Ligand exchange provides new insight into the role of humic substances in the marine iron cycle

Organic complexation of iron plays a crucial role in preventing its precipitation, facilitating its transport, and modulating its reactivity and bioavailability in natural waters. Although humic substances (HS) complexes serve as the primary source of terrestrial iron reaching ocean waters, the transition from Fe-HS species to other forms of organic complexation with ocean autochthonous ligands has not yet been properly described. Taking advantage of the electrolability of Fe-HS complexes, we monitored the ligand exchange of iron-saturated Suwannee River fulvic and humic acids (SRFA and SRHA) after the addition of desferrioxamine B (DFOB) and other ligands for comparison. We observed that Fe-HS concentrations gradually decreased until reaching an apparent steady state, typical of a reversible reaction within 1 to 15 h. The dissociation kinetics and species partitioning of Fe-SRHS complexes at the equilibrium showed some features contrary to the current paradigm of HS iron complexation. The affinity of SRFA to bind iron is close to that of DFOB and for SRHA is even higher. The heterogeneity of the HS iron binding groups was confirmed, although experiments in NaCl solutions revealed that in seawater it is substantially caused by the interaction of major divalent ions. The different dissociation kinetics of Fe-SRHS complexes obtained with different competing ligands and the absence of Fe-DFOB dissociation in the presence of iron-free SRFA indicate an intimate associative mechanism of ligand exchange, with the presence of a ternary complex (SRHS-Fe-DFOB) that does not form if the departing complex is Fe-DFOB. We hypothesize that at the concentrations of HS and siderophores found in the open ocean, iron ligand exchange is limited and organic iron speciation will be close to being regulated on a "first come, first served" basis. Experiments conducted under saturation of all iron complexes support the formation of a permanent concentration of a ternary complex. Our findings show the real complexity of cation-ligand interactions in seawater, with implications for the interpretation of recent chromatographic and electrochemical measurements and for the understanding of iron partitioning in the presence of ubiquitous HS.