Asymmetric flow field-flow fractionation of manufactured silver nanoparticles spiked into soil solution

• Development of AF4 method characterizing Ag nanoparticles in soil solution.
• Choice of mobile phase is the critical factor for AF4 fractionation.
• AF4 and DLS sizes of Ag nanoparticles in soil solution closely agree.
• Elution of coated Ag nanoparticles can be delayed by suspended clay particles.
• Colloid-facilitated transport of Ag nanoparticles can be an environmental risk.

Manufactured metallic silver nanoparticles (AgNP) are intensively utilized in consumer products and this will inevitably lead to their release to soils. To assess the environmental risks of AgNP in soils, quantification of both their concentration and size in soil solution is essential. We developed a methodology consisting of asymmetric flow field-flow fractionation (AF4) in combination with on-line detection by UV–vis spectroscopy and off-line HR-ICP-MS measurements to quantify the concentration and size of AgNP, coated with either citrate or polyvinylpyrrolidone (PVP), in water extracts of three different soils. The type of mobile phase was a critical factor in the fractionation of AgNP by AF4. In synthetic systems, fractionation of a series of virgin citrate- and PVP-coated AgNP (10–90 nm) with reasonably high recoveries could only be achieved with ultrahigh purity water as a mobile phase. For the soil water extracts, 0.01% (w:v) sodium dodecyl sulfate (SDS) at pH 8 was the key to a successful fractionation of the AgNP. With SDS, the primary size of AgNP in all soil water extracts could be determined by AF4, except for PVP-coated AgNP when clay colloids were present. The PVP-coated AgNP interacted with colloidal clay minerals, leading to an overestimation of their primary size. Similar interactions between PVP-coated AgNP and clay colloids can take place in the environment and facilitate their transport in soils, aquifers, and surface waters. In conclusion, AF4 in combination with UV–vis spectroscopy and HR-ICP-MS measurements is a powerful tool to characterize AgNP in soil solution if the appropriate mobile phase is used.