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This study examined upper-ocean particulate organic carbon (POC) export using 234Th approach as part of the second KErguelen Ocean and Plateau compared Study expedition (KEOPS2). Our aim was to characterize the spatial and the temporal variability of POC export during austral spring (October-November 2011) in the Fe-fertilized area of the Kerguelen Plateau region. POC export fluxes were estimated at high productivity sites over and downstream of the plateau and compared to a high-nutrient low-chlorophyll (HNLC) area upstream of the plateau in order to assess the impact of iron-induced productivity on the vertical export of carbon. Deficits in 234Th activities were observed at all stations in surface waters, indicating early scavenging by particles in austral spring. 234Th export was lowest at the reference station R-2 and highest in the recirculation region (E stations) where a pseudo-Lagrangian survey was conducted. In comparison 234Th export over the central plateau and north of the polar front (PF) was relatively limited throughout the survey. However, the 234Th results support that Fe fertilization increased particle export in all iron-fertilized waters. The impact was greatest in the recirculation feature (3-4 fold at 200m depth, relative to the reference station), but more moderate over the central Kerguelen Plateau and in the northern plume of the Kerguelen bloom (~2-fold at 200m depth). The C : Th ratio of large (>53 μm) potentially sinking particles collected via sequential filtration using in situ pumping (ISP) systems was used to convert the 234Th flux into a POC export flux. The C : Th ratios of sinking particles were highly variable (3.1±0.1 to 10.5±0.2 μmol dpm-1) with no clear site-related trend, despite the variety of ecosystem responses in the fertilized regions. C : Th ratios showed a decreasing trend between 100 and 200m depth suggesting preferential carbon loss relative to 234Th possibly due to heterotrophic degradation and/or grazing activity. C : Th ratios of sinking particles sampled with drifting sediment traps in most cases showed very good agreement with ratios for particles collected via ISP deployments (>53 μm particles). Carbon export production varied between 3.5±0.9 and 11.8±1.3 mmol m-2 d-1 from the upper 100m and between 1.8±0.9 and 8.2±0.9 mmol m-2 d-1 from the upper 200 m. The highest export production was found inside the PF meander with a range of 5.3±1.0 to 11.8±1.1 mmol m-2 d-1 over the 19-day survey period. The impact of Fe fertilization is highest inside the PF meander with 2.9-4.5-fold higher carbon flux at 200m depth in comparison to the HNLC control station. The impact of Fe fertilization was significantly less over the central plateau (stations A3 and E-4W) and in the northern branch of the bloom (station F-L) with 1.6-2.0- fold higher carbon flux compared to the reference station R. Export efficiencies (ratio of export to primary production and ratio of export to new production) were particularly variable with relatively high values in the recirculation feature (6 to 27 %, respectively) and low values (1 to 5 %, respectively) over the central plateau (station A3) and north of the PF (station F-L), indicating spring biomass accumulation. Comparison with KEOPS1 results indicated that carbon export production is much lower during the onset of the bloom in austral spring than during the peak and declining phases in late summer. [ABSTRACT FROM AUTHOR]

The particulate matter distribution and phytoplankton community structure of the iron-fertilized Kerguelen region were investigated in early austral spring (October-November 2011) during the KEOPS2 cruise. The iron-fertilized region was characterized by a complex mesoscale circulation resulting in a patchy distribution of particulate matter. Integrated concentrations over 200m ranged from 72.2 to 317.7 mgm-2 for chlorophyll a 314 to 744 mmolm-2 for biogenic silica (BSi), 1106 to 2268 mmolm-2 for particulate organic carbon, 215 to 436 mmolm-2 for particulate organic nitrogen, and 29.3 to 39.0 mmolm-2 for particulate organic phosphorus. Three distinct high biomass areas were identified: the coastal waters of Kerguelen Islands, the easternmost part of the study area in the polar front zone, and the southeastern Kerguelen Plateau. As expected from previous artificial and natural iron-fertilization experiments, the iron-fertilized areas were characterized by the development of large diatoms revealed by BSi size-fractionation and high performance liquid chromatography (HPLC) pigment signatures, whereas the ironlimited reference area was associated with a low biomass dominated by a mixed (nanoflagellates and diatoms) phytoplankton assemblage. A major difference from most previous artificial iron fertilization studies was the observation of much higher Si : C, Si : N, and Si : P ratios (0.31±0.16, 1.6±0.7 and 20.5±7.9, respectively) in the iron-fertilized areas compared to the iron-limited reference station (0.13, 1.1, and 5.8, respectively). A second difference is the patchy response of the elemental composition of phytoplankton communities to large scale natural iron fertilization. Comparison to the previous KEOPS1 cruise also allowed to address the seasonal dynamics of phytoplankton bloom over the southeastern plateau. From particulate organic carbon (POC), particulate organic nitrogen (PON), and BSi evolutions, we showed that the elemental composition of the particulate matter also varies at the seasonal scale. This temporal evolution followed changes of the phytoplankton community structure as well as major changes in the nutrient stocks progressively leading to silicic acid exhaustion at the end of the productive season. Our observations suggest that the specific response of phytoplankton communities under natural iron fertilization is much more diverse than what has been regularly observed in artificial iron fertilization experiments and that the elemental composition of the bulk particulate matter reflects phytoplankton taxonomic structure rather than being a direct consequence of iron availability. [ABSTRACT FROM AUTHOR]

