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  • Publication
    Accès libre
    Mineral characterization and composition of Fe-rich flocs from wetlands of Iceland: Implications for Fe, C and trace element export
    (2022) ;
    Luiza Notini
    ;
    Jeremiah Shuster
    ;
    Tabea Nydegger
    ;
    Sophie Vontobel
    ;
    Stefan Fischer
    ;
    Andreas Kappler
    ;
    Ruben Kretzschmar
    In freshwater wetlands, redox interfaces characterized by circumneutral pH, steep gradients in O2, and a continual supply of Fe(II) form ecological niches favorable to microaerophilic iron(II) oxidizing bacteria (FeOB) and the formation of flocs; associations of (a)biotic mineral phases, microorganisms, and (microbially-derived) organic matter. On the volcanic island of Iceland, wetlands are replenished with Fe-rich surface-, ground- and springwater. Combined with extensive drainage of lowland wetlands, which forms artificial redox gradients, accumulations of bright orange (a)biotically-derived Fe-rich flocs are common features of Icelandic wetlands. These loosely consolidated flocs are easily mobilized, and, considering the proximity of Iceland's lowland wetlands to the coast, are likely to contribute to the suspended sediment load transported to coastal waters. To date, however, little is known regarding (Fe) mineral and elemental composition of the flocs. In this study, flocs from wetlands (n = 16) across Iceland were analyzed using X-ray diffraction and spectroscopic techniques (X-ray absorption and 57Fe Mössbauer) combined with chemical extractions and (electron) microscopy to comprehensively characterize floc mineral, elemental, and structural composition. All flocs were rich in Fe (229–414 mg/g), and floc Fe minerals comprised primarily ferrihydrite and nano-crystalline lepidocrocite, with a single floc sample containing nano-crystalline goethite. Floc mineralogy also included Fe in clay minerals and appreciable poorly-crystalline aluminosilicates, most likely allophane and/or imogolite. Microscopy images revealed that floc (bio)organics largely comprised mineral encrusted microbially-derived components (i.e. sheaths, stalks, and EPS) indicative of common FeOB Leptothrix spp. and Gallionella spp. Trace element contents in the flocs were in the low μg/g range, however nearly all trace elements were extracted with hydroxylamine hydrochloride. This finding suggests that the (a)biotic reductive dissolution of floc Fe minerals, plausibly driven by exposure to the varied geochemical conditions of coastal waters following floc mobilization, could lead to the release of associated trace elements. Thus, the flocs should be considered vectors for transport of Fe, organic carbon, and trace elements from Icelandic wetlands to coastal waters.
  • Publication
    Accès libre
    Iron speciation changes and mobilization of colloids during redox cycling in Fe-rich, Icelandic peat soils
    (2022) ;
    Ruben Kretzschmar
    Soils of Iceland are characterized by an abundance of short-range order (SRO) iron (Fe) minerals and aluminosilicates. Interactions between these SRO mineral phases and soil organic carbon (OC) promote long-term stabilization of the latter through the formation of mineral-organic complexes and aggregates. However, Icelandic soils are also exposed to high rainfall events, which induce anoxic conditions, facilitate microbial reduction of ferric Fe, and may lead to the mobilization of mineral-associated OC. Here, we explored the fate of OC during Fe redox cycling by incubating six organic-rich soil horizons from three typical soil types across Iceland (Histosols, Histic and Gleyic Andosols) as soil slurries under anoxic conditions for up to 5 weeks and followed the effects of re-oxidation after 1, 2, and 5 weeks. Changes in solid-phase Fe speciation were assessed by combining Fe K-edge X-ray absorption spectroscopy with time-resolved parallel selective chemical extractions, and trends in aqueous element contents were measured in both the dissolved (<3 kDa) and fine colloidal fractions (3 kDa to 0.45 µm). In all soils, anoxic incubation resulted in microbial reduction of Fe(III) and concomitant increases in soil solution pH. However, soils containing SRO Fe minerals underwent more extensive Fe reduction. Rapid (<1 wk) increases in aqueous element contents (including Fe, Al, and OC) were recorded in all soil slurries, and mobilization of colloids occurred in soil horizons which reached the highest pH values (>4.6). Mobilized colloids persisted during re-oxidation of the soil slurries, which also resulted in the formation of new Fe mineral phases, the composition of which was influenced by initial soil Fe mineralogy. Collectively, our results suggest that increases in the frequency of redox cycles in Icelandic soils are likely to result in shifts in Fe mineralogy and may contribute to the increased mobilization of soil OC as organic-Fe-/Al-colloids.