Volatile species of technetium and rhenium during waste vitrification

Volatile loss of technetium (Tc) during vitrification of low-activity wastes is a technical challenge for treating and immobilizing the large volumes of radioactive and hazardous wastes stored at the U.S. Department of Energy's Hanford Site. Various research efforts are being pursued to develop technologies that can be implemented for cost effective management of Tc, including studies to understand the behavior of Tc during vitrification, with the goal of eventually increasing Tc retention in glass. One of these studies has focused on identifying the form or species of Tc and Re (surrogate for Tc) that evolve during the waste-to-glass conversion process. This information is important for understanding the mechanism of Tc volatilization. In this paper, available information collected from the literature is critically evaluated to clarify the volatile species of Tc and Re and, more specifically, whether they volatilize as alkali pertechnetate and perrhenate or as technetium and rhenium oxides after decomposition of alkali pertechnetate and perrhenate. The evaluated data ranged from mass spectrometric identification of species volatilized from pure and binary alkali pertechnetate and perrhenate salts to structural and chemical analyses of volatilized materials during crucible melting and scaled melter processing of simulated wastes.