents and mixing at the non-buoyant plume level during ebb flow. Periods of strong mixing were associated with increased internal wave activity and frequent occurrence of turbulent overturns. Additional effects of mixing on plume dispersal include bifurcation of the particle plume, likely as a result of the interplay between the modulated mixing strength and current speed, as well as high frequency internal waves in the effluent plume layer, possibly triggered by the buoyant plume via nonlinear interaction with the elevated background turbulence or penetrative convection. (C) 2010 Elsevier Ltd. All rights reserved.

Description: We present hafnium (Hf) and neodymium (Nd) isotopic compositions and concentrations in surface waters of the eastern Atlantic Ocean between the coast of Spain and South-Africa. These data are complemented by Hf and Nd isotopic and concentration data, as well as rare earth element (REE) concentrations, in Saharan dust. Hafnium concentrations range between a maximum of 0.52 pmol/kg in the area of the Canary Islands and a minimum value of 0.08 pmol/kg in the southern Angola Basin. Neodymium concentrations also show a local maximum in the area of the Canary Islands (26 pmol/kg) but are even higher between ~20N and ~4N reaching maximum concentrations of 35 pmol/kg. These elevated concentrations provide evidence of inputs from weathering of the Canary Islands and from the partial dissolution of dust from the Sahara/Sahel region. The inputs from ocean island weathering are also reflected in radiogenic Hf and Nd isotopes. The Hf isotopic compositions of dust samples themselves are highly variable, ranging between eHf = 20 and 0.6. The combined Hf and Nd isotopic compositions of dust plot close to the “terrestrial array” during periods of appreciable dust load in the atmosphere. During low atmospheric dust loading combined Hf and Nd isotopic compositions similar to seawater are observed. Most of the variability can be explained in terms of variable degrees of zircon loss from the dust samples, which in turn is linked to sorting during atmospheric transport to the eastern Atlantic Ocean and possibly presorting by sedimentary redistribution on the continent. In addition, increasing relative proportions of radiogenic clay minerals with decreasing grain size may contribute to the radiogenic Hf isotopic compositions observed. While the Nd isotopic composition in the surface ocean reflects the Nd isotopic composition of the Saharan dust adjacent to the Sahara/Sahel region, the release of Hf from that dust appears to be incongruent and results in surface ocean Hf isotopic compositions which are ~10 eHf more radiogenic than the bulk dust. Radiogenic Hf appears to be released from clays and possibly from trace apatite. Rare earth element patterns of dust samples indicate the presence of apatite but provide no evidence for ferromanganese grain coatings, suggesting that such coatings are insignificant in the release of Hf and Nd from Saharan dust to the surface ocean. The Nd isotopic composition of the surface waters becomes less radiogenic south of the equator, most likely reflecting the release of Nd from Congo river sediments. The release of Hf from Saharan dust and the Congo river sediments, however, does not produce distinct Hf isotopic signatures in the surface ocean, implying that the mobile fraction of Hf integrated over large continental areas is isotopically uniform. The Hf isotopic uniformity in the surface ocean means that the limited variability in deep water isotopic compositions is consistent with a short deep water residence time and reflects homogenous continental inputs rather than efficient deep water homogenization.

Description: During segment-scale studies of the southern Mid-Atlantic Ridge (MAR), 7–12° S, we found evidence in the water column for high-temperature hydrothermal activity, off-axis, east of Ascension Island. Extensive water column and seafloor work using both standard CTD and deep submergence AUV and ROV deployments led to the discovery and sampling of the “Drachenschlund” (“Dragon Throat”) black smoker vent at 8°17.87′ S/13°30.45′ W in 2915 m water depth. The vent is flanked by several inactive chimney structures in a field we have named “Nibelungen”. The site is located 6 km south of a non-transform offset between two adjacent 2nd-order ridge-segments and 9 km east of the presently-active, northward-propagating A2 ridge-segment, on a prominent outward-facing fault scarp. Both vent-fluid compositions and host-rock analyses show this site to be an ultramafic-hosted system, the first of its kind to be found on the southern MAR. The thermal output of this single vent, based on plume rise-height information, is estimated to be 60 ± 15 MW. This value is high for a single “black smoker” vent but small for an entire field. The tectonic setting and low He content of the vent fluids imply that high-temperature off-axis venting at “Drachenschlund” is driven not by magmatic processes, as at the majority of on-axis hydrothermal systems, but by residual heat “mined” from the deeper lithosphere. Whether this heat is being extracted from high-temperature mantle peridotites or deep crustal cumulates formed at the “duelling” non-transfrom offset is unclear, in either case the Drachenschlund vent provides the first direct observations of how cooling of deeper parts of the lithosphere, at least at slow-spreading ridges, may be occurring.

Description: Aerosol (soluble and total) iron and water-column dissolved (DFe, 〈 0.2 μm) and total dissolvable (TDFe, unfiltered) iron concentrations were determined in the Canary Basin and along a transect towards the Strait of Gibraltar, in order to sample across the Saharan dust plume. Cumulative dust deposition fluxes estimated from direct aerosol sampling during our one-month cruise are representative of the estimated deposition fluxes based on near surface water dissolved aluminium concentrations measured on board. Iron inventories in near surface waters combined with flux estimates confirmed the relatively short residence time of DFe in waters influenced by the Saharan dust plume (6-14 months). Enhanced near surface water concentrations of DFe (5.90-6.99 nM) were observed at the Strait of Gibraltar mainly due to inputs from metal-rich rivers. In the Canary Basin and the transect towards Gibraltar, DFe concentrations (0.07-0.76 nM) were typical of concentrations observed in the surface North Atlantic Waters, with the highest concentrations associated with higher atmospheric inputs in the Canary Basin. Depth profiles showed that DFe and TDFe were influenced by atmospheric inputs in this area with an accumulation of aeolian Fe in the surface waters. The sub-surface minimum of both DFe and TDFe suggests that a simple partitioning between dissolved and particulate Fe is not obvious there and that export may occur for both phases. At depths of around 1000-1300 m, both regeneration and Meddies may explain the observed maximum. Our data suggest that, in deep waters, higher particle concentrations likely due to dust storms may increase the scavenging flux and thus decrease DFe concentrations in deep waters. © 2007 Elsevier B.V. All rights reserved.