ALBERT

Description: Processes of cobalt (Co) entrainment from shelf sediments over the Kerguelen Plateau were studied during the KEOPS (Kerguelen Ocean Plateau compared Study) in order to explain the exceptionally high dissolved cobalt concentrations that have been measured in the surface waters above the Kerguelen Plateau, and in intermediate and deep waters above its eastern slope. Lateral advection and dissolution of Co contained in basalt sediments around Heard Island, a main source of lithogenic Co in the study area, were shown to imprint the process of surface enrichment over the plateau. Dissolved Co enrichment was strongest at the intercept of the eastern slope with intermediate and deep waters, probably due to more efficient mobilisation of the sediments in the slope current, in addition to advection of Co-enriched and low oxygenated ocean water-masses. In surface waters, strong sedimentary Co inputs were estimated to be much higher than biological Co uptake in phytoplankton blooms, underlining the potential role of cobalt as lithogenic tracer. Based on a simple, steady state balance equation of the external input of dissolved iron over the plateau, the fertilization of iron inferred by using Co as a tracer of basalt sources is estimated to be 28 × 102 ± 21 × 102 ton yr−1 in surface waters of the Kerguelen Plateau. This estimate is consistent with preceding ones and the required iron supply matching the phytoplankton demand.

Description: At Eqe, on the western border of the Greenland Ice Cap, measurements of the crystals by Seligman’s method give a mean crystal diameter of 2.16 cm. at a place where the ice velocity is ceto m.fday. The “heterometry index” measured from granulometric curves by Cailleux’s method shows that melting, active ice crystals have reasonably homogeneous dimensions, with a mean diameter from 2 to 2.4 cm.

Description: At Eqe, on the western border of the Greenland Ice Cap, measurements of the crystals by Seligman’s method give a mean crystal diameter of 2.16 cm. at a place where the ice velocity is ceto m.fday. The “heterometry index” measured from granulometric curves by Cailleux’s method shows that melting, active ice crystals have reasonably homogeneous dimensions, with a mean diameter from 2 to 2.4 cm.

Description: Comprehensive synoptic datasets (surface water down to 4000 m) of dissolved cadmium (Cd), copper (Cu), manganese (Mn), lead (Pb) and silver (Ag) are presented along a section between 34° S and 57° S in the southeastern Atlantic Ocean and the Southern Ocean to the south off South Africa. The vertical distributions of Cu, Ag, and of Cd display nutrient-like profiles similar to silicic acid, and phosphate, respectively. The distribution of Mn shows a subsurface maximum in the oxygen minimum zone, whereas Pb concentrations are rather invariable with depth. Dry deposition of aerosols is thought to be an important source of Pb to surface waters close to South Africa, and dry deposition and snowfall may have been significant sources of Cu and Mn at the higher latitudes. Furthermore, the advection of water-masses enriched in trace metals following contact with continental margins appeared to be an important source of trace elements to the surface, intermediate and deep waters in the southeastern Atlantic Ocean and the Antarctic Circumpolar Current. Hydrothermal inputs appeared to have formed a source of trace metals to the deep waters over the Bouvet Triple Junction ridge crest, as suggested by relatively enhanced dissolved Mn concentrations. The biological utilization of Cu and Ag was proportional to that of silicic acid across the section, suggesting that diatoms formed an important control over the removal of Cu and Ag from surface waters. However uptake by dino- and nano-flagelattes may have influenced the distribution of Cu and Ag in the surface waters of the subtropical Atlantic domain. Cadmium correlated strongly with phosphate (P), yielding lower Cd/P ratios in the subtropical surface waters where phosphate concentrations were below 0.95 μM. The greater depletion of Cd relative to P observed in the Weddell Gyre compared to the Antarctic Circumpolar Current could be due to increase Cd-uptake induced by iron-limiting conditions in these High-Nutrient Low-Chlorophyll waters. Similarly, an increase of Mn uptake under Fe-depleted conditions may have caused the highest depletion of Mn relative to P in surface waters of the Weddell Gyre. In addition, a cellular Mn-transport channel of Cd was possibly activated in the Weddell Gyre, which in turn may have yielded depletion of both Mn and Cd in these surface waters.

