Adsorption of tetravalent thorium by geomedia

Abstract

We measured the pH-dependent adsorption of Th(IV), an analogue for Pu(IV) and other tetravalent actinides, to two geomedia: goethite (α-FeOOH(s)) and a heterogeneous Fe-containing sand from the southeastern USA. The goal was to examine whether or not the Th(IV)-goethite adsorption data could be used to predict the adsorption of Th(IV) by the heterogeneous sand. In the absence of either geomedia, after forty-eight hours the measured pH-dependent “adsorption” was consistent with the solubility of solid amorphous ThO₂(am, aged), despite the fact that ThO₂(am, aged) is generally not formed until approximately seventy days. We concluded that ThO₂(am, aged) was stabilized by precipitating on the walls of the reaction vessels. Ignoring this phenomenon could lead to experimental artifacts in Th(IV) adsorption studies. Thorium adsorption by both goethite and the sand was strongly pH dependent, with adsorption increasing sharply from pH ∼ 2 to pH ∼ 4. Two methods were utilized to predict the pH-dependent adsorption of Th(IV) by the sand using the Th(IV)-goethite adsorption data. Using the Fe content of the sand and the Th(IV)-goethite adsorption data, we were able to predict the maximum amount of Th(IV) adsorption by the sand within 78% of the actual value (i.e., an error of 22%). In contrast, on a surface-area-normalized basis, we were only able to predict the maximum adsorption of Th(IV) by the sand within a factor of two. These results have important implications to scaling and extrapolating the results of batch-scale tetravalent actinide adsorption studies with pure minerals to predict their field-scale adsorption by and transport in heterogeneous subsurface media.