Sorption of phenanthrene by humic acid-coated nanosized TiO2 and ZnO.

Phenanthrene sorption by nano-TiO2 and nano-ZnO particles was enhanced significantly by coated humic acids (HAs), implying that additional toxicity can be potentially given to these nanooxides by adsorbed HOCs once released to the environment. Phenanthrene isotherms of adsorbed HA on nano-TiO2 and nano-ZnO were more nonlinear than that of their respective bulk HA. Both HA conformation changes and fractionation were observed upon HA adsorption on nano-TiO2 and nano-ZnO, which further affected phenanthrene sorption. Nano-TiO2 and nano-ZnO interacted with differentfunctional groups of HA (i.e., phenolic OH with nano-TiO2, while COOH with nano-ZnO), leading to different conformations of adsorbed HA. Interaction of HA phenolic OH with nano-TiO2 increased the pi-polarity/polarizability of adsorbed HA and, consequently, its phenanthrene adsorption affinity and isotherm nonlinearity. Interactions of COOH groups on HA aromatic rings with nano-ZnO would also increase the pi-polarity/polarizability of adsorbed HA and its phenanthrene adsorption affinity, whereas interactions of COOH groups on HA aliphatic chains with nano-ZnO would make the adsorbed HA be in a more condensed state with lower partitioning affinity. Increase in adsorption and decrease in partitioning were responsible for the more nonlinear phenanthrene isotherms of adsorbed HA than bulk HA.