A procedure to assess the importance of chemical kinetics in the humic-mediated transport of radionuclides in radiological performance assessment calculations

Previous work has shown that humic substances can bind metal ions in two fractions: the exchangeable, where it is available instantaneously for reaction with other sinks (such as mineral surfaces); and the non-exchangeable, from which it may only dissociate slowly. In the absence of metal ion/humic/mineral surface ternary complexes, if the dissociation rate is slow compared to the solution residence time in the groundwater column, then metal in the non-exchangeable will have a significantly higher mobility than that in the exchangeable. The critical factor is the ratio of the non-exchangeable first order dissociation rate constant and the residence time in the groundwater column, metal ion mobility increasing with decreasing rate constant. Sorption of humic/metal complexes at mineral surfaces may reduce mobility. In addition to direct retardation, sorption also increases the residence time of the non-exchangeable fraction, giving more time for dissociation and immobilisation. The magnitude of the effect depends upon the concentrations of the mineral surface humic binding sites and the humic in solution, along with the magnitudes of the equilibrium constant and the forward and backward rate constants. The non-exchangeable dissociation reaction and the sorption reaction may be classified in terms of two Damkohler numbers, which can be used to determine the importance of chemical kinetics during transport calculations. These numbers could be used to determine when full chemical kinetic calculations are required for a reliable prediction, and when equilibrium may be assumed, or when the reactions are sufficiently slow that they may be ignored completely

The role of humic non-exchangeable binding in the promotion of metal ion

Metal ions form strong complexes with humic substances. When the metal ion is first complexed by humic material, it is bound in an ‘exchangeable’ mode. The metal ion in this fraction is strongly bound, however, if the metal–humic complex encounters a stronger binding site on a surface, then the metal ion may dissociate from the humic substance and be immobilised. However, over time, exchangeably-bound metal may transfer to a ‘non-exchangeable’ mode. Transfer into this mode and dissociation from it are slow, regardless of the strength of the competing sink, and so immobilisation may be hindered. A series of coupled chemical transport calculations has been performed to investigate the likely effects of non-exchangeable binding upon the transport of metal ions in the environment. The calculations show that metal in the nonexchangeable mode will have a significantly higher mobility than that in the exchangeable mode. The critical factor is the ratio of the non-exchangeable first-order dissociation rate constant and the residence time in the groundwater column, metal ion mobility increasing with decreasing rate constant. A second series of calculations has investigated the effect of the sorption to surfaces of humic/metal complexes on the transport of the non-exchangeably bound metal. It was found that such sorption may reduce mobility, depending upon the humic fraction to which the metal ion is bound. For the more weakly sorbing humic fractions, under ambient conditions (humic concentration etc.) the non-exchangeable fraction may still transport significantly. However, for the more strongly sorbed fractions, the non-exchangeable fraction has little effect upon mobility. In addition to direct retardation, sorption also increases the residence time of the nonexchangeable fraction, giving more time for dissociation and immobilisation. The nonexchangeable dissociation reaction, and the sorption reaction have been classified in terms of two Damkohler numbers, which can be used to determine the importance of chemical kinetics during transport calculations. These numbers have been used to develop a set of rules that determine when full chemical kinetic calculations are required for a reliable prediction, and when equilibrium may be assumed, or when the reactions are sufficiently slow that they may be ignored completely