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Reduction-Driven Mobilization of Structural Fe in Clay Minerals with High Fe Content

Lookup NU author(s): Dr Anke Neumann

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This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).


Abstract

© 2025 by the authors.Clay minerals contain significant amounts of Fe in their alumosilicate framework, and this structural Fe can be reduced and re-oxidized, constituting a potentially renewable source of reduction equivalents in sedimentary environments. However, dissolution and/or clay mineral transformations during microbial Fe reduction contradict this concept. Here, we investigate how Fe reduction and re-oxidation affect the propensity of Fe to be released from the clay mineral structure and use selective sequential extractions in combination with Mössbauer spectroscopy. Negligible amounts of Fe were released in the sequential extraction of high Fe content clay minerals NAu-1 and NAu-2. Once aqueous Fe(II) was added as a reductant, the extraction procedure recovered the initially added Fe amount and up to 30% of the Fe from the clay mineral structure as both Fe(II) and Fe(III). Similar extents of Fe mobilization were found for clay minerals partly reduced (7%–20%) with dithionite, suggesting that mobilization was reduction-induced and independent of the source of reduction equivalents (Fe(II), dithionite). Although higher Fe reduction extents mobilized more structural Fe, i.e., >90% in fully reduced clay minerals, re-oxidation largely reverted the reduction-induced Fe mobilization in clay minerals. Our finding of reduction-driven Fe mobilization provides a plausible explanation for conflicting reports on Fe release from clay minerals and how extensive Fe atom exchange between aqueous and clay mineral Fe occurs.


Publication metadata

Author(s): Neumann A, Notini L, Premaratne WAPJ, Latta DE, Scherer MM

Publication type: Article

Publication status: Published

Journal: Minerals

Year: 2025

Volume: 15

Issue: 7

Online publication date: 04/07/2025

Acceptance date: 27/06/2025

Date deposited: 04/08/2025

ISSN (electronic): 2075-163X

Publisher: MDPI

URL: https://doi.org/10.3390/min15070713

DOI: 10.3390/min15070713

Data Access Statement: The original contributions presented in this study are included in the article/Supplementary Materials. Further inquiries can be directed to the corresponding author


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Funding

Funder referenceFunder name
German Research Foundation (grant number NE 1715/1-1).
Swiss National Science Foundation (grant number PBEZP2_137292)

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