基质分散固相萃取-液相色谱-串联质谱法测定蔬菜和水果中50种农药残留  

Determination of 50 kinds of pesticide residues in vegetables and fruits by QuEChERS-liquid chromatography-tandem mass spectrometry

作　　者：赵亚华[1] 裴昌鑫 李勇[1] ZHAO Yahua;PEI Changxin;LI Yong(Ma’anshan Municipal Center for Disease Control and Prevention,Ma’anshan,Anhui 243000,China)

机构地区：[1]马鞍山市疾病预防控制中心,安徽马鞍山243000

出　　处：《实用预防医学》2024年第12期1531-1537,共7页Practical Preventive Medicine

摘　　要：目的 通过优化基质分散固相萃取(quick, easy, cheap, effective, rugged and safe, QuEChERS)前处理方法并结合液相色谱-串联质谱(liquid chromatography-tandem mass spectrometry, LC-MS/MS)技术建立了蔬菜和水果中50种农药多残留快速测定方法。方法 试样用乙腈提取后,以150 mg乙二胺-N-丙基硅烷化硅胶(primary secondary amine, PSA)、100 mg十八烷基键合硅胶(octadecyl bonded silica gel, C18)、20 mg石墨化炭黑(graphitized carbon black, GCB)作为基质提取液净化剂,在Acquity UPLC HSS T3色谱柱上,以水溶液(2 mmol/L甲酸胺+0.01%甲酸)-甲醇溶液(2 mmol/L甲酸胺+0.01%甲酸)作为流动相进行梯度洗脱,采用电喷雾正离子模式下多反应监测模式(multiple reaction monitoring, MRM)进行测定,基质匹配标准溶液外标法定量。结果 结果表明,在最佳实验条件下,50种农药在0.125 ng/ml~500 ng/ml浓度内呈现良好的线性关系,线性相关系数(r)>0.999,方法检出限为0.1μg/kg~1.2μg/kg,在蔬菜水果中加标回收率为70.2%~112.6%,相对标准偏差为0.3%~8.6%。采用该方法对60份蔬菜样品进行检测,其中14份检出噻虫嗪、多菌灵、丙环唑等6种农药,含量为0.00545 mg/kg~0.278 mg/kg;对20份水果样品进行检测,其中4份检出吡虫啉、噻虫嗪、啶虫脒,含量为0.0172 mg/kg~0.0596 mg/kg。结论 该方法前处理快速简单、溶剂消耗少、灵敏度高、定性定量准确,适合大批量蔬菜和水果中农药多残留的快速筛查检测。Objective After optimization of a quick,easy,cheap,effective,rugged and safe(QuEChERS)-based extraction pretreatment method combined with liquid chromatography-tandem mass spectrometry(LC-MS/MS)technology,a rapid multi-residue determination method was established for detecting 50 kinds of pesticides in vegetables and fruits.Methods The samples were extracted with acetonitrile,purified with 150 mg primary secondary amine(PSA),100 mg octadecyl bonded silica gel(C18)and 20 mg graphitized carbon black(GCB).A gradient elution was carried out on Acquity UPLC HSS T3 column with aqueous solution(2 mmol/L ammonium formate+0.01%formic acid)-methanol solution(2 mmol/L ammonium formate+0.01%formic acid)as the mobile phase.The determination was performed by multiple reaction monitoring(MRM)mode under electrospray positive ionization mode,and the quantification was performed by the matrix-matched external standard method.Results The results revealed that 50 kinds of pesticides showed good linearity in the concentration range of 0.125 ng/ml-500 ng/ml under the optimal experimental conditions,the linear correlation coefficients(r)were greater than 0.999,and the method detection limits were between 0.1μg/kg and 1.2μg/kg.The recoveries of added standard were 70.2%-112.6%,with the relative standard deviations(RSD)of 0.3%-8.6%in vegetables and fruits.The method established was used to determine 60 vegetable samples,and 6 kinds of pesticides like thiamethoxam,carbendazim and propiconazole were detected in 14 samples,with the concentrations ranging from 0.005,45mg/kg to 0.278mg/kg.Imidacloprid,thiamethoxam and acetamiprid were detected in 4 of 20 fruit samples,with the concentrations ranging from 0.017,2mg/kg to 0.059,6mg/kg.Conclusion The method has fast and simple pretreatment,low solvent consumption,high sensitivity,and accurate qualitative and quantitative analysis.It is suitable for the rapid screening of pesticide multi-residues in large quantities of vegetable and fruit samples.

关 键 词：基质分散固相萃取 液相色谱-串联质谱法 蔬菜 水果 农药残留 

分 类 号：R155.6[医药卫生—营养与食品卫生学]