Effects of iron oxidation states on the surface and structural properties of smectites

Abstract

The oxidation state of iron (Fe) in the crystal structure of smectite clay minerals profoundly alters their physical-chemical properties. Among the properties affected are layer charge, cation exchange and fixation capacity, swelling in water, particle size, specific surface area, layer stacking order, magnetic exchange interactions, octahedral site occupancy, surface acidity, and reduction potential. Also affected is the surface chemistry of the clay, which alters clay–water and clay–organic interaction mechanisms. Rates and extents of degradation of pesticides are increased in the presence of reduced smectites compared to oxidized and reduced-reoxidized counterparts. A hypothesis regarding the mechanism for Fe reduction in clay minerals was first developed in 1963, and subsequent modifications have been proposed periodically through the present time. Recent studies clearly reveal that the process of Fe reduction involves more than the mere transfer of an electron to octahedral Fe(III) in the clay crystal. Ancillary reactions occur that produce significant structural modifications, some of which are reversible and others of which are not. Such changes in the crystal-chemical environment of structural Fe are thought to play a dominant role in altering the clay surface chemistry.