色谱2024，Vol.42Issue(9)：856-865,10.DOI:10.3724/SP.J.1123.2023.11010
固相萃取-液相色谱-串联质谱法测定污水中8种新烟碱类农药
Determination of eight neonicotinoid pesticides in wastewater by solid phase extraction combined with liquid chromatography-tandem mass spectrometry
摘要
Abstract
Neonicotinoid pesticides are a relatively new class of pesticides that have garnered significant attention owing to their potential ecological risks to nontarget organisms.A method combining solid phase extraction with liquid chromatography-tandem mass spectrometry(SPE-LC-MS/MS)was developed for the rapid and accurate detection of eight neonicotinoid pesti-cides(dinotefuran,E-nitenpyram,thiamethoxam,clothianidin,imidacloprid,imidaclothiz,ac-etamiprid,and thiacloprid)in wastewater.The chromatographic mobile phase and MS parame-ters were selected,and a single-factor method was used to determine the optimal column type,extraction volume,sample loading speed,and pH for SPE.The optimal parameters were as fol-lows:column type,HLB column(500 mg/6 mL);sample extraction volume,500 mL;sample loading speed,10 mL/min;and sample pH,6-8.The matrix effects of the wastewater samples were reduced by optimizing the chromatographic gradient-elution program,examining the dilu-tion factor of the samples,and using the isotope internal standard calibration method.Prior to analysis,the wastewater samples were diluted 5-fold with ultrapure water for pretreatment.Subsequently,2 mmol/L ammonium acetate aqueous solution containing 0.1%(v/v)formic acid and methanol was used as mobile phases for gradient elution on a ZORBAX Eclipse Plus C18 column(100 mm×2.1 mm,1.8 μm).The samples were quantified using positive-ion multi-ple reaction monitoring(MRM)mode for 10 min.Imidacloprid-d4 was used as the isotope in-ternal standard.The SPE process was further optimized by applying response surface methodol-ogy to select the type and mass of rinsing and elution solvents.The optimal pretreatment of the SPE column included rinsing with 10%methanol aqueous solution and elution with methanol-acetonitrile(1∶1,v/v)mixture(7 mL).The eight neonicotinoid pesticides showed satisfactory linearity within the relevant range,with linear correlation coefficients(r)all greater than 0.9990.The method detection limits(MDLs)ranged from 0.2 to 1.2 ng/L,and the method quantification limits(MQLs)ranged from 0.8 to 4.8 ng/L.The average recoveries of the eight neonicotinoid pesticides were in the range of 82.6%-94.2%at three spiked levels,with relative standard deviations(RSDs)ranging from 3.9%to 9.4%.Finally,the optimized method was successfully applied to analyze wastewater samples collected from four sewage treatment plants.The results indicated that the eight neonicotinoid pesticides could be generally detected at concentrations ranging from not detected(ND)to 256 ng/L.The developed method has a low MDL and high accuracy,rendering it a suitable choice for the trace detection of the eight neonicotinoid pesticides in wastewater when compared with other similar methods.The pro-posed method can be utilized to monitor the environmental impact and assess the potential risks of neonicotinoid pesticides in wastewater,thus promoting the protection of nontarget organisms and the sustainable use of these pesticides in agriculture.关键词
液相色谱-串联质谱/固相萃取/新烟碱类农药/污水/基质效应/响应曲面法Key words
liquid chromatography-tandem mass spectrometry(LC-MS/MS)/solid phase ex-traction(SPE)/neonicotinoid pesticides/wastewater/matrix effect/response surface method-ology(RSM)分类
化学化工引用本文复制引用
王海棠,李含音,陆启伟,何士龙..固相萃取-液相色谱-串联质谱法测定污水中8种新烟碱类农药[J].色谱,2024,42(9):856-865,10.基金项目
国家重点研发计划项目(2020YFC1908801) （2020YFC1908801）
江苏省生态环境保护地下水监测监控与污染预警重点实验室开放课题基金项目(GWKL2205).National Key Research and Development Program of China(No.2020YFC1908801) （GWKL2205）
Key Laboratory of Groundwater Monitoring and Pollution Early Warning of Ecological Environment Protection in Jiangsu Prov-ince Open Project Fund(No.GWKL2205). （No.GWKL2205）
