Coupled dynamics of As-containing ferrihydrite transformation and As desorption/re-adsorption in presence of sulfide

Abstract

This study investigated the coupled dynamics of the redox transformation of arsenic-containing ferrihydrite, and arsenate desorption and re-adsorption in presence of sulfide. Batch experiments, various microscopic and spectroscopic analyses collectively revealed that electrons from sulfide competitively transferred to ferrihydrite and no arsenate was reduced. The reductive dissolution of ferrihydrite by sulfide led to the quick formation of FeS that competitively decreased the availability of sulfide for its subsequent reduction of ferrihydrite. The quick formation of FeS was followed by a relatively slow transformation of ferrihydrite to magnetite and other Fe(II)-Fe(III) minerals that were primarily bound to the residual ferrihydrite surfaces. As a result of the preservation of As-containing ferrihydrite and surface covering by the secondary minerals, the majority (> 90%)of sorbed arsenate resided in the solid phase, and <10% of arsenate participated in the desorption process during the ferrihydrite dissolution and transformation. The desorption of arsenate was fast, and followed by the kinetic re-adsorption. The rate and extent of the re-adsorption was consistent with the dynamic transformation of the secondary minerals and their sorption affinity toward As. The results have a strong implication to understanding of As concentration changes during the redox transformation of As-containing minerals in groundwater systems.