Description: The distributions of the bio-essential trace element dissolved Co (DCo) and the apparent particulate Co (PCo) are presented along the GEOTRACES-A02 deep section from 64° N to 50° S in the West Atlantic Ocean. PCo was determined as the difference between total cobalt (TCo, unfiltered samples) and DCo. DCo concentrations ranged from 14.7 pM to 94.3 pM, and PCo concentrations from undetectable values to 18.8 pM. The lowest DCo concentrations were observed in the subtropical domains, and the highest in the low-oxygenated Atlantic Central Waters (ACW) that appeared to be the major reservoir of DCo in the West Atlantic. In the Antarctic Bottom Waters, the enrichment in DCo with ageing of the water-mass can be related to suspension and redissolution of bottom sediments a well as diffusion of DCo from abyssal sediments. Mixing and dilution of deep water-masses, rather than scavenging of DCo onto settling particles, generated the meridional decrease of DCo along the southward large-scale circulation in the deep West Atlantic. Furthermore the apparent scavenged profile of DCo observed in the deep waters likely resulted from the persistence of relatively high concentrations in intermediate waters and low DCo concentrations in underlaying bottom waters. We suggested that the 2010 Icelandic volcanic eruption can be a source of DCo that could have been transported in the core of the North-East Atlantic Deep Waters. At intermediate depths, the high concentrations of DCo recorded in the ACW linearly correlated with the apparent utilization of oxygen (AOU), indicating that remineralization of DCo can be significant (representing up to 29% of the DCo present). Furthermore the preferential remineralization of phosphate (P) compared to Co in these low-oxygenated waters suggested a decoupling between the deep cycles of P and Co. The vertical diffusion of DCo from the ACW appeared to be a significant source of DCo into the surface waters of the equatorial domain. Summarizing the dilution and mixing processes rather than scavenging of DCo, and the remineralization can be the two major pathways controlling the cycling of DCo in the intermediate and deep West Atlantic.

Description: Meridional and vertical distributions of several biogeochemical parameters were studied along a section in the southeastern Atlantic and the Southern Ocean south of South Africa during the austral summer 2008 of the International Polar Year to characterize the biogeochemical provinces and to assess the seasonal net diatom production. Based on analyses of macro-nutrients, ammonium (NH4), chlorophyll a, (chl a) phaeopigments, biogenic silica (BSi), particulate inorganic carbon (PIC), and particulate organic carbon and nitrogen (POC and PON, respectively) four biogeochemical domains were distinguished along the section: the subtropical Atlantic, the confluence zone of the subtropical and subantarctic domains, the Polar Frontal Zone (PFZ) in the Antarctic Circumpolar Current (ACC) and the north-eastern branch of the Weddell Gyre. The subtropical region displayed extremely low nutrient concentrations featuring oligotrophic conditions, and sub-surface maxima of chl a and phaeopigments never exceeded, 0.5 μg l−1 and 0.25 μg l−1 respectively. The anticyclonic and cyclonic eddies crossed in the Cape Basin were characterized by a deepening and a rise, respectively, of the nutrients isolines. Mesoscale eddies can bring episodic pulse of nutrients into the photic zone. The confluence zone of the subtropical domain and the northern side of the ACC within the subantarctic domain displayed remnant nitrate and phosphate levels, whereas silicate concentrations kept to extremely low levels. In this area chl a level of 0.4–0.5 μg l−1 distributed homogenously within the mixed layer, and POC and PON accumulated to values up to 10 μM and 1.5 μM, respectively; still indicative of biomass accumulation along the confluence zone during the late productive period. In the ACC domain, the Polar Frontal Zone was marked by a postbloom of diatoms that extended beyond the Polar Front (PF) during this late summer condition, as primarily evidenced by the massive depletion of silicic acid in the surface waters. The accumulation of NH4 to values up to 1.25 μM at 100 m depth centred on the PF and the accumulation of BSi up to 0.5 μM in the surface waters of the central part of the PFZ also featured a late stage of the seasonal diatom bloom. Similar southward displacement of the silicic acid depletion beyond the PF has been previously observed throughout the productive period, associated with the development and extension of the seasonal bloom of diatoms. The silica daily net production rate based on the seasonal depletion of silicic acid was estimated to be 11.9 ± 6.5 mmol m−2 d−1 in the domain of the vast diatom post-bloom, agreeing well with the previously recorded values in this province. The Weddell Gyre occasionally displayed relative surface depletion of silicic acid suggesting a late stage of a relatively minor diatom bloom, possibly driven by iceberg drifting releases of iron. An accumulation of BSi up to 0.5 μM was recorded in the top 350 m of the southern branch of the ACC and in the Weddell Gyre which may be seen as the presence of heavily silicified diatoms due to lack of iron in this HNLC area. In this domain the estimated range of silica daily net production rate (e.g. 21.1 ± 8.8 mmol m−2 d−1) is consistent with previous studies, but was not significantly higher than that in the Polar Front region.

