Ferrihydrite is the most common iron oxyhydroxide found in soil and is a key sequester of contaminants in the environment. Ferrihydrite formation is also a common component of many treatment processes for cleanup of industrial effluents. Here we characterize ferrihydrite formation during the titration of an acidic ferric nitrate solution with NaOH. In situ SAXS measurements supported by ex situ TEM indicate that initially Fe13 Keggin clusters (radius ∼ 0.45 nm) form in solution at pH 0.12-1.5 and are persistent for at least 18 days. The Fe13 clusters begin to aggregate above ∼ pH 1, initially forming highly linear structures. Above pH ∼ 2 densification of the aggregates occurs in conjunction with precipitation of low molecular weight Fe(III) species (e.g., monomers, dimers) to form mass fractal aggregates of ferrihydrite nanoparticles (∼3 nm) in which the Fe13 Keggin motif is preserved. SAXS analysis indicates the ferrihydrite particles have a core-shell structure consisting of a Keggin center surrounded by a Fe-depleted shell, supporting the surface depleted model of ferrihydrite. Overall, we present the first direct evidence for the role of Fe13 clusters in the pathway of ferrihydrite formation during base hydrolysis, showing clear structural continuity from isolated Fe13 Keggins to the ferrihydrite particle structure. The results have direct relevance to the fundamental understanding of ferrihydrite formation in environmental, engineered, and industrial processes.

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The distribution of 152Eu between magnesium hydroxide bulk, colloids and solution has been assessed under alkaline conditions, such as those in nuclear fuel storage ponds. The colloidal phase has been characterised by two complementary methods: coupled ultrafiltration-ICP-AES and scanning electron microscopy. The quantity and the size distribution of the colloidal phase is strongly ionic strength-dependent. A decrease of the quantity of colloids, in particular the larger size ranges, has been observed with increasing ionic strength. Small colloids (1 kDa-10 kDa fraction) are predominant at all ionic strengths. The morphology of colloids, observed by field-emission gun scanning electron microscopy, appears to change from hexagonal prismatic (characteristic to the mineral) to spherical (energetically more favourable) as size decreases. The distribution of 152Eu between the solid and liquid/colloidal phases has been investigated at carbonate concentrations ranging from 0 to 10(-2) M by coupled ultrafiltration and gamma-spectrometry. Mg(OH)2 bulk appears to be a very strong sorbent for 152Eu, since complete sorption onto the bulk happens for carbonate concentrations as high as 10(-3) M. Scavenging of 152Eu by Mg(OH)2 colloids is negligible in the presence of Mg(OH)2 bulk. The distribution of 152Eu between liquid and colloidal phases has been investigated in the absence of bulk at various carbonate concentrations. A significant uptake of 152Eu by the colloids in solution has been observed, which decreases with increasing carbonate concentration. 152Eu appears to be mainly associated to the smallest colloids (1 kDa-10 kDa fraction). There is a strong correlation between the sorption properties and the surface area of the colloids.