Labile Fe(II) concentrations in the Atlantic sector of the Southern Ocean along a transect from the subtropical domain to the Weddell Sea Gyre

[EN]Labile Fe(II) distributions were investigated in the Sub-Tropical South Atlantic and the Southern Ocean during the BONUS-GoodHope cruise from 34 to 57_ S (February? March 2008). Concentrations ranged from below the detection limit (0.009 nM) to values as high 5 as 0.125 nM. In the surface mixed layer, labile Fe(II) concentrations were always higher than the detection limit, with values higher than 0.060nM south of 47_ S, representing between 39% and 63% of dissolved Fe (DFe). Biological production was evidenced. At intermediate depth, local maxima were observed, with the highest values in the Sub-Tropical domain at around 200 m, and represented more than 70% of DFe. Remineralization processes were likely responsible for those sub-surface maxima. Below 1500 m, concentrations were close to or below the detection limit, except at two stations (at the vicinity of the Agulhas ridge and in the north of the Weddell Sea Gyre) where values remained as high as _0.030?0.050 nM. Hydrothermal or sediment inputs may provide Fe(II) to these deep waters. Fe(II) half life times (t1/2) at 4 _C were measured in the upper and deep waters and ranged from 2.9 to 11.3min, and from 10.0 to 72.3 min, respectively. Measured values compared quite well in the upper waters with theoretical values from two published models, but not in the deep waters. This may be due to the lack of knowledge for some parameters in the models and/or to organic complexation of Fe(II) that impact its oxidation rates. This study helped to considerably increase the Fe(II) data set in the Ocean and to better understand the Fe redox cycle.

Effect of organic exudates of Phaeodactylum tricornutum on the Fe(II) oxidation rate constant

[EN] Fe(II) oxidation kinetics were studied in seawater and in seawater enriched with exudates excreted by Phaeodactylum tricornutum as an organic ligand model. The exudates produced after 2, 4, and 8 days of culture at 6.21 .. 107, 2.29 .. 108, and 4.98 .. 108 cell L?1 were selected. The effects of pH (7.2?8.2), temperature (5?35 ºC), and salinity (10?36.72) on the Fe(II) oxidation rate were studied. All the data were compared with the results for seawater without exudates (control). The Fe(II) rate constant decreased as a function of culture time and cell concentration in the culture at different pH, temperature, and salinity. All the experimental data obtained in this study were fitted to a polynomial function in order to quantify the fractional contribution of the organic exudates from the diatoms to the Fe(II) oxidation rate in natural seawater. Experimental results showed that the organic exudates excreted by P. tricornutum affect Fe(II) oxidation, increasing the lifetime of Fe(II) in seawater. A kinetic model approach was carried out to account for the speciation of each Fe(II) type together with its contribution to the overall rate.

Chemistry of Fe(II) in the presence of organic exudates from phytoplankton and of copper in seawater

Programa de doctorado de Oceanografía ; 2006-2008