Description: The organic speciation of dissolved cobalt was investigated in the subtropical region of the southeastern Atlantic, and in the Antarctic Circumpolar Current (ACC) and the northern Weddell Gyre in the Southern Ocean between 33°58′S and 57°33′S along the Greenwich Meridian during the austral summer of 2008. The organic speciation of cobalt was determined by Competing Ligand Exchange Adsorptive Cathodic Stripping Voltammetry (CLE-AdCSV) using nioxime as a competing ligand. The conditional stability constants (log K'CoL) of the organic complexes of Co ranged between 17.9 and 20.1, and the concentrations of the organic ligands (L) between 26 and 73 pM. Most dissolved cobalt (DCo) was organically complexed in the water-column (60 to ≥99.9 %). There were clear vertical and meridional patterns in the distribution of L and the organic speciation of DCo along the section. These patterns suggested a biological source of the organic ligands in the surface waters of the subtropical domain and northern subantarctic region, potentially driven by the cyanobacteria, and a removal of the organic Co by direct or indirect biological uptake. The highest L:DCo ratio (e.g. 5.81 ± 1.07 pM pM–1) observed in these surface waters reflected the combined effects of ligand production and consumption of DCo. As a result of these combined effects, the calculated concentrations of free, unbound Co ([Co′]) in subtropical and subantarctic surface waters were very low, generally between 10–19 and 10–17 M. In intermediate and deep waters, the South African margins can be a source of organic ligands, as it was suggested to be for DCo (Bown et al., 2011), although a significant portion of DCo (up to 15 %) can be stabilized and transported as inorganic species in those DCo-enriched water-masses. Contrastingly, the distribution of L did not suggest an intense biological production of L around the Antarctic Polar Front where a diatom bloom had recently occurred. Here [Co′] can be several orders of magnitude higher than those reported in the subtropical domain, suggesting that cobalt limitation was unlikely in the ACC domain. The almost invariant L:DCo ratio of ~1 recorded in these surface waters also reflected the conservative behaviours of both the organic ligands and DCo. In deeper waters relatively higher ligand concentrations were observed in waters previously identified as DCo sources (Bown et al., 2011). At those depths the eastward increase of DCo could be associated with a large scale transport and remineralisation of DCo as organic complexes; here, the fraction stabilized as inorganic Co was much lower but still significant (up to 25 %) in the low oxygenated Upper Circumpolar Deep Waters. The organic speciation may thus be a central factor in the biogeochemical cycle of DCo in those areas, playing a major role in the bioavailability and the geochemistry of Co.

Description: Atmospheric dust inputs to the surface ocean are a major source of trace metals likely to be bio-available for phytoplankton after their dissolution in seawater. Among them, cobalt (Co) and zinc (Zn) are essential for phytoplankton growth and for the distribution of the major groups such as coccolithophorids, cyanobacteria and diatoms. The solubility in seawater of Co and Zn present in natural and anthropogenic dusts was studied using an open-flow reactor with and without light irradiation. Those dusts can be transported in the atmosphere by the wind before being deposited to the surface ocean. The analyses of cobalt and zinc were conducted using voltammetric methods and the global elemental composition of dust was determined by ICP-AES. This study highlighted the role of the dust origin in revealing the solubility characteristics. Much higher dust solubility was found for zinc as compared to cobalt; cobalt in anthropogenic particles was much more soluble (0.78%) in seawater after 2 h of dissolution than Co in natural particles (0.14%). Zinc showed opposite solubility, higher in natural particles (16%) than in anthropogenic particles (5.2%). A natural dust event to the surface ocean could account for up to 5% of the cobalt inventory and up to 50% of the Zn inventory in the mixed layer in the Pacific Ocean whereas the cobalt and zinc inventories in the mixed layer of the Atlantic Ocean might already include the effects of natural dust inputs and the subsequent metal dissolution. Anthropogenic sources to the surface ocean could be as important as the natural sources, but a better estimate of the flux of anthropogenic aerosol to the surface ocean is needed to further estimate the anthropogenic inputs. Variations in natural and anthropogenic inputs may induce large shifts in the Co/Zn ratio in the surface ocean; hence it could impact the phytoplankton community structure.

Description: Comprehensive synoptic datasets (surface water down to 4000 m) of dissolved cadmium (Cd), copper (Cu), manganese (Mn), lead (Pb) and silver (Ag) are presented along a section between 34° S and 57° S in the southeastern Atlantic Ocean and the Southern Ocean to the south off South Africa. The vertical distributions of Cu and Ag display nutrient-like profiles similar to silicic acid, and of Cd similar to phosphate. The distribution of Mn shows a subsurface maximum in the oxygen minimum zone, whereas Pb concentrations are rather invariable with depth. Dry deposition of aerosols is thought to be an important source of Pb to surface waters close to South Africa, and dry deposition and snowfall may have been significant sources of Cu and Mn at the higher latitudes. Furthermore, the advection of water masses enriched in trace metals following contact with continental margins appeared to be an important source of trace elements to the surface, intermediate and deep waters in the southeastern Atlantic Ocean and the Antarctic Circumpolar Current. Hydrothermal inputs may have formed a source of trace metals to the deep waters over the Bouvet Triple Junction ridge crest, as suggested by relatively enhanced dissolved Mn concentrations. The biological utilization of Cu and Ag was proportional to that of silicic acid across the section, suggesting that diatoms formed an important control over the removal of Cu and Ag from surface waters. However, uptake by dino- and nano-flagellates may have influenced the distribution of Cu and Ag in the surface waters of the subtropical Atlantic domain. Cadmium correlated strongly with phosphate (P), yielding lower Cd / P ratios in the subtropical surface waters where phosphate concentrations were below 0.95 μM. The greater depletion of Cd relative to P observed in the Weddell Gyre compared to the Antarctic Circumpolar Current could be due to increase Cd uptake induced by iron-limiting conditions in these high-nutrient–low-chlorophyll waters. Similarly, an increase of Mn uptake under Fe-depleted conditions may have caused the highest depletion of Mn relative to P in the surface waters of the Weddell Gyre. In addition, a cellular Mn-transport channel of Cd was possibly activated in the Weddell Gyre, which in turn may have yielded depletion of both Mn and Cd in these surface waters.