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Transport and retention behavior of multi-walled carbon nanotubes (MWCNTs) was studied in mixtures of negatively charged quartz sand (QS) and positively charged goethite-coated sand (GQS) to assess the role of chemical heterogeneity. The linear equilibrium sorption model provided a good description of batch results, and the distribution coefficients (KD) drastically increased with the GQS fraction that was electrostatically favorable for retention. Similarly, retention of MWCNTs increased with the GQS fraction in packed column experiments. However, calculated values of KD on GQS were around 2 orders of magnitude smaller in batch than packed column experiments due to differences in lever arms associated with hydrodynamic and adhesive torques at microscopic roughness locations. Furthermore, the fraction of the sand surface area that was favorable for retention (Sf) was much smaller than the GQS fraction because nanoscale roughness produced shallow interactions that were susceptible to removal. These observations indicate that only a minor fraction of the GQS was favorable for MWCNT retention. These same observations held for several different sand sizes. Column breakthrough curves were always well described using an advective-dispersive transport model that included retention and blocking. However, depth-dependent retention also needed to be included to accurately describe the retention profile when the GQS fraction was small. Results from this research indicate that roughness primarily controlled the retention of MWCNTs, although goethite surfaces played an important secondary role.

Column experiments were conducted with undisturbed loamy sand soil under unsaturated conditions (around 90% saturation degree) to investigate the retention of surfactant stabilized silver nanoparticles (AgNPs) with various input concentration (Co), flow velocity, and ionic strength (IS), and the remobilization of AgNPs by changing the cation type and IS. The mobility of AgNPs in soil was enhanced with decreasing solution IS, increasing flow rate and input concentration. Significant retardation of AgNP breakthrough and hyperexponential retention profiles (RPs) were observed in almost all the transport experiments. The retention of AgNPs was successfully analyzed using a numerical model that accounted for time- and depth-dependent retention. The simulated retention rate coefficient (k1) and maximum retained concentration on the solid phase (Smax) increased with increasing IS and decreasing Co. The high k1 resulted in retarded breakthrough curves (BTCs) until Smax was filled and then high effluent concentrations were obtained. Hyperexponential RPs were likely caused by the hydrodynamics at the column inlet which produced a concentrated AgNP flux to the solid surface. Higher IS and lower Co produced more hyperexponential RPs because of larger values of Smax. Retention of AgNPs was much more pronounced in the presence of Ca(2+) than K(+) at the same IS, and the amount of AgNP released with a reduction in IS was larger for K(+) than Ca(2+) systems. These stronger AgNP interactions in the presence of Ca(2+) were attributed to cation bridging. Further release of AgNPs and clay from the soil was induced by cation exchange (K(+) for Ca(2+)) that reduced the bridging interaction and IS reduction that expanded the electrical double layer. Transmission electron microscopy, energy-dispersive X-ray spectroscopy, and correlations between released soil colloids and AgNPs indicated that some of the released AgNPs were associated with the released clay fraction.