Trace Monitoring of Phthalate Esters in Environmental Water Samples by Ionic Liquid-based Ultrasound-assisted In-situ Solvent Formation Microextraction Combined with High-performance Liquid Chromatography


1 Department of Applied Chemistry, Faculty of Science, Islamic Azad University, South Tehran Branch, Tehran, Iran

2 Research Institute of Petroleum Industry (RIPI), Tehran, Iran


A simple and efficient ionic liquid-based ultrasound-assisted in-situ solvent formation microextraction (IL-UA-ISFME) in combination with high-performance liquid chromatography-ultraviolet detection (HPLC-UV) has been gainfully developed for the trace determination of four phthalate esters (PEs) in environmental water samples. In this method, a hydrophobic ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate) was created by addition of a hydrophilic ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate) to sample solution constituting an ion-pairing agent (NaPF6). The analytes were extracted inside the ionic liquid phase while the microextraction solvent was dispersed through the sample by utilizing ultrasonic radiation. The sample was then centrifuged and extracting phase retracted into the microsyringe, diluted with acetonitrile, and injected to HPLC. At first, vigorous parameters controlling the performance of the microextraction process were considered and optimized. The limit of detections (LOD, S/N = 3) were in the range of 0.22-0.33 µg L-1 while the RSD% values were below than 6.1% (n = 5). A good linearity (0.996 ≥ r2 ≥ 0.992) and a broad linear over the concentration range from 1.0 to 500 µg L-1 were achieved. At last, the method was applied for the preconcentration and sensitive determination of the PEs in several environmental water samples. The accuracy of the method in the real samples was examined by the relative recovery experiments with results ranging from 90-107%, which approved that intricate matrixes had approximately slight effect on the developed procedure.


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