Dispersive liquid-liquid microextraction coupled with dispersive micro-solid-phase extraction for the fast determination of polycyclic aromatic hydrocarbons in environmental water samples.

A new two-step microextraction technique, combining dispersive liquid-liquid microextraction (DLLME) and dispersive microsolid-phase extraction (D-micro-SPE), was developed for the fast gas chromatographic-mass spectrometric determination of polycyclic aromatic hydrocarbons (PAHs) in environmental samples. A feature of the new procedure lies in that any organic solvent immiscible with water can be used as extractant in DLLME. A special apparatus, such as conical-bottom test tubes, and tedious procedures of centrifugation, refrigeration of the solvent, and then thawing it, associated with classical DLLME or similar techniques are not necessary in the new procedure, which potentially lends itself to possible automation. In the present D-micro-SPE approach, hydrophobic magnetic nanoparticles were used to retrieve the extractant of 1-octanol in the DLLME step. It is noteworthy that the target of D-micro-SPE was the 1-octanol rather than the PAHs. Because of the rapid mass transfer associated with the DLLME and the D-micro-SPE steps, fast extraction could be achieved. Parameters affecting the extraction efficiency were investigated in detail. The optimal conditions were as follows: vortex at 3200 rpm in the DLLME step for 2 min and in D-micro-SPE for 1 min and then desorption by sonication for 4 min with acetonitrile as the solvent. The results demonstrated that enrichment factors ranging from 110- to 186-fold were obtained for the analytes. The limits of detection and the limits of quantification were in the range of 11.7-61.4 pg/mL and 0.04-0.21 ng/mL, respectively. The linearities were 0.5-50, 1-50, or 2-50 ng/mL for different PAHs. Finally, the two-step extraction method was successfully used for the fast determination of PAHs in river water samples. This two-step method, combining two different and efficient miniaturized techniques, provides a fast means of sample pretreatment for environmental water samples.