Mn, Fe, Zn and As speciation in a fast-growing ferromanganese marine nodule

The speciation of Mn, Fe, As and Zn in a fast-growing (0.02mm/yr), shallow-marine ferromanganese nodule has been examined by micro X-ray fluorescence, micro X-ray diffraction, and micro X-ray absorption spectroscopy. This nodule exhibits alternating Fe-rich and Mn-rich layers reflecting redox variations in water chemistry. Fe occurs as two-line ferrihydrite. The As is strictly associated with Fe and is mostly pentavalent, with an environment similar to that of As sorbed on or coprecipitated with synthetic ferrihydrite. The Mn is in the form of turbostratic birnessite with ~10 % trivalent manganese in the layers and probably ~8 % corner-sharing metal octahedra in the interlayers. The Zn is enriched on the rim of the nodule, associated with Mn. The Zn is completely (>90 %) tetrahedrally coordinated and sorbed in the interlayers of birnessite on vacant layer Mn sites. The Zn and Mn species are similar to ones found in soils, suggesting common structural principles, despite the differing formation conditions in these systems.