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Electron Spin Resonance Micro-imaging of Live Species for Oxygen Mapping

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Published on: August 26, 2010

Manganese oxides: parallels between abiotic and biotic structures.

Ian Saratovsky¹, Peter G Wightman, Pablo A Pastén

¹Department of Chemistry, Northwestern University, Evanston, Illinois 60208, USA.

Journal of the American Chemical Society

|August 24, 2006

Summary

Microorganisms like Leptothrix discophora SP6 create manganese oxide (MnO(x)) with unique structures. This biogenic MnO(x) contains significant cation vacancies, impacting its chemical properties in aquatic systems.

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Area of Science:

Geochemistry
Environmental Microbiology
Materials Science

Background:

Microbial oxidation of Mn(2+) to MnO(x) is a key process in aquatic environments.
Understanding the structure of biogenic MnO(x) is crucial for biogeochemical cycling.
Leptothrix discophora SP6 is known to produce manganese oxides.

Purpose of the Study:

To determine the structure of biogenic manganese oxides (MnO(x)) produced by Leptothrix discophora SP6.
To quantitatively analyze cation vacancies within the biogenic MnO(x).
To elucidate the formation mechanism and chemical formula of the biogenic MnO(x).

Main Methods:

Transmission electron microscopy (TEM) for morphology and structure.
X-ray absorption spectroscopy (XAS) for oxidation state and local structure.
Powder X-ray diffraction (XRD) for crystallographic analysis.
Extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) for detailed analysis.

Main Results:

Biogenic MnO(x) forms nanoparticles (10x100 nm) with a fibrillar, sheet-like morphology.
The structure consists of edge-sharing Mn(4+)O(6) octahedra forming layers.
Detailed EXAFS analysis revealed 12 +/- 4% cation vacancies in the Mn(4+) layer sites.
XANES analysis indicated an average Mn oxidation state of 3.8 +/- 0.3.

Conclusions:

The biogenic MnO(x) produced by L. discophora SP6 is characterized by significant cation vacancies.
The structure is described by the formula M(n)(y+)Mn(3+)(0.12)[square(0.12)Mn(4+)(0.88)]O(2).zH(2)O.
These findings provide insights into microbial manganese oxidation and the properties of resulting materials.