Electro membrane extraction followed by low-density solvent based ultrasound-assisted emulsification microextraction combined with derivatization for determining chlorophenols and analysis by gas chromatography–mass spectrometry

A highly efficient and simple two-step method, electro membrane extraction (EME) followed by low-density solvent based ultrasound-assisted emulsification microextraction (EME–LDS-USAEME) combined with derivatization and analysis by gas chromatography–mass spectrometry (GC–MS), was developed for the determination of trace level chlorophenols in environmental water samples. In the first step, the analytes were extracted, under electrical potential, from the sample solution into the acceptor solution, which was held in a polypropylene membrane sheet with 1-octanol as the supported liquid membrane. The acceptor solution from the first step was then employed as the sample solution for the second step of LDS-USAEME. In this step, the target analytes were extracted into a solvent with lower density than water that was dispersed in the sample solution with the assistance of ultrasound. The extract was separated from the sample solution by centrifugation and collected as the upper layer. Finally, the extract with a derivatization reagent were injected into a GC–MS system for analysis. Six chlorophenols, 2-chlorophenol, 4-chlorophenol, 2,3-dichlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol and pentachlorophenol were selected here as model compounds for developing and evaluating the method. Several factors influencing the extraction and derivatization were investigated. With the EME–LDS-USAEME procedure, high enrichment factors of up to 2198 were achieved. Under the most favorable conditions, good limits of detection (down to 0.005 μg/L), linearity (from 0.05–10 to 0.2–10 μg/L, depending on the analytes), and repeatability of extraction (RSDs below 9.7%, n = 5) were obtained. The proposed method was applied to determine chlorophenols in drainwater samples.

► Electro membrane extraction followed by ultrasound emulsification microextraction is reported.
► Flexible pipette allows convenient retrieval of lower density extract in USAEME.
► On-column derivatization avoids separate derivatization and expedites the procedure.
► High extraction efficiency for chlorophenols from aqueous samples obtained.
► The approach is fast and gives low LODs, good linearity and repeatability.