Selective extraction of emerging contaminants from water samples by dispersive liquid–liquid microextraction using functionalized ionic liquids

Functionalized ionic liquids containing the tris(pentafluoroethyl)trifluorophosphate (FAP) anion were used as extraction solvents in dispersive liquid–liquid microextraction (DLLME) for the extraction of 14 emerging contaminants from water samples. The extraction efficiencies and selectivities were compared to those of an in situ IL DLLME method which uses an in situ metathesis reaction to exchange 1-butyl-3-methylimidazolium chloride (BMIM-Cl) to 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide (BMIM-NTf2). Compounds containing tertiary amine functionality were extracted with high selectivity and sensitivity by the 1-(6-amino-hexyl)-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate (HNH2MPL-FAP) IL compared to other FAP-based ILs and the BMIM-NTf2 IL. On the other hand, polar or acidic compounds without amine groups exhibited higher enrichment factors using the BMIM-NTf2 IL. The detection limits for the studied analytes varied from 0.1 to 55.1 μg/L using the traditional IL DLLME method with the HNH2MPL-FAP IL as extraction solvent, and from 0.1 to 55.8 μg/L using in situ IL DLLME method with BMIM-Cl + LiNTf2 as extraction solvent. A 93-fold decrease in the detection limit of caffeine was observed when using the HNH2MPL-FAP IL compared to that obtained using in situ IL DLLME method. Real water samples including tap water and creek water were analyzed with both IL DLLME methods and yielded recoveries ranging from 91% to 110%.