Iron distribution in the octahedral sheet of dioctahedral smectites. An Fe K-edge X-ray absorption spectroscopy study

The distribution of iron atoms in the octahedral sheet of a series of dioctahedral smectites with varying unit-cell composition and iron content was investigated by Fe K-edge XAS spectroscopy. First-step analysis reveals that the patterns corresponding to backscattering by atoms located between 3 and 4 Å from the absorbing atom are very sensitive to the relative amount of light (Si, Al, Mg) and heavy (Fe) atoms. Detailed modelling of this domain then provides valuable information on the number of iron atoms surrounding octahedral iron. By comparing the number of iron neighbours deduced from EXAFS with that determined from unit-cell composition assuming a statistical distribution, three groups of montmorillonites can be distinguished: (1) clay samples from Wyoming display an ordered distribution of iron atoms; (2) clay samples from Georgia, Milos, China and Washington exhibit a close to random distribution of iron atoms; (3) clay samples from North Africa, Germany, Texas and Arizona display extensive iron clustering. These results complement previously obtained IR results and show that the combination of these two spectroscopic techniques could provide an additional crystal-chemistry-based framework for typological analysis of montmorillonite deposits.