Development of a filter-based method for detecting silver nanoparticles and their heteroaggregation in aqueous environments by surface-enhanced Raman spectroscopy

The rising application of silver nanoparticles (AgNPs) and subsequent release into aquatic systems have generated public concerns over their potential risk and harm to aquatic organisms and human health. Effective and practical analytical methods for AgNPs are urgently needed for their risk assessment. In this study we established an innovative approach to detect trace levels of AgNPs in environmental water through integrating a filtration technique into surface-enhanced Raman spectroscopy (SERS) and compared it with previously established centrifuge-based method. The purpose of filtration was to trap and enrich salt-aggregated AgNPs from water samples onto the filter membrane, through which indicator was then passed and complexed with AgNPs. The enhanced SERS signals of indicator could reflect the presence and quantity of AgNPs in the samples. The most favorable benefit of filtration is being able to process large volume samples, which is more practical for water samples, and greatly improves the sensitivity of AgNP detection. In this study, we tested 20 mL AgNPs-containing samples and the filter-based method is able to detect AgNPs as low as 5 μg/L, which is 20 folds lower than the centrifuge-based method. In addition, the speed and precision of the detection were greatly improved. This approach was used to detect trace levels of AgNPs in real environmental water successfully. Meanwhile, the heteroaggregation of AgNPs with minerals in water was reliably monitored by the new method. Overall, a combination of the filtration-SERS approach provides a rapid, simple, and sensitive way to detect AgNPs and analyze their environmental behavior. - Highlights: • We developed a filtration-SERS method for analyzing AgNPs in water. • Detection limit can be improved by increasing sample volume for filtration. • Trace levels of AgNPs in natural water samples can be successfully detected. • Filtration-SERS is more efficient and precise than centrifugation-SERS. • Filtration-SERS is well suited to monitor AgNP heteroaggregation with minerals. - We developed an innovative SERS approach that can rapidly, sensitively and reliably detect trace levels of AgNPs in environmental waters and monitor their heteroaggregation with minerals.