Organic complexation and translocation of ferric iron in podzols of the Negro River watershed. Separation of secondary Fe species from Al species

The development of podzols in lateritic landscapes of the upper Amazon basin contributes to the exportation of organic carbon and associated metals in the black waters of the Negro River watershed. We have investigated the distribution of Fe(III) in the clay-size fraction of eight organic-rich horizons of waterlogged plateau podzols, to unravel the weathering conditions and mechanisms that control its transfer to the rivers. The speciation and amount of Fe(III) stored in residual mineral phases of laterites, or bound to organic compounds of weakly and well-expressed podzols, were determined by electron paramagnetic resonance spectroscopy combined with chemical analyses.Reducing conditions restrict the production of organo-Fe complexes in the subsoil B-horizons of waterlogged podzols and most of the Fe(2+) released from the dissolution of Fe-oxides is exported to the rivers via the perched groundwater. However, significant amounts of diluted Fe(III). bound to organic ligands (Fe(OM)(III)) and nano Fe-oxides are produced at the margin of the depression in the topsoil A horizons of weakly expressed podzols due to shorter periods of anoxia. The downward translocation of organically bound metals from topsoil A to subsoil B-horizons of podzols occurs in shorter distances for Fe than it does for Al. This separation of secondary Fe species from Al species is attributed to the physical fractionation of their organic carriers in texture contrasted B-horizons of podzols, as well as to the effect. of pH on metal speciation in soil solutions and metal binding onto soil organic ligands (mostly for Al). This leads us to consider the topsoil A horizons of weakly expressed podzols, as well as the subsoil Bh horizon of better-expressed ones, as the main sources for the transfer of Fe(OM)(III) to the rivers. The concentration of Fe(OM)(III) rises from soil sources to river colloids, suggesting drastic biogeochemical changes in more oxygenated black waters of the Negro River watershed. The contribution of soil organic matter to the transfer of Fe to rivers is likely at the origin of the peculiar Fe isotope pattern recently recognized in podzolic environments. (c) 2009 Elsevier Ltd. All rights reserved.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP