Fe-Binding Dissolved Organic Ligands in the Oxic and Suboxic Waters of the Black Sea

In the oxygen-rich layer of the Black Sea, above the permanent halocline, the Fe and nitrate concentrations are low where fluorescence is relatively high, indicating uptake by phytoplankton. In this study we used ligand exchange adsorptive cathodic stripping voltammetry (CLE-aCSV), using 2-(2-Thiazolylazo)-p-cresol (TAC) as measuring ligand, to investigate the role of Fe-binding dissolved organic ligands in keeping Fe in the dissolved phase and potentially biologically available. The conditional stability constant, logK, was between 21 and 22 in most samples, which is on average lower than in ocean water. The Fe-binding dissolved organic ligand concentrations varied between 0.35 and 4.81 nEq of M Fe, which was higher than the dissolved concentration of Fe (DFe) as found in most samples. At two stations ligands were saturated in the surface. At one station ligands were saturated near the oxycline, where ligand concentrations seemed to increase, indicating that they play a role in keeping Fe in the dissolved phase across the redox gradient. At the fluorescence maximum (between 40 and 50 m), the dissolved organic ligand binding capacity (alphaFeL = K[L]) of Fe was at its highest while the concentration DFe was at its lowest. Here, we find a statistically significant, positive relationship between fluorescence and the logarithm of alphaFeL, along with fluorescence and the ratio of the total ligand concentration over DFe. These relationships are best explained by phytoplankton utilizing Fe from Fe-binding organic ligands, resulting in an increase in free Fe-binding ligands.