Contaminant-Organic Complexes, Their Structure and Energetics in Surface Decontamination Processes

There are a wide variety of compounds that are naturally occurring biodegradable organic chelates (siderophores) that appear to be more effective at oxide dissolution and actinide complexation than EDTA or other organic acids now used in decontamination processes. These chelates bind hard acids [Fe(III) and actinides(IV)] with extraordinarily high affinities. For example, the binding constant for the siderophore enterobactin with iron is about 1050, and its binding constant for Pu(IV) is estimated to be as high. Hence, this project is investigating the efficacy of using siderophores (or siderophore-like chelates) as decontamination agents of metal surfaces. The specific goals of this project are as follows: 1. develop an understanding of the surface interaction between siderophores (and their functional moieties), iron, and actinide oxides; their surface chemical properties that foster their dissolution; and the conditions that maximize that dissolution 2. develop the computational tools necessary to predict the reactivity of different siderophore functional groups toward oxide dissolution and actinide(IV) solubilization 3. identify likely candidate chelates for use in decontamination processes. To meet these objectives, the project combines molecular spectroscopy and computational chemistry to provide basic information on the structure and bonding of siderophore functional groups to metal (iron and uranium) oxide specimens common to corrosion products and scales on carbon steel and stainless steel encountered in U.S. Department of Energy (DOE) facilities. The project explores fundamental scientific aspects of oxide mineral surface chemistry and dissolution related to chelate-induced solubilization. The spectroscopic and computational aspects of this project are complemented by macroscopic dissolution and solubilization studies of oxides and associated contaminants. From this combination of molecular, macroscopic, and computational studies, structure-function and structure-reactivity relationships will be developed