The occurrence of β-blocker drugs in aquatic environments worldwide has caused increasing attention to their threat to human health in recent years. It is essential to monitor these widely prescribed pharmaceuticals in natural waters and sediments, helping us investigate their potential risk to humans and ecosystems. In this study, a passive sampling technique, diffusive gradients in thin-films (DGT), was systematically developed for eight frequently detected β-blockers. The effective capacities of target compounds were large enough for the devices to deploy for several weeks. The uptake of all compounds was linearly correlated with deployment times during the 7-day laboratory experiment and agreed well with the theoretical line, except for several compounds (e.g., ATL) due to their relatively slow uptake rate. The performance of most compounds was independent of varying pH values and organic matter contents; only a few compounds were affected, while the application in high-salinity environments needs to be conducted with caution. Field deployments of DGT to detect β-blockers in situ in rivers and sediments proved that DGT is an effective tool to monitor β-blocker drugs and their fate in the natural aquatic environment, while DGT probes can provide information for us to investigate the biogeochemical processes occurred in sediment, especially at the sediment–water interface. This novel approach will help us understand the behaviour of β-blocker drugs in the aquatic environment, assess their risks, finally protect human health and maintain the sustainable development of the ecosystem.
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