Extracellular polymeric substances altered ferrihydrite (trans)formation and induced arsenic mobilization

The behavior of As is closely related to trans(formation) of ferrihydrite, which often coprecipitates with extracellular polymeric substances (EPS), forming EPS-mineral aggregates in natural environments. While the effect of EPS on ferrihydrite properity, mineralogy reductive transformation, and associated As fate in sulfate-reducing bacteria (SRB)-rich environments remains unclear. In this research, ferrihydrite-EPS aggregates were synthesized and batch experiments combined with spectroscopic, microscopic, and geochemical analyses were conducted to address these knowledge gaps. Results indicated that EPS blocked micropores in ferrihydrite, and altered mineral surface area and susceptibility. Although EPS enhanced Fe(III) reduction, it retarded ferrihydrite transformation to magnetite by inhibiting Fe atom exchange in systems with low SO₄^2-. As a result, 16% of the ferrihydrite was converted into magnetite in the Fh-0.3 treatment, and no ferrihydrite transformation occurred in the Fh-EPS-0.3 treatment. In systems with high SO₄^2-, however, EPS promoted mackinawite formation and increased As mobilization into the solution. Additionally, the coprecipitated EPS facilitated As(V) reduction to more mobilized As(III) and decreased conversion of As into the residual phase, enhancing the potential risk of As contamination. These findings advance our understanding on biogeochemistry of elements Fe, S, and As and are helpful for accurate prediction of As behavior.