Previously, it has been suggested that metal ions complexed to humic acid in the environment might show slower dissociation than those added to humic substances in the laboratory, which has serious implications for the transport of radionuclides in the environment. The dissociation of lanthanide and anthropogenic actinide ions from humic substance complexes has been studied as a function of humic concentration and metal ion: humic concentration ratio. The results suggest that the apparently slower kinetics observed for metal ions complexed in the environment are probably due to the large humic concentrations that are used in those studies. Further, there is no evidence that the dissociation rate constant varies at very low metal ion concentrations. Although humic samples size-fractionated by ultrafiltration showed that more metal may be bound non-exchangeably, there was no evidence for different rate constants. Ultrafiltration of Eu(III)/humic acid mixtures did showa shift in Eu from smaller to larger fractions over a period of two days. Therefore, the results suggest that dissociation rate constants determined in the laboratory at metal ion concentrations higher than those expected in the environment may be used in predicting radionuclide mobility, provided that the humic acid concentration is in the range expected at the site.

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 non-exchangeable 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 non-exchangeable fraction, giving more time for dissociation and immobilisation. The non-exchangeable 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.

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.

The kinetic stability of radionuclides bound to aqueous colloids is a determining factor in their migration from a radioactive waste repository. The cation exchangers Chelex-100, Dowex 50Wx4, and Cellphos (cellulose phosphate) have been shown a promising tool for kinetic investigations. This study assesses the applicability of different exchange resins for Eu humate dissociation kinetics investigations. All resins were found to produce satisfactory results. A systematic study of parameters affecting the dissociation rates of Eu(III) humate complexes was performed. A set of purified humic substances was found to behave in the same way. However, unpurified Aldrich humic acid showed significant differences.

This chapter discusses the effects of humic substances on radioactivity in the environment. Humic substances are an important class of organic molecules that play a vital role in both the carbon cycle and the biogeochemistry of virtually all metallic elements. Most research relevant to environmental radioactivity has examined generic metal-humate behavior. However, these studies are applicable to radionuclides. The chapter discusses various types and families of models, from the models of humic structure, which tend to be conceptual, to the various metal binding models, which tend to be more mathematical. Much of the metal-humate modeling has been driven by the need to predict the behavior of radionuclides in the environment. In particular, much of the effort has been directed at models designed to test the long-term safety of radioactive waste repositories. The classification and characterization of humic substances is presented in the chapter.

In a review the effect of humic substances on the environmental radioactivity are outlined. The definition and classification of humic substances are given, as well as their origin and colloidal properties. Further topics were the binding of metals to humic substances, with specific considerations to radionuclide binding kinetics, and the modeling of the mobility of radionuclides in an environment contg. humic substances. [on SciFinder (R)]