Electrochemical evaluation of iron-binding ligands along the Australian GEOTRACES southwestern Pacific section (GP13)

In this work, we performed electrochemical investigations of Fe-binding ligands in water samples collected in autumn 2011 along the Australian GEOTRACES southwestern Pacific section (GP13, between 153 degrees E and 170 degrees W longitude along the 30 degrees S line East of Australia, 0-1000 m depth). We determined the capacity of the bulk organic ligands to complex Fe using competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLEAdCSV) with salicylaldoxime as the competing ligand. Two categories of organic ligands, humic substances (HS-like) and catalytically active polymers (Cat. P) were electrochemically quantified in order to better define the bulk of Fe-binding ligands. Finally, Fe speciation results have been linked to oceanographic data, phytoplankton biomass, and two groups of cyanobacteria (Prochlorococcus and Synechococcus) which are prominent members of the phototrophic community in the study region. Across the section, higher total ligand concentrations over dissolved Fe concentrations were observed, as well as the predominance of "weak" Fe-binding ligands (log K'(Fe'L) < 12). Highest "excess ligands" were mostly concentrated in the upper layer of the water column, suggesting a direct link with biological activity. None of the two groups of organic ligands measured (HS-like and Cat. P) accounted for the bulk of the total Fe-binding ligands concentration, hindering a better characterization of the nature of in-situ Fe-binding ligands. Cat. P concentrations showed statistically significant positive correlations with all biomarker pigments and the abundance of Prochlorococcus, suggesting that this material, resembling polysaccharides, could be a good parameter to probe organic compounds from specific biological origin. Amongst the biological parameters, only Prochlorococcus was related to Fe' concentrations.