Vortex-assisted solid-phase extraction based on metal-organic framework/chitosan-functionalized hydrophilic sponge column for determination of triazine herbicides in environmental water by liquid chromatography-tandem mass spectrometry

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In the presented work, MIL-101(Cr) and chitosan were directly embedded on the skeleton of melamine sponge material using a simple and environmentally friendly method. Chitosan acts not only as an adhesive during the preparation of functionalized sponges, but also as an adsorption adjuvant in herbicide detection. Unlike other polymers, chitosan has excellent hydrophilicity and contains numerous adsorption sites; thus, it enables the sponge material to be used for determination of contaminants in an aqueous phase. Scanning electron microscopic (SEM) analysis showed that the coating material was uniformly distributed on the skeleton of melamine sponge. The prepared material was used as a sorbent in a vortex-assisted solid-phase extraction and combined with high performance liquid phase tandem mass spectrometry for the extraction and trace determination of six triazines in water samples (Atraton, Desmetryn, Prometon, Ametryn, Prometryn and Dimethametryn). Several parameters that affect the extraction efficiencies were investigated. Under the optimal conditions (MIL-101(Cr) loading, 150 mg; sample pH, 7; salt concentration, 0%; adsorption time, 3 min; desorption solvent, 1.5 mL acetonitrile; desorption time, 4 min), the proposed method was successfully used in the determination of trace triazines in five real water samples (drinking water, tap water, lake waters and river water), satisfactory recoveries were obtained in the range of 78.9%–118.6%. The limits of detection of the proposed method in detecting triazine herbicides in spiked water samples ranged from 0.014 to 0.045 ng mL−1.