Low-density solvent based ultrasound-assisted emulsification microextraction and on-column derivatization combined with gas chromatography–mass spectrometry for the determination of carbamate pesticides in environmental water samples

A fast and efficient method for the determination of trace level of carbamate pesticides using a lower-density-than-water solvent for ultrasound-assisted emulsification microextraction coupled to on-column derivatization and analysis by GC–MS has been developed and studied. In this approach, a soft plastic Pasteur pipette was employed as a convenient extraction device. Fifty microliters of extraction solvent, of lower density than water, was injected into the sample solution held in the pipette. The latter was immediately immersed in an ultrasound water bath to form an emulsion. After 2 min extraction, the emulsion was fractionated into two layers by centrifugation. The upper layer (organic extract) could be collected conveniently by squeezing the bulb of the pipette, now held upside down, to move it into the narrow stem of the device, facilitating its retrieval for analysis. The extract was then combined with trimethylphenylammonium hydroxide and directly injected into a gas chromatography–mass spectrometry (GC–MS) system for on-column derivatization and analysis. The on-column derivatization provided an added convenience (since a separate step was not necessary). Parameters affecting the derivatization and extraction were investigated. Under the most favorable conditions, the method demonstrated high extraction efficiency with low limits of detection of between 0.01 and 0.1 μg/L, good linearity in the range of 0.05–50 μg/L, to 0.5–100 μg/L, and good repeatability (RSD below 9.2%, n = 5). The proposed method was evaluated by determining carbamate pesticides in river water samples.

► Low-density solvent ultrasound emulsification microextraction with derivatization.
► Plastic pipette allows convenient use of lower-density-than-water solvents in DLLME.
► On-column derivatization avoids separate derivatization and expedites the procedure.
► Fast simple and efficient approach with low LODs, good linearity, and good repeatability.