ISSN:
1573-1421
Keywords:
sorption
;
uranium
;
uranyl
;
clays
;
montmorillonite
;
surface complexation
;
diffuse layer model
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
,
Geosciences
Notes:
Abstract Sorption interactions with montmorillonite and other clay minerals in soils, sediments, and rocks are potentially important mechanisms for attenuating the mobility of U(6+) and other radionuclides through the subsurface environment. Batch experiments were conducted (in equilibrium with atmospheric % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiiYdd9qrFfea0dXdf9vqai-hEir8Ve% ea0de9qq-hbrpepeea0db9q8as0-LqLs-Jirpepeea0-as0Fb9pgea% 0lrP0xe9Fve9Fve9qapdbaqaaeGacaGaaiaabeqaamaabaabcaGcba% acbiGaiWiG-bfadaWgaaWcbaacbaGaa43qaiaa+9eadaWgaaqaaiaa% +jdaaWqabaaaleqaaaaa!400D!\[P_{CO_2 } \])to determine the effects of varying pH (2 to 9), solid-mass to solution-volume ratio (M/V = 0.028 to 3.2 g/L), and solution concentration (2 × 10−7 and 2 × 10−6 M 233U) on U(6+) sorption on SAz-1 montmorillonite. The study focused on U(6+) surface complexation on hydroxylated edge sites as the sorption mechanism of interest because it is expected to be the predominant sorption mechanism at pHs typical of natural waters (pH ≈6 to ≈9). Thus, the experiments were conducted with a 0.1 M NaNO3 matrix to suppress ion-exchange between U(6+) in solution and interlayer cations. The results show that U(6+) sorption on montmorillonite is a strong function of pH, reaching a maximum at near-neutral pH (≈6 to ≈6.5) and decreasing sharply towards more acidic or more alkaline conditions. A comparison of the pH-dependence of U(6+) sorption with that of U(6+) aqueous speciation indicates a close correspondence between U(6+) sorption and the predominance field of U(6+)-hydroxy complexes. At high pH, sorption is inhibited due to formation of aqueous U(6+)-carbonate complexes. At low pH, the low sorption values indicate that the 0.1 M NaNO3 matrix was effective in suppressing ion-exchange between the uranyl (UO2 2+) species and interlayer cations in montmorillonite. At pH and carbonate concentrations typical of natural waters, sorption of U(6+) on montmorillonite can vary by four orders of magnitude and can become negligible at high pH. The experimental results were used to develop a thermodynamic model based on a surface complexation approach to permit predictions of U(6+) sorption at differing physicochemical conditions. A Diffuse-Layer model (DLM) assuming aluminol (〉AlOHℴ) and silanol (〉SiOHℴ) edge sites and two U(6+) surface complexation reactions per site effectively simulates the complex sorption behavior observed in the U(6+)-H2O-CO2-montmorillonite system at an ionic strength of 0.1 M and pH 〉 3.5. A comparison of model predictions with data from this study and from published literature shows good agreement and suggests that surface complexation models based on parameters derived from a limited set of data could be useful in extrapolating radionuclide sorption over a range of geochemical conditions. Such an approach could be used to support transport modeling by providing a better alternative to the use of constant K d s in transport calculations.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00119855
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