Part-per-trillion determination of chlorobenzenes in water using dispersive liquid–liquid microextraction combined gas chromatography–electron capture detection

Abstract

In this study, a simple, rapid and efficient method, dispersive liquid–liquid microextraction (DLLME) combined gas chromatography–electron capture detection (GC–ECD), for the determination of chlorobenzenes (CBs) in water samples, has been described. This method involves the use of an appropriate mixture of extraction solvent (9.5 μl chlorobenzene) and disperser solvent (0.50 ml acetone) for the formation of cloudy solution in 5.00 ml aqueous sample containing analytes. After extraction, phase separation was performed by centrifugation and the enriched analytes in sedimented phase were determined by gas chromatography–electron capture detection (GC–ECD). Our simple conditions were conducted at room temperature with no stiring and no salt addition in order to minimize sample preparation steps. Parameters such as the kind and volume of extraction solvent, the kind and volume of disperser solvent, extraction time and salt effect, were studied and optimized. The method exhibited enrichment factors and recoveries ranging from 711 to 813 and 71.1 to 81.3%, respectively, within very short extraction time. The linearity of the method ranged from 0.05 to 100 μg l −1 for dichlorobenzene isomers (DCB), 0.002–20 μg l −1 for trichlorobenzene (TCB) and tetrachlorobenzene (TeCB) isomers and from 0.001 to 4 μg l −1 for pentachlorobenzene (PeCB) and hexachlorobenzene (HCB). The limit of detection was in the low μg l −1 level, ranging between 0.0005 and 0.05 μg l −1. The relative standard deviations (R.S.D.s) for the concentration of DCB isomers, 5.00 μg l −1, TCB and TeCB isomers, 0.500 μg l −1, PeCB and HCB 0.100 μg l −1 in water by using the internal standard were in the range of 0.52–2.8% ( n = 5) and without the internal standard were in the range of 4.6–6.0% ( n = 5). The relative recoveries of spiked CBs at different levels of chlorobenzene isomers in tap, well and river water samples were 109–121%, 105–113% and 87–120%, respectively. It is concluded that this method can be successfully applied for the determination of CBs in tap, river and well water samples.