Evaluation of a conceptual model for the subsurface transport of plutonium involving surface mediated reduction of Pu(V) to Pu(IV)

A conceptual model is proposed to explain the transport behavior of plutonium in laboratory columns packed with a sandy coastal soil from the U.S. Department of Energy (DOE)'s Savannah River Site. The column transport experiments involved the introduction of a finite step input of plutonium, predominately in the +5 oxidation state, into the columns followed by elution with a low-carbonate solution of 0.02 M NaClO4 at pH 3, 5, and 8. Total plutonium concentrations were measured in the effluent as a function of time. These elution profiles suggest at least two distinct physical/chemical forms of plutonium, each with a different mobility. To explain the observed behavior, the following conceptual model was evaluated: [1] equilibrium partitioning of plutonium (V) and plutonium (IV) between the aqueous and sorbed phases as defined by pH-dependent, oxidation-state specific distribution coefficients and [2] kinetic reduction of plutonium (V) to plutonium (IV) in the sorbed phase. The conceptual model was applied to the column experiments through a one-dimensional advective/dispersive mathematical model, and predictions of the mathematical model were compared with the experimental data. Overall, the model was successful in predicting some of the major features observed in the experiments. It also yielded quantitative estimates of the rate constant for surface mediated reduction of plutonium (V) to plutonium (IV) that were of the same order (10(-4) to 10(-5) s(-1)) as those calculated from batch data both for this soil and for goethite. (C) 2003 Elsevier B.V. All rights reserved