Aggregation and stability of selenium nanoparticles: Complex roles of surface coating, electrolytes and natural organic matter

The application of selenium nanoparticles (SeNPs) as nanofertilizers may lead to the release of SeNPs into aquatic systems. However, the environmental behavior of SeNPs is rarely studied. In this study, using alginate-coated SeNPs (Alg-SeNPs) and polyvinyl alcohol-coated SeNPs (PVA-SeNPs) as models, we systematically investigated the aggregation and stability of SeNPs under various water conditions. PVA-SeNPs were highly stable in mono- and polyvalent electrolytes, probably due to the strong steric hindrance of the capping agent. Alg-SeNPs only suffered from a limited increase in size, even at 2500 mmol/L NaCl and 200 mmol/L MgCl₂, while they underwent apparent aggregation in CaCl₂ and LaCl₃ solutions. The binding of Ca²⁺ and La³⁺ with the guluronic acid part in alginate induced the formation of cross-linking aggregates. Natural organic matter enhanced the stability of Alg-SeNPs in monovalent electrolytes, while accelerated the attachment of Alg-SeNPs in polyvalent electrolytes, due to the cation bridge effects. The long-term stability of SeNPs in natural water showed that the aggregation sizes of Alg-SeNPs and PVA-SeNPs increased to several hundreds of nanometers or above 10 µm after 30 days, implying that SeNPs may be suspended in the water column or further settle down, depending on the surrounding water chemistry. The study may contribute to the deep insight into the fate and mobility of SeNPs in the aquatic environment. The varying fate of SeNPs in different natural waters also suggests that the risks of SeNPs to organisms living in diverse depths in the aquatic compartment should be concerned.