Siderophore-Mediated Mobilization of Manganese Limits Iron Solubility in Mixed Mineral Systems

Kang, Kyounglim; Peña, Jasquelin

doi:10.1021/acsearthspacechem.2c00271

Siderophore-Mediated Mobilization of Manganese Limits Iron Solubility in Mixed Mineral Systems

Journal Article · Thu Mar 09 00:00:00 EST 2023 · ACS Earth and Space Chemistry

DOI:https://doi.org/10.1021/acsearthspacechem.2c00271· OSTI ID:2470619

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Univ. of California, Davis, CA (United States)
Univ. of California, Davis, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Recent laboratory and field studies show the need to consider the formation of aqueous Mn(III)-siderophore complexes in manganese (Mn) and iron (Fe) geochemical cycling, a shift from the historical view that aqueous Mn(III) species are unstable and thus unimportant. In this study, we quantified Mn and Fe mobilization by desferrioxamine B (DFOB), a terrestrial bacterial siderophore, in single (Mn or Fe) and mixed (Mn and Fe) mineral systems. We selected manganite (γ-MnOOH), δ-MnO₂, lepidocrocite (γ-FeOOH), and 2-line ferrihydrite (Fe₂O₃·0.5H₂O) as relevant mineral phases. We found that DFOB mobilized Mn(III) as Mn(III)-DFOB complexes to varying extents from both Mn(III,IV) oxyhydroxides but reduction of Mn(IV) to Mn(III) was required for the mobilization of Mn(III) from δ-MnO₂. The initial rates of Mn(III)-DFOB mobilization from manganite and δ-MnO₂ were not affected by the presence of lepidocrocite but decreased by a factor of 5 and 10 for manganite and δ-MnO₂, respectively, in the presence of 2-line ferrihydrite. Additionally, the decomposition of Mn(III)-DFOB complexes through Mn-for-Fe ligand exchange and/or ligand oxidation led to Mn(II) mobilization and Mn(III) precipitation in the mixed-mineral systems (~10% (mol Mn/mol Fe)). As a result, the concentration of Fe(III) mobilized as Fe(III)-DFOB decreased by up to 50% and 80% in the presence of manganite and δ-MnO₂, respectively, compared to the single mineral systems. Our results demonstrate that siderophores, through their complexation of Mn(III), reduction of Mn(III,IV), and mobilization of Mn(II), can redistribute Mn to other soil minerals and limit the bioavailability of Fe in natural systems.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515

OSTI ID:: 2470619

Journal Information:: ACS Earth and Space Chemistry, Journal Name: ACS Earth and Space Chemistry Journal Issue: 4 Vol. 7; ISSN 2472-3452

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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