Rapid and simple determination of organophosphorus pesticides in urine using polydopamine-modified monolithic spin column extraction combined with liquid chromatography–mass spectrometry

Abstract

The determination of organophosphorus pesticides in urine is useful for evaluating human exposure. In this study, a simple micro-solid-phase extraction method based on a polydopamine-modified monolithic spin column combined with liquid chromatography–mass spectrometry (LC-MS) was developed for the determination of six organophosphorus pesticides (dimethoate, dichlorvos, carbofuran, methidathion, phosalone, and chlorpyrifos) in urine samples. A methacrylate polymer monolithic support was prepared in situ in the spin column, and dopamine solution was repeatedly passed through the monolith matrix via centrifugation to generate a polydopamine layer in the polymeric network. All extraction steps were performed via centrifugation. The monolith exhibited good permeability, which enabled high-flow-rate sample loading and significantly reduced the sample pre-treatment time. The addition of polydopamine significantly improved the extraction efficiency of the monolithic spin column owing to the catechol and amine groups in dopamine, which can enhance hydrogen bonding and π–π stacking. Factors affecting the extraction, including the solution pH, centrifugation speed, and desorption solvent, were investigated to determine the optimal extraction conditions. Under the optimal conditions, the OPP detection limits were 0.02–1.32 µg/L. The relative standard deviations of the single column (n = 5) and column-to-column (n = 3) precision for the extraction method were <11%. The monolithic spin column exhibited high stability and could be used for more than 40 extraction cycles. The recoveries for spiked urine samples were 72.1–109.3% (RSDs: 1.6–7.9%). The developed method was successfully applied to the simple and rapid analysis of organophosphorus pesticides in urine samples.