Abstract: The distribution and chemical state of Si in a synthetic 2-line ferrihydrite with a Si/(Si + Fe) molar ratio of 0.11 was studied. Heat treatment under oxidizing conditions shows that Si-rich ferrihydrite is stable to 400°C. The transformation to hematite and the formation of a polymerized amorphous-silica phase occur at 850°C. At this temperature, the specific surface area decreases greatly and the average pore diameter increases, which is indicative of sintering. Heating under severe reducing conditions causes a segregation of Si from Fe and results in a mixture of elemental Fe and SiO2. Surface and structural data suggest that Si is located near the particle surface where it limits the rearrangement of Fe octahedra to form hematite.