A preliminary investigation of chlorine XANES in silicate glasses

Chlorine speciation in silicate melts affects volatile exsolution, rheology, and thermodynamic properties of the melt but is poorly known. X-Ray Absorption Near Edge Structure (XANES) spectra have been used to investigate Cl speciation in 26 silicate glasses and to test the hypothesis that Cl in silicate melts is hosted by species that combine Cl and network-modifying cations such as Ca and Mg. Results indicate that Cl in CMAS (CaO-MgO-Al2O 3-SiO2) plus Na2O, K2O, or MnO silicate glasses exists as a combination of Ca-Clx and Mg-Clx species or, possibly, as mixed Ca-Mgy-Clx species. The geometry and stoichiometry of the proposed species is unknown, but there are similarities between spectra from Ca-bearing melts and the spectra of hydrated CaCl2.2H2O, suggesting that the Ca-Clx species could have a salt-like atomic arrangement and ionic bonding. Further investigations using XANES, alternative spectroscopic techniques, and forward modeling approaches are required to distinguish between these possibilities