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Abstract

An ascorbic acid extraction at pH 7.5 has been examined to assess the influence of reaction conditions (pH, ascorbic acid concentration) on the dissolution of Fe from synthetic 2-line ferrihydrite and from other Fe-bearing minerals. The method was highly selective for Fe in ferrihydrite with only small amounts of Fe extracted from other (oxyhydr)oxides or clays. The labile Fe extracted from the synthetic 2-line ferrihydrite stored as a slurry decreased with time, and high resolution microscopy showed that the older materials formed networked aggregates that slow down the dissolution. The apparent rate constant for the dissolution of fresh 2-line ferrihydrite (similar to 10(-3) s(-1)) was an order of magnitude larger than that for aged suspensions (similar to 10(-4) s(-1)). Fresh 2-line ferrihydrite that was filtered, freeze-dried, frozen and freeze-dried, and stored in the dry was even less readily dissolved (apparent rate constants similar to 10(-6) s(-1)). These ferrihydrites also contained networked aggregates and, additionally, appear to occur as granular aggregates (visible to the naked eye) during the early stages of dissolution. Storage of filtered, freeze-dried, and frozen and freeze-dried ferrihydrites, whether in water or air, produced similar dissolution behaviour because aggregation caused by de-watering decreases the labile Fe content and is not reversed by re-hydration. The determination of labile Fe in ferrihydrite requires that natural samples should be collected, stored and extracted wet. The most aged samples dissolved by parabolic dissolution kinetics indicate that the rates of dissolution were controlled by the diffusion of reactant into the internal porosity of aggregates. (C) 2010 Elsevier B.V. All rights reserved.