XANES reflects coordination change and underlying surface disorder of zinc adsorbed to silica

Zinc K-edge X-ray absorption near-edge structure (XANES) spectroscopy of Zn adsorbed to silica and Zn-bearing minerals, salts and solutions was conducted to explore how XANES spectra reflect coordination environment and disorder in the surface to which a metal ion is sorbed. Specifically, XANES spectra for five distinct Zn adsorption complexes (Zn_ads) on quartz and amorphous silica [SiO_2(am)] are presented from the Zn-water-silica surface system: outer-sphere octahedral Zn_ads on quartz, inner-sphere octahedral Zn_ads on quartz, inner-sphere tetrahedral Zn_ads on quartz, inner-sphere octahedral Zn_ads on SiO_2(am) and inner-sphere tetrahedral Zn_ads on SiO_2(am). XANES spectral analysis of these complexes on quartz versus SiO_2(am) reveals that normalized peak absorbance and K-edge energy position generally decrease with increasing surface disorder and decreasing Zn-O coordination. On quartz, the absorption-edge energy of Zn_ads ranges from 9663.0 to 9664.1 eV for samples dominated by tetrahedrally versus octahedrally coordinated species, respectively. On SiO_2(am), the absorption-edge energy of Zn_ads ranges from 9662.3 to 9663.4 eV for samples dominated by tetrahedrally versus octahedrally coordinated species, respectively. On both silica substrates, octahedral Zn_ads presents a single K-edge peak feature, whereas tetrahedral Zn_ads presents two absorbance features. The energy space between the two absorbance peak features of the XANES K-edge of tetrahedral Zn_ads is 2.4 eV for Zn on quartz and 3.2 eV for Zn on SiO_2(am). Linear combination fitting of samples with a mixture of Zn_ads complex types demonstrates that the XANES spectra of octahedral and tetrahedral Zn_ads on silica are distinct enough for quantitative identification. These results suggest caution when deciphering Zn speciation in natural samples via linear combination approaches using a single Zn_ads standard to represent sorption on a particular mineral surface. Correlation between XANES spectral features and prior extended X-ray absorption fine structure (EXAFS) derived coordination environments for these Zn_ads on silica samples provides insight into Zn speciation in natural systems with XANES compatible Zn concentrations too low for EXAFS analysis.