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  • Publication
    Accès libre
    Contact with soil impacts ferrihydrite and lepidocrocite transformations during redox cycling in a paddy soil
    (2023)
    Katrin Schulz
    ;
    Luiza Notini
    ;
    Andrew R. C. Grigg
    ;
    L. Joëlle Kubeneck
    ;
    Worachart Wisawapipat
    ;
    ;
    Ruben Kretzschmar
    Iron (Fe) oxyhydroxides can be reductively dissolved or transformed under Fe reducing conditions, affecting mineral crystallinity and the sorption capacity for other elements. However, the pathways and rates at which these processes occur under natural soil conditions are still poorly understood. Here, we studied Fe oxyhydroxide transformations during reduction–oxidation cycles by incubating mesh bags containing ferrihydrite or lepidocrocite in paddy soil mesocosms for up to 12 weeks. To investigate the influence of close contact with the soil matrix, mesh bags were either filled with pure Fe minerals or with soil mixed with 57Fe-labeled Fe minerals. Three cycles of flooding (3 weeks) and drainage (1 week) were applied to induce soil redox cycles. The Fe mineral composition was analyzed with Fe K-edge X-ray absorption fine structure spectroscopy, X-ray diffraction analysis and/or 57Fe Mössbauer spectroscopy. Ferrihydrite and lepidocrocite in mesh bags without soil transformed to magnetite and/or goethite, likely catalyzed by Fe(II) released to the pore water by microbial Fe reduction in the surrounding soil. In contrast, 57Fe-ferrihydrite in mineral-soil mixes transformed to a highly disordered mixed-valence Fe(II)–Fe(III) phase, suggesting hindered transformation to crystalline Fe minerals. The 57Fe-lepidocrocite transformed to goethite and small amounts of the highly disordered Fe phase. The extent of reductive dissolution of minerals in 57Fe-mineral-soil mixes during anoxic periods increased with every redox cycle, while ferrihydrite and lepidocrocite precipitated during oxic periods. The results demonstrate that the soil matrix strongly impacts Fe oxyhydroxide transformations when minerals are in close spatial association or direct contact with other soil components. This can lead to highly disordered and reactive Fe phases from ferrihydrite rather than crystalline mineral products and promoted goethite formation from lepidocrocite.
  • Publication
    Accès libre
    A New Approach for Investigating Iron Mineral Transformations in Soils and Sediments Using 57Fe-Labeled Minerals and 57Fe Mössbauer Spectroscopy
    (2023)
    Luiza Notini
    ;
    Katrin Schulz
    ;
    L. Joëlle Kubeneck
    ;
    Andrew R. C. Grigg
    ;
    Katherine A. Rothwell
    ;
    Giulia Fantappiè
    ;
    ;
    Ruben Kretzschmar
    Iron minerals in soils and sediments play important roles in many biogeochemical processes and therefore influence the cycling of major and trace elements and the fate of pollutants in the environment. However, the kinetics and pathways of Fe mineral recrystallization and transformation processes under environmentally relevant conditions are still elusive. Here, we present a novel approach enabling us to follow the transformations of Fe minerals added to soils or sediments in close spatial association with complex solid matrices including other minerals, organic matter, and microorganisms. Minerals enriched with the stable isotope 57Fe are mixed with soil or sediment, and changes in Fe speciation are subsequently studied by 57Fe Mössbauer spectroscopy, which exclusively detects 57Fe. In this study, 57Fe-labeled ferrihydrite was synthesized, mixed with four soils differing in chemical and physical properties, and incubated for 12+ weeks under anoxic conditions. Our results reveal that the formation of crystalline Fe(III)(oxyhydr)oxides such as lepidocrocite and goethite was strongly suppressed, and instead formation of a green rust-like phase was observed in all soils. These results contrast those from Fe(II)-catalyzed ferrihydrite transformation experiments, where formation of lepidocrocite, goethite, and/or magnetite often occurs. The presented approach allows control over the composition and crystallinity of the initial Fe mineral, and it can be easily adapted to other experimental setups or Fe minerals. It thus offers great potential for future investigations of Fe mineral transformations in situ under environmentally relevant conditions, in both the laboratory and the field.
