A field-deployable surface-enhanced Raman scattering (SERS) method for sensitive analysis of silver nanoparticles in environmental waters

The proliferation of silver nanoparticles (AgNPs) in the environment and resultant transport into aquatic systems have raised concerns regarding their potential toxicity to various organisms. These environmental and ecological concerns demand reliable AgNP detection methods which can measure environmentally relevant quantities of AgNPs in real aquatic systems. This study developed a method that couples a rapid vacuum filtration technique with a portable Raman spectrometer to achieve on-site detection of ultra-low levels of AgNPs in typical and complex aquatic systems. To extract and detect AgNPs, aluminum chloride and ferbam were added for AgNP aggregation and labelling, respectively. The AgNP aggregates were filtered through a membrane, and their presence and quantity were determined based upon the surface-enhanced Raman scattering (SERS) peak intensity of ferbam. Under the optimized conditions, the extraction efficiencies are 99 ± 0.001% in ultrapure water and 98 ± 0.025% in marine water for 1 mg/L AgNPs. This method enables simple volume adjustment and improves the consistency of AgNP distribution on the membrane. The performance of the method was evaluated in different environmental waters, including marine water, fresh waters (pond water, river water, and reservoir outlet water) and drinking waters (municipal tap water and well water), with highest signal intensity in marine water and lowest signals in fresh waters. The signal intensity difference was suggested to be caused by the amount of natural organic matter (NOM) in these environmental waters. Using pond water as an example, the interference was minimized by changing the aggregating salt from AlCl ₃ to MgCl ₂ , and AgNPs as low as 5 μg/L were reliably detected with a volume of 100 mL. At the same volume, the developed method was sensitive enough to detect 1 μg/L AgNPs in marine water and also holds promise for assessing the time-dependent transformation of AgNPs.