Extraction of phthalic acid esters from soft drinks and infusions by dispersive liquid-liquid microextraction based on the solidification of the floating organic drop using a menthol-based natural deep eutectic solvent

Abstract

In this work, a natural deep eutectic solvent (NADES) consisting of L-menthol and acetic acid in a 1:1 molar ratio has been applied as extraction solvent for the dispersive liquid-liquid microextraction based on the solidification of the floating organic drop (DLLME-SFO) of a group of nine phthalic acid esters (dipropyl phthalate, DPP; butyl benzyl phthalate, BBP; dibutyl phthalate, DBP; dicyclohexyl phthalate, DCHP; diisopentyl phthalate, DIPP; di-n-pentyl phthalate, DNPP; di(2-ethylhexyl) phthalate, DEHP; diisononyl phthalate, DINP; and diisodecyl phthalate, DIDP) from three common infusions (camomile, pennyroyal mint, and linden teas) and three soft drinks (green tea, tonic, and lime and lemon drink), using dihexyl phthalate (DHP) and di-n-octyl phthalate (DNOP) as internal standards. After the DLLME-SFO procedure, analyses were carried out by high-performance liquid chromatography with UV detection. Method calibration showed good linearity for all the analytes and matrices, with determination coefficients (R²) higher than 0.9910. Relative recovery values were between 71 and 125 %, with relative standard deviation values in the range 1-22 % for the six types of samples, while the limits of quantification of the method were in the range 4.3-51.1 µg/L for infusions and in the range 3.5-33.3 µg/L for soft drinks. Several samples purchased in different local supermarkets were analysed, finding DPP, DBP, DIPP, DEHP and DINP, although only DPP, DBP and DEHP could be quantified in some of them.

Keywords: Dispersive liquid-liquid microextraction based on the solidification of the floating organic drop; High-performance liquid chromatography; L-menthol; Natural deep eutectic solvent; Phthalic acid esters.