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.

Even with state of the art forecasting methods, the short-term generation of wind farms cannot be predicted with a high degree of accuracy. In a market situation, these forecasting errors lead to commercial risk through imbalance costs when advance contracting. This situation is one that needs to be addressed due to the steady increase in the amount of grid connected wind generation, combined with the rise of deregulated, market orientated electricity systems. In the presence of imbalance prices and uncertain generation, a method is required to determine the optimum level of contract energy to be sold on the advance markets. Such a method is presented here using Markov Probabilities for a wind farm and demonstrates substantial reductions in the imbalance costs. The effect of market closure delays and forecasting window lengths are also shown.

Understanding interactions between iron (oxyhydr)oxide nanoparticles and plutonium is essential to underpin technology to treat radioactive effluents, in cleanup of land contaminated with radionuclides, and to ensure the safe disposal of radioactive wastes. These interactions include a range of adsorption, precipitation, and incorporation processes. Here, we explore the mechanisms of plutonium sequestration during ferrihydrite precipitation from an acidic solution. The initial 1 M HNO 3 solution with Fe(III) (aq) and 242 Pu(IV) (aq) underwent controlled hydrolysis via the addition of NaOH to pH 9. The majority of Fe(III) (aq) and Pu(IV) (aq) was removed from solution between pH 2 and 3 during ferrihydrite formation. Analysis of Pu− ferrihydrite by extended X-ray absorption fine structure (EXAFS) spectroscopy showed that Pu(IV) formed an inner-sphere tetradentate complex on the ferrihydrite surface, with minor amounts of PuO 2 present. Best fits to the EXAFS data collected from Pu−ferrihydrite samples aged for 2 and 6 months showed no statistically significant change in the Pu(IV)−Fe oxyhydroxide surface complex despite the ferrihydrite undergoing extensive recrystallization to hematite. This suggests the Pu remains strongly sorbed to the iron (oxyhydr)oxide surface and could be retained over extended time periods.