In situ characterization of silver nanoparticles sulfidation processes in aquatic solution by hollow fiber flow-field flow fractionation coupled with ICP-QQQ.

The sulfidation is considered as one of the most important environmental transformation processes of silver nanoparticles (AgNPs), which affects their transport, uptake and toxicity. Herein, based on the hollow fiber flow-field flow fractionation coupled with triple quadrupole inductively coupled plasma mass spectrometry (HF5-ICP-QQQ), we developed an efficient approach to accurately characterize the sulfidation process of AgNPs in aquatic solutions. HF5 could efficiently remove interferential ions and separate nanoparticles with different sizes online, and ICP-QQQ could accurately detect S element through monitoring 32S16O+ in mass shift mode. By the proposed method, two kinds of AgNPs, citrate-coated AgNPs and PVP-coated AgNPs, were selected as models to trace their transfer behaviors during the sulfidation. The results showed once AgNPs were exposed to Na2S solution, the overlapping fractograms of 32S16O+ and 107Ag+ were rapidly detected by HF5-ICP-QQQ to indicate the co-presence of Ag and S, and thus confirming the production of Ag2S and AgNPs underwent a rapid sulfidation process. There were substantial differences in the influence of the two coated agents on the stability of the particles under the conditions examined. In the presence of sulfide, PVP-coated AgNPs could maintain initial size distribution with higher stability, while the size distribution of citrate-coated AgNPs changed considerably. The developed HF5-ICP-QQQ method provides a reliable tool to identify and characterize the transformation process of AgNPs in aquatic solution, which contributed to a deeper understanding of the environmental fate and behavior of AgNPs with different coating.