Spectroscopic evidence for interfacial Fe(II)-Fe(III) electron transfer in a clay mineral.
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 (57)Fe 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 (56)Fe(II) (which is invisible to (57)Fe Mössbauer spectroscopy) showed direct evidence for reduction of NAu-2 by sorbed Fe(II). Mössbauer spectra using aqueous (57)Fe(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.
Civil and Environmental Engineering, University of Iowa, Iowa City, Iowa 52242, United States of America.
Michael V
MV
Schaefer
Christopher A
CA
Gorski
Michelle M
MM
Scherer
D000538:Aluminum Silicates / Q000737:chemistry*; D000077215:Clay; D004583:Electrons; D005290:Ferric Compounds / Q000737:chemistry; D007501:Iron / Q000737:chemistry*; D046529:Microscopy, Electron, Transmission; D010084:Oxidation-Reduction; D017640:Silicates / Q000737:chemistry; D012989:Soil Pollutants / Q000737:chemistry; D015204:Spectroscopy, Mossbauer; D014961:X-Ray Diffraction
D000538:Aluminum Silicates; D005290:Ferric Compounds; D017640:Silicates; D012989:Soil Pollutants; C000499:ferric oxide; C033214:Smectite; D007501:Iron; D000077215:Clay