Development of Simultaneous Determination Method of Pesticide High Toxic Metabolite 3,4-Dichloroaniline and 3,5 Dichloroaniline in Chives Using HPLC-MS/MS

• Published in: Foods 2023-07, Vol.12 (15), p.2875
• Main Authors: Dong, Yibo, Yao, Xiaolong, Zhang, Wanping, Wu, Xiaomao
• Format: Article
• Language: English
• Subjects: 3,4-Dichloroaniline; 3,5-dichloroaniline; Acetonitrile; Agricultural production; Analysis; Aqueous solutions; Bioaccumulation; Black carbon; Carbon black; chive; Chromatography; Computer simulation; Correlation coefficient; Correlation coefficients; Dicarboximide; Food science; Fungicides; Health risk assessment; Health risks; Herbicides; High performance liquid chromatography; Ions; Liquid chromatography; Mass spectrometry; Mass spectroscopy; Metabolites; Methods; Optimization; Pesticide toxicity; Pesticides; Phenylurea; Plants (botany); Purification; Residues; Resveratrol; Scientific imaging; simultaneous determination; Toluene; Toxicity; UPLC-MS/MS; Vegetables
• ISSN: 2304-8158; 2304-8158
• DOI: 10.3390/foods12152875

3,4-dichloroaniline (3,4-DCA) and 3,5-dichloroaniline (3,5-DCA) are, respectively, the primary metabolites deriving from the breakdown of phenylurea herbicides and dicarboximide fungicides in both soils and plants, whose residues in vegetable products have a heightened concern considering their higher health risks to humans and greater toxicity than the parent compounds in the environment. In this study, a sensitive high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method was developed for the simultaneous determination of 3,4-DCA and 3,5-DCA residues in chive products based on the optimization of HPLC-MS/MS chromatographic and mass-spectrometric conditions using the standard substances and the modified QuEChERS preparation technique. The preparation efficiency of 3,4-DCA and 3,5-DCA from chive samples showed that acetonitrile was the best extractant. The combination of the purification agent graphite carbon black + primary secondary amine and the eluting agent acetonitrile + toluene (4:1, / ) had a satisfactory purification effect. The linear correlation coefficients ( ) were more than 0.996 with the six concentration range of 0.001-1.000 mg/L for 3,4-DCA and 3,5-DCA. The limit of detection and limit of quantitation of this method was 0.6 and 2.0 µg/kg for 3,4-DCA, as well as 1.0 and 3.0 µg/kg for 3,5-DCA, respectively. The matrix effect range of 3,4-DCA and 3,5-DCA in chive tissues was from -9.0% to -2.6% and from -4.4% to 2.3%, respectively. The fortified recovery of 3,4-DCA and 3,5-DCA in chive samples at four spiked levels of 0.001-1.000 mg/kg was 75.3-86.0% and 78.2-98.1%, with the relative standard deviation of 2.1-8.5% and 1.4-11.9%, respectively. The limit of detection ( ) and limit of quantification ( ) of the method were 0.6, 2.0, and 1.0, 3.03 for 4-DCA and 3,5-DCA, respectively. This study highlights that the analytical method established here can efficiently and sensitively detect residues of 3,4-DCA and 3,5-DCA residues for monitoring chive products. The method was successfully applied to 60 batches of actual vegetable samples from different regions.