Iron(II)-activated phase transformation of Cd-bearing ferrihydrite: Implications for cadmium mobility and fate under anaerobic conditions

Abstract

The factors and mechanisms affecting the fate of the associated Cd during the Fe(II)-activated Cd-bearing ferrihydrite transformation remain poorly understood. Herein we have conducted a series of batch reactions containing ferrihydrite with diverse pH values and initial Fe(II) and Cd concentrations coupled with chemical analyses and spectroscopic examination on the transformation products to probe the mechanisms of the Cd partitioning and the processes of Fe(II)-activated Cd-bearing ferrihydrite transformation under anaerobic conditions. Chemical analyses, Fourier transform infrared spectroscopy (FTIR), and powder X-ray diffraction (PXRD) results show that the initial Fe(II) and Cd concentrations as well as pH values all have significant effects on the rates and pathways of ferrihydrite transformation. Increasing Cd loading enhances the inhibition of the Fe(II)-activated ferrihydrite transformation rates. High Cd loading alters the Fe(II)-activated ferrihydrite transformation pathways by hindering the recrystallization of both ferrihydrite to more stable iron minerals and the newly formed lepidocrocite to goethite. Chemical analyses show that the release of Cd to solutions during ferrihydrite transformation is accompanied by a reduction in the 0.4 M HCl extractable Cd fraction and that a significant amount of the released Cd is transformed to a 0.4 M HCl unextractable form. Moreover, enhanced Cd release during the Fe(II)-activated ferrihydrite transformation is observed by reducing the pH value or increasing the initial Cd concentration. Results from synchrotron X-ray absorption spectroscopy (XAS) confirm that the majority of the 0.4 M HCl unextractable Cd form is associated with structural incorporation into the recrystallized iron (hydr)oxides via isomorphous substitution for Fe(III). These findings not only provide molecular-level understanding on the behavior of Cd under natural anoxic environments, but also are useful in predicting the geochemical cycling of Cd and developing long-term Cd contaminant management strategies.