Redox cycles are common in nature and likely have a profound effect on the behavior of soils and sediments. This study examined a key component of redox cycles in smectites, namely, the reoxidation process, which has received little attention compared to the reduction process. Unaltered (oxidized) and reoxidized ferruginous smectites (nontronites) were compared using infrared and Mössbauer spectroscopies, and thermal gravimetric analysis. The infrared and thermal gravimetric data revealed that the structural OH content of reduced-reoxidized clay is about 15 to 20% less than in the original (oxidized) sample, indicating that the structure remains partially dehydroxylated even after reoxidation. Mössbaner spectra of reoxidized samples consisted of larger quadrupole splitting for Fe(III) doublets than in the unaltered samples, suggesting that the environment of Fe(III) is more distorted after the reduction-reoxidation treatment.

Environmental transmission electron microscopy (ETEM) is opening an important window for in situ studies of interaction of water with oxides. Studies of MgO smoke nanocrystals under partial pressures of water ranging from 10 mTorr to 10 Torr found their {100} neutral surfaces to be extremely resistant to dissociative adsorption of water and hydroxylation, in agreement with recent theoretical predictions. ETEM observations of electron irradiation driven MgO smoke nanocrystal hydroxylation displayed the anticipated volume expansion, but revealed complex shape changes with elongations toward oxide corners. The reaction rate was found to increase with electron flux at constant water pressure. In situ selected area diffraction studies of MgO single crystals showed that the hydroxide grows with its basal (0001) plane parallel to the polar MgO (111) planes. This is the same crystallographic relationship as in dehydroxylation experiments, but with four variants. Electron energy loss spectroscopy found oxygen K-edge changes consistent with bulk hydroxylation.