固相萃取-气相色谱-串联质谱法同时测定红茶中113种农药残留
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摘要
目的建立一种固相萃取净化(solid phase extraction, SPE)-气相色谱-串联质谱法(gas chromatography-tandem mass spectrometry, GC-MS/MS)测定红茶中113种农药多残留的分析方法。方法样品采用1%(V:V)醋酸乙腈水溶液(2:1,V:V),加入6 g MgS04, 1.5 g乙酸钠进行提取。考虑到农药化合物结构的差异性影响,本文采用2种不同的净化方法,方法I是采用Cleanert TPT柱对95种农药进行净化,方法II采用PSA柱与50 mg石墨化碳黑(graphitized carbon black, GCB)对18种平面或类平面结构的农药进行净化,然后用GC-MS/MS进行分析,基质匹配标准溶液内标法定量。结果结果表明,113种农药在5～200 ng/mL范围内线性关系良好,相关系数均大于0.993,方法的添加回收率为50%～134.2%,相对标准偏差(relative standard deviations, RSD)为0.1%～13.7%,定量限(limits of the quantitation, LOQ)为10～50μg/kg。结论该方法灵敏度、准确度和精密度均能满足红茶中农药多残留的分析要求。
Objective To establish a method for the determination of 113 kinds of pesticide residues in tea by solid phase extraction purification(SPE)-gas chromatography-tandem mass spectrometry(GC-MS/MS). Methods The samples were extracted with 1%(V:V) acetic acid-acetonitrile water solution(2:1, V:V) and 6 g MgSO_4 and 1.5 g sodium acetate. As the influences of the compound structures, the extracts were purified by two methods. In purified method I, 95 pesticide residues were used by the SPE of Cleanert TPT, while the other 18 planar structure compounds or the compounds with some planar groups were used by the SPE of PSA and 50 mg GCB. After filtration, the target compounds were detected by GC-MS/MS and quantified with internal standard method by the matrix match standard solutions. Results The results showed that 113 pesticides had good linear relationships in the range of 5-200 ng/mL,with the correlation coefficients were all better than 0.993. The average recoveries of the 113 pesticide residues ranged from 50%-134.2%, with the relative standard deviations of 0.1%-13.7%. The limits of the quantitation were10-50 μg/kg. Conclusion The sensitivity,accuracy and precision of the method can meet the analysis requirements of pesticide residues in black tea.
Objective To establish a method for the determination of 113 kinds of pesticide residues in tea by solid phase extraction purification(SPE)-gas chromatography-tandem mass spectrometry(GC-MS/MS). Methods The samples were extracted with 1%(V:V) acetic acid-acetonitrile water solution(2:1, V:V) and 6 g MgSO_4 and 1.5 g sodium acetate. As the influences of the compound structures, the extracts were purified by two methods. In purified method I, 95 pesticide residues were used by the SPE of Cleanert TPT, while the other 18 planar structure compounds or the compounds with some planar groups were used by the SPE of PSA and 50 mg GCB. After filtration, the target compounds were detected by GC-MS/MS and quantified with internal standard method by the matrix match standard solutions. Results The results showed that 113 pesticides had good linear relationships in the range of 5-200 ng/mL,with the correlation coefficients were all better than 0.993. The average recoveries of the 113 pesticide residues ranged from 50%-134.2%, with the relative standard deviations of 0.1%-13.7%. The limits of the quantitation were10-50 μg/kg. Conclusion The sensitivity,accuracy and precision of the method can meet the analysis requirements of pesticide residues in black tea.
引文
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[5]鲍治帆,官兴丽,谢吉林,等.分散固相萃取-气相色谱法快速测定茶叶中27种常见含卤素农药残留[J].食品科学,2014, 35(10):174-178.Bao ZF, Guan XL, Xie JL, et al. Rapid Determination of 27 kinds of common halogen-containing pesticide residues in tea by dispersive solid-phase extraction and gas chromatography[J]. Food Sci, 2014, 35(10):174-178.
[6]王晓亮,毛卫中,汪新华,等.QuEchERS-高效液相色谱柱后衍生法测定茶叶中10种氨基甲酸酯类农药残留[J].食品工业科技,2018,39(14):190-193.Wang XL, Mao WZ, Wang XH, et al. Simultaneous determination of ten carbamate pesticide residues in tea by QuEChERS-HPLC with post-column derivatization[J]. Sci Technol Food Ind, 2018, 39(14):190-193.
[7]黄微,李娜,徐瑞晗,等.加速溶剂萃取-固相萃取净化-气相色谱-串联质谱法检测茶叶中9种拟除虫菊酯类农药残留[J].色谱,2018, 36(12):1303-1310.Huang H, Li N, Xu RH, et al