Sensitivity analysis of radionuclide migration in compacted bentonite: a mechanistic model approach

Mechanistic model calculations for the migration of Cs, Ra, Am and Pb in compacted bentonite have been carried out to evaluate sensitivities with respect to different parameter variations. A surface chemical speciation/electric double layer model is used to calculate: (i) porewater composition and radionuclide speciation in solution and at the bentonite surface, yielding the distribution of mobile and sorbed species and (ii) interaction of diffusing species with negatively charged pore walls to obtain diffusion parameters. The basic scenario considers the interaction of compacted bentonite with a fresh-type groundwater; variations include the presence of bentonite impurities and saline groundwater. It is shown that these scenarios result in significant variations of porewater composition that affect migration via three mechanisms that can partly compensate each other: (1) effects on sorption through radionuclide complexation in solution, and competition of major cations for surface sites; (2) changes in radionuclide solution speciation leading to different diffusing species under different conditions; (3) effects on diffusion through changes in the electric double layer properties of the clay pores as a function of ionic strength.     

Cosolvent effects on sorption isotherm linearity

Sorption-desorption hysteresis, slow desorption kinetics, and other nonideal phenomena have been attributed to the differing sorptive characteristics of the natural organic polymers associated with soils and sediments. In this study, aqueous and mixed solvent systems were used to investigate the effects of a cosolvent, methanol, on sorption isotherm linearity with natural organic matter (NOM), and to evaluate whether these results support, or weaken, the rubbery/glassy polymer conceptualization of NOM. All of the sorption isotherms displayed some nonlinear character. Our data indicates that all of the phenanthrene and atrazine isotherms were nonlinear up to the highest equilibrium solution concentration to solute solubility in water or cosolvent ratios (Ce/Sw,c) used, approximately 0.018 and 0.070, respectively. Isotherm linearity was also observed to increase with volumetric methanol content (fc). This observation is consistent with the NOM rubbery/glassy polymer conceptualization: the presence of methanol in NOM increased isotherm linearity as do solvents in synthetic polymers, and suggests that methanol is interacting with the NOM, enhancing its homogeneity as a sorptive phase so that sorption is less bimodal as fc increases. When the equilibrium solution concentration was normalized for solute solubility in water or methanol-water solutions, greater relative sorption magnitude was observed for the methanol-water treatments. This observation, in conjunction with the faster sorption kinetics observed in the methanol-water sediment column systems, indicates that the increase in relative sorption magnitude with fc may be attributed to the faster sorption kinetics in the methanol-water systems, and hence, greater relative sorptive uptake for the rubbery polymer fraction of NOM at similar time scales.     

Effects of lipids on the sorption of hydrophobic organic compounds on geosorbents: a case study using phenanthrene

The impact of the lipid fraction of natural geosorbents on the sorption of a polycyclic aromatic hydrocarbon was assessed using several experiments. In the first set of experiments phenanthrene was sorbed on a coastal sediment as well as on its humin and humic acid fractions before and after lipid extraction. Before lipid extraction, sorption shows dominantly partitioning characteristics. However, the extraction of lipids from sediment and humin drastically increases, by up to one order of magnitude, their sorption affinity for phenanthrene at low sorbate concentrations, resulting in increased isotherm nonlinearity. This effect is less pronounced for humic acids. One mechanism proposed for the increasing sorption is that lipids, despite their very low relative abundance in the sediments, can compete with phenanthrene for specific high affinity sorption sites (e.g., matrix pores and adsorption sites). This competition is not surprising considering the similar hydrophobic nature of lipids and phenanthrene. Lipids, or any non-polar molecules, could also act like plasticizers by swelling rigid domains and disrupting high affinity sites. In both cases, the removal of lipids (and extraction solvents) makes those sites available for phenanthrene. These provide alternative explanations to the previously proposed “solvent conditioning effect” believed to occur when geosorbents are treated with non-polar solvents modifying the matrix structure, an effect yet to be proven at molecular scale. To further investigate the impact of lipids on sorption, other independent experiments were performed. In a second experiment, re-addition of lipids to the extracted sediment restored the sorption isotherm linearity observed in the native material supporting the absence of irreversible extraction artifacts. However, high addition of lipids (i.e., after saturation of high affinity sites) seems to also enlarge the low affinity partitioning domain. These results are consistent with dual-mode, hole-filling, sorption models involving diffusion. In the final set of experiments, solid-state ¹⁹F-NMR using F-labeled lipids sorbed onto the sediments confirmed that lipids may be in different domains (mobile or rigid) that interact or not with phenanthrene. The possible effects of lipid removal on sorption have been overlooked and should be considered when geosorbents are pretreated.     

Formation process and mechanism of humic acid-kaolin complex determined by carbamazepine sorption experiments and various characterization methods

To explore the formation process and mechanism of organic matter and organic-mineral complex under humification and mineralization conditions, a series of samples including humic acid, kaolin, and humic acid-kaolin complex were prepared using a subcritical water treatment method(SWT) under specific temperature, pressure and reaction time conditions. HA was used as a surrogate for natural organic matter because it has a similar abundant pore structure,variety of carbon types, and chemical components. These samples were used in carbamazepine(CBZ) sorption experiments and characterized by a variety of techniques. The polymerization of humic acid under the conditions of increased temperature and pressure resulted in an increase in specific surface area and molecular quantity. In addition, the degree of aromaticity rose from59.52% to 70.90%. These changes were consistent with the transformation from ‘soft carbon' to‘hard carbon' that occurs in nature. The results of sorption experiments confirmed the interaction between humic acid and kaolin from the difference between the predicted and actual Qevalues. The conceptual model of humic acid-kaolin complex could be deduced and described as follows. Firstly, the aromatic components of humic acid preferentially combine with kaolin through the intercalation effect, which protects them from the treatment effects.Next, the free carboxyl groups and small aliphatic components of humic acid interact on the surface of kaolin, and these soft species transform into dense carbon through cyclization and polymerization. As a result, humic acid-kaolin complex with a mineral core and dense outer carbonaceous patches were formed.     

