Journal article
Spectroscopic Evidence for Interfacial Fe(II)−Fe(III) Electron Transfer in a Clay Mineral
Environmental science & technology, Vol.45(2), pp.540-545
01/15/2011
DOI: 10.1021/es102560m
PMID: 21138293
Abstract
Interfacial electron transfer has been shown to occur between sorbed Fe(II) and structural Fe(III) in Fe oxides, but it is unknown whether a similar reaction occurs between sorbed Fe(II) and Fe(III)-bearing clay minerals. Here, we used the isotopic specificity of 57Fe Mössbauer spectroscopy to demonstrate electron transfer between sorbed Fe(II) and structural Fe(III) in an Fe-bearing smectite clay mineral (NAu-2, nontronite). Mössbauer spectra of NAu-2 reacted with aqueous 56Fe(II) (which is invisible to 57Fe Mössbauer spectroscopy) showed direct evidence for reduction of NAu-2 by sorbed Fe(II). Mössbauer spectra using aqueous 57Fe(II) showed that sorbed Fe(II) is oxidized upon sorption to the clay and pXRD patterns indicate that the oxidation product is lepidocrocite. Spectra collected at different temperatures indicate that reduction of structural Fe(III) by sorbed Fe(II) induces electron delocalization in the clay structure. Our results also imply that interpretation of room temperature and 77 K Mössbauer spectra may significantly underestimate the amount of Fe(II) in Fe-bearing clays. These findings provide compelling evidence for abiotic reduction of Fe-bearing clay minerals by sorbed Fe(II), and require us to reframe our conceptual model for interpreting biological reduction of clay minerals, as well as contaminant reduction by reduced clays.
Details
- Title: Subtitle
- Spectroscopic Evidence for Interfacial Fe(II)−Fe(III) Electron Transfer in a Clay Mineral
- Creators
- Michael V SchaeferChristopher A GorskiMichelle M Scherer
- Resource Type
- Journal article
- Publication Details
- Environmental science & technology, Vol.45(2), pp.540-545
- DOI
- 10.1021/es102560m
- PMID
- 21138293
- NLM abbreviation
- Environ Sci Technol
- ISSN
- 0013-936X
- eISSN
- 1520-5851
- Publisher
- American Chemical Society
- Language
- English
- Date published
- 01/15/2011
- Academic Unit
- Civil and Environmental Engineering
- Record Identifier
- 9983991946102771
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