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• W2897535890 abstract "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)." @default.
• W2897535890 created "2018-10-26" @default.
• W2897535890 creator A5017032128 @default.
• W2897535890 creator A5054889884 @default.
• W2897535890 creator A5066752579 @default.
• W2897535890 creator A5089102233 @default.
• W2897535890 date "2018-10-16" @default.
• W2897535890 modified "2023-10-17" @default.
• W2897535890 title "Impact of Organic Matter on Iron(II)-Catalyzed Mineral Transformations in Ferrihydrite–Organic Matter Coprecipitates" @default.
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• W2897535890 doi "https://doi.org/10.1021/acs.est.8b03206" @default.
• W2897535890 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/30991468" @default.
• W2897535890 hasPublicationYear "2018" @default.
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