Radionuclide sorption

MMT (32) is a 1- or 2-dimensional solute transport numerical groundwater model, to be driven off-line by a flow transport, such as VTT (Variable Thickness Transport). MMT employs the random-walk numerical method and was originally developed for radionuclide transport. The model accounts for advection, sorption and decay. 

Sorption can significantly diminish the mobility of certain dissolved components in solution, especially those present in minor amounts. Sorption, for example, may retard the spread of radionuclides near a radioactive waste repository or the migration of contaminants away from a polluting landfill (see Chapters 21 and 32). In acid mine drainages, ferric oxide sorbs heavy metals from surface water, helping limit their downstream movement (see Chapter 31). A geochemical model useful in investigating such cases must provide an accurate assessment of the effects of surface reactions. 

The retardation equation can also be applied to inorganic soluble substances (ions, radionuclides, metals). But here we have to consider, in addition to the sorption or ion exchange process, that the speciation of metal ions or ligands in a multi-... 

The interaction and sorption of metal ions with metal oxide and clay surfaces has occupied the attention of chemists, soil scientists, and geochemists for decades (1-4). Transition metal oxides receiving particular emphasis have included various oxides of manganese and iron (5). Interest in sorption phenomena is promoted by the desire to better understand incorporation of metals into minerals, especially marine deposits ( ), the removal of trace metal pollutants and radionuclides from rivers and streams, via sorption and/or precipitation phenomena (1,6), and the deposition of metals on solid substrates in the preparation of catalysts (7,8). 

How stvongty is water transport of the radionuclides retoj ded by sorption on the backfill and sealing materials and the enclosing rocks ... 

Studies of the sorption of natural radionuclides from groundwater have established that minor minerals, such as clays coating the fractures in crystalline rock and Fe- and Mn-oxyhydroxides, are important sinks for radionuclides. For example, investigations carried out at the Aspo facility (Smellie Karlsson 1999) showed qualitatively that rare earth elements (REEs), Sc, Th, U, Ra, and Ba have been scavenged by Fe-oxyhydroxide and calcite precipitates,... 

The reliable long-term safety assessment of a nuclear waste repository requires the quantification of all processes that may affect the isolation of the nuclear waste from the biosphere. The colloid-mediated radionuclide migration is discussed as a possible pathway for radionuclide release. As soon as groundwater has access to the nuclear waste, a complicated interactive network of physical and chemical reactions is initiated, and may lead to (1) radionuclide mobilization (2) radionuclide retardation by surface sorption and co-precipitation reactions and (3) radionuclide immobilization by mineralization reactions, that is, the inclusion of radionuclides into thermodynamically or kinetically stabilized solid host matrices. 

Equilibrium thermodynamics is one of the pillars supporting the safety analyses of radioactive waste repositories. Thermodynamic constants are used for modelling reference porewaters, calculating radionuclide solubility limits, deriving case-specific sorption coefficients, and analysing experimental results. It is essential to use the same data base in all instances of the modelling chain in order to ensure internally consistent results. 

Bradbury Baeyens (2002a, b) provided sorption data bases for Opalinus Clay and MX-80 bentonite, respectively, based on numerous experiments with varying aqueous solution compositions. Since sorption can be influenced by the complexa-tion of radionuclides with various ligands, corrections had to be made to account for the differences in speciation between the experimental solutions and the Opalinus Clay and bentonite porewaters. For this purpose, the Nagra/PSI TDB 01 /01 was used to model the speciation of all safety-relevant radionuclides in the experimental solutions and in the Opalinus Clay and bentonite porewaters. 

The modelling chain described in this section, linking the reference porewaters, radionuclide concentration limits, and sorption data bases, is summarized in Fig. 6. 

Among the properties of the two-phase system rock/groundwa-ter that would be of importance for the sorption of an individual radionuclide are... 

Nuclide Concentrations. The two nuclide concentrations chosen for the experiments, <10- M and =10" M, are so low that the ionic strength of the water is not significantly affected. Nor is it likely that the solid sorbent would be saturated with respect to the sorption capacity of any individual radionuclide species. 

By direct measurements of the radionuclide sorption on exposed rocks, surface related distribution coefficients K can be determined and conversion factors calculated according to )... 

Allard, B., Kipatsi, H. and Rydberg, J., "Sorption of Long-Lived Radionuclides on Clay and Rock". Part I, KBS TR 55, 1977 Allard, B., Kipatsi, H. and Torstenfelt, B., "Sorption of Long-Lived Radionuclides on Clay and Rock", Part II, KBS TR 98,... 

In previous work (l.> > ) it was found that the kinetics of sorption was an important parameter affecting the migration of nuclides in geologic media. For example, in experiments designed to measure the kinetics of reaction for radionuclides in solution with tablets of rock, it was found that periods from several minutes to several hours were required for the radionuclides to reach steady state concentrations on the rock tablets and in the solutions. Figure 1 shows the reaction curves found for the sorption of plutonium and americium from solution by a tablet of granite. The reaction rates for the sorption of plutonium and americium from solution are not the same, and both require a number of hours to reach steady state concentrations. 

In most mathematical analyses used to establish bounds for radionuclide migration rates through the abyssal red clays, the sorption properties of the sediment are generally represented mathematically by the sorption equilibrium distribution coefficients for each of the species involved. These coefficients are usually denoted by Kp. and are defined by... 

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