Defective Zr-based metal-organic frameworks as sorbent for the determination of fungicides in environmental water samples by rapid dispersive micro-solid-phase extraction coupled to liquid chromatography/mass spectrometry.

In this work, defective Zr-based metal-organic framework was successfully synthesized and evaluated as a dispersive micro-solid-phase extraction sorbent for efficient preconcentration and determination of fungicides in complex water samples. The defective Zr-based metal-organic framework crystal with increased adsorption capacity was successfully synthesized by employing formic acid as the modulator. The extraction conditions, including the pH, extraction time, desorption solvent and desorption time, were comprehensively investigated. Under optimum conditions, it was found that dispersive micro-solid-phase extraction method, coupled with liquid chromatography/mass spectrometry, exhibited a good linear relationship with correlation coefficients greater than 0.9980. The relative standard deviations of inter-day and intra-day precisions ranged from 2.6 to 9.2% and the limits of detection ranged from 0.004 to 0.036 μg/L. These merits, combined with their satisfactory recoveries (>80%), suggested the great potential of defective Zr-based metal-organic framework as a new adsorbent for efficient extraction of trace fungicides. This method exhibits good application potential for the pretreatment of fungicides from environmental water samples.