Impact of Organic Matter on Iron(II)-Catalyzed Mineral Transformations in Ferrihydrite-Organic Matter Coprecipitates

Poorly crystalline Fe(III) (oxyhydr)oxides like ferrihydrite are abundant in soils and sediments and are often associated with organic matter (OM) in the form of mineralorganic aggregates. Under anoxic conditions, interactions between aqueous Fe(II) and ferrihydrite lead to the formation of crystalline secondary minerals, like lepidocrocite, goethite, or magnetite. However, the extent to which Fe(II)-catalyzed mineral transformations are influenced by ferrihydrite-associated OM is not well understood. We therefore reacted ferrihydrite-PGA coprecipitates (PGA = polygalacturonic acid, C:Fe molar ratios = 0-2.5) and natural Fe-rich organic flocs (C:Fe molar ratio = 2.2) with 0.5-5.0 mM isotopically labeled Fe-57(II) at pH 7 for 5 weeks. Relying on the combination of stable Fe isotope tracers, a novel application of the PONKCS method to Rietveld fitting of X-ray diffraction (XRD) patterns, and Fe-57 Mossbauer spectroscopy, we sought to follow the temporal evolution in Fe mineralogy and elucidate the fate of adsorbed Fe-57(II). At low C:Fe molar ratios (0-0.05), rapid oxidation of surface-adsorbed Fe-57(II) resulted in Fe-57 enriched crystalline minerals and nearly complete mineral transformation within days. With increasing OM content, the atom exchange between the added aqueous Fe-57(II) and Fe in the organic-rich solids still occurred; however, XRD analysis showed that crystalline mineral precipitation was strongly inhibited. For high OM-content materials (C:Fe >= 1.2), Mossbauer spectroscopy revealed up to 39% lepidocrocite in the final Fe(II)-reacted samples. Because lepidocrocite was not detectable by XRD, we suggest that the Mossbauer-detected lepidocrocite consisted of nanosized clusters with lepidocrocite-like local structure, similar to the lepidocrocite found in natural flocs. Collectively, our results demonstrate that the C content of ferrihydrite-OM coprecipitates strongly impacts the degree and pathways of Fe mineral transformations and iron atom exchange during reactions with aqueous Fe(II).