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和三唑类杀菌剂的残留量
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摘要
目的建立超高效液相色谱-串联质谱法同时快速测定水果蔬菜中35种甲氧基丙烯酸酯类和三唑类杀菌剂残留量的分析方法。方法样品用乙腈提取及QuEChERS方法净化,制得含有残留杀菌剂的上清液。采用Waters ACQUITY HSS T3 C_(18)柱(2.1 mm×100 mm, 1.8μm)以0.2%甲酸溶液-乙腈作为流动相进行梯度洗脱,质谱(ESI+)电喷雾正离子模式电离,采用多离子检测模式对35种杀菌剂的定量离子和定性离子进行监测。结果在1.0～50μg/L的浓度范围内35种杀菌剂线性关系良好,相关系数r~2为0.9990～0.9997;在5.0、50、100μg/kg添加水平的回收率为61.8%～125%,方法检出限为0.3～0.5μg/kg,定量限为1.0～1.5μg/kg。结论该方法快速、环境友好、准确、灵敏,适合水果蔬菜甲氧基丙烯酸酯类和三唑类杀菌剂残留的检测。
Objective To establish a fast method for simultaneous determination of 35 kinds of strobilurin fungicides and triazole fungicide in fruits and vegetables by ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS). Methods The fungicides residues were extracted from the samples by acetonitrile and cleaned-up with QuEChERS, and then eluted by a column of Waters ACQUITY HSS T3 C_(18)(2.1 mm×100 mm, 1.8 μm) with the gradient elution of acetonitrile(A) and 0.2% formic acid solution(B). Mass spectrometry(ESI+) electrospray positive ion mode ionization was performed with multi-ion detection mode(MRM) to monitor quantitative and qualitative ions of 35 kinds of fungicides. Results Under the optimal experimental conditions, 35 kinds of fungicides had good linearity in the range of 1.0-50 μg/L with correlation coefficients(r~2) of 0.9990-0.9997.The recoveries were ranged from 61.8%-125% for the 35 kinds of fungicides residues with 3 spiked levels of 5.0, 50 and100 μg/kg, and the limits of detection(LOD) and limits of quantitation(LOQ) were 0.3-0.5 μg/kg and 1.0-1.5 μg/kg, respectively. Conclusion The established method is fast, environmental friendly with high sensitivity and good reproducibility, which is suitable for the determination of the residual content of 35 kinds of strobilurin fungicides and triazole fungicides in fruits and vegetables.
Objective To establish a fast method for simultaneous determination of 35 kinds of strobilurin fungicides and triazole fungicide in fruits and vegetables by ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS). Methods The fungicides residues were extracted from the samples by acetonitrile and cleaned-up with QuEChERS, and then eluted by a column of Waters ACQUITY HSS T3 C_(18)(2.1 mm×100 mm, 1.8 μm) with the gradient elution of acetonitrile(A) and 0.2% formic acid solution(B). Mass spectrometry(ESI+) electrospray positive ion mode ionization was performed with multi-ion detection mode(MRM) to monitor quantitative and qualitative ions of 35 kinds of fungicides. Results Under the optimal experimental conditions, 35 kinds of fungicides had good linearity in the range of 1.0-50 μg/L with correlation coefficients(r~2) of 0.9990-0.9997.The recoveries were ranged from 61.8%-125% for the 35 kinds of fungicides residues with 3 spiked levels of 5.0, 50 and100 μg/kg, and the limits of detection(LOD) and limits of quantitation(LOQ) were 0.3-0.5 μg/kg and 1.0-1.5 μg/kg, respectively. Conclusion The established method is fast, environmental friendly with high sensitivity and good reproducibility, which is suitable for the determination of the residual content of 35 kinds of strobilurin fungicides and triazole fungicides in fruits and vegetables.
引文
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[14]黄超群,丁慧瑛,朱晓雨,等.液相色谱-串联质谱法同时测定蔬菜中7种三唑醇类杀菌剂的残留量[J].分析测试学报,2011,30(6):656-660.Huang CQ,Ding HY,Zhu XY,et al.Simultaneous determination of 7triazole alcohol fungicides in vegetables by liquid chromatography-tandem mass spectrometry[J].J Instru Anal,2011,30(6):656-660.
[15]沈伟健,余可垚,桂茜雯,等.分散固相萃取-气相色谱-串联质谱法测定蔬菜中107种农药的残留量[J].色谱,2009,27(4):39l-400.Shen WJ,Yu KY,Gui QW,et al.Determination of 107 pesticide residues in vegetables using off-line dispersive solid-phase extraction and gas chromatography-tandem mass spectrometry[J].Chin J Chromatogr,2009,27(4):39l-400.
[16]陈达捷,张志刚,周昱,等.串联固相萃取-液相色谱-串联质谱法测定食品中嘧啶胺类杀菌剂残留[J].色谱,2012,30(9):896-902.Chen DJ,Zhang ZG,Zhou Y,et al.Determination of fungicide anilinopyrimidine residues in food by series solid phase extraction-high performance liquid chromatography-tandem mass spectrometry[J].Chin JChromatogr,2012,30(9):896-902.