Sorption of heavy metals on organic and inorganic soil constituents

Sorption of heavy metals to organic matter and mineral soil constituents can hardly be separated experimentally. Here we studied the retention capacity of organic matter and minerals from soils in a long-term field experiment in which the organic carbon content had been altered, but the mineral phase had remained constant over time. The sorption of Cu, Cd and Zn showed a non-additive contribution of soil organic matter and minerals to the sorption capacity of soil. Sorption on organic matter exceeded mineral sorption from 6 to 13 times. This is the first time that sorption to soil organic matter is quantified in bulk soils.     

Effect of metallic cations on the sorption of pesticides on soil

We studied the adsorption and desorption of two pesticides, namely isoproturon and dimetomorph, onto a model soil sample. We first show that the adsorption of isoproturon depends on pH, from 1 mg g⁻¹ at pH 4 to 2 mg g⁻¹ at pH 10, contrary to the adsorption of dimetomorph (5.8 mg g⁻¹). We also studied the influence of metallic cations, copper(II), iron(III), manganese(II), and chromium(III), on the sorption of isoproturon and dimetomorph. We found that in the case of isoproturon, the presence of metallic cations does influence the retention capacity of the soil sample. The sorption becomes very weak in the presence of copper and chromium, whereas in the case of iron and manganese the sorption properties are slightly modified.     

Distribution of tritium in estuarine waters: the role of organic matter

Tritium is an important environmental radionuclide whose reactivity with ligands and solids in aquatic systems is assumed to be limited. We studied the fractionation and sorption of tritium (added as tritiated water) in river water and seawater, and found that its distribution appears to be influenced by its affinity for organic matter. Tritium rapidly equilibrates with dissolved organic ligands that are retained by a reverse-phase C18 column, and with suspended sediment particles. Significantly, a measurable fraction of sorbed tritium associates with proteinaceous material that is potentially available to sediment-feeding organisms. These characteristics have not been reported previously and cannot be accounted for solely by isotopic exchange with hydrogen. Nevertheless, they are in qualitative agreement with available measurements of tritium in estuarine and coastal waters where its principal discharge is as tritiated water. Further research into the estuarine biogeochemical behaviour of tritium is required and radiological distribution coefficients and concentration factors that are assumed for this radionuclide may require reconsideration.     

Bisolute Equilibrium Studies for the Sorption of Basic Dyes on a GAC from Almond Shells: A Nonlinear Approach

Aqueous phase adsorption of three textile dyes onto a granular activated carbon produced from acid activation of almond shells is presented. Primarily, the sorption of three basic dyes, methylene blue, rhodamine b, and malachite green oxalate were studied. Four models, the Freundlich, the Langmuir, the Redlich-Peterson, and the Toth isotherms were compared for their quality of fit to the single-solute sorption data. Next, sorption of the three likely binary systems was examined. Four bi-solute models, the extended Langmuir with and without an interaction term, the extended Redlich-Peterson with an interaction term, and the empirical extended Freundlich model were used to predict sorption in the binary systems. Nonlinearly determined constants of the corresponding single-solute isotherms were used in the binary models to compare with experimental binary sorption data. For the single-solute system, the three-parameter models of the Redlich-Peterson and the Toth isotherms outperformed the Langmuir and Freundlich models. The empirical extended Freundlich model produced the closest comparison to the binary data in each system. In general, the nonlinear method provided a simple and computationally effective technique of producing optimal fitting parameters for the bi-solute sorption models.     

Dissipation and metabolism of C-spiroxamine in soil under laboratory condition

Spiroxamine [SPX] belongs to a spiroketalamine group of substances. The biodegradation of [1,3-dioxolane-4-¹⁴C]-SPX has been examined in 2 soils of different physicochemical properties. The total recovery of radioactivity from soils was 98.6-103.5% of that applied. The total amount of extractable radioactivity declined with a simultaneous increase in non-extractable radioactivity. Volatile organics were detected at lower levels; however, mineralization played a marked effect on the route of SPX dissipation. The half-life ranges between 37 and 44 d. SPX does not undergo any enantioselective degradation. 4 metabolites: despropyl-SPX, desethyl-SPX, SPX N-oxide and SPX acid were identified, applying mass spectrometric technique. Sorption-desorption data fitted well with a Freundlich model in log form (r², 0.99). K_Dsorp ranged between 44 and 230, suggesting SPX ought to be considered as a substance with low leaching potential [groundwater ubiquity score (GUS), <1.8]. Furthermore, an overall low desorption of 1-11% indicates firm retention of SPX by the soils.     

Radionuclide transport and retardation in rock fracture and crushed rock column experiments

Transport and retardation of non-sorbing tritiated water and chloride and slightly sorbing sodium was studied in Syyry area SY-KR7 mica gneiss, in altered porous tonalite and in fresh tonalite. Experiments were performed using dynamic fracture and crushed rock column methods. Static batch method for sodium was introduced to compare retardation values from static and dynamic experiments. The ¹⁴C-PMMA method was used to study the pore structure of matrices. The pore aperture distribution was evaluated from Hg-porosimetry determinations and the surface areas were determined using the B.E.T. method. The flow characteristics and transport behavior of tracers were interpreted using a numerical compartment model for dispersion. The effect of matrix diffusion was calculated using an analytical solution to the advection-matrix diffusion problem in which surface retardation was taken into account. Radionuclide transport behavior in rock fractures was explained on the basis of rock structure.