Development and validation of diffusive gradients in thin-films for in situ monitoring of ionic liquids in waters

Due to their wide applications, occurrence and "PFAS-like" environmental behaviors, ionic liquids (ILs) represent a new challenge for the environmental monitoring community, who require robust analytical methods that can determine accurately and efficiently their environmentally relevant concentrations. A new passive sampling method based on the diffusive gradients in thin films (DGT) technique was developed for the measurement of imidazole-based ILs in waters using a mixed-mode cation exchange (MCX) resin as the adsorbent. The selected binding gel had a high binding capacity (>170 μg per disc) for ILs. Diffusion coefficients measured using a diffusion cell correlated well with alkyl chain lengths (r² = 0.95) and retention times (r² = 0.88), providing a simple and rapid prediction approach for other ILs. The assembled MCX-DGT sampler exhibited a linear accumulation for at least 120 h. MCX-DGT also showed good performance under typical freshwater conditions (pH 5-8, ionic strength 0.001-0.01 M, and humic acid 0-5 mg L^-1), while still being problematic for aquatic conditions with higher ionic strength (>0.1 M) or DOM (>10 mg L^-1). Laboratory deployment (for up to 3 days) in spiked natural freshwater (SNW) resulted in linear mass uptakes for the short-chain ILs (C2-C8), and their DGT-measured concentrations agreed well with solution concentrations. However, MCX-DGT significantly overestimated the concentrations of the long-chain ILs (C10-C12) when deployed in SNW for one day or more, which is attributed to the strong competitive adsorption of the long-chain ILs by natural organic matter. In situ field evaluation along with grab sampling found no target ILs in a wastewater treatment plant and its receiving river, implying that these new chemicals might not be widely used in South China now. This is the first report on the DGT technique for ILs and might provide an effective tool for monitoring short chain length ILs in the aquatic environment in the near future.