ZIF-67-modified magnetic nanoparticles for extraction of phenoxy carboxylic acid herbicides†

Abstract

Phenoxy carboxylic acid (PCA) herbicides are commonly used herbicides that can easily accumulate in soil, groundwater, crops, and vegetable surfaces. Thus, they pose a serious risk to human health. Accurate detection of trace amounts of PCAs in various matrixes is crucial. Herein, ZIF-67-modified magnetic nanoparticles (MNPs, ZIF-67@Fe₃O₄) were prepared by growing ZIF-67 on the surface of Fe₃O₄ MNPs. The introduction of ZIF-67 improved the dispersion of Fe₃O₄ nanoparticles in water and enhanced their extraction performance for PCAs. When an eluent consisting of ammonia water and acetonitrile (5% : 95%; v/v) was employed, 10 mg of ZIF-67@Fe₃O₄ displayed optimal extraction performance for PCAs in a 20 mL sample solution at a pH of 3. We achieved a limit of detection ranging from 0.014 μg L⁻¹ to 0.056 μg L⁻¹ for four types of PCA herbicides by using the newly developed method. Notably, the values were considerably lower than the maximum concentration levels of PCAs in drinking water set by the Environmental Protection Agency. The relative recovery rate of PCAs using ZIF-67@Fe₃O₄ ranged from 83.75% to 117.07% when applied to river water and apple samples. These results demonstrate the great potential of ZIF-67@Fe₃O₄ in determining the residues of organic pesticides in real samples.