Mechanistic Study of Ni(II) Sorption by Green Rust Sulfate

The sorption of Ni(II) by green rust sulfate (GR-sulfate) was studied in anoxic pre-equilibrated suspensions at pH 7.0 and pH 7.8 with combined batch kinetic experiments, X-ray diffraction measurements, and Ni K-edge X-ray absorption spectroscopy (XAS) analyses. Continuous removal of aqueous Ni(II) was observed over the course of the reaction (1-2.5 weeks) at both pH values, with no concurrent changes in aqueous Fe(II) levels or detectable mineralogical modifications of the GR sorbent. XAS results indicate that Ni(II) is not retained as mononuclear adsorption complexes on the GR surface but rather incorporated in the octahedral layers of an Fe^II_0.67-Ni^IIFe^III_0.33(OH)₂-layered double hydroxide (LDH) phase with 0 < x < 0.67. The combined macroscopic and spectroscopic data suggest that Ni(II) substitutes into the GR lattice during Fe(II)-catalyzed recrystallization of the sorbent and/or forms secondary Ni(II)/Fe(II)-Fe(III)-LDH phases with a higher stability than that of GR, complemented likely by Ni(II)-Fe(II) exchange at GR particle edges. The results of this study reveal GR to be a dynamic sorbent that engages in dissolution-reprecipitation and exchange reactions, causing extensive incorporation of trace metal Ni(II)_aq. Additional work is needed to further define the mechanisms involved and to assess the sorptive reactivity of GR with other trace metal species.