Properties of impurity-bearing ferrihydrite I. Effects of Al content and precipitation rate on the structure of 2-line ferrihydrite

The association of Al with ferrihydrite (Fh) may have a considerable effect on the composition, structure, and surface properties of Fh nanoparticles, and thus impact its reactivity and interaction with pollutant species. Aluminous Fh is abundant in natural environments, but the mode of association of Al with this nanomineral is not yet fully understood. Al3+ speciation may vary from true chemical substitution for Fe3+, to adsorption or surface precipitation, and/or to formation of a mixture of two (or more) individual nanoscale phases. The conditions of formation (i.e. slow vs. rapid precipitation) may also affect the nature of Fh nanoparticles in terms of their crystallinity, phase purity, and Al speciation. In this study we used a variety of laboratory (TEM, NMR, ICP-AES) and synchrotron-based techniques (X-ray total scattering and PDF analysis, scanning transmission X-ray microscopy, Al K-edge XANES spectroscopy) to characterize two synthetic Al-bearing Fh series formed at different precipitation rates in the presence of 5-40 mol% Al. We find that Al is dominantly octahedrally coordinated in the synthetic Fh samples and that up to 20-30 mol% Al substitutes for Fe in the Fh structure, regardless of the synthesis method we used. Formation of separate aluminous phases (e. g., gibbsite) was most significant at Al concentrations above 30 mol% Al in slowly precipitated samples. However, small amounts (<6% of total Al) of Al-hydroxide phases were also detected by NMR spectroscopy in samples with lower Al content (as low as 15 mol% Al), particularly in the Fh series that was precipitated slowly. Furthermore, it appears that the amount of Al incorporated in Fh is not affected by the synthesis methods we used and is more likely controlled by the accumulated strain caused by Al substitution in the Fh lattice. Given the prevalence of naturally occurring aluminous ferrihydrite, assumptions about ferrihydrite reactivity in natural environments should consider the impact of Al substitution on reduction potential, Fe bioavailability, as well as sorption reactions. (C) 2012 Elsevier Ltd. All rights reserved.