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Birnessite Dissolution at the Mineral-Ligand Interface: A Deferoxamine Pathway
1Department of Chemistry, Sharif University of Technology, Tehran 11155-9516, Iran.
Deferoxamine (DEFO) interacts with manganese oxides, reducing Mn(IV) to Mn(II) via Mn(III) intermediates. This process involves DEFO oxidation and radical formation, clarifying manganese extraction mechanisms.
Area of Science:
- Environmental Science
- Geochemistry
- Microbiology
Background:
- Siderophores, like deferoxamine (DEFO), chelate iron for microorganisms.
- The interaction between DEFO and manganese (hydr)oxides is not fully understood.
- Birnessite is a common layered manganese(IV) oxide.
Purpose of the Study:
- To elucidate the mechanism of manganese extraction by DEFO from birnessite.
- To investigate the redox reactions and radical species formation during DEFO-birnessite interaction.
Main Methods:
- X-ray diffraction (XRD)
- UV-Vis spectroscopy
- Electron paramagnetic resonance (EPR) spectroscopy
- EDX-mapping
- FE-SEM
Main Results:
- DEFO interacts with birnessite, leading to manganese reduction (Mn(IV) → Mn(III) → Mn(II)).
- A transient Mn(III) intermediate coordinates with DEFO, forming a Mn(II)-DEFO complex.
- Radical intermediates were observed, indicating DEFO oxidation during manganese reduction.
Conclusions:
- DEFO facilitates manganese extraction from birnessite through a redox mechanism.
- The study clarifies the role of DEFO in manganese biogeochemical cycling.
- Radical intermediates are key to understanding DEFO-manganese oxide interactions.
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