PNNL

Abstract

In most natural subsurface settings cesium sorbs very strongly to sediments, effectively limiting its transport. At the Hanford Site in Washington State (USA), vadose zone migration of 137Cs from subsurface high-level radioactive waste tanks has been detected over 40 meters below the ground surface. Batch and saturated laboratory column studies provided the basis for a quantitative multisite, multicomponent ion exchange model of Cs+ competition with Na+, K+, Ca++, and Mg++ in a composite Hanford soil. The validity of this model under unsaturated conditions was examined in a series of reactive transport column experiments performed in an ultracentrifuge at different liquid saturations. For each experiment, a constant, uniform saturation was maintained using a steady influx of a 5 M sodium nitrate solution with 5.4E-5 M cesium iodide. Of interest was the potential for enhanced cesium transport due to the presence of immobile liquid and/or bypassed regions. Mobile and immobile fluid fractions, dispersion, and the rate of mass transfer between mobile and immobile regions were determined from the tracer breakthrough. At higher saturations (~ 65%), the tracer and cesium behavior could be predicted to a large degree using a single mobile region with the previously developed multicomponent ion exchange model. At lower saturations (~ 23%), however, the tracer breakthrough indicated a relatively large immobile fluid fraction, which could be described with a multi-region approach. In this experiment, cesium broke through earlier and at higher concentrations than predicted by multi-region theory combined with the existing cesium ion exchange model. This behavior is consistent with a higher density of exchange sites in the immobile fluid region.