[17]贾楠.凝胶渗透色谱气相色谱串联质谱法测定农产品中种三唑类杀菌剂残留的研究[D].郑州:郑州大学,2013.Jia N.The Study on the determination of 18 triazole fungicide residues in agricultural products by GPC-GC-MSMS[D].Zhengzhou:Zhengzhou University,2013.
[18]Urairat K,Steven JL,Shui M,et al.High throughput analysis of 150pesticides in fruits and vegetables using QuEChERS and low-pressure gas chromatography-time-of-flight mass spectrometry[J].J Chromatogr A,2010,1217(43):6692-6703.
[19]高阳,徐应明,孙扬,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.Gao Y,Xu YM,Su Y,et al.Research progress of QuEChERS extraction method in pesticide residues determination in agricultural products[J].JAgric Resour Environ,2014,31(2):110-117.
[20]王建忠,郭春景,李娜,等.改进的QuEChERS方法结合UPLC-MS/MS同时快速检测8种蔬菜中77种农药残留[J].江苏农业科学,2014,(4):248-252.Wang JZ,Guo CJ,Li N,et al.Determination of 77 fungicides in 8 kinds vegetables by improved QuEChERS and UPLC-MS/MS[J].Jiangsu Agric Sci,2014,(4):248-252.
[21]乐渊,刘春华,黎舒怀,等.QuEChERS净化-超高效液相色谱-串联质谱测定芒果中3种杀菌剂残留[J].农药学学报,2015,17(6):723-728.Le Y,Liu CH,Li SH,et al.Determination of three fungicides in mango using QuEChERS method and ultra-performance liquid chromatography-tandem mass spectrometry[J].Chin J Pestic Sci,2015,17(6):723-728.
[22]郭春景,王建忠,郝晓莉.利用QuEChERS-UPLC-MS/MS法测定甘蓝、草莓中7种农药残留的实验条件优化探索[J].质谱学报,2013,34(2):121-127.Guo CJ,Wang JZ,He XL.The condition optimization determination of multi-residue of pesticides in cabbage and strawberry by QuEChERS-uplc-MS/MS[J].J Chin Mass Spectrom Soc MAR,2013,34(2):121-127.
[23]许欣欣,王冰,陈慧玲,等.超高效液相色谱-串联质谱法同时测定水果蔬菜中11种杀菌剂[J].食品安全质量检测学报,2018,9(1):141-148.Xu XX,Wang B,Chen HL,et al.Simultaneous determination of 11 kinds of fungicides in fruit and vegetable by ultra performance liquid chromatography-tandem mass spectrometry[J].J Food Saf Qual,2018,9(1):141-148.
[2]GB 2763-2016食品中农药最大残留限量[S].GB 2763-2016 Maximum residue limits for pesticides in food[S].
[3]任书瑶.蔬菜中农药残留的种类、危害及应对措施[J].现代农业科技,2015,(4):282-284.Ren SY.Types,hazards and countermeasures of pesticide residues in vegetables[J].Mod Agric Sci Technol,2015,(4):282-284.
[4]宋卫国,李宝聚,赵志辉,等.杀菌剂安全风险及解决途径[J].中国蔬菜,2008,(9):1-4.Song WG,Li BJ,Zhao ZH,et al.Safety risk and solutions of fungicides[J].China Veget,2008,(9):1-4.
[5]陆丹,杨秀鸿,吴军,等.嘧菌酯原药毒理学安全性评价[J].毒理学杂志,2013,27(4):316-318.Lu D,Yang XH,Wu J,et al.Toxicological safety evaluation of the original isopyrazam[J].J Toxicol,2013,27(4):316-318.
[6]宋稳成,单炜力,叶纪明,等.国内外农药最大残留限量标准现状与发展趋势[J].药学学报,2009,11(4):414-420.Song WC,Shan WL,Ye JM,et al.Present situation and development trend of MRLs for pesticides in and outside China[J].Chin J Pestic Sci,2009,11(4):414-420.
[7]陈宗懋.食品中农药残留检测发展的新趋势[J].农产品质量与安全,2010,(1):9-12.Chen ZM.Research progress on methods for detection of pesticide residues in food[J].Qual Saf Agro-Prod,2010,(1):9-12.
[8]欧盟食品中农兽药残留限量标准[S].EU veterinary drug residue limits for food[S].
[9]师真,陈俊秀,李旭,等.高效液相色谱-串联质谱法测定蔬菜中13种氨基甲酸酯类农药和杀菌剂残留[J].食品安全质量检测学报,2018,9(20):5438-5443.Shi Z,Chen JX,Li X,et al.Determination of 13 kinds of carbamate pesticides and fungicides in vegetables by high performance liquid chromatography-tandem mass spectrometry[J].J Food Saf Qual,2018,9(20):5438-5443.
[10]GBT 5009.218-2008水果和蔬菜中多种农药残留量的测定[S].GBT 5009.218-2008 Determination of multi pesticide residues in fruits and vegetables[S].
