Zr-MOF modified cotton fiber for pipette tip solid-phase extraction of four phenoxy herbicides in complex samples

Phenoxy herbicides are widely applied in agricultural weeding. The determination of herbicides is important in environmental protection, agricultural production, food safety, and public health. In this study, a facile and efficient analytical method was proposed for the trace detection of phenoxy herbicides in soil, cucumber, and tap water samples by coupling pipette tip solid phase extraction (PT-SPE) with high performance liquid chromatography. UiO-66-funtionalized cotton (Cotton@UiO-66) was packed into pipette-tip as sorbent to fabricate extraction device. The modification of UiO-66 on cotton fiber was confirmed using scanning electron microscope, Fourier transform infrared spectroscopy, and X-ray diffraction. The main factors affecting the adsorption of Cotton@UiO-66 for four phenoxy herbicides were evaluated by response surface methodology in detail. Under optimized conditions, Cotton@UiO-66 displayed excellent properties in the extraction of phenoxy herbicides with good peak shape. Linear ranges of 4-chlorophenoxyacetic acid, dicamba, 2,4-dichlorophenoxyacetic acid, and 2-(2,4-dichlorophenoxy) propionic acid were 1.4-72 μg/L, 5.6-280 μg/L, 2.8-140 μg/L and 3.2-160 μg/L (RSDs < 6.3%), respectively. The recoveries were between 83.3 and 106.8% with RSDs <6.7%, with detection limits ranging from 0.1 μg/L to 0.3 μg/L. The results show that Cotton@UiO-66 in PT-SPE is an effective method for monitoring phenoxy herbicides in complex samples.