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 inwastewater by solid phase extraction combined withliquid chromatography-tandem mass spectrometry

作　　者：王海棠 李含音 陆启伟 何士龙[1] WANG Haitang;LI Hanyin;LU Qiwei;HE Shilong(School of Environment and Spatial Informatics,China University of Mining and Technology,Xuzhou 221116,China;Xuzhou Environmental Monitoring Center of Jiangsu,Xuzhou 221000,China;Xuzhou High-tech Industrial Development Zone,Xuzhou 221000,China)

机构地区：[1]中国矿业大学环境与测绘学院,江苏徐州221116 [2]江苏省徐州环境监测中心,江苏徐州221000 [3]徐州高新技术产业开发区,江苏徐州221000

出　　处：《色谱》2024年第9期856-865,共10页Chinese Journal of Chromatography

基　　金：国家重点研发计划项目(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).

摘　　要：新烟碱类农药作为一类新型农药,由于其对非靶标生物造成生态风险而引起广泛关注。为了实现污水中痕量新烟碱类农药的快速、准确定量,本研究建立了同时检测污水中8种新烟碱类农药(呋虫胺、E-烯啶虫胺、噻虫嗪、噻虫胺、吡虫啉、氯噻啉、啶虫脒和噻虫啉)的固相萃取-液相色谱-串联质谱法。确定选择色谱流动相类型和质谱参数后,采用单因素法确定固相萃取(SPE)的条件:萃取柱类型为HLB(500 mg/6 mL),上样体积为500 mL,上样速度为10 mL/min,样品pH为6~8。通过优化色谱梯度洗脱程序、样品的稀释倍数并采用同位素内标定量法降低污水样品的基质效应,确定污水稀释5倍进行前处理,采用ZORBAX Eclipse Plus C18色谱柱(100 mm×21 mm,18μm),以含01%甲酸的2 mmol/L乙酸铵水溶液和甲醇为流动相进行梯度洗脱,在正离子多反应监测模式下分析10 min,用吡虫啉-d4作为同位素内标进行定量。通过响应曲面法进一步优化SPE的淋洗液及洗脱液类型和用量,确定用10%甲醇水溶液淋洗,7 mL甲醇-乙腈(1∶1,v/v)混合溶液洗脱。8种新烟碱类化合物在相应范围内线性关系良好(线性相关系数(r)均大于09990),方法检出限(MDL)为02~12 ng/L,方法定量限(MQL)为08~48 ng/L,在低、中、高3个加标水平下的加标回收率为826%~942%,RSD为39%~94%。该方法成功用于4个城镇污水处理厂进水水样的分析,8种新烟碱类农药的检出含量为ND~256 ng/L。与类似方法相比,该方法检出限低,准确度高,适用于污水中8种新烟碱类农药的痕量检测。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 01%(v/v)formic acid and methanol was used as mobile phases for gradient elution on a ZORBAX Eclipse Plus C18 column(100 mm×21 mm,18μm).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 09990.The method detection limits(MDLs)ranged from 02 to 12 ng/L,and the method quantifi

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 

分 类 号：O658[理学—分析化学]