A XAFS study on the mechanism of isotopic fractionation of molybdenum during its adsorption on ferromanganese oxides

Due to its potential as a paleoredox proxy, there have been many studies on Mo isotopic fractionation during adsorption onto ferromanganese oxides in seawater. However, the mechanisms of both adsorption and isotopic fractionation are still under debate due to the lack of structural information on the adsorbed species. In this study, XAFS analyses were performed to reveal the mechanism, based on structural information at the molecular level, of Mo isotopic fractionation during adsorption onto ferromanganese oxides. Molybdenum L-3-edge XANES and K-edge EXAFS revealed that Mo species adsorbed on the surface of ferrihydrite was a tetrahedrally coordinated outer-sphere complex, while that on delta-MnO2 was an octahedrally coordinated inner-sphere complex. Additionally, it was also revealed that delta-MnO2 was the dominant host phase of Mo in the hydrogenetic ferromanganese nodules from the comparison of their XAFS spectra. Previous studies reported that lighter isotopes of Mo were preferentially incorporated into ferromanganese oxides from seawater. This fractionation can be explained based on the structural difference between tetrahedral MoO42- (=a major species in seawater) and the octahedral species adsorbed on the Mn oxide phase in ferromanganese nodules. In contrast, little change in Mo local structures during its adsorption onto ferrihydrite also suggested the little or no fractionation of Mo isotopes in the presence of Fe hydroxides without Mn oxides. These facts imply that the Mo isotopic composition in ancient marine sediments can distinguish redox boundaries of Fe2+/Fe(OH)(3) and of the more oxic Mn2+/MnO2.