Mechanisms and Kinetics of Organic Aging and Characterization of Intermediates in High-Level Waste

Abstract

The objective of this project is to characterize significant chemical degradation pathways of organic chemicals in nuclear waste storage and treatment streams. The effort at Pacific Northwest National Laboratory (PNNL) is closely coordinated with a Notre Dame Radiation Laboratory project (EMSP No. 73832, ''The NOx System in Nuclear Waste'', D. Meisel, Principal Investigator) that focuses on radiolytically induced degradation of organic complexants. An understanding of the chemistry of the organic chemicals present in tank wastes is needed to manage the wastes and related site cleanup activities. The underlying chemistries of high-level waste are (1) the chemistry initiated by radioactive decay and the reactions initiated by heat from radioactive decay and (2) the chemistry resulting from waste management activities (waste transfers between tanks, concentration through evaporators, caustic and other chemical additions). Recognizing that experiments cannot reproduce every conceivable scenario, the PNNL and Notre Dame projects work to develop predictive computational models of these chemistries. Participants in both projects combine experimental observations, electronic structure computations, and theoretical methods developed to achieve this goal. The resulting model will provide an accurate evaluation of the hazardous material generated, including flammable gases, and will support decision-making processes regarding safety, retrieval, and treatment issues. The utility of developing an understanding of tank chemistry has been demonstrated in earlier work. None of the Hanford tanks is currently on a watch list, partially due to predictive understanding of organic aging and flammable gas generation that resulted from previous research. Furthermore, concerns that arise from pretreatment and tank closure issues (e.g., Tc speciation) may be rationalized with the mechanistic knowledge provided by these projects.