Iodine valence and local environments in borosilicate waste glasses using X-ray absorption spectroscopy

Article history: Received 19 August 2014 Accepted 15 September 2014 The radioisotope I, a fission product in spent nuclear fuel, has a long half-life, and can be highly mobile in the environment. Iodine K-edge X-ray absorption spectra were collected to characterize the iodine valence and coordination environment in simulated Hanford low activity waste glasses. Both iodine XANES and EXAFS data for eleven borosilicate glasses indicate iodide-like environments within the glass structure, where I has Na or Li nearest-neighbors, and where the nearest-neighbor cation-type correlates to the most common network-modifying cation in the glass. This is further supported by the systematic increase of iodine incorporation with the combined Na2O + Li2O content in the glass. EXAFS analyses determined I–Na distances near 3.04 Å with coordination numbers near 4.0 and I–Li distances near 2.80 Å with coordination numbers near 3.0. I–Na environments determined for the glasses are similar to the tetrahedral INa4 coordination found in NaI-sodalite. These weakly bound iodine-alkali configurations may be the only pathways for iodine to be retained in the glass. These environments may be precursors to NaI-sodalite crystallization in Na-rich glass. Iodine also shows distinct differences from chlorine in terms of the preferred sites in the glass structure. 2014 Elsevier B.V. All rights reserved.