Agglomeration behaviour of titanium dioxide nanoparticles in river waters: A multi-method approach combining light scattering and field-flow fractionation techniques.

Titanium dioxide nanoparticles (TiO2 NPs) are currently one of the most prolifically used nanomaterials, resulting in an increasing likelihood of release to the environment. This is of concern as the potential toxicity of TiO2 NPs has been investigated in several recent studies. Research into their fate and behaviour once entering the environment is urgently needed to support risk assessment and policy development. In this study, we used a multi-method approach combining light scattering and field-flow fractionation techniques to assess both the aggregation behaviour and aggregate structure of TiO2 NPs in different river waters. Results showed that both the aggregate size and surface-adsorbed dissolved organic matter (DOM) were strongly related to the initial DOM concentration of the tested waters (i.e. R(2) > 0.90) suggesting that aggregation of TiO2 NPs is controlled by the presence and concentration of DOM. The conformation of the formed aggregates was also found to be strongly related to the surface-adsorbed DOM (i.e. R(2) > 0.95) with increasing surface-adsorbed DOM leading to more compact structures. Finally, the concentration of TiO2 NPs remaining in the supernatant after sedimentation of the larger aggregates was found to decrease proportionally with both increasing IS and decreasing DOM concentration, resulting in more than 95% sedimentation in the highest IS sample.

Aggregation behaviour of engineered nanoparticles in natural waters: characterising aggregate structure using on-line laser light scattering.

Adsorption of natural organic matter, aggregation and disaggregation have been identified as three of the main processes affecting the fate and behaviour of engineered nanoparticles (ENPs) in aquatic environments. However, although several methods have been developed to study the aggregation behaviour of ENPs in natural waters, there are only a few studies focusing on the fate of such aggregates and their potential disaggregation behaviour. In this study, we proposed and demonstrated a simple method for characterising the aggregation behaviour and aggregate structure of ENPs in different natural waters. Both the aggregate size of ENPs and their adsorption capacity for dissolved organic matter (DOM) were strongly related (R(2)>0.97, p<.05) to the combined effect of initial concentration of dissolved organic matter (DOM) and the ionic strength of the natural waters. The structure of the formed aggregates was strongly correlated (R(2)>0.95, p<.05) to the amount of DOM adsorbed by the ENPs during the aggregation process. Under high ionic strength conditions, aggregation is mainly governed by diffusion and the aggregates formed under these conditions showed the lowest stability and fractal dimension, forming linear, chain-like aggregates. In contrast, under low ionic strength conditions, the aggregate structure was more compact, most likely due to strong chemical binding with DOM and bridging mechanisms involving divalent cations formed during reaction-limited aggregation.

Stability of Fe-oxide nanoparticles coated with natural organic matter under relevant environmental conditions.

Manufactured nanoparticles (MNPs) are increasingly released into the environment and thus research on their fate and behaviour in complex environmental samples is urgently needed. The fate of MNPs in the aquatic environment will mainly depend on the physico-chemical characteristics of the medium. The presence and concentration of natural organic matter (NOM) will play a significant role on the stability of MNPs by either decreasing or exacerbating the aggregation phenomenon. In this study, we firstly investigated the effect of NOM concentration on the aggregation behaviour of manufactured Fe-oxide nanoparticles. Then, the stability of the coated nanoparticles was assessed under relevant environmental conditions. Flow field-flow fractionation, an emerging method which is gaining popularity in the field of nanotechnology, has been employed and results have been compared to another size-measurement technique to provide increased confidence in the outcomes. Results showed enhanced stability when the nanoparticles are coated with NOM, which was due to electrosteric stabilisation. However, the presence of divalent cations, even at low concentration (i.e. less than 1 mM) was found to induce aggregation of NOM-coated nanoparticles via bridging mechanisms between NOM and Ca(2+).