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Importance of oxidation products in coumarin-mediated Fe(hydr)oxide mineral dissolution

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Abstract

Due to the low iron solubility in alkaline soils, plants have evolved different iron acquisition strategies, which are either based on ferric iron reduction (strategy I) or complexation by phytosiderophores (strategy II). Recently, a prominent role of coumarins for iron acquisition has been discovered, but details of the respective mechanism remain unclear. Since coumarins may act as iron-binding ligands but also as reductants, various reaction sequences are possible, resulting in different iron species and oxidized coumarins. In this context, it is often overlooked that oxidized coumarins are not just byproducts of iron(III) reduction, but may be actively involved in further steps of iron mobilization. In order to verify this active role of oxidized coumarins in Fe(hydr)oxide dissolution, we complemented iron dissolution data with data of single coumarins (esculetin, scopoletin, fraxetin) and their oxidation products, as a function of time, pH, and mineral (goethite, lepidocrocite). Our results demonstrate that there are four different routes for coumarin oxidation, leading to quinones, dimers, hydroxylated coumarins, demethylated coumarins, and combinations of these. The time-dependent species pattern differs with respect to mineral, pH, and coumarin molecule. Oxidized coumarins are often more reactive than the original coumarins, explaining unexpected iron mobilization by scopoletin, which is demethylated to esculetin. Also oxidative hydroxylation and dimerization increase the number of phenolic groups and yield new chelating properties. Several iron-species are identified for the three coumarins. Since oxidation reactions are initiated directly at mineral surfaces, they are often very effective—but this does not always result in more iron mobilization.

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Acknowledgements

Funding by the DFG (Grant WE 2422/8-1), and financial support by the‚ Ministerium für Innovation, Wissenschaft und Forschung des Landes Nordrhein-Westfalen ‘and by the‚ Bundesministerium für Bildung und Forschung’ is greatfully acknowledged.

Funding

Deutsche Forschungsgemeinschaft. Ministerium für Innovation, Wissenschaft und Forschung des Landes Nordrhein-Westfalen. Bundesministerium für Bildung und Forschung.

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Author notes

  1. Günther Weber

    Present address: Justusweg 2, 44149, Dortmund, Germany

Authors and Affiliations

  1. Leibniz-Institut f. Analytische Wissenschaften – ISAS, Dortmund, Germany

    Matthias Baune & Günther Weber

  2. Environmental Geochemistry, Centre for Microbiology and Environmental Systems Science, University of Vienna, Vienna, Austria

    Kyounglim Kang & Stephan M. Kraemer

  3. Copernicus Institute of Sustainable Development, Faculty of Geosciences, Utrecht University, Utrecht, The Netherlands

    Walter D. C. Schenkeveld

  4. Institute of Inorganic and Analytical Chemistry, University of Münster, Münster, Germany

    Heiko Hayen

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  1. Matthias Baune
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Correspondence to Günther Weber.

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Baune, M., Kang, K., Schenkeveld, W.D.C. et al. Importance of oxidation products in coumarin-mediated Fe(hydr)oxide mineral dissolution. Biometals 33, 305–321 (2020). https://doi.org/10.1007/s10534-020-00248-y

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