Transport and retention of TiO2 and polystyrene nanoparticles during drainage from tall heterogeneous layered columns

• Significant retention of TiO2 nanoparticles was observed above the water table.
• Retention in unsaturated medium sand layers was often greater than adjacent fine sand.
• Retention by unsaturated media correlated strongly with elevation.

Recent developments in nanotechnology have seen an increase in the use of manufactured nanomaterials. Although their unique physicochemical properties are desirable for many products and applications, concern continues to exist about their environmental fate and potential to cause risk to human and ecological health. The purpose of this work was to examine one aspect of nanomaterial environmental fate: transport and retention in the unsaturated zone during drainage. The work made use of tall segmented columns packed with layers of two different porous media, one medium sand and one fine sand. The use of tall columns allowed drainage experiments to be conducted where the water table remained within the height of the column, permitting control of final saturation profiles without the need for capillary barrier membranes which can potentially complicate analyses. Experiments were conducted with titanium dioxide (TiO2) and polystyrene nanomaterials. For the strongly negatively-charged polystyrene nanomaterials, little retention was observed under the conditions studied. For the TiO2 nanomaterials, results of the work suggest that while saturated fine sand layers may retain more nanomaterials than saturated coarse sand layers, significantly greater retention is possible in unsaturated media. Furthermore, unsaturated medium sand layers exhibited significantly greater retention than adjacent saturated fine sand layers when present at low saturations high above the water table. Retention by unsaturated media were found to correlate strongly with elevation. Free drainage experiments including both primary and secondary drainages in homogeneous columns showed evidence of redistribution during imbibition and secondary drainage, but still showed substantial unsaturated retention of TiO2 nanoparticles high in the column, despite re-saturation with- and drainage of nanoparticle-free water.