Fe(Ⅱ)-mediated transformation of schwertmannite associated with calcium from acid mine drainage treatment

Schwertmannite is an important Fe(Ⅲ)-oxyhydroxysulfate in acid mine drainage (AMD) polluted areas and its stability depends on surrounding environmental factors and previously bound elements.The treatment and neutralization of AMD normally involve the use of lime,which leads to the discharge of abundant Ca in the mining area.Such an environmental disturbance brings up an important and less considered problem of how the reductive transformation of schwertmannite associated with coexisting Ca occurred.Here,the Fe(Ⅱ)-mediated transformation of Ca-adsorbed schwertmannite and subsequent Ca repartitioning behaviors were investigated.Results showed that adsorbed Ca had a weak inhibitory effect on Fe(Ⅱ)-mediated schwertmannite transformation.Release of SO_(4)2-and SEM images both indicated that transformation rates of schwertmannite decreased under the influence of adsorbed Ca.XRD patterns indicated that adsorbed Ca altered schwertmannite transformation pathways and product compositions upon treatment with 0.4 mmol/L Fe(Ⅱ).The end products of Sch notably contained both goethite and lepidocrocite;however,transformation products of SchCa only contained goethite all along.Approximately 33.5%of the surface adsorbed-Ca was released into solution within 6 hr after Fe(Ⅱ) injection.Aqueous Ca behaved in a“first release and then im-mobilization”manner,which indicated dissolution and secondary mineralization drove Ca migration during the Fe(Ⅱ)-mediated transformation of SchCa.Adsorbed Ca blocked the surface sites for subsequent Fe(Ⅱ) adsorption,limited the Fe(Ⅱ)-Fe(Ⅲ) ETAE,and decreased the transformation rates.This work sheds light on the complex geochemical behavior of schwertmannite under the influences of environmental perturbations in AMD environments.

Thiocyanate-induced labilization of schwertmannite: Impacts and mechanisms

Schwertmannite is an amorphous iron(III)-oxyhydroxysulfate that forms in acid mine drainage(AMD) environments. The characteristic of high heavy metal adsorption capability makes schwertmannite a potentially useful, environmentally friendly material in wastewater treatment. Unstable schwertmannite is prone to recrystallization.Understanding the mechanisms that induce schwertmannite labilization and affect its capacity to remove heavy metals are of great environmental and geochemical significance.Thiocyanate(SCNˉ) is a hazardous pseudohalide that is also normally found in AMD.However, little is known about the impact of Fe(III)-binding ligand SCNˉ on schwertmannite stability and its subsequent capacity to bind trace elements. Here, we investigated the adsorption of SCNˉ on schwertmannite and subsequent mineral transformation to characterize this little-known process. The appearance of Fe2+indicated that the interactions between schwertmannite and SCNˉ may involve complexation and reduction reactions. Results showed that the majority of the adsorbed-SCNˉ was immobilized on schwertmannite during the 60-days transformation. The transformation rates of schwertmannite increased with increasing concentrations of SCNˉ. Goethite was detected as the dominant transformation product with or without SCNˉ. The mechanisms of SCNˉ-promoted dissolution of schwertmannite can be described as follows:(1) formation of Fe(III)–NCS complexes on the schwertmannite surface and in solution, a process which increases the reactivity of solid phase Fe(III);(2) the extraction of Fe(III) from schwertmannite by SCNˉ and subsequent schwertmannite dissolution; and(3) the formation of secondary minerals from extracted Fe(III). These findings may improve AMD treatment strategies and provide insight into the use and potential reuse of schwertmannite as a trace element sorbent.