Surface Adsorption of Suwannee River Humic Acid on TiO2 Nanoparticles: A Study of pH and Particle Size.

TiO2 nanoparticles are some of the most widely used metal oxide nanomaterials mainly because of their diverse industrial applications. Increasing usage of these nanoparticles raises concerns about the potential adverse effects on the environment. Humic acid is a ubiquitous component of the natural organic matter in the environment that is known to get adsorbed onto nanoparticle surfaces. In this study, adsorption of humic acid on TiO2 nanoparticles of two different sizes (5 and 22 nm) is studied at different environmentally relevant pH values using attenuated total reflectance Fourier transformation infrared spectroscopy. These vibrational spectra provide insights into the nature of the adsorption process (extent of adsorption and reversibility) as a function of pH as well as information about the bonding to the surface. Additionally, the impact of humic acid adsorption on surface charge and agglomeration has been investigated. Interestingly, the results show that the humic acid adsorption is strongly pH-dependent and that adsorption of humic acid on TiO2 nanoparticles alters the extent of agglomeration and modifies the zeta potential and surface charges depending on the pH, thus potentially increasing the bioavailability of TiO2 nanoparticles in the environment.