Analytical method for sequential determination of persistent herbicides and their metabolites in fish tissues by UPLC–MS/MS. (February 2022)

• Record Type: Journal Article
• Authors: Zhang, Cuifang; Wang, Zhuang; Liu, Sheng; Tan, Huihua; Zeng, Dongqiang; Li, Xuesheng
• Is Part Of: Chemosphere. Volume 288:Part 2(2022)
• Publication Date: 2022-02
• Subjects: Herbicides -- Metabolites -- Fish tissues -- QuEChERS -- UPLC–MS/MS; Pollution -- Periodicals; Pollution -- Physiological effect -- Periodicals; Environmental sciences -- Periodicals; Atmospheric chemistry -- Periodicals; 551.511
• DOI: 10.1016/j.chemosphere.2021.132591
• Languages: English
• ISSNs: 0045-6535

Abstract

Abstract: A novel and accurate liquid chromatography–tandem mass spectrometry method was developed to sequentially determine three persistent herbicides (atrazine (ATZ), acetochlor (ACE), and metolachlor (MET)) and seven characteristic metabolites (desethylatrazine (DEA), deisopropylatrazine (DIA), diaminochlorotriazine (DACT), MET–oxanilic acid (MET-OA), MET-ethanesulfonic acid (MET-ESA), ACE-ESA, and ACE-OA) in fresh fish tissues from six fish species. A modified QuEChERS method was conducted to extract the target compounds from fish tissues. Matrix-matched calibrations of the target analytes were carried out at spiking levels of 1, 10, 100, and 1000 ng g −1 . The method was validated in accordance with Codex guidelines (CAC/GL 71–2009). Recoveries for the target analytes were 67–120% with relative standard deviations below 20%, and the matrix effects ranged from −58.7% to 59.3%. The limits of detection and quantitation were 0.01–1.90 and 0.02–6.35 ng g −1, respectively. Moreover, the method was successfully applied to analyze the concentrations of the target chemicals in fresh tissue samples of six fish species (n = 67) collected from four markets in Nanning City, Guangxi Province, China. The concentrations in all samples were 1.1–140.5 ng g −1 . Interestingly, this study was the first to measure DEA and DIA in fish liver, and their highest concentrations were 10.7 and 14.2 ng g −1, respectively. This method provides a basis for studying the pathways of biotransformation, bioaccumulation, detoxification, and exposure patterns of ACE, ATZ, MET, and their metabolites in aquatic environments. Graphical abstract: Image 1 Highlights: UPLC–MS/MS analysis for detecting herbicides and their metabolites in fish tissue. High sensitivity for 3 herbicides and 7 metabolites within wide polarity ranges. The developed method was successfully applied in real fish samples. Two metabolites of atrazine were detected for the first time in fish liver samples.