Evaporation-assisted dispersive liquid-liquid microextraction based on the solidification of floating organic droplets for the determination of triazole fungicides in water samples by high-performance liquid chromatography.

A simple, rapid, and effective analytical procedure for determining three triazole fungicides (myclobutanil, epoxiconazole, and tebuconazole) in water samples is developed by high-performance liquid chromatography-diode array detection after evaporation-assisted dispersive liquid-liquid microextraction based on the solidification of floating organic droplets. The extraction procedure involves the sequential addition of the extraction solvent 1-dodecanol (low density), volatile solvent dichloromethane (high density), and calcium oxide to the aqueous sample (the latter reacting exothermically). The CaO reaction can promote the volatilization of the dichloromethane which disperses the 1-dodecanol as fine droplets in the aqueous sample due to the bubbles generated. Therefore, a dispersive solvent is not required. Then, the floating 1-dodecanol is solidified using an ice bath for easy separation from the sample. The variables (the volumes of extraction and volatile solvents, amounts of calcium oxide and sodium chloride, pH values, and extraction time) in the extraction procedure are further optimized. Under optimized conditions, the linearity ranges are 0.05-5 μg mL-1 with correlation coefficients greater than 0.99. The limits of detection and quantification are 0.0051-0.0090 μg mL-1 and 0.0169-0.0299 μg mL-1, respectively. The recoveries of myclobutanil, epoxiconazole, and tebuconazole in tap, reservoir, and river water range between 77.6% and 104.4% with relative standard deviations ranging from 0.6% to 7.8%. Hence, the method was reliable for analysis of myclobutanil, epoxiconazole, and tebuconazole in water samples.