Low bioavailability of iron due to poor solubility of iron(hydr)oxides limits the growth of microorganisms and plants in soils and aquatic environments. Previous studies described accelerated dissolution of iron(hydr)oxides under continuous illumination, but did not distinguish between photoreductive dissolution and non-reductive processes in which photogenerated Fe(II) catalyzes ligand-controlled dissolution. Here we show that short illuminations (5-15 min) accelerate the dissolution of iron(hydr)oxides by ligands during subsequent dark periods under anoxic conditions. Suspensions of lepidocrocite (Lp) and goethite (Gt) (1.13 mM) with 50 μM EDTA or DFOB were illuminated with UV-A light of comparable intensity to sunlight (pH 7.0, bicarbonate-CO₂ buffered solutions). During illumination, the rate of Fe(II) production was highest with Gt-EDTA; followed by Lp-EDTA > Lp-DFOB > Lp > Gt-DFOB > Gt. Under anoxic conditions, photochemically produced Fe(II) increased dissolution rates during subsequent dark periods by factors of 10-40 and dissolved Fe(III) reached 50 μM with DFOB and EDTA. Under oxic conditions, dissolution rates increased by factors of 3-5 only during illumination. With DFOB dissolved Fe(III) reached 35 μM after 10 h of illumination, while with EDTA it peaked at 15 μM and then decreased to below 2 μM. The observations are explained and discussed based on a kinetic model. The results suggest that in anoxic bottom water of ponds and lakes, or in microenvironments of algal blooms, short illuminations can dramatically increase the bioavailability of iron by Fe(II)-catalyzed ligand-controlled dissolution. In oxic environments, photostable ligands such as DFOB can maintain Fe(III) in solution during extended illumination.

Groundwater contaminated with geogenic arsenic (As) is frequently used as drinking water in Burkina Faso, despite adverse health effects. This study focused on testing low-cost filter systems based on zero-valent iron (ZVI), which have not yet been explored in West Africa for As removal. The active ZVI bed was constructed using small-sized iron nails, embedded between sand layers. Household filters were tested for nine months in a remote village relying on tube well water with As concentrations of 400 - 1350 μg/L. Daily filtered volumes were 40 - 60 L, with flow rates of ~10 L/h. In parallel, downscaled laboratory filter columns were run to find the best set-up for optimal As removal, with special attention given to the influence of input pH, flow rate and water/nail contact time. Arsenic removal efficiencies in the field were 60 - 80% in the first six months of operation. The laboratory experiments revealed that trapped air in the nail layer greatly lowered As removal due to preferential flow and decreased water/nail contact time. Measures taken to avoid trapped air led to a partial improvement in the field filters, but effluent As remained >50 μg/L. Similar structural modifications were however very successful in the laboratory columns, where As removal efficiencies were consistently > 95% and effluent concentrations frequently < 10 μg/L, despite inflow As > 1000 μg/L. A constantly saturated nail bed and careful flow control is necessary for optimal As removal. Slow flow and longer pauses between filtrations are important for sufficient contact times and for transformation of brown amorphous Fe-hydroxides to dense magnetite with incorporated As(V). This preliminary study has shown that nail-based filters have the potential to achieve As removal >90% in a field context if conditions (filter bed saturation, flow rate, pauses between filtrations) are well controlled.

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.

Dissolution of Fe(III) (hydr)oxide minerals by siderophores (i.e., Fe-specific, biogenic ligands) is an important step in Fe acquisition in environments where Fe availability is low. The observed coexudation of reductants and ligands has raised the question of how redox reactions might affect ligand-controlled (hydr)oxide dissolution and Fe acquisition. We examined this effect in batch dissolution experiments using two structurally distinct ligands (desferrioxamine B (DFOB) and N,N′-di(2-hydroxybenzyl)- ethylene-diamine-N,N′-diacetic acid (HBED)) and four Fe(III) (hydr)oxide minerals (lepidocrocite, 2-line ferrihydrite, goethite and hematite) over an environmentally relevant pH range (4-8.5). The experiments were conducted under anaerobic conditions with varying concentrations of (adsorbed) Fe(II) as the reductant. We observed a catalytic effect of Fe(II) on ligand-controlled dissolution even at submicromolar Fe(II) concentrations with up to a 13-fold increase in dissolution rate. The effect was larger for HBED than for DFOB. It was observed for all four Fe(III) (hydr)oxide minerals, but it was most pronounced for goethite in the presence of HBED. It was observed over the entire pH range with the largest effect at pH 7 and 8.5, where Fe deficiency typically occurs. The occurrence of this catalytic effect over a range of environmentally relevant conditions and at very low Fe(II) concentrations suggests that redox-catalyzed, ligand-controlled dissolution may be significant in biological Fe acquisition and in redox transition zones.

Dissolution of iron(III)phases is a key process in soils, surface waters, and the ocean. Previous studies found that traces of Fe(II) can greatly increase ligand controlled dissolution rates at acidic pH, but the extent that this also occurs at circumneutral pH and what mechanisms are involved are not known. We addressed these questions with infrared spectroscopy and ⁵⁷Fe isotope exchange experiments with lepidocrocite (Lp) and 50 μM ethylenediaminetetraacetate (EDTA) at pH 6 and 7. Addition of 0.2-10 μM Fe(II) led to an acceleration of the dissolution rates by factors of 7-31. Similar effects were observed after irradiation with 365 nm UV light. The catalytic effect persisted under anoxic conditions, but decreased as soon as air or phenanthroline was introduced. Isotope exchange experiments showed that added ⁵⁷Fe remained in solution, or quickly reappeared in solution when EDTA was added after ⁵⁷Fe(II), suggesting that catalyzed dissolution occurred at or near the site of ⁵⁷Fe incorporation at the mineral surface. Infrared spectra indicated no change in the bulk, but changes in the spectra of adsorbed EDTA after addition of Fe(II) were observed. A kinetic model shows that the catalytic effect can be explained by electron transfer to surface Fe(III) sites and rapid detachment of Fe(III)EDTA due to the weaker bonds to reduced sites. We conclude that the catalytic effect of Fe(II) on dissolution of Fe(III)(hydr)oxides is likely important under circumneutral anoxic conditions and in sunlit environments.

Oxalate, together with other ligands, plays an important role in the dissolution of iron(hdyr)oxides and the bio-availability of iron. The formation and properties of oxalate surface complexes on lepidocrocite were studied with a combination of infrared spectroscopy (IR), density functional theory (DFT) calculations, dissolution, and photochemical experiments. IR spectra measured as a function of time, concentration, and pH (50-200 μM oxalate, pH 3-7) showed that several surface complexes are formed at different rates and in different proportions. Measured spectra could be separated into three contributions described by Gaussian line shapes, with frequencies that agreed well with the theoretical frequencies of three different surface complexes: an outer-sphere complex (OS), an inner-sphere monodentate mononuclear complex (MM), and a bidentate mononuclear complex (BM) involving one O atom from each carboxylate group. At pH 6, OS was formed at the highest rate. The contribution of BM increased with decreasing pH. In dissolution experiments, lepidocrocite was dissolved at rates proportional to the surface concentration of BM, rather than to the total adsorbed concentration. Under UV-light (365 nm), BM was photolyzed at a higher rate than MM and OS. Although the comparison of measured spectra with calculated frequencies cannot exclude additional possible structures, the combined results allowed the assignment of three main structures with different reactivities consistent with experiments. The results illustrate the importance of the surface speciation of adsorbed ligands in dissolution and photochemical reactions.