New insights on the role of organic speciation in the biogeochemical cycle of dissolved cobalt in the southeastern Atlantic and the Southern Ocean

Abstract

Abstract. 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.