Hydroxyl, Fe(2+), and Acidithiobacillus ferrooxidans Jointly Determined the Crystal Growth and Morphology of Schwertmannite in a Sulfate-Rich Acidic Environment

[Image: see text] Schwertmannite, ubiquitously found in iron and sulfate-rich acid mine drainage, is generated via biological oxidation of ferrous ions by Acidithiobacillus ferrooxidans (A. ferrooxidans). However, little information on the mechanisms of biogenic schwertmannite formation and crystal growth is available. This study deliberately investigated the relationships among mineral morphology, solution chemistry, and phase transformation of schwertmannite in A. ferrooxidans-containing ferrous sulfate solutions. The formation of schwertmannite could be divided into three stages. In the first nucleation stage, crystallites are presented as nonaggregative or aggregative forms via a successive polymerization process. In the second stage, ellipsoidal aggregates, which are identified as ferrihydrite and/or schwertmannite, are formed. In the third stage, needles appear on the surface of ellipsoidal aggregates, which is caused by the phase transformation of ferrihydrite or schwertmannite to lepidocrocite and goethite through a Fe(2+) (aq) catalysis-driven pathway. After three stages, a typical characteristic “hedgehog” morphology finally appears. In addition, A. ferrooxidans could significantly speed up the mineral transformation. Solution pH affects the morphology of schwertmannite by acid leaching. The experimental results also reveal that the formation of schwertmannite depend on the content of hydroxyl complexes or the transformation of the monomers to polymers, which are greatly affected by the solution pH.