ADSORPTION MECHANISMS OF TRIVALENT GOLD ON IRON- AND ALUMINUM-(OXY) HYDROXIDES. PART 1: X-RAY ABSORPTION AND RAMAN SCATTERING SPECTROSCOPIC STUDIES OF AU(III) ADSORBED ON FERRIHYDRITE, GOETHITE, AND BOEHMITE

Abstract

Gold adsorption products on powdered ferrihydrite, goethite, and boehmite samples, prepared by reacting Au(III)-Cl solutions ([Au] = 4.2 × 10⁻⁵-9.0 × 10⁻³ M; [Cl] = 0.017–0.6 M) with these adsorbents at pH values of 4 to 9 and Au adsorption densities ranging from 0.046 to 1.53 μmol/m² were characterized using Au-LIII XAFS spectroscopy. The solutions (before and after uptake) were investigated by Raman scattering to determine speciation and by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) to determine solution composition. We present an analysis of several effects that are observed in the Au LIII-edge XAFS spectra, including X-ray beam-induced photo-reduction, multi-electronic excitations, disorder effects, and multiple scattering, that would complicate interpretation of the spectra if not accounted for. A combination of methods (spectral deconvolution, principal component analysis, spectral inversion, and wavelet analysis) was used to identify and quantify these effects, to characterize the nature of mixed ligands around gold, and to distinguish between multiple-scattering features and features due to next-nearest neighbors in the XAFS spectra.