Effects of Fe(II) bio-oxidation rate and alkali control on schwertmannite microstructure and adsorption of oxyanions: Characteristics, performance and mechanism

Schwertmannite has attracted increasing interest for its excellent sorption of oxyanions such as AsO43−, CrO42−, and Sb(OH)6−. Controlling biomineralization by adjusting the Fe(II) oxidation rate and implementing alkali control can enhance the yield and adsorption performance of schwertmannite. However, the adsorption improvement mechanism is still unclear. The morphology, crystallinity, specific surface area (SSA) and oxyanion adsorption of schwertmannite synthesized with alkali control of solution pH and different Fe(II) oxidation rates were analyzed in this study. The differences in the adsorption mechanisms of As(V), Cr(VI) and Sb(V) on schwertmannite obtained under different synthesis conditions were also studied. Reducing the Fe(II) oxidation rate or maintaining the solution pH through alkali control significantly increased the SSA of schwertmannite and the proportion of outer-sphere sulfate. Alkali-controlled schwertmannite (Sch-C) exhibited superior As(V) and Sb(V) adsorption performance and slightly greater Cr(VI) adsorption than non-alkali-controlled schwertmannite. The As(V) and Sb(V) adsorption capacities of Sch-C greatly improved because the ultra-high SSA increased the surface hydroxyl content and reduced the passivation effect of amorphous precipitates on the mineral surface, allowing continuous sulfate exchange at inner mineral sites. An increased surface hydroxyl content had little effect on Cr(VI) adsorption, but an increased proportion of outer-sphere sulfate caused a slight increase in Cr(VI) adsorption. Sb(V) has a stronger hydroxyl exchange ability than As(V), but due to its octahedral structure, it exchanges only with outer-sphere sulfate on schwertmannite and hardly exchanges with inner-sphere sulfate. [Display omitted] •Schwertmannite synthesized with alkali control showed an ultra-high SSA.•Schwertmannite synthesized with alkali control showed a higher adsorption capacity.•As(V) exchanges simultaneously with many sulfate and hydroxy groups on schwertmannite.•Cr(VI) exchanges with more sulfate and fewer hydroxy groups on schwertmannite.•Sb(V) exchanges with hydroxy groups and some outer-sphere sulfate on schwertmannite.