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The application of x-ray absorption spectroscopy methods to both materials and life sciences is well appreciated. However, the power of extended x-ray absorption fine structure (EXAFS) spectroscopy as a quantitative structural technique has largely been limited by its application to the microscopically homogeneous systems, in which the local environment around each absorbing atom in the sample is the same. The growing interest in time-resolved EXAFS studies of systems in physics, chemistry, biology, and materials science has reintroduced the requirement for an analytical tool to probe heterogeneous mixtures in situ. While long being recognized as a premiere technique for this role, EXAFS studies of mixtures have been particularly difficult due to the strong model dependence and correlations between parameters in the fit. To circumvent these drawbacks, we introduce two new techniques in EXAFS analysis: the principal component analysis and the residual phase analysis. Using a test case of a heterogeneous mi...

The use of principal component (factor) analysis for the interpretation of EXAFS spectra is described. The components derived from EXAFS spectra share mathematical properties with the original spectra. As a result, the abstract components can be analyzed using standard EXAFS methodology to yield bond distances and other coordination parameters. The number of components that must be analyzed is usually less than the number of original spectra. The method is demonstrated using a series of spectra from aqueous solutions of uranyl ions.

X-ray absorption spectroscopy has often been used to examine the local environment around an absorbing cation in both the solid and the liquid state. In order to examine the properties of a transition-metal ion under conditions in which the degree of solvation can be regulated, the authors have placed cupric ions within a smectite clay. Smectite clays consist of negatively charged sheets of aluminosilicates which are separated by an interlayer whose thickness changes upon absorption of solvent. In the native clay used for these experiments, bentonite, the calcium was replaced with copper by stirring the clay in a 0.1 M aqueous solution of CuCl[sub 2]. For the experiments described here, Cu K-edge spectra were acquired at the National Synchrotron Light Source and Stanford Synchrotron Radiation Laboratory in both transmission and fluorescence modes. Four samples of Cu-bentonite powder, dried from water, methanol, ethanol, and ethylene glycol, were examined, as well as slurries of these samples in their respective solvents. The normalized X-ray absorption near edge (XANES) spectra are obtained for copper ion in the Cu-bentonite dried from methanol and for the Cu-clay as a slurry in the same solvent. The spectrum of the dry material clearly shows the electronic 1s-4p transitionmore » as a resolved shoulder on the absorption edge at 8986 eV. This transition, which is characteristic of a copper ion with square planar coordination, has broadened and almost disappeared in the slurry. The observed change suggests that as the solvent penetrates into the clay, some of the solvent molecules enter the coordination sphere of the copper(II) ion. The addition of two axial oxygen ligands shifts the coordination geometry of the Cu(II) from a square planar configuration to a distorted octahedron. There is an obvious change in the EXAFS data between the dry clay and the slurry which cannot be readily discerned by examination of the radial distributions alone. 23 refs., 2 figs., 1 tab.« less