Dispersive liquid–liquid microextraction for the determination of macrocyclic lactones in milk by liquid chromatography with diode array detection and atmospheric pressure chemical ionization ion-trap tandem mass spectrometry

Eprinomectin (EPRI), abamectin (ABA), doramectin (DOR), moxidectin (MOX) and ivermectin (IVM) were determined in milk samples using dispersive liquid–liquid microextraction (DLLME) and liquid chromatography with diode array detection (LC-DAD) coupled to atmospheric pressure chemical ionization in negative ion mode ion-trap tandem mass spectrometry (APCI-IT-MS/MS). Milk proteins were removed by precipitation with trichloroacetic acid and the analytes were preconcentrated using 2 mL of acetonitrile containing 200 μL of chloroform as extraction mixture. The effect of several parameters for the liquid–liquid microextraction efficiency was evaluated. Standard additions method was used for quantification purposes, the correlation coefficients were better than 0.9970 in all cases and the quantification limits ranged from 1.0 to 4.7 ng g−1 and from 0.1 to 2.4 ng g−1 when using DAD and MS, respectively. The DLLME-LC-APCI-IT-MS/MS optimized method was successfully applied to different milk samples and none of the studied analytes was detected in the samples studied. The recoveries for milk samples spiked at concentration levels ranging between 0.5 and 50 ng g−1, depending on the compound, were between 89.5 and 105%, with relative standard deviations lower than 9% (n = 135). Simplicity, rapidity and reliability are important advantages of the proposed method, while the sample preparation step can be regarded as environmentally friendly.