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Environmental context The fate of nanomaterials in the environment is related to their colloidal stability. Although numerous studies have examined their homoagglomeration, their low concentration and the presence of high concentrations of natural particles implies that heteroagglomeration rather than homoagglomeration is likely to occur under natural conditions. In this paper, two state-of-the art analytical techniques were used to identify the conditions under which nanosilver was most likely to form heteroagglomerates in natural waters. Abstract The environmental risk of nanomaterials will depend on their persistence, mobility, toxicity and bioaccumulation. Each of these parameters is related to their fate (especially dissolution, agglomeration). The goal of this paper was to understand the heteroagglomeration of silver nanoparticles in natural waters. Two small silver nanoparticles (nAg, ~3nm; polyacrylic acid- and citrate-stabilised) were covalently labelled with a fluorescent dye and then mixed with colloidal silicon oxides (SiO2, ~18.5nm) or clays (~550nm SWy-2 montmorillonite). Homo- and heteroagglomeration of the nAg were first studied in controlled synthetic waters that were representative of natural fresh waters (50μg Ag L–1; pH 7.0; ionic strength 10–7 to 10–1 M Ca) by following the sizes of the nAg by fluorescence correlation spectroscopy. The polyacrylic acid-coated nanosilver was extremely stable under all conditions, including in the presence of other colloids and at high ionic strengths. However, the citrate-coated nanosilver formed heteroaggregates in presence of both colloidal SiO2 and clay particles. Nanoparticle surface properties appeared to play a key role in controlling the physicochemical stability of the nAg. For example, the polyacrylic acid stabilized nAg-remained extremely stable in the water column, even under conditions for which surrounding colloidal particles were agglomerating. Finally, enhanced dark-field microscopy was then used to further characterise the heteroagglomeration of a citrate-coated nAg with suspensions of colloidal clay, colloidal SiO2 or natural (river) water.

Heteroagglomeration of nanosilver with colloidal SiO2 and clay