[11]宋鑫,杭学宇,王芹,等.蔬菜和水果中杀菌剂的高效液相色谱-串联质谱检测法[J].职业与健康,2018,34(1):44-47.Song X,Hang XY,Wang Q,et al.Determination of microbicides in vegetables and fruits by LC-MS/MS[J].Occup Health,2018,34(1):44-47.
[12]GB/T 20769-2008水果和蔬菜中450种农药及相关化学品残留的测定液相色谱-串联质谱法[S].GB/T 20769-2008 Determination of 450 pesticides and related chemicals residues in fruits and vegetables LC-MS-MS method[S].
[13]王菲,李彤,马辰.超高效液相色谱-串联质谱法测定中药材中三唑类杀菌剂及三嗪类除草剂的残留量[J].色谱,2013,31(3):191-199.Wang F,Li T,Ma C.Determination of triazole fungicide and triazine herbicide residues in Chinese herbs by ultra-performance liquid chromatography-tandem mass spectrometry[J].Chin J Chromatogr,2013,31(3):191-199.
[14]黄超群,丁慧瑛,朱晓雨,等.液相色谱-串联质谱法同时测定蔬菜中7种三唑醇类杀菌剂的残留量[J].分析测试学报,2011,30(6):656-660.Huang CQ,Ding HY,Zhu XY,et al.Simultaneous determination of 7triazole alcohol fungicides in vegetables by liquid chromatography-tandem mass spectrometry[J].J Instru Anal,2011,30(6):656-660.
[15]沈伟健,余可垚,桂茜雯,等.分散固相萃取-气相色谱-串联质谱法测定蔬菜中107种农药的残留量[J].色谱,2009,27(4):39l-400.Shen WJ,Yu KY,Gui QW,et al.Determination of 107 pesticide residues in vegetables using off-line dispersive solid-phase extraction and gas chromatography-tandem mass spectrometry[J].Chin J Chromatogr,2009,27(4):39l-400.
[16]陈达捷,张志刚,周昱,等.串联固相萃取-液相色谱-串联质谱法测定食品中嘧啶胺类杀菌剂残留[J].色谱,2012,30(9):896-902.Chen DJ,Zhang ZG,Zhou Y,et al.Determination of fungicide anilinopyrimidine residues in food by series solid phase extraction-high performance liquid chromatography-tandem mass spectrometry[J].Chin JChromatogr,2012,30(9):896-902.
[17]贾楠.凝胶渗透色谱气相色谱串联质谱法测定农产品中种三唑类杀菌剂残留的研究[D].郑州:郑州大学,2013.Jia N.The Study on the determination of 18 triazole fungicide residues in agricultural products by GPC-GC-MSMS[D].Zhengzhou:Zhengzhou University,2013.
[18]Urairat K,Steven JL,Shui M,et al.High throughput analysis of 150pesticides in fruits and vegetables using QuEChERS and low-pressure gas chromatography-time-of-flight mass spectrometry[J].J Chromatogr A,2010,1217(43):6692-6703.
[19]高阳,徐应明,孙扬,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.Gao Y,Xu YM,Su Y,et al.Research progress of QuEChERS extraction method in pesticide residues determination in agricultural products[J].JAgric Resour Environ,2014,31(2):110-117.
[20]王建忠,郭春景,李娜,等.改进的QuEChERS方法结合UPLC-MS/MS同时快速检测8种蔬菜中77种农药残留[J].江苏农业科学,2014,(4):248-252.Wang JZ,Guo CJ,Li N,et al.Determination of 77 fungicides in 8 kinds vegetables by improved QuEChERS and UPLC-MS/MS[J].Jiangsu Agric Sci,2014,(4):248-252.
[21]乐渊,刘春华,黎舒怀,等.QuEChERS净化-超高效液相色谱-串联质谱测定芒果中3种杀菌剂残留[J].农药学学报,2015,17(6):723-728.Le Y,Liu CH,Li SH,et al.Determination of three fungicides in mango using QuEChERS method and ultra-performance liquid chromatography-tandem mass spectrometry[J].Chin J Pestic Sci,2015,17(6):723-728.
[22]郭春景,王建忠,郝晓莉.利用QuEChERS-UPLC-MS/MS法测定甘蓝、草莓中7种农药残留的实验条件优化探索[J].质谱学报,2013,34(2):121-127.Guo CJ,Wang JZ,He XL.The condition optimization determination of multi-residue of pesticides in cabbage and strawberry by QuEChERS-uplc-MS/MS[J].J Chin Mass Spectrom Soc MAR,2013,34(2):121-127.
[23]许欣欣,王冰,陈慧玲,等.超高效液相色谱-串联质谱法同时测定水果蔬菜中11种杀菌剂[J].食品安全质量检测学报,2018,9(1):141-148.Xu XX,Wang B,Chen HL,et al.Simultaneous determination of 11 kinds of fungicides in fruit and vegetable by ultra performance liquid chromatography-tandem mass spectrometry[J].J Food Saf Qual,2018,9(1):141-148.