Abstract
Dissolution of Fe(III) phases is a key process in making iron available to biota and in the mobilization of associated trace elements. Recently, we have demonstrated that submicromolar concentrations of Fe(II) significantly accelerate rates of ligand-controlled dissolution of Fe(III) (hydr)oxides at circumneutral pH. Here, we extend this work by studying isotope exchange and dissolution with lepidocrocite (Lp) and goethite (Gt) in the presence of 20 or 50 μM desferrioxamine-B (DFOB). Experiments with Lp at pH 7.0 were conducted in carbonate-buffered suspensions to mimic environmental conditions. We applied a simple empirical model to determine dissolution rates and a more complex kinetic model that accounts for the observed isotope exchange and catalytic effect of Fe(II). The fate of added tracer 57Fe(II) was strongly dependent on the order of addition of 57Fe(II) and ligand. When DFOB was added first, tracer 57Fe remained in solution. When 57Fe(II) was added first, isotope exchange between surface and solution could be observed at pH 6.0 but not at pH 7.0 and 8.5 where 57Fe(II) was almost completely adsorbed. During dissolution of Lp with DFOB, ratios of released 56Fe and 57Fe were largely independent of DFOB concentrations. In the absence of DFOB, addition of phenanthroline 30 min after tracer 57Fe desorbed predominantly 56Fe(II), indicating that electron transfer from adsorbed 57Fe to 56Fe of the Lp surface occurs on a time scale of minutes to hours. In contrast, comparable experiments with Gt desorbed predominantly 57Fe(II), suggesting a longer time scale for electron transfer on the Gt surface. Our results show that addition of 1–5 μM Fe(II) leads to dynamic charge transfer between dissolved and adsorbed species and to isotope exchange at the surface, with the dissolution of Lp by ligands accelerated by up to 60-fold.
Highlights
Iron (Fe) mobilization from poorly soluble Fe(III) phases by natural ligands is a key Fe acquisition strategy for organisms in Fe-deficient conditions.[1−14] Siderophore-promoted dissolution rates of Fe(III)(oxyhydr)oxides have been reported to be slow at circumneutral pH, but can be accelerated by synergistic effects of two or more ligands.[15−21] For example, the dissolution rates of hematite,[20,22] ferrihydrite,[23] and goethite with bacterial siderophore desferrioxamine-B (DFOB) were accelerated 2−10 times by addition of oxalate,[15−17,21] Suwannee river fulvic acid,[24] and ascorbate.[20,25]
The catalytic effect (CE) of Fe(II) on the dissolution of Lp at pH 6 with EDTA could be described by a kinetic model in which accelerated dissolution was attributed to electron transfer (ET)
Note that the time interval between addition of the two reactants, here DFOB first followed by Fe(II), was always 1800 s
Summary
Empirical modeling of Lp dissolution at pH 7.0 with Fe(II) added 1800 s after 20 or 50 μM DFOB was conducted to describe the full time course of the experimentally measured dissolved Fe concentrations.
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