Abstract :
Iron occurs at very low concentrations in seawater of oceanic origin and its low abundance is thought to limit primary production in offshore waters (Martin and Fitzwater, 1988). A new electrochemical method, cathodic stripping voltammetry (CSV), is used here to determine the speciation of iron in seawater originating from the Western Mediterranean taking advantage of ligand competition of an added electroactive ligand with the natural organic complexing matter to evaluate whether iron is organically complexed. The measurements indicate that iron occurs 99% (or 99.9% depending on which value is selected for αFe′) complexed by organic complexing ligands throughout the water column of the Western Mediterranean and by analogy probably also in other oceanic waters. The composition of the organic complexing ligands is as yet unknown, but the data indicate a major source from microorganisms (bacteria or phytoplankton) in and immediately below the fluorescence maximum in the upper water column. The organic complexes are apparently reversible releasing iron when the competing ligand is added and binding more iron when its concentration is increased. The organic complexing ligands occur at concentrations well above those of iron ensuring full complexation of this biologically essential element, and buffer the free iron concentration at a very low level against fluctuations as a result of removal by primary producers or inputs from atmospheric sources. The new data indicate that a re-evaluation of the concept of the bioavailable fraction of iron is required.
