Comparison of three analytical methods to measure the size of silver nanoparticles in real environmental water and wastewater samples

•Three emerging techniques to detect NPs in the aquatic environment were evaluated.•The pretreatment of centrifugation to decrease the interference was established.•Asymmetric flow field flow fractionation has a low recovery of NPs.•Hydrodynamic chromatography is recommended to be a low-cost screening tool.•Single particle ICPMS is recommended to accurately measure trace NPs in water. Due to the widespread application of engineered nanoparticles, their potential risk to ecosystems and human health is of growing concern. Silver nanoparticles (Ag NPs) are one of the most extensively produced NPs. Thus, this study aims to develop a method to detect Ag NPs in different aquatic systems. In complex media, three emerging techniques are compared, including hydrodynamic chromatography (HDC), asymmetric flow field flow fractionation (AF4) and single particle inductively coupled plasma-mass spectrometry (SP-ICP-MS). The pre-treatment procedure of centrifugation is evaluated. HDC can estimate the Ag NP sizes, which were consistent with the results obtained from DLS. AF4 can also determine the size of Ag NPs but with lower recoveries, which could result from the interactions between Ag NPs and the working membrane. For the SP-ICP-MS, both the particle size and concentrations can be determined with high Ag NP recoveries. The particle size resulting from SP-ICP-MS also corresponded to the transmission electron microscopy observation (p>0.05). Therefore, HDC and SP-ICP-MS are recommended for environmental analysis of the samples after our established pre-treatment process. The findings of this study propose a preliminary technique to more accurately determine the Ag NPs in aquatic environments and to use this knowledge to evaluate the environmental impact of manufactured NPs.