The Transformation of Two-Line Ferrihydrite into Crystalline Products: Influence of the Media (Sulfate vs. Nitrate)

Ferrihydrite is ubiquitous in soils, groundwater and aquatic sediments and is usually classified as "2-line" or "6-line" according to the number of diffuse XRD peaks. It has high surface area and reactivity; therefore, it may serve as a sink for sequestering trace metals, metalloids and organic matters via adsorption and co-precipitation. Although considerable attention was paid to the transformation process of this thermodynamically metastable solid, there are still some controversies on the mechanisms of the formation of goethite or hematite from the ferrihydrite precursor. This work systematically investigated the transformation of 2-line ferrihydrite produced by using different neutralization regent (CaO vs. NaOH) into crystalline products at different pHs (4, 7 and 8), three temperatures (25, 40, 75 °C) and in different media (sulfate vs. nitrate). X-ray diffraction (XRD), Raman, Fourier transform infrared spectroscopy (FTIR) and chemical extraction were employed to characterize the transformed solids as well as the redistribution of Fe between the amorphous and more crystalline phases. The results showed that the transformation product in nitrate media was hematite (major) and goethite (minor), which was independent of pH, temperature or neutralization reagent. In sulfate media, goethite was the dominant solid under slightly acidic conditions (pH 4) with 6-line ferrihydrite as the intermediate product, whereas neutral to slightly alkaline conditions still favor the formation of hematite. Chemical extraction results indicated that there was only ~3 % of amorphous phase detectable after aging at 25 °C for 280 days at slight acidic pH. In contrast,~70 % of the iron remained as an amorphous phase under neutral to slightly alkaline conditions. The results suggested that the pH as well as the reaction media (sulfate ion) plays an important role in the 2-line ferrihydrite transformation process.