Radionuclide sorption effects

Effects of Groundwater Composition and Eh. Radionuclide sorption on geologic solids is dependent on the chemical composition of the groundwater solution and the redox potential (Eh) of the solid-groundwater system. Aquifers at various depths in the Columbia Plateau formation have -been observed to have significant differences in composition. To accurately model radionuclide migration, it is necessary to understand the effects of chemical components and Eh on sorption and solubility of key radionuclides. An additional benefit of this work is to better understand the mechanisms of sorption and desorption of the radionuclides. 

Between the simplicity of the model and the complexity of the TLM, there are several other sorption models. These include various forms of isotherm equations (e.g., Langmuir and Freundlich isotherms) and models that include kinetic effects. The generalized two-layer model (Dzombak and Morel, 1990) (also referred to as the DLM) recently has been used to model radionuclide sorption by several research groups (Langmuir, 1997a Jenne, 1998 Davis, 2001). Constants used in this model are dependent upon the concentration of background electrolytes and... 

Clogging and sorption effects have also been investigated for aluminum in natural waters. On the basis of the results obtained and studies of distribution patterns for aluminum, iron, and zinc as well as some radionuclides in natural waters, it has been shown that the main advantages with hollow-fibre fractionation are minimal clogging and sorption problems and a high filtering capacity in comparison to those of stirred-cell techniques. 

Although decay of because of its long half-life of 4.5 billion yr, plays almost no role in U plume attenuation, soil transport of U is affected by most of the processes that control transport of other radionuclides (sorption, indirect effects of biologic activity, etc.) hence consideration of U plumes is a useful starting place. After an overview describing U plume sources, a general review of U chemistry and transport is presented, which is itself followed by a description of plume case studies. The sequence of source identification, fate and transport, and plume description will be the path followed for subsequent treatment of Sr, Cs (half-life = 30.1 yr), Pu, and tritium. 

The pronounced effects of aqueous chemistry on actinide sorption behavior suggest that sorption modeling should account for changing physicochemical conditions. A number of different modeling approaches of varying complexity can be used to incorporate the effects of chemistry on radionuclide sorption. A class of models that has been used with success in modeling pH-dependent sorption for actinides and other metals is the electrostatic surface complexation model (SCM). These models are equilibrium representations of sorption at the mineral-water interface and are discussed in detail elsewhere (Davis Kent, 1990 Dzombak Morel, 1990 Hayes etal., 1991 Seme etal., 1990 Turner, 1995), with only a brief overview presented here. 

Batch-sorption studies of the effect of important organic materials on radionuclide sorption have been conducted ... 

These studies have included sorption of plutonium, uranium and thorium onto a wide range of BVG rock types, both matrix tuff and fracture mineral assemblages. Some typical results are shown in Figs 7 to 9. The effect of organic material on radionuclide sorption varied... 

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. 

Radionuclide transport in natural waters is strongly dependent on sorption, desorption, dissolution, and precipitation processes. The first two sections discuss laboratory investigations of these processes. Descriptions of sorption and desorption behavior of important radionuclides under a wide range of environmental conditions are presented in the first section. Among the sorbents studied are basalt interbed solids, granites, clays, sediments, hydrous oxides, and pure minerals. Effects of redox conditions, groundwater composition and pH on sorption reactions are described. 

Field measurements of radionuclide migration can be used to help substantiate laboratory measurements of sorption, solubility, and identification of important chemical species. The fourth section describes three field investigations that provide information on the effects of organics, colloids and environmental conditions (Eh, pH, and temperature) on radionuclide transport. The chemical species of radionuclides that are mobile under specific field conditions are identified. 

Sorption and desorption isotherms were obtained for sorption of radionuclides under oxidizing and reducing conditions. The Freundlich equation accurately describes most of these isotherms. Most radionuclides are apparently irreversibly sorbed on each of the geologic solids since the slopes of sorption and desorption isotherms for a given radionuclide are different. This hysteresis effect is very large and will cause a significant delay in radionuclide transport. It, therefore, should be included in modeling radionuclide transport to accurately assess the isolation capabilities of a repository in basalt. 

The groundwater transport of radionuclides through waterbearing interbed layers in the Columbia River basalt formation will be controlled by reactions of the radionuclides with groundwater and interbed solids. These interactions must be understood to predict possible migration of radionuclides from a proposed radioactive waste repository in basalt. Precipitation and sorption on interbed solids are the principle reactions that retard radionuclide movement in the interbeds. The objective of the work described herein was to determine the sorption and desorption behavior of radionuclides important to safety assessment of a high-level radioactive waste repository in Columbia River basalt. The effects of groundwater composition, redox potential, radionuclide concentration, and temperature on these reactions were determined. 

High-level radioactive defense waste solutions, originating from plutonium recovery and waste processing operations at the U.S. Department of Energy s Hanford Site, currently are stored in mild steel-lined concrete tanks located in thick sedimentary beds of sand and gravel. Statistically designed experiments were used to identify the effects of 12 major chemical components of Hanford waste solution on radionuclide solubility and sorption. 

Chemical components in the waste solutions potentially could affect radioelement solubility and sorption reactions, and thus enhance or reduce radionuclide transport. The effects of 12 chemical components on the solubility and sorption of cobalt, strontium, neptunium, plutonium, and americium were studied to... 

Solubility estimates made by the techniques discussed above are reported in the last column of Table H. In addition to the limited number of such measurements, the results do not compare favorably in all cases with the theoretical values listed. This fact is hardly surprising considering the recognized limitations in the thermodynamic data base and difficulties encountered in interpreting results of solubility experiments. Furthermore, the theoretical estimates are based on the assumption that the thermodynamically most stable solid for a radionuclide controls its solubility. The effects of metastability are not included and, in this sense, theoretical solubility estimates are not conservative. A series of sorption-type experiments designed to yield solubility estimates for a number of the radionuclides included in this paper is in progress, and the results will be reported at a later date. 

One can attempt to overlay the effects of sorption on this scenario. It is apparent that strong sorption of radionuclides will tend to depress the equilibrium concentration of the element in... 

Investigations of redox processes in natural water systems have emphasized the disequilibrium behavior of many couples (e.g., 37). The degree of coupling of redox reactions with widely varying rates, and its effect on radionuclide transport in an NWRB needs to be considered. Because of the generally slow kinetics of autoxidation reactions, the potential surface catalyzed reduction of a radionuclide at low temperatures in the presence of trace levels of DO may explain certain sorption data (e.g., 38). 

Figure 4 compares several of these models with respect to the nature of the constants that each uses. The simplest model (linear sorption or Ai ) is the most empirical model and is widely used in contaminant transport models. values are relatively easy to obtain using the batch methods described above. The Aid model requires a single distribution constant, but the Aid value is conditional with respect to a large number of variables. Thus, even if a batch Aid experiment is carefully carried out to avoid introduction of extraneous effects such as precipitation, the Aid value that is obtained is valid only for the particular conditions of the experiment. As Figure 4 shows, the radionuclide concentration, pH, major and minor element composition, rock mineralogy, particle size and solid-surface-area/solution volume ratio must be specified for each Aid value. 

Uranium(VI) readily precipitates in the presence of phosphate to form a number of sparingly soluble U-phosphate phases (U phases, such as saleeite, meta-autunite, and autunite) and also is removed by sorption and co-precipitation in apatite. Several studies have shown that hydroxyapatite is extremely effective at removing heavy metals, uranium, and other radionuclides from solution (Gauglitz et al., 1992 Arey and Seaman, 1999). 

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