Abstract:

Fungicides can lead to soil and plant diseases after long-term enrichment in the environment; they can also penetrate deeper into the soil and groundwater by rainwater or irrigation, threatening the water environment and human health. Therefore, it is crucial to develop a simple, rapid, efficient, and sensitive analytical method for the detection of fungicides in the water environment. Sample pretreatment is important for the extraction and enrichment of pollutants from environmental water. Magnetic solid phase extraction (MSPE) is a new sample pretreatment method, which uses magnetic materials as adsorbents dispersed in solution, and rapid separation can be achieved by the aid of external magnets. Because of its advantages of short analytical time, less organic solvent consumption, and easy separation of adsorbents, MSPE has attracted much attention. The key to MSPE is the preparation of highly selective magnetic adsorbents. Covalent organic frameworks have the advantages of large surface area, good chemical and thermal stability, tunable porous structure, low density, and easy functionalization, all of which are ideal for adsorbing fungicides. The concentration of fungicides in environmental water is low. Ultrahigh performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) has high sensitivity and high selectivity, which is suitable for the analysis of fungicides. In this work, a magnetic covalent organic framework Fe₃O₄@TpBD was prepared by an in situ method, as the MSPE sorbent material to enrich of benzimidazole fungicides (thiabendazole, carbendazim, fuberidazole) and organic sulfur fungicide (isoprothiolane) in environmental water. An extraction method based on π-π conjugation, hydrogen bonding, and electrostatic interaction between Fe₃O₄@TpBD and the fungicides, in combination with UHPLC-MS/MS, was developed for the determination of four trace fungicides in water. Transmission electron microscopy (TEM), X-ray diffractometry (XRD), and Fourier transform-infrared spectroscopy (FT-IR) were performed to confirm the successful synthesis of Fe₃O₄@TpBD and to characterize this material. A series of experiments were carried out to decide the optimal extraction conditions, i. e., the magnetic ratio and dosage of Fe₃O₄@TpBD, pH of the water sample, adsorption time, type and volume of the eluent, elution time, and salinity. Gradient elution was carried out with methanol-water as the mobile phase. The target analytes were separated on an ACQUITY UPLC BEH C18 column (100 mm×2.1 mm, 1.7 μm), and multiple reaction monitoring (MRM) was conducted in the positive electrospray ionization mode. The ion source temperature and ion source voltage were set to 500 ℃ and 5 kV, respectively. The analytical method was established under the optimized extraction conditions. The four fungicides showed good linearity in the range of 3-1200 ng/L, with linear correlation coefficients greater than 0.998. The limits of detection (LODs) and limits of quantification (LOQs) of this developed method were 0.06-0.28 ng/L and 0.20-0.92 ng/L, respectively. Recovery tests were performed at three spiked levels of 15, 150, and 600 ng/L, with relative standard deviations of 2.8% to 10.0% (intra-day) and 4.4% to 15.7% (inter-day). The accuracy of the established analytical method was investigated by using it to test real water samples, and satisfactory recoveries for the four analytes were achieved within 77.1% to 119.1%. Trace amounts of carbendazim were detected in the reservoir water at 27.5 ng/L. The method has good sensitivity, accuracy, and precision, and the operation process is convenient.

Key words: ultrahigh performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), magnetic solid phase extraction (MSPE), covalent organic frameworks (COFs), fungicide, environmental waters