Optimization of micro-QuEChERS extraction coupled with gas chromatography-mass spectrometry for the fast determination of phthalic acid esters in mussel samples

Abstract

In this study, a new miniaturized version of the analytical method based on the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) technique using Florisil in the cleanup step for extracting six phthalic acid esters (PAEs) in mussel samples was developed by using a design of experiments. For this purpose, 1.5 mL of ultrapure water and later, 1.5 mL of acetonitrile were added to 0.1 g of the lyophilized sample, followed by 0.3 g of a commercial extraction salt packet (magnesium sulfate, sodium chloride, sodium citrate dihydrate, and sodium hydrogencitrate sesquihydrate). The recovered extract was purified using 0.1 g of Florisil. The final extract was evaporated and reconstituted in 1 mL of hexane. The six phthalates were determined by a GC-MS (SIM) system. The whole method was validated at two concentration levels. Recoveries ranged from 79% to 108%. Reproducibility in terms of coefficients of variation was between 4.9% and 12.1%. The limits of quantification of the whole method were between 0.53 and 38.0 μg per kg dry weight. Five mussel samples coming from the Galician Rías were analysed using this method. Except for three of the five samples where DnOP (di-n-octyl phthalate) was below the limit of quantification, all PAEs were found in concentrations that ranged between 1.99 and 372.7 μg per kg dry weight.