  • Publication
    Accès libre
    Ferrihydrite transformations in flooded paddy soils: rates, pathways, and product spatial distributions
    (2022)
    Andrew R. C. Grigg
    ;
    ;
    Katrin Schulz
    ;
    Katherine A. Rothwell
    ;
    Ralf Kaegi
    ;
    Ruben Kretzschmar
    Complex interactions between redox-driven element cycles in soils influence iron mineral transformation processes. The rates and pathways of iron mineral transformation processes have been studied intensely in model systems such as mixed suspensions, but transformation in complex heterogeneous porous media is not well understood. Here, mesh bags containing 0.5 g of ferrihydrite were incubated in five watersaturated paddy soils with contrasting microbial iron-reduction potential for up to twelve weeks. Using X-ray diffraction analysis, we show near-complete transformation of the ferrihydrite to lepidocrocite and goethite within six weeks in the soil with the highest iron(II) release, and slower transformation with higher ratios of goethite to lepidocrocite in soils with lower iron(II) release. In the least reduced soil, no mineral transformations were observed. In soils where ferrihydrite transformation occurred, the transformation rate was one to three orders of magnitude slower than transformation in comparable mixed-suspension studies. To interpret the spatial distribution of ferrihydrite and its transformation products, we developed a novel application of confocal micro-Raman spectroscopy in which we identified and mapped minerals on selected cross sections of mesh bag contents. After two weeks of flooded incubation, ferrihydrite was still abundant in the core of some mesh bags, and as a rim at the mineral–soil interface. The reacted outer core contained unevenly mixed ferrihydrite, goethite and lepidocrocite on the micrometre scale. The slower rate of transformation and uneven distribution of product minerals highlight the influence of biogeochemically complex matrices and diffusion processes on the transformation of minerals, and the importance of studying iron mineral transformation in environmental media.
  • Publication
    Accès libre
    Stabilization of Ferrihydrite and Lepidocrocite by Silicate during Fe(II)-Catalyzed Mineral Transformation: Impact on Particle Morphology and Silicate Distribution
    (2022)
    Katrin Schulz
    ;
    ;
    Ralf Kaegi
    ;
    Ruben Kretzschmar
    Interactions between aqueous ferrous iron (Fe(II)) and secondary Fe oxyhydroxides catalyze mineral recrystallization and/or transformation processes in anoxic soils and sediments, where oxyanions, such as silicate, are abundant. However, the effect and the fate of silicate during Fe mineral recrystallization and transformation are not entirely understood and especially remain unclear for lepidocrocite. In this study, we reacted (Si-)ferrihydrite (Si/Fe = 0, 0.05, and 0.18) and (Si-)lepidocrocite (Si/Fe = 0 and 0.08) with isotopically labeled 57Fe(II) (Fe(II)/Fe(III) = 0.02 and 0.2) at pH 7 for up to 4 weeks. We followed Fe mineral transformations with X-ray diffraction and tracked Fe atom exchange by measuring aqueous and solid phase Fe isotope fractions. Our results show that the extent of ferrihydrite transformation in the presence of Fe(II) was strongly influenced by the solid phase Si/Fe ratio, while increasing the Fe(II)/ Fe(III) ratio (from 0.02 to 0.2) had only a minor effect. The presence of silicate increased the thickness of newly formed lepidocrocite crystallites, and elemental distribution maps of Fe(II)-reacted Si-ferrihydrites revealed that much more Si was associated with the remaining ferrihydrite than with the newly formed lepidocrocite. Pure lepidocrocite underwent recrystallization in the low Fe(II) treatment and transformed to magnetite at the high Fe(II)/Fe(III) ratio. Adsorbed silicate inactivated the lepidocrocite surfaces, which strongly reduced Fe atom exchange and inhibited mineral transformation. Collectively, the results of this study demonstrate that Fe(II)-catalyzed Si-ferrihydrite transformation leads to the redistribution of silicate in the solid phase and the formation of thicker lepidocrocite platelets, while lepidocrocite transformation can be completely inhibited by adsorbed silicate. Therefore, silicate is an important factor to include when considering Fe mineral dynamics in soils under reducing conditions.