Calixarene-Based Miniaturized Solid-Phase Extraction of Trace Triazine Herbicides from the Honey and Milk Samples

A fast, simple, and cost-effective miniaturized solid-phase extraction method using calixarenes as adsorbent was developed for the micro-extraction of cyanazine, simazine, atrazine, and propazine from complex samples. The ultrahigh-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry was employed for the structural identification of target compounds. The parameters affecting the performance of extraction, such as the type of sorbents, the amount of the sorbent, desorption solvents, breakthrough volume, and adsorption capacity, were optimized. Under optimal conditions, the linear range was 6–600 ng mL−1 with the coefficients of determination from 0.9943 to 0.9998. The limits of detection and quantification for the four triazines were 0.01–0.04 and 0.04–0.15 ng mL−1, respectively. The proposed method was successfully used to determine triazine herbicides in the honey and milk samples.