An in situ XAS study of ferric iron hydrolysis and precipitation in the presence of perchlorate, nitrate, chloride and sulfate

Using a novel combination of in situ potentiometric experiments and quick-scanning XAS we present Fe K-edge XAS spectra (to k = 12 Å−1) during FeIII hydrolysis and precipitation in 0.33 M Fe(ClO4)3, Fe(NO3)3, FeCl3 and Fe2(SO4)3 solutions up to pH 4.8. Edge-sharing FeIII polymers appeared almost immediately upon hydrolysis with strong evidence for a μ-oxo dimer species forming in the Fe(ClO4)3, Fe(NO3)3 and FeCl3 solutions. The effects of SO4 on hydrolysis and polymerization pathways included inhibition of both the formation of the μ-oxo dimer and double corner FeIII bonding, ultimately resulting in the precipitation of schwertmannite. As such, under these experimental conditions, double corner FeIII bonding appears to be critical to the formation of ferrihydrite. The spectral trends indicated that the decomposition/transformation of the dimer was sudden and broadly coincident with shortening average Fe-O bond distances, increased Fe neighbors at ∼3.43 Å and a pre-edge energy transformation suggestive of decreased ligand field strength as well as increasing proportions of tetrahedral FeIII. This result suggests that the incorporation of tetrahedral FeIII into ferrihydrite occurs only at the latter stages of extended polymerization.