The purpose of this paper is to introduce a novel hollow fiber stir bar sorptive extraction for collecting and determining of phthalic acid esters in environmental and biological matrices. Shell-core ZrO /SiO composite microspheres and porous C silica microspheres were compared as the sorbents, which were loaded in the lumen of a microporous hollow fiber membrane. A thin stainless-steel wire was also inside of the hollow fiber membrane acting as the magnetic stirrer, thus affording the procedures like stir bar sorptive extraction to perform the active trapping of the analytes. Variables affecting the extraction (salt addition and pH of samples, extraction temperature, and time) and desorption (microwave time and eluted solvents) have been optimized. Under the optimal conditions, good linearity (r > 0.9968) of all calibration curves was obtained in validation experiments. And the limits of quantification ranged from 0.01 to 1000 ng/mL. The recoveries in different matrices were in the range of 64.90-112.60% with relative standard deviations less than 8.60%. The present work demonstrated the applicability of the developed method for the determination of phthalic acid esters in environmental and biological sample, allowing the selective extraction of phthalate esters in complex samples with low consumption of organic solvents and no sample clean-up.
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