Photochemical cycling of iron in the surface ocean mediated by microbial iron(iii)-binding ligands

Iron is a limiting nutrient for primary production in large areas of the oceans1,2,3,4. Dissolved iron(iii) in the upper oceans occurs almost entirely in the form of complexes with strong organic ligands5,6,7 presumed to be of biological origin8,9. Although the importance of organic ligands to aquatic iron cycling is becoming clear, the mechanism by which they are involved in this process remains uncertain. Here we report observations of photochemical reactions involving Fe(iii) bound to siderophores—high-affinity iron(iii) ligands produced by bacteria to facilitate iron acquisition10,11,12. We show that photolysis of Fe(iii)–siderophore complexes leads to the formation of lower-affinity Fe(iii) ligands and the reduction of Fe(iii), increasing the availability of siderophore-bound iron for uptake by planktonic assemblages. These photochemical reactions are mediated by the α-hydroxy acid moiety, a group which has generally been found to be present in the marine siderophores that have been characterized13,14,15. We suggest that Fe(iii)-binding ligands can enhance the photolytic production of reactive iron species in the euphotic zone and so influence iron availability in aquatic systems.