Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
8910390 | Chemical Geology | 2018 | 59 Pages |
Abstract
We explored these issues by synthesizing a host of cation-exchanged birnessite specimens whose long-range symmetrical character could be determined by X-ray diffraction without ambiguity. Through a combination of Fourier transform infrared spectroscopy (FTIR), extended X-ray absorption fine structure (EXAFS), and X-ray photoelectron spectroscopy (XPS), we have examined the relationships among structural symmetry, Mn oxidation state, and interlayer composition. Our results confirm prior models that as the concentration of Mn3+ increases, the departure from hexagonal symmetry also increases. Rietveld refinements indicate that the Jahn-Teller distortions associated with Mn3+ induce systematic variations in unit-cell parameters, particularly an increase in the a-axis and the β angle of the unit cell. Interlayer cation composition also controls structural distortions, and Ca-rich birnessites showed less deviation from hexagonality than did Na-, K-, and Ba-birnessites. Our linear combination fits of X-ray absorption spectra sometimes yielded misleading results, reinforcing the difficulty and importance of selecting appropriate standards.
Related Topics
Physical Sciences and Engineering
Earth and Planetary Sciences
Geochemistry and Petrology
Authors
Florence T. Ling, Jeffrey E. Post, Peter J. Heaney, Eugene S. Ilton,