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Soot nanoparticles (SNPs) undergo aging processes in aqueous systems, altering their physicochemical properties and affecting their fate and transport. This study investigated the aging effects via ultraviolet irradiation on aggregation kinetics of SNPs in water. The results showed that, compared to fresh SNPs, those irradiated for 1 day aggregated more easily in NaCl and CaCl2 solutions, with reduction of critical coagulation concentrations by 72% and 40%, respectively. Similar phenomena were found in additional six electrolyte solutions, and SNPs irradiated for > 3 days had no measurable difference in aggregation rate. The aggregation-enhancement of irradiated SNPs was more prominent at low electrolyte concentrations and pH > 4. However, in the presence of macromolecules, irradiated SNPs could be stabilized against aggregation via steric hindrance with strength of bovine serum albumin > humic acid > alginate > fulvic acid, whereas alginate further destabilized aged SNPs via calcium bridging. The fitted Hamaker constant increased from 7.8 × 10−20 (fresh) to 1.2 × 10−19 J (7-day irradiated), suggesting that decarboxylation during irradiation may weaken electrical repulsion and enhance van der Waals attraction, promoting aggregation. These results demonstrated the vital role of UV-induced aging in fate and transport of SNPs in wet environments.

Nanoplastics (NPs) derived from degradation of macroplastics and microplastics possess potential threat to aquatic biota and human health. Their fate and transport in aquatic systems are mainly governed by aging processes and aggregation behavior. In this study, we simulated plastic aging process using UV-irradiation and compared the aggregation kinetics of fresh versus aged polystyrene NPs (PSNPs) under aqueous conditions. The results showed that fresh PSNPs had strong negative surface charge and exhibited both reaction- and diffusion-limited aggregation regimes, in agreement with classic Derjaguin−Landau−Verwey−Overbeek (DLVO) theory. Divalent electrolytes were 10–15 times more effective in inducing PSNP aggregation than monovalent electrolytes. The aging process inhibited PSNP aggregation in NaCl solutions by increasing the negative charge on PSNP surface and the organic matter content in solution, while promoted PSNP aggregation in CaCl2 solutions due to interactions between Ca2+ and carboxyl groups formed on aged PSNP surface. Such distinct behaviors were consistent with characterizations by contact angle measurements, potentiometric titration, total organic carbon (TOC) analysis, Fourier Transform Infrared Spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). Hamaker constants obtained from DLVO fitting decreased from 3.5 × 10−21 J for fresh PSNPs to 1.5 × 10−21 J for aged PSNPs. This study indicated that UV-irradiation plays a vital role in governing the fate, transport, and potential hazards of PSNPs in aquatic environments.

The transport of stabilized zerovalent iron nanoparticles (nZVI) has recently been the topic of extensive research due to its proven potential as an in situ remediation tool. However, these studies have ignored the effects of biofilms-complex aggregations of bacterial cells and excreted extracellular polymeric substances present in nearly all aquatic systems-on the transport of these particles. This study examines the effects of Pseudomonas aeruginosa (PAO1) biofilm, at a cell concentration similar to that reported for saturated aquifers, on the transport of commercially available, poly (acrylic acid) stabilized nZVI (pnZVI) in 14 cm long columns packed with saturated glass beads at salt concentrations of 1 and 25 mM NaCl. Compared to retention on uncoated columns, in the presence of biofilm the retention of pnZVI increased at higher ionic strength, while ionic strength played no role in retention of these nanoparticles in the absence of biofilm. The Tufenkji-Elimelech correlation equation predicts lower retention of pnZVI on biofilm coated columns compared to uncoated columns due to a lower Hamaker constant, and DLVO energy considerations predict the most favorable attachment to uncoated porous media at higher ionic strength. A steric (polymer-mediated) model that considers the combined influence of steric effects of polymers and DLVO interactions is shown to adequately describe particle retention in columns.

The stability of nanoparticles in aquatic environment plays an important role in determining their environmental implication and potential risk to human health. This research studied the impact of natural organic matter (NOM) and divalent cations (Ca(2+)) on the stability of engineered metal oxide nanoparticles (e.g. ZnO, NiO, TiO(2), Fe(2)O(3) and SiO(2)). When nanoparticles were present in neutral water, a relatively weak electrolyte concentration (0.01 M KCl) could result in their aggregation; however, with the addition of 1 mg/L NOM, the negative surface charge of nanoparticles increased significantly and therefore their propensity to aggregate is reduced. 4 mg/L NOM stabilized most nanoparticles by producing -30 mV or higher zeta potentials. On the other hand, the negative charge that NOM imparted to nanoparticles could be neutralized by divalent cations (calcium ions). 0.04 M-0.06 M Ca(2+) induced the aggregation of NOM-coated nanoparticles. It should be noted that among all the studied nanoparticles, SiO(2) exhibited the unique stability due to its low NOM adsorption capacity and small Hamaker constant. SiO(2) remained stable no matter whether the solution contained NOM or Ca(2+).

The wide application of nanosized titanium dioxide (nano-TiO2) will result in high concentrations of the molecule in the aquatic environment, especially in the influent of wastewater treatment plants. The present study focuses on the potential effect of nano-TiO2 on the physicochemical stability of activated sludge flocs after long-term exposure, on which limited information is currently available. Kelvin probe force microscopy (KPFM) was innovatively applied to assess the surface potential of the activated sludge in situ. The physicochemical characteristics of the bioflocs with and without long-term exposure to nano-TiO2 were well elucidated by the thermodynamic approach. The results showed that the repulsive force predominated the bioflocs system as the concentration of nano-TiO2 increased, owing to the corresponding increase in the density of the negative charge. The bioflocs exposed to 100 ppm nano-TiO2 presented the strongest stability compared to the other two samples with low concentrations of nano-TiO2, which also indicated that the bioflocs with long-term exposure to nano-TiO2 had a low settlement efficiency of the corresponding activated sludge. Further, the extended Derjaugin, Landau, Verwey, and Overbeek (XDLVO) theory was used to explore the flocculation stability of the bioflocs system. As the concentration of nano-TiO2 increased, the ΔGiwi(LW)attraction (the van der Waals interaction) and the effective Hamaker constant decreased, the ΔGiwi(EL)(the electrostatic double-layers interaction) increasingly contributed to the interfacial repulsion, the ΔGiwi(AB)(the Lewis acid-base interaction) also exhibited a repulsive contribution to the total interaction energy and the ΔGiwi(TOT) (the total free energy of interaction) exhibited a repulsive contribution. These results are the keys for interpreting the adverse effects of nano-TiO2 on the activated sludge flocs of wastewater treatment plant (WWTP).