Analytical method for sequential determination of persistent herbicides and their metabolites in fish tissues by UPLC-MS/MS

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.

Automated summary

A novel and accurate liquid chromatography-tandem mass spectrometry method was developed to determine persistent herbicides and their metabolites in fresh fish tissues. The method was validated according to Codex guidelines and successfully applied to analyze the concentrations of target chemicals in fish samples collected from markets in Nanning City, Guangxi Province, China. This study also identified DEA and DIA concentrations in fish liver for the first time.