Stereoselective quantitation of mecoprop and dichlorprop in natural waters by supramolecular solvent-based microextraction, chiral liquid chromatography and tandem mass spectrometry

Liquid chromatography (LC)/tandem mass spectrometry (MS/MS) after supramolecular solvent-based microextraction (SUSME) was firstly used in this work for the enantioselective determination of chiral pesticides in natural waters. The method developed for the quantitation of the R- and S-enantiomers of mecoprop (MCPP) and dichlorprop (DCPP) involved the extraction of the herbicides in a supramolecular solvent (SUPRAS) made up of reverse aggregates of dodecanoic acid (DoA), analyte re-extraction in acetate buffer (pH = 5.0), separation of the target enantiomers on a chiral column of permethylated α-cyclodextrin under isocratic conditions, and detection of the daughter ions (m/z = 140.9 and 160.6 for MCPP and DCPP, respectively) using a hybrid triple quadrupole mass spectrometer equipped with an electrospray source operating in the negative ion mode. Similar recoveries (ca. 75%) and actual concentration factors (ca. 94) were obtained for both phenoxypropanoic acids (PPAs). The quantitation limits were 1 ng L−1 for R- and S-MCPP, and 4 ng L−1 for R- and S-DCPP, and the precision, expressed as relative standard deviation (n = 6) was in the ranges 2.4–2.7% ([R-MCPP] = [S-MCPP] = 5 ng L−1 and [R-DCPP] = [S-DCPP] = 15 ng L−1) and 1.6–1.8% (100 ng L−1 of each enantiomer). The SUSME-LC–MS/MS method was successfully applied to the determination of the enantiomers of MCPP and DCPP in river and underground waters, fortified at concentrations between 15 and 180 ng L−1 at variable enantiomeric ratios (ER = 1–9).

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► R- and S-mecoprop and dichlorprop are firstly determined by LC–MS/MS.
► Sample treatment consists of a simple, single-step microextraction and clean-up.
► Sensitivity is similar to GC–MS (LOQs 1–4 ng L−1) but the procedure is faster and simpler.
► The approach is a convenient method for the stereoselective quantitation of polar pesticides.