Nucleation and growth of feitknechtite from nanocrystalline vernadite precursor

Abstract

ernadite is a nanocrystalline manganese oxide, which controls the fate of many trace elements in soils and sediments through sorption and oxidative-degradation mechanisms. This exceptional reactivity directly results from its crystal structure, which may however evolve upon contact with redox-sensitive species. Understanding these changes is a prerequisite to predict and model the geochemical cycle of trace elements in the environment. Here, the structural and morphological modifications affecting synthetic nanocrystalline vernadite (δ-MnO2) upon contact with increasing concentrations of Mn2+ were investigated using wet chemistry, synchrotron X-ray diffraction and transmission electron microscopy. Fresh δ-MnO2 crystals had an Mn oxidation state of 3.94 ± 0.05 and a ~10 A layer-to-layer distance. Crystal size was ~10 nm in the layer plane, and ~1 nm perpendicular to that. Upon contact with aqueous Mn2+ under anoxic conditions, δ-MnO2 crystals underwent several morphological and mineral evolutions, starting with the stacking, perpendicular to the layer plane, of d -MnO2 crystals to form crystals ~10 nm 2 nm which were then subjected to oriented aggregation both along and perpendicular to the layer plane to form lath-like crystals with dimensions o ~100 nm 20 nm. Finally, these laths stacked perpendicular to the layer plane to form synthetic feitknechtite (β-MnOOH) crystals with sizes up to ~100 nm 500 nm when the Mn2+ loading reached 31.9 mmol g1. Structural transformation from d -MnO2 to synthetic feitknechtite was detected at Mn2+ loading equal to or higher than 3.27 mmol g-1. These mechanisms are likely to influence the geochemical fate of trace elements in natural settings where Mn2+ is abundant. Firstly, the systematic increase in crystal size with increasing Mn2+ loading may impact the sorption capacity of vernadite and feitknechtite by reducing the density of reactive edge sites. Secondly, the fate of trace elements initially sorbed at the vernadite surface is unclear, as they could either be released in solution or incorporated into the feitknechtite lattice.