Sorption of ferric iron from ferrioxamine B to synthetic and biogenic layer type manganese oxides

Siderophores are biogenic chelating agents produced in terrestrial and marine environments that increase the bioavailability of ferric iron. Recent work has suggested that both aqueous and solid-phase Mn(III) may affect siderophore-mediated iron transport, but scant information appears to be available about the potential roles of layer type manganese oxides, which are relatively abundant in soils and the oligotrophic marine water column. To probe the effects of layer type manganese oxides on the stability of aqueous Fe–siderophore complexes, we studied the sorption of ferrioxamine B [Fe(III)HDFOB+, an Fe(III) chelate of the trihydroxamate siderophore desferrioxamine B (DFOB)] to two synthetic birnessites [layer type Mn(III,IV) oxides] and a biogenic birnessite produced by Pseudomonas putida GB-1. We found that all of these predominantly Mn(IV) oxides greatly reduced the aqueous concentration of Fe(III)HDFOB+ at pH 8. Analysis of Fe K-edge EXAFS spectra indicated that a dominant fraction of Fe(III) associated with the Mn(IV) oxides is not complexed by DFOB as in solution, but instead Fe(III) is specifically adsorbed to the mineral structure at multiple sites, thus indicating that the Mn(IV) oxides displaced Fe(III) from the siderophore complex. These results indicate that layer type manganese oxides, including biogenic minerals, may sequester iron from soluble ferric complexes. We conclude that the sorption of iron–siderophore complexes may play a significant role in the bioavailability and biogeochemical cycling of iron in marine and terrestrial environments.