Novel Dispersive Micro-Solid-Phase Extraction Combined with Ultrahigh-Performance Liquid Chromatography High-Resolution Mass Spectrometry To Determine Morpholine Residues in Citrus and Apples

This paper presents a new analytical method for the determination of morpholine residues in citrus and apples using a novel dispersive micro-solid-phase extraction (DMSPE), followed by ultrahigh-performance liquid chromatography-high-resolution mass spectrometry (UHPLC-HRMS). Samples were extracted with 1% formic acid in acetonitrile/water (1:1, v/v) and then cleaned up using the DMSPE procedure. Morpholine from the extract was adsorbed to a polymer cation exchange sorbent and eluted with ammonium hydroxide/acetonitrile (3:97, v/v) through a 1 mL syringe with a 0.22 mu m nylon syringe filter. All of the samples were analyzed by UHPLC-HRMS/MS on a Waters Acquity BEH hydrophilic interaction chromatography column using 0.1% formic acid and 4 mM ammonium formate in water/acetonitrile as the mobile phase with gradient elution. The method showed good linearity (R(2) > 0.999) in the range of 1-100 mu g/L for the analyte. The limit of detection and limit of quantitation values of morpholine were 2 and 5 mu g/kg, respectively. The average recoveries of morpholine from the citrus and apple samples spiked at three different concentrations (5, 20, and 100 mu g/kg) were in a range from 78.4 to 102.7%.