Coupled biogeochemical cycling of iron and manganese as mediated by microbial siderophores

Duckworth, Owen W.; Bargar, John R.; Sposito, Garrison

doi:10.1007/s10534-009-9220-9

Cited by 62 publications

(45 citation statements)

References 59 publications

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“…Nevertheless, siderophores may play an important role in biogenic cycling of manganese [10,19,37,38] .…”

Section: Discussionmentioning

confidence: 99%

“…In a similar fashion to siderophore-mediated extraction of Fe(III) from iron oxide minerals, siderophores have been shown to dissolve manganite (-MnOOH) and hausmannite (Mn 3 O 4 ) through pH-dependent processes [7][8][9]. Thus siderophores may be involved in biogenic cycling of manganese [10][11][12]. Mn(III) is not stable in aqueous solutions and readily disproportionates to Mn(II) and a variety of Mn(IV) oxides and hydroxides [13].…”

Section: Introductionmentioning

confidence: 99%

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Magnetic susceptibility of Mn(III) complexes of hydroxamate siderophores

Springer

Butler

2015

Journal of Inorganic Biochemistry

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ABSTRACT:The hydroxamate siderophores putrebactin, desferrioxamine B, and desferrioxamine E bind Mn(II) and promote the air oxidation of Mn(II) to Mn(III) at pH >7.1.The magnetic susceptibility of the manganese complexes were determined by the Evans method and the stoichiometry was probed with electrospray ionization mass spectrometry (ESIMS). The room temperature magnetic moments (µ eff ) for the manganese complexes of desferrioxamines B and E were 4.85 BM and 4.84 BM, respectively, consistent with a high spin,

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“…Nevertheless, siderophores may play an important role in biogenic cycling of manganese [10,19,37,38] .…”

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Magnetic susceptibility of Mn(III) complexes of hydroxamate siderophores

Springer

Butler

2015

Journal of Inorganic Biochemistry

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“…Surface water content may be mediated through competition by organic species, ranging from small molecules with carboxylic or phenolic groups to proteins generated by microorganisms (23)(24)(25). When such molecules chelate strongly, they may compete with water at the mineral−solution interface and thus may affect surface redox reactions and contribute to weathering processes, which in turn are critical for microbial activity (26)(27)(28) and manganese bioavailability (29).…”

Section: Discussion: Geochemical and Technological Implicationsmentioning

confidence: 99%

Rapidly reversible redox transformation in nanophase manganese oxides at room temperature triggered by changes in hydration

Birkner

Navrotsky

2014

Proc. Natl. Acad. Sci. U.S.A.

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Chemisorption of water onto anhydrous nanophase manganese oxide surfaces promotes rapidly reversible redox phase changes as confirmed by calorimetry, X-ray diffraction, and titration for manganese average oxidation state. Surface reduction of bixbyite (Mn 2 O 3 ) to hausmannite (Mn 3 O 4 ) occurs in nanoparticles under conditions where no such reactions are seen or expected on grounds of bulk thermodynamics in coarse-grained materials. Additionally, transformation does not occur on nanosurfaces passivated by at least 2% coverage of what is likely an amorphous manganese oxide layer. The transformation is due to thermodynamic control arising from differences in surface energies of the two phases (Mn 2 O 3 and Mn 3 O 4 ) under wet and dry conditions. Such reversible and rapid transformation near room temperature may affect the behavior of manganese oxides in technological applications and in geologic and environmental settings.phase transformation | oxidation/reduction | water adsorption/desorption M anganese oxides are ubiquitous in the natural environment, often occurring as very fine grained (nanopahase) precipitates and coatings, and also find numerous technological applications, especially in catalysis. Easy variation of manganese oxidation state (Mn 2+ , Mn 3+ , Mn 4+ ) lends complexity to phase behavior and physical and chemical properties of manganese oxides. The thermodynamic stability of manganese oxide nanoparticles helps determine the robustness of such oxides and their behavior in soils and larger-scale geochemical cycles, as well as in applications in catalysis, renewable energy, and environmental remediation. The structure and energetics of nanoparticle surfaces are influenced by the phase present and its oxidation state and by the extent of surface hydration; thus dry surfaces are structurally and thermodynamically distinct from hydrated surfaces (1, 2). Using Mn 3 O 4 (hausmannite), Mn 2 O 3 (bixbyite), and MnO 2 (pyrolusite), previously, we showed that the position in temperature−oxygen fugacity space, of oxidation−reduction (redox) phase equilibria, is shifted at the nanoscale due to differences in nanophase surface energy as a function of particle size and surface hydration and that this thermodynamic shift is in favor of the lower surface energy phase (3). In the manganese oxides, the surface energy increases in the order hausmannite, bixbyite, pyrolusite, so small particle size favors the more reduced oxide phase.This paper summarizes observations in the nanoscale Mn 2 O 3 − Mn 3 O 4 system, which is found to undergo rapidly reversible redox phase transformations at room temperature induced by the adsorption/desorption of surface water. It is expected that the degree of reduction is a function of both average particle size and particle size distribution, but this work focuses on only one representative material to provide proof of concept. The rapid response of activated surfaces to changing hydration condition implies thermodynamic control and has implications for geochemistry, planetary scie...

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“…Fe(III)-siderophore stability constants can be as high as 10 52 (1,40), which is many orders of magnitude higher than the stability constants for low-molecular-weight organic acids, such as oxalic acid [for Fe(III) ϩ 3 oxalate % Fe(oxalate) 3 , K ϭ 10 18.6 ] (45). While their high affinity for Fe(III) is clearly important for helping siderophores mobilize Fe from Fe(III) (hydr)oxides in the aqueous phase, the mechanisms of Fe mobilization appear to be complex and are the subject of much recent study (14,17,18,26,28,49). In particular, the role of siderophores in ligand-promoted dissolution mechanisms has undergone careful evaluation in vitro.…”

Section: Is 10mentioning

confidence: 99%