Transformation of vivianite in intertidal sediments with contrasting sulfide conditions

Kubeneck, L. Joëlle; Notini, Luiza; Rothwell, Katherine A.; Fantappiè, Giulia; Huthwelker, Thomas; ThomasArrigo, Laurel K.; Kretzschmar, Ruben

doi:10.1016/j.gca.2024.01.020

Geochimica et Cosmochimica Acta

2024

DOI: 10.1016/j.gca.2024.01.020

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Transformation of vivianite in intertidal sediments with contrasting sulfide conditions

L. Joëlle Kubeneck,

Luiza Notini,

Katherine A. Rothwell

et al.

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2024

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Cited by 4 publications

References 100 publications

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Sulfate-mediated Fe(III) mineral reduction accelerates arsenic mobilization by a Desulfovibrio strain isolated from paddy soil

Wu,

Huang,

Zhang

et al. 2024

Science of The Total Environment

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Sulfate-mediated Fe(III) mineral reduction accelerates arsenic mobilization by a Desulfovibrio strain isolated from paddy soil

Wu,

Huang,

Zhang

et al. 2024

Science of The Total Environment

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The Influence of Seawater on Fe(II)-Catalyzed Ferrihydrite Transformation and Its Subsequent Consequences for C Dynamics

Dong,

Wang,

et al. 2024

Environ. Sci. Technol.

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Short-range-ordered minerals like ferrihydrite often bind substantial organic carbon (OC), which can be altered if the minerals transform. Such mineral transformations can be catalyzed by aqueous Fe(II) (Fe(II) aq ) in redox-dynamic environments like coastal wetlands, which are inundated with seawater during storm surges or tidal events associated with sea-level rise. Yet, it is unknown how seawater salinity will impact Fe(II)-catalyzed ferrihydrite transformation or the fate of bound OC. We reacted ferrihydrite with Fe(II) aq under anoxic conditions in the absence and presence of dissolved organic matter (DOM). We compared treatments with no salts (DI water), NaCl−KCl salts, and artificial seawater mixes (containing Ca and Mg ions) with or without SO 4 2− /HCO 3 − . Both XRD and Mossbauer showed that NaCl−KCl favored lepidocrocite formation, whereas Ca 2+ /Mg 2+ /SO 4 2− /HCO 3 − ions in seawater overrode the effects of NaCl−KCl and facilitated goethite formation. We found that the highly unsaturated and phenolic compounds (HuPh) of DOM selectively bound to Fe minerals, promoting nanogoethite formation in seawater treatments. Regardless of salt presence, only 5−9% of Fe-bound OC was released during ferrihydrite transformation, enriching HuPh relative to aliphatics in solution. This study offers new insights into the occurrence of (nano)goethite and the role of Fe minerals in OC protection in coastal wetlands.

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Geochemical Decoupling of Iron and Zinc during Transformation of Zn-Bearing Ferrihydrite in Reducing Sediments

Lefebvre,

Grigg,

Kretzschmar

2024

Environ. Sci. Technol.

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The transformation of the mineral ferrihydrite in reducing environments, and its impact on the mobility of incorporated trace metals, has been investigated in model laboratory studies, but studies using complex soil or sediment matrices are lacking. Here, we studied the transformation of zinc (Zn)-bearing ferrihydrite labeled with 57 Fe and mixed with natural sediments, incubated in reducing conditions for up to six months. We tracked the evolution of Fe and Zn speciation with 57 Fe Mossbauer spectroscopy and with bulk and micro-X-ray absorption spectroscopy. We show that Fe was readily reduced and incorporated into a poorly crystalline mixed-valence Fe(II)− Fe(III) phase resembling green rust. In parallel, Zn was released in the surrounding porewater and scavenged by precipitation with available ligands, particularly as zinc sulfide (ZnS) or Zncarbonates. Early in the mineral transformation process, the chemical behavior of Fe was decoupled from Zn, suppressing the impact of Zn on the rates and products of the ferrihydrite transformation. Our results underline the discrepancy between model experiments and complex field-like conditions and highlight the importance of sediment and soil geochemistry and ligand competition on the fate of divalent metal contaminants in the environment.

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Transformation of vivianite in intertidal sediments with contrasting sulfide conditions

Cited by 4 publications

References 100 publications

Sulfate-mediated Fe(III) mineral reduction accelerates arsenic mobilization by a Desulfovibrio strain isolated from paddy soil

Sulfate-mediated Fe(III) mineral reduction accelerates arsenic mobilization by a Desulfovibrio strain isolated from paddy soil

The Influence of Seawater on Fe(II)-Catalyzed Ferrihydrite Transformation and Its Subsequent Consequences for C Dynamics

Geochemical Decoupling of Iron and Zinc during Transformation of Zn-Bearing Ferrihydrite in Reducing Sediments

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