The origin, composition, and reactivity of dissolved iron(III) complexes in coastal organic- and iron-rich sediments

The redox chemistry and speciation of Fe in both solid and dissolved phases were characterized in the organic- and Fe-rich sediments of the Satilla River estuary in South-East Georgia (USA) on a series of four cruises between July 2007 and January 2008. Results indicate that dissolved Fe is present in relatively high concentration in the overlying waters at the freshwater end of the estuary and flocculates along the river as the salinity increases downstream. Soluble organic-Fe(III) complexes comprise the majority of dissolved Fe (<0.2 μm) in the suboxic pore waters of the upriver stations that are characterized by high concentrations of poorly crystalline Fe(III) (oxy)hydroxides. In contrast, SO42−-reducing conditions downstream prevent the accumulation of organic-Fe(III) in the pore waters by titrating Fe from the sediment. Separation of dissolved Fe by size exclusion chromatography revealed that Fe(II) is complexed by organic ligands in the pore waters while the organic-Fe(III) complexes are either small or highly reactive with the column matrix. Finally, dissimilatory Fe(III) reduction, stimulated by inoculating anaerobic sediments with a Fe(III)-reducing bacterium (FeRB), Shewanella putrefaciens strain 200, increased production of soluble organic-Fe(III) complexes, and addition of reactive Fe(III) hydroxides accelerated the non-reductive dissolution of Fe(III) (oxy)hydroxides irrespective of the presence of exogenous FeRB. These findings suggest soluble organic-Fe(III) complexes in suboxic pore waters may be produced both as intermediates during the dissimilatory reduction of Fe(III) (oxy)hydroxides by Fe(III)-reducing microorganisms and during the oxidation of organic-Fe(II) complexes by Fe(III) (oxy)hydroxides. These soluble organic-Fe(III) complexes are stable in pore waters and may flux from the sediments to the continental shelf.