Transport of Titanium Dioxide Nanoparticles in Porous Media: Characterization and Quantification of Retention Informed by Atomic Force Microscopy

Manufactured nanoparticles are used in many consumer products and industries, and are known to enter our waste streams. Transport of nanoparticles in porous media has been studied extensively; however, the forces governing the interactions between nanoparticles and naturally porous media surfaces are still not fully understood. To examine the retention mechanisms and forces involved in nanoparticle transport, miscible–miscible transport experiments were performed and followed by force profile measurements by Atomic Force Microscopy (AFM). TiO₂ nanoparticles were used as the model nanoparticle, with silica sand as the model natural porous medium. Solution chemistries were varied from pH 4.5 (favorable attachment) to 8 (unfavorable attachment), and at 0.0015–30 mM ionic strength. Detachment transport experiments were performed for the unfavorable attachment conditions to determine if secondary minima attachment was present. DLVO calculations were performed to evaluate their predictive ability for force profiles under the experimental conditions. Mass recoveries for the transport experiments ranged from 28% to 80%, indicating significant attachment. Detachment was observed, indicating the presence of secondary minima. The magnitudes of attachment measured for the transport experiments were generally consistent with the results of the AFM measurements. In addition, the detachment observed at the highest pH was also consistent with the predictions, indicating the presence of secondary minima. DLVO theory underestimated the magnitudes of the attractive and repulsive forces measured by AFM but was able to qualitatively represent behavior observed at the lower two pHs. In contrast, it provided a poor representation of behavior at the highest pH. The integrated AFM measurements and miscible–displacement experiments employed in this study have provided insight into the retention of TiO₂, with implications for other nanoparticles during transport in porous media.