The increasing use of nanotechnology will most likely lead to the appearance of nanoparticles in aqueous phase. It is necessary to find effective methods to remove these nanoparticles from water. In this study, we found TiO2 nanoparticles (NPs) could be removed effectively by poly-ferric sulfate (PFS) and ferric chloride (FeCl3) coagulants. The effects of pH, ionic strength and humic acid (HA) on the performance of these two coagulants in this application were investigated. The effective pH range of FeCl3 is very narrow (95-10.6). For PFS, its effective pH range is broader (7-10.8). The behaviour of PFS is different from FeCl3 for the removal of TiO2 NPs. Liquid PFS contains many polymerization cations, which have the role of charge neutralization and bridging flocculation in the removal of TiO2 NPs. The main mechanism for removing TiO2 NPs by PFS is the formation of polymerization cations during the hydrolysis process. For both PFS and FeCl3 coagulants, the increase of ionic strength can significantly improve the coagulation effect, although this effect is influenced by pH. For both coagulants, higher HA concentration makes the TiO2 NPs suspension more stable, and the TiO2 NPs removal rate decreased significantly because of the steric hindrance effect of HA molecules. © 2014 Elsevier B.V.

With the increasingly widespread use of titanium dioxide nanoparticles (TiO2 NPs), the particles' environmental impacts have attracted concern, making it necessary to understand the fate and transport of TiO2 NPs in aqueous media. In this study, we investigated TiO2 NP aggregation caused by the effects of humic acid (HA), ionic strength (IS) and different pH using dynamic light scattering (DLS) to monitor the size distribution of the TiO2 NPs continuously. It was determined that HA can influence the stability of TiO2 NPs through charge neutralization, steric hindrance and bridging effects. In the absence of IS, aggregation was promoted by adding HA only when the pH (pH=4) is less than the point of zero charge for the TiO2 NPs (pHPZC≈6) because HA reduces the zeta potential of the TiO2 NPs via charge neutralization. At pH=4 and when the concentration of HA is 94.5 μg/L, the zeta potential of TiO2 NPs is close to zero, and they reach an aggregation maximum. A higher concentration of HA results in more negatively charged TiO2 NP surfaces, which hinder their aggregation. When the pH is 5.8, HA enhances the negative zeta potential of the TiO2 NPs and increases their stability via electrostatic repulsion and steric hindrance. When the pH (pH=8) is greater than pHpzc, the zeta potential of the TiO2 NPs is high (~40 mV), and it barely changes with increasing HA concentration. Thus, the TiO2 NPs are notably stable, and their size does not grow at pH8. The increase in the critical coagulation concentration (CCC) of TiO2 NPs indicated that there is steric hindrance after the addition of HA. HA can enhance the coagulation of TiO2 NPs, primarily due to bridging effect. These findings are useful in understanding the size change of TiO2 NPs, as well as the removal of TiO2 NPs and HA from aqueous media.

The increasing and wide use of nanoparticles (NPs), including TiO2 and Ag NPs, have raised concerns due to their potential toxicity and environmental impacts. Kaolin is a very common mineral in aquatic systems, and there is a very high probability that nanoparticles (NPs) will interact with these clay minerals. We studied the effect of kaolin particles on the aggregation of NPs under different conditions, including the role of pH, ionic strength (IS), and humic acid (HA). We show that kaolin reduces the energy barrier and the Critical Coagulation Concentration (CCC) at pH 4. At pH 8, even though the energy barrier of the system without kaolin increases, kaolin promotes NP aggregation via heteroaggregation. When IS is equal to or greater than the CCC, on the one hand HA promotes aggregation of TiO2 NPs, but on the other hand HA decreases the rate of Ag NP aggregation because the existence of a surface coating may limit the adsorption of HA on these Ag NPs. In addition, the presence of HA increases the energy barrier and the CCC of the binary system (kaolin + NPs). Thus, the complex interactions of clay, NPs, IS, pH, and HA concentration determine the colloidal stability of the NPs. We find that kaolin is a potential coagulant for removal of NPs that behave like Ag and TiO2.