Iodine local environment in high pressure borosilicate glasses: An X-ray photoelectron spectroscopy and X-ray absorption spectroscopy investigation

Abstract

• Iodine is dissolved as iodide (I − ) in high pressure borosilicate glasses. • Both alkali and alkaline-earth cations act as a charge compensator to I − species. • The absence of iodate (I 5+ ) suggests that there is a complex interplay between I − species and oxygen species within the glass structure. The 129 I radioactive isotope is a by-product of nuclear plants activity. Owing to its strong volatility, there is currently no ideal protocol to immobilize 129 I in nuclear waste borosilicate glasses. Recently, we have proposed the use of high-pressure syntheses to dissolve iodine in various glass compositions; however, I speciation and dissolution mechanism could not be determined. We have adopted an approach combining X-ray Photoelectron Spectroscopy (XPS) and X-ray Absorption Spectroscopy (XAS) methods to determine I speciation and molecular environment in glasses containing from 0.5 to 2.5 mol.% I. The XPS spectra reveal that I is mostly dissolved as iodide (>85% I − ) with a small proportion of elemental iodine (<15% I 0 ) and the absence of iodate species (I 5+ ). For borosilicate glasses, the XAS results and subsequent spectrum simulations suggested that Na and Ca are involved in the I − vicinity with averaged derived coordination number (CN) of 3.6 and 2.0 and bond length to the nearest neighbour (r X-I ) 2.98 and 2.85 Å, respectively. These results suggest that the coexistence of both I − and I 5+ species is not requested for electric neutrality but instead, we explain the I speciation by the possible interplay with oxygen species from the borosilicate matrix. In addition, the results imply that the borosilicate network is affected by the I dissolution.