The volatilities of simulated, high‐level nuclear waste glasses have been measured using thermogravimetric analysis (TGA). These volatilities were measured in the region of the glass transition temperature (Tg) of the waste glasses, which is between 450° and 500°C. These data were obtained because the Waste Acceptance Preliminary Specifications require that no foreign materials be released into the canistered waste form upon heating of the canister to this glass transition temperature. In fact, all of the waste glass samples studied actually exhibited a net weight gain upon heating. This weight gain was shown to be due to oxygen uptake through oxidation of FeO. Powdered glass samples did show a small weight loss which was smaller in magnitude than the weight gain and was associated with water desorption. No true volatility was detected to the level of sensitivity (0.01 wt%) of the TGA instrument. This converts to a sensitivity of 330μg/m2of glass surface and a corresponding minimum value of 41 mg of volatiles for each Defense Waste Processing Facility conistered waste form. TGA experiments carried out at higher temperatures (800°C) revealed that organic concentrations in the waste glasses are less than 0.01 wt%. Thus, these results demonstrate that the Defense Waste Processing Facility will be able to comply with the Waste Acceptance Preliminary Specifications on the exclusion of foreign materials from the canistered waste forms, after exposure