The organic speciation of dissolved cobalt (DCo) was investigated in the subtropical region of the southeastern Atlantic, and in the Southern Ocean in the Antarctic Circumpolar Current (ACC) and the northern Weddell Gyre, between 34°25' S and 57°33' S along the Greenwich Meridian during the austral summer of 2008. The organic speciation of dissolved cobalt was determined by competing ligand exchange adsorptive cathodic stripping voltammetry (CLE-AdCSV) using nioxime as a competing ligand. The concentrations of the organic ligands (L) ranged between 26 and 73 pM, and the conditional stability constants (log K'CoL) of the organic complexes of Co between 17.9 and 20.1. Most dissolved cobalt 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 suggest 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 highestL:DCo ratio (5.81 ± 1.07 pM pM-1) observed in these surface waters reflected the combined effects of ligand production and DCo consumption. As a result of these combined effects, the calculated concentrations of inorganic Co ([Co']) were very low in the subtropical and subantarctic surface waters, 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 in organic species in those DCo-enriched water-masses. Contrastingly, the distribution of L does 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 L and DCo. In deeper waters higher ligand concentrations were observed in waters previously identified as DCo sources (Bown et al., 2011). At those depths the eastward increase of DCo from the Drake Passage to the Greenwich Meridian could be associated with a large scale transport and remineralisation of DCo as organic complexes; here, the fraction stabilized as inorganic Co was also significant (up to 25%) in the low oxygenated Upper Circumpolar Deep Waters. 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. [ABSTRACT FROM AUTHOR]

An upgraded version of the biogeochemical model SWAMCO is coupled to the ocean-sea-ice model NEMOLIM to explore processes governing the spatial distribution of the iron supply to phytoplankton in the Southern Ocean. The 3-D NEMO-LIM-SWAMCO model is implemented in the ocean domain south of latitude 30°S and runs are performed over September 1989-December 2000. Model scenarios include potential iron sources (atmospheric deposition, iceberg calving/melting and continental sediments) as well as iron storage within sea ice, all formulated based on a literature review. When all these processes are included, the simulated iron profiles and phytoplankton bloom distributions show satisfactory agreement with observations. Analyses of simulations and sensitivity tests point to the key role played by continental sediments as a primary source for iron. Iceberg calving and melting contribute by up to 25% of Chl-a simulated in areas influenced by icebergs while atmospheric deposition has little effect at high latitudes. Activating sea ice-ocean iron exchanges redistribute iron geographically. Stored in the ice during winter formation, iron is then transported due to ice motion and is released and made available to phytoplankton during summer melt, in the vicinity of the marginal ice zones. Transient iron storage and transport associated with sea ice dynamics stimulate summer phytoplankton blooming (up to 3 mg Chl-a m-3) in the Weddell Sea and off East Antarctica but not in the Ross, Bellingshausen and Amundsen Seas. This contrasted feature results from the simulated variable content of iron in sea ice and release of melting ice showing higher ice-ocean iron fluxes in the continental shelves of the Weddell and Ross Seas than in the Eastern Weddell Sea and the Bellingshausen-Amundsen Seas. This study confirms that iron sources and transport in the Southern Ocean likely provide important mechanisms in the geographical development of phytoplankton blooms and associated ecosystems. [ABSTRACT FROM AUTHOR]