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 mineral-organic 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 57Fe(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 57Fe Mössbauer spectroscopy, we sought to follow the temporal evolution in Fe mineralogy and elucidate the fate of adsorbed 57Fe(II). At low C:Fe molar ratios (0-0.05), rapid oxidation of surface-adsorbed 57Fe(II) resulted in 57Fe-enriched crystalline minerals and nearly complete mineral transformation within days. With increasing OM content, the atom exchange between the added aqueous 57Fe(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), Mössbauer spectroscopy revealed up to 39% lepidocrocite in the final Fe(II)-reacted samples. Because lepidocrocite was not detectable by XRD, we suggest that the Mössbauer-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).