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Denatonium benzoate (DB), a commonly used bitter agent in numerous products, has recently been recognized as a waterborne contaminant due to concern about its potential persistence, mobility and toxicity (PMT). However, its occurrence, levels and fate in global aquatic environments are largely unknown. In this study, a new sampling method, based on diffusive gradients in thin films (DGT) with mixed-mode cation exchange (MCX) as the binding agent, was developed for measuring DB in waters. MCX shows a rapid adsorption and high capacity for DB. DB is linearly accumulated by MCX-DGT. pH (6–8), ionic strength (0.01–0.5 M), or DOM (0–10 M) do not show any significant effect on the MCX-DGT performance, confirming its reliability. The DGT measurements in a wastewater treatment plant (WWTP) are comparable to those by paralleled grab sampling. The field results suggest DB is persistent in WWTPs and could be a potential domestic wastewater indicator. Therefore, MCX-DGT is a promising technique for understanding the environmental occurrence, levels and fate of DB. This is a first report of using DGT for DB monitoring and of DB occurrence in Chinese environments. Further exploration of DGT as a reliable passive monitoring tool for a wide range of PMT substances in different applications is warranted.

Poly- and perfluoroalkyl substances (PFASs) are contaminants of global concern. Studies in Pearl River, south China have focused on the delta area, while the upstream contributions are unclear. Here, we systematically investigated the fate, trends and potential sources of 57 PFASs in river water, sediment and fish of the North and West Rivers of the Pearl River system. Perfluorooctanoic acid (PFOA), Perfluorooctanesulfonic acid (PFOS) and 6:2 chlorinated polyfluoroalkyl ether sulfonate (6:2Cl-PFESA) were frequently found compounds in waters, sediments and fish, suggesting their wide usage in this area and potential for bioaccumulation. Waters showed a higher ∑PFASs in the wet season compared to the dry season, but sediments did not. The North River contributed higher PFAS loads to the Pearl River Delta. Our results also reflect the current shift in PFAS usage from legacy substances to alternatives. This study, for the first time, reports data on PFASs in two upstream rivers of the Pearl River and on alternative PFASs such as PFESA in this area, which can better the understanding of their use, fate, risk assessment and further controls and management.

Fluoroquinolones (FQs) have raised significant concerns due to their ubiquitous occurrence and promoting of antimicrobial resistance (AMR). In this study, a molecularly imprinted polymer-diffusive gradient in thin-films (MIP-DGT) sampler is developed for selective measurement of FQs in waters by using a commercial available MIP material as the binding agent. The MIP-DGT shows selective adsorption of the FQs and linearly accumulates the FQs over the deployment time. MIP-DGT measurement is independent of pH (6-8) and ionic strength (IS) (0.01-0.5 M) but is affected by DOM at higher concentrations (~10 mg•L-1), which is due to the altered diffusion coefficients and reduced adsorption on the MIP binding gel. Significant interaction effects of DOM with pH or IS indicate that this is the predominant influence on the MIP-DGT performance, which results in a lower measurement by the MIP-DGT but this is curtailed to some extend with increasing IS or pH. The MIP-DGT measurements, however, correlate well with those by grab sampling in a wastewater treatment plant, suggesting it is reliable for measuring FQs in waters. For the first time, we demonstrate that key water chemistry parameters do have interaction effects on the DGT measurements, which should be considered for the data interpretation. The MIP-DGT is a promising tool to understand the interaction effects of the environmental parameters on the fate, behaviours and bioavailability/toxicity of organic contaminants and improve environmental risk assessments in the environment and modelling.