Impacts of Cation Type and Clay on Transport of Surface-modified Nanoparticles through Saturated Sand Columns

Transport of three different nanoparticles (NPs) was studied in columns packed with different sands (unwashed Accusand, washed Accusand, and ultrapure quartz) at different ionic strengths (IS) and cation types. The NPs were functionalized (polyacrylic acid) quantum dots (QDs), carboxylic-modified latex, and bare silica. Scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX) analysis showed there were regions on the unwashed Accusand grains covered with clay particles. The SEM images of washed Accusand showed that the sand surfaces contained significantly less clay coatings. The breakthrough curves (BTCs) of QDs and latex NPs from unwashed Accusand columns showed minute deposition at 50 and 100 mM Na+. However, significant NP deposition occurred in unwashed Accusand columns at 0.5, 1, and 2 mM Ca2+. The amount of deposition increased as the Ca2+ concentration was increased. These results suggest that, in contrast to monovalent Na+, divalent Ca2+ enhanced deposition of the NPs. The BTCs of QDs and latex NPs in washed Accusand exhibited a similar trend as those of unwashed Accusand, however, much less deposition occurred at any given IS. The BTCs from the ultrapure quartz sand column showed negligible QD deposition at 2 mM Ca2+. Following completion of column experiments, a few Accusand sand grains were analyzed with SEM and the images showed that most of QDs were deposited on the clay surfaces. In contrast with our results from surface-modified NPs, the column experiments using bare silica NPs at 5 mM Ca2+ in unwashed Accusand showed negligible deposition. The enhanced deposition of surface-modified NPs may be attributed to cation bridging in which Ca2+ cations serve as a bridge between the NP, which contain carboxyl group on its surface, and negatively charged clay surfaces at 7. Because Ca2+ is commonly a major cation in groundwater, our results suggest that transport of carboxylic ligand-modified NPs may be very limited in subsurface environments.