建立了采用QuEChERS方法提取净化,气相色谱-串联质谱法(gas chromatography-tandem mass spectrometry,GC-MS/MS)同时测定番茄中9种甲氧基丙烯酸酯(啶氧菌酯、E-苯氧菌酯、Z-苯氧菌酯、嘧螨酯、肟菌酯、醚菌胺、肟嘧菌胺、醚菌酯、嘧菌酯)杀菌剂残留量的方法。样品经乙腈提取,采用正交试验优选N-丙基乙二胺和C18以及石墨化炭黑的净化用量。使用Rtx-5色谱柱程序升温分离,以EI源电离,在多反应监测模式(multiple reaction monitoring,MRM)进行定性分析,用基质匹配校准曲线外标法进行定量分析。9种甲氧基丙烯酸酯类杀菌剂在5~800 ng/mL范围内线性关系良好,相关系数为0.993 9~0.999 5,检出限为0.5~2.5 μg/kg,定量限为2~8 μg/kg。向番茄样品中分别加入3个不同浓度进行加标回收试验,加标回收率为73.24%~91.38%,相对标准偏差为2.51%~10.18%。该方法准确度高、精密度好、操作简单、成本低廉,满足番茄中9种甲氧基丙烯酸酯类杀菌剂的痕量检测要求。
A method was established for the simultaneous determination of nine strobilurin fungicides in tomatoes by GC-MS/MS. The samples were extracted by acetonitrile and purified by anhydrous magnesium sulfate, n-propyl ethylenediamine (PSA), C18 and GCB and optimization by orthogonal test. Rtx-5 chromatographic column was used for temperature programmed separation, EI ionization source was used for qualitative analysis in MRM monitoring mode. And matrix calibration curve external standard method was used for quantitative analysis. The results showed that a good linear relationships for all kinds of strobilurin fungicides were good in the range of 5-800 ng/mL with the correlation coefficient of 0.993 9-0.999 5. The detection limit was from 0.5 μg/kg to 2.5 μg/kg, while the quantification limit was from 2-8 μg/kg. The recovery rate in samples were 73.24%-91.38%, and the relative standard deviations were 2.51%-10.18%. The method is accurate, precise, simple and economic. It suits the requirements of trace detection of nine strobilurin fungicides in tomatoes.
[1] 赵平,严秋旭,李新,等.甲氧基丙烯酸酯类杀菌剂的开发及抗性发展现状[J].农药,2011,50(8):547-551;572.
[2] 王璐芳,李春梅,许佳彬,等.QuEChERS-超高效液相色谱-串联质谱法测定不同植被类型土壤中11种甲氧基丙烯酸酯类杀菌剂[J].色谱,2018,36(8):730-737.
[3] 吴洁珊,冯家望,任永霞,等.气相色谱测定柑橘中多种甲氧基丙烯酸酯类杀菌剂的残留量[J].农药,2011,50(10):754-755;766.
[4] 薄海波,王金花,郭春海,等.气相色谱/质谱法测定食品中甲氧基丙烯酸酯类杀菌剂残留[J].分析化学,2008(11):1 471-1 475.
[5] 王云凤,葛宝坤,高建会,等.液相色谱-质谱法测定果蔬中8种甲氧基丙烯酸酯类杀菌剂残留量[J].食品研究与开发,2009,30(4):130-133.
[6] 张瑶,孙谦,马桂娟,等.GC/MS/MS法测定水果中10种甲氧基丙烯酸酯类杀菌剂残留量[J].环境化学,2019,38(5):1 204-1 206.
[7] 郑兆姗,寿淼钧,裴晓华,等.快速溶剂萃取-气相色谱质谱法联用测定大米中6种甲氧基丙烯酸酯类杀菌剂残留量[J].分析仪器,2019(2):51-56.
[8] 中华人民共和国国家卫生和计划生育委员会,中华人民共和国农业部,国家食品药品监督管理总局.GB 23200.54-2016 食品安全国家标准 食品中甲氧基丙烯酸酯类杀菌剂残留量的测定 气相色谱-质谱法[S].北京:中国标准出版社,2016.
[9] 马楠,张玉娟,张志强.QuEChERS/GC-MS法检测韭菜中19种农药残留[J].食品工业,2020, 41(1):323-326.
[10] 侯雪,韩梅,邱世婷,等.改进的QuEChERS-气相色谱-串联质谱法测定草莓中21种杀菌剂残留[J].农药学学报,2017, 19(1):46-52.
[11] 李志,冉茂乾,张馨允,等.QuEChERS-GC-MS/MS法同时测定刺梨中15种有机氯农药残留[J].中国酿造,2020,39(3):166-171.
[12] 高阳,徐应明,孙扬雄,等.QuEChERS提取法在农产品农药残留检测中的应用进展[J].农业资源与环境学报,2014,31(2):110-117.
[13] 杜磊,徐华超,周卓为,等.QuEChERS/气相色谱质谱法同时测定膨化食品中多环芳烃类物质[J].广州化学,2020,45(2):22-27.
[14] 许秀敏,龙朝阳,黄伟雄,等.QuEChERS-超高效液相色谱-串联质谱法同时快速检测果蔬中35种甲氧基丙烯酸酯类杀和三唑类杀菌剂的残留量[J].食品安全质量检测学报,2019,10(4):1 039-1 047.
[15] 刘亚伟,董一威,孙宝利,等.QuEChERS在食品中农药多残留检测的应用研究进展[J].食品科学,2009,30(9):285-289.
[16] 黄何何, 张缙,徐敦明,等.QuEChERS-高效液相色谱-串联质谱法同时测定水果中21种植物生长调节剂的残留量[J].色谱,2014,32(7):707-716.
[17] 黄诚,郭梅.正交试验法优选黄瓜中拟除虫菊酯类农残检测的净化剂组合[J].中国食品卫生杂志,2012 24(5):438-440.
[18] DONG Fengshou,CHEN Xiu,LIU Xinggang,et al. Simultaneous determination of five pyrazole fungicides in cereals,vegetables and fruits using liquid chromatography/tandem mass spectrometry[J].J Chromatogr A,2012,126(2):98-106.
[19] 刘进玺,秦珊珊,冯书惠,等.高效液相色谱-串联质谱法测定食用菌中农药多残留的基质效应[J].食品科学,2016,37(18):171-177.
[20] 汪传炳,黄秀根,樊晓青,等.微量叠加定量法校准蔬菜农药残留色谱分析中的基质效应[J].上海农业学报,2013,29(4):36-41.
