Resolving the Structure, Morphology, and Trace Metal Association of Nanominerals: The Case for Schwertmannite

Schwertmannite, a ferric oxyhydroxysulfate mineral typically found under acidic, high sulfate and iron aqueous conditions, such as acid mine drainage environments, was studied using analytical high resolution transmission electron microscopy (HRTEM). HRTEM offers advantages over bulk techniques such as powder x-ray diffraction and pair distribution function (PDF) analysis of synchrotron data, in its ability to discern multiple phases within poorly crystalline nanominerals. Based on extensive HRTEM observations of both natural and synthetic schwertmannite samples, the authors suggest that schwertmannite should not be described as a single phase mineral with a repeating unit cell, but as a polyphasic nanomineral with crystalline areas spanning less than a few nanometers within an amorphous matrix. The few visible lattice fringes observable in both natural and synthetic schwertmannite agree well with d-spacings of goethite (and jarosite in natural samples) implying that the transformation from schwertmannite to these phases occurs as a gradual structural reordering at the nanoscale. In the synthetic study, the complete transformation from schwertmannite to goethite nanorods and nanoparticles within 24 hours at 75°C was observed, indicating a low energetic barrier to schwertmannite's phase transformation. We also found that amorphous silica can be intimately entrained within natural schwertmannite, and that high concentrations of arsenic can be held in close association of nanocrystalline regions of the mineral.