The study of iodine in glasses and melts is critical in many areas, from geosciences to materials science to waste management. Glasses in the ternary system Na 2 O-B 2 O 3 -SiO 2 were studied with the goal of identifying a glass matrix able to dissolve large quantities of this element, and to identify the main parameters affecting the solubility of iodine. Two sets of experiments were carried out: the first one with the aim of determining the solubility limit of iodine, and the second one to identify the structural variations occurring within the glass network upon iodine incorporation, and to identify the parameters influencing the most both iodine solubility and speciation. We demonstrated that there is a strong dependence of iodine incorporation on bulk chemistry and glass physical properties. A solubility limit of ~5 mol% I has been assessed for B 2 O 3 -rich glasses and of ~1 mol% for SiO 2 -rich ones, and this composition dependence has been explained by considering the fragility parameter of the glass network. Structural variations in the iodine local environment and in the glass network were characterized by Raman, X-ray Absorption Spectroscopy, and 11 B NMR. Spectroscopy data point out the coexistence of different I species within the glasses, with iodide being the predominant one, surrounded by Na + ions.

Two glass series in the ternary systems K2O-B2O3-SiO2 (KBS) and Na2O-B2O3-SiO2 (NBS) were studied in order to identify the main factors influencing the solubility of iodine. We established that iodine incorporation is strongly linked to the bulk chemistry, i.e. the SiO2/(B2O3+SiO2) molar ratio, and to the physical properties of the glasses, and we assessed three different solubility limits. Iodine in Si-rich glasses has a low solubility (≤1 mol% I) regardless of the alkali ion present. On the contrary, in B-rich glasses, the solubility is five times higher than in Si-rich glasses for Na-glasses, and more than six times higher for K-glasses. The strong dependence of iodine solubility on the bulk chemistry is related to the adaptability of the glass network. Furthermore, our data suggest that iodine is stable with different redox states in the glasses here analyzed.