Sulfur systematics in model glass compositions from West Valley

Sulfur is incorporated into model glass melts, representative of West Valley compositions for the vitrification of high level nuclear waste, as the sulfate ion under oxidizing conditions and as the sulfide ion under reducing conditions. A narrow range of oxygen fugacities, around 10-8.8 atm at 1150 degrees C, under which the two redox forms of sulfur coexist is also the minimum in the sulfur solubility. Under the redox conditions prescribed for waste processing, sulfur dissolves as the sulfate ion. The capacity to dissolve sulfur as sulfate is about 1 to 2.5 wt% sulfur; an immiscible sulfate layer floats on the glass melt if waste loading introduces sulfur contents greater than this under oxidizing conditions. If the waste/melt system is exposed to sufficiently reducing conditions, the first phase to separate from the melt is likely nickel sulfide. The presence of the immiscible sulfate or sulfide layer buffers the iron redox ratio of the resulting glass