Fe(III)-montmorillonite: Basic properties and diffusion of tracers relevant to alteration of bentonite in deep geological disposal

In the deep geological repository of high-level nuclear waste (HLW), the interaction of carbon steel (Fe) overpack container and the back-fill clay mineral, montmorillonite (mont), is an important issue to be clarified in view of the long-term performance of clay mineral as an engineered barrier. To arrive at some understanding of the altered clay at the Fe/clay interface, Fe(III)-mont is used here for preliminary investigation to see if there is any considerable difference in the basic properties, mainly diffusion of tracers with respect to Na-mont, although Fe(III)-mont is not a realistic analogue of altered clay in the reducing chemistry conditions anticipated in the subsurface of HLW, unlike Fe(II)-mont which is difficult to prepare and handle in the ambient atmosphere due to its gradual oxidation. Fe(III)-mont was prepared by the conventional cation exchange method with 0.4 M FeCl3 solution. The total Fe(III) ions adsorbed was about 1.42 meq/g, while the CEC of parent clay was 1.2 meq/g. Thus similar to 18% excess Fe (III) ions were present presumably as iron oxy hydroxide, i.e., about 2 wt.% with respect to FeOOH or Fe(OH)(3) in the bulk sample. The sample was further characterized by X-ray diffraction (XRD), infrared (IR), thermogravimetry, magnetization, and the methylene blue (MB) adsorption. From these conventional techniques, the minor Fe-oxide phase associated with the Fe(III)-mont could not be detected, although we cannot rule out its existence. The paramagnetic behavior of Fe(III)-mont was evident from the Curie-Weiss plot (300 K down to 5 K). Some basic properties like osmotic swelling, diffusion of tracers and thermal stability are evaluated here. The osmotic swelling of Fe(III)-mont was very low, similar to 5 ml/g, while that of Na-mont was >40 ml/g. Apparent diffusion coefficient (D-a) of tracers ViZ., Na-22(-), HTO and Cl-36(-) was determined using compacted (dry density, rho(d) = 1.0, 1.6 Mg m(-3)), water-saturated Fe(III)-mont. There was no considerable change in D-a of these tracers in Fe(III)-mont when compared to that in Na-mont, in spite of higher pore water availability in Fe(III)-mont due to reduced swelling. For instance at rho(d) = 1.6 and 25 degrees C, D-a(x10(-11) m(2)/s) of Na-22(+)(2.6) was same as that in Na-mont whereas D-a of HTO (11.4) and Cl-36(-) (1.0) have varied marginally. For comparison, the corresponding D-a(x10(-11) m(2)/s) values in Na-mont were 2.7, 7.2 and 3.4, respectively. Also, at rho(d) = 1.6, the diffusion activation energy (E-A. kJ mol(-1)) of HTO (17.5) in Fe (III)-mont was comparable to that in free water, however, EA of Cl-36(-) (13.1) was remarkably low, which may be ascribed to the so-called 'anion exclusion' effect. Furthermore, thermal stability of Fe(III)-mont indicated the existence of interlayer Fe(III) in the ionic state up to similar to 190 degrees C, based on the XRD and MB adsorption test. On heating to > 200 degrees C, irreversible dehydration of interlayer cations occurred, and the chemisorption of NH3 indicated two distinct acid sites at about 300 degrees C and 600 degrees C. (C) 2008 Elsevier B.V. All rights reserved.