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: 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: 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: Atmospheric iron and underway sea-surface dissolved (〈0.2 μm) iron (DFe) concentrations were investigated along a north-south transect in the eastern Atlantic Ocean (27°N/16°W-19°S/5°E). Fe concentrations in aerosols and dry deposition fluxes of soluble Fe were at least two orders of magnitude higher in the Saharan dust plume than at the equator or at the extreme south of the transect. A weaker source of atmospheric Fe was also observed in the South Atlantic, possibly originating in southern Africa via the north-easterly outflow of the Angolan plume. Estimations of total atmospheric deposition fluxes (dry plus wet) of soluble Fe suggested that wet deposition dominated in the intertropical convergence zone, due to the very high amount of precipitation and to the fact that a substantial part of Fe was delivered in dissolved form. On the other hand, dry deposition dominated in the other regions of the transect (73-97), where rainfall rates were much lower. Underway sea-surface DFe concentrations ranged 0.02-1.1 nM. Such low values (0.02 nM) are reported for the first time in the Atlantic Ocean and may be (co)-limiting for primary production. A significant correlation (Spearman's rho = 0.862, p〈0.01) was observed between mean DFe concentrations and total atmospheric deposition fluxes, confirming the importance of atmospheric deposition on the iron cycle in the Atlantic. Residence time of DFe in the surface waters relative to atmospheric inputs were estimated in the northern part of our study area (17 ± 8 to 28 ± 16 d). These values confirmed the rapid removal of Fe from the surface waters, possibly by colloidal aggregation. © 2003 Elsevier Ltd. All rights reserved.

Description: We studied clinopyroxenes from spinel-facies peridotite xenoliths sampled by the Quaternary intra-plate volcanism of the Middle Atlas (Morocco) and present new trace element and Sr–Nd–Hf isotope data. However, we focus in particular on Pb isotope data and 238U/204Pb and 232Th/204Pb ratios of these clinopyroxenes. This data allows us to investigate: (a) the timing of metasomatic events, (b) the prevalence and persistence of elevated 238U/204Pb, 232Th/238U and 232Th/204Pb in continental mantle roots and (c) the 238U/204Pb and 232Th/204Pb composition of putative basaltic melts generated from such metasomatised sub-continental lithospheric mantle (SCLM). Incompatible trace element concentrations in these clinopyroxenes are elevated, marked by high-field strength element depletion and fractionated elemental ratios (e.g., U/Nb, Zr/Hf) most consistent with enrichment due to carbonatitic liquids. Sr, Nd and Hf isotopes have an affinity to HIMU. U, Th and Pb abundances in the clinopyroxenes generally exceed estimates of primitive mantle clinopyroxene. Pb isotope compositions of these clinopyroxenes are radiogenic and vary between 206Pb/204Pb = 19.93–20.25, 207Pb/204Pb = 15.63–15.66 and 208Pb/204Pb = 39.72–40.23. These Pb isotope systematics result in generally negative Δ7/4 but positive Δ8/4; setting these samples distinctly apart from typical HIMU. These Pb isotope compositions are also distinct from the associated host volcanic rocks. 238U/204Pb and 232Th/204Pb of these clinopyroxenes, which range from 26 to 81 and 136 to 399, respectively, are elevated and more extreme than estimates of MORB- and HIMU-source mantle. The Pb isotope evolution of the clinopyroxenes suggests that the metasomatic enrichment is younger than 200 Ma, which discounts the volcanic activity due to the opening of the Atlantic and the onset of the collision of the African and Eurasian plates as processes generating the lithophile element and isotope composition of this continental mantle root. Instead, the enrichment is thought to be associated with the Quaternary intra-plate volcanism in the Middle Atlas. However, the erupted mafic melts have unradiogenic Pb isotopes and lower 238U/204Pb, 232Th/204Pb and 232Th/238U relative to the clinopyroxene and do not seem to have equilibrated with the clinopyroxenes. The high Th abundances and the high 232Th/238U also suggest that the metasomatism was due to carbonatitic liquids. When literature data for Pb isotopes in mantle minerals are considered, the Pb isotope range of Archean, Proterozoic and Phanerozoic continental mantle roots is remarkable in that they are similar to the convecting mantle. This observation does not support the existence of sub-continental lithospheric mantle with high 238U/204Pb and 232Th/204Pb for long periods of time. Consequently, the narrow range of Pb isotopes in SCLM worldwide suggests that only the youngest metasomatic events are recorded by incompatible elements such as U, Th and Pb. Numerical modelling of putative magmas generated from Middle Atlas SCLM by fractional, non-modal melting calculations yield extremely high 238U/204Pb and 232Th/204Pb ratios. For example, pure SCLM magmas generated from 0.5% to 10% melting are anticipated to have 232Th/204Pb ratios exceeding those known from terrestrial basalts.