Low-density solvent-based dispersive liquid–liquid microextraction combined with single-drop microextraction for the fast determination of chlorophenols in environmental water samples by high performance liquid chromatography-ultraviolet detection

A new format of fast three-phase microextraction by combining low-density solvent-based dispersive liquid–liquid microextraction (DLLME) and single-drop microextraction (SDME) was for the first time developed for the determination of chlorophenols in environmental water samples. The extraction procedure includes a 2 min DLLME pre-extraction and a 10 min SDME back-extraction. A portion of low-density solvent (toluene) was used as organic phase and injected into the aqueous sample (donor phase) with methanol as disperser. The analytes were pre-extracted into the organic phase within 2 min. A thin layer of the organic phase formed on the top of the aqueous phase by a 2 min centrifugation. Then a drop of acceptor solution was introduced into the upper layer and SDME was carried out for the back-extraction. The stirring step typically involved in SDME and LLLME is avoided with the benefit of the high speed and efficiency of DLLME pre-extraction. After extraction, the acceptor drop was withdrawn and directly injected into a high performance liquid chromatography instrument with ultraviolet detection for analysis. Five chlorophenols, 4-chlorophenol, 2-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol, were selected as model compounds for developing and evaluating the method. Factors affecting extraction efficiency were studied, including the organic solvent, the disperser solvent, the composition of donor phase and acceptor phase, the volume of acceptor microdrop, and the extraction time. At optimal conditions, the method showed low detection limit (0.016–0.084 μg/L) for the five chlorophenols, good linearity (from 0.2–250 to 1.0–250 μg/L, depending on the analytes) and repeatability (RSD below 8.2, n = 5). The simple, fast, and efficient feature of the proposed method was demonstrated by the analysis of chlorophenols in environmental water samples.

► A new format of fast three-phase microextraction was for the first time developed.
► The method includes a 2-min DLLME pre-extraction and a 10-min SDME back-extraction.
► The typical stirring step in SDME and LLLME is avoided with the help of DLLME.
► The procedure is simple, fast and easy to implement.
► Five chlorophenols in environmental water samples were analyzed.