Effects of Oxyanion Surface Loading on the Rate and Pathway of Ferrihydrite Transformation

In natural environments, ferrihydrite (Fh) reacts readily with the contaminant and nutrient oxyanions through surface complexation. While previous experiments showed that the transformation of Fh to Gt and Hm under oxic conditions at 70 °C is controlled by the type and strength of oxyanion surface complexes, the impact of surface loading on this process is only partly understood. Synchrotron scattering methods and chemical analysis were used to develop a kinetic model that describes the impact of oxyanion surface loading on the rate and pathway of Fh transformation by using arsenate (AsO43-) and phosphate (PO43-). Kinetic modeling showed that AsO43- and PO43- adsorption decreased the rate of transformation and favored Hm formation over Gt. Higher surface loadings increasingly inhibited Fh transformation with a greater effect for PO43- compared with AsO43-. This information has implications for understanding the impacts of oxyanions on the transformation of natural Fe to Gt and Hm in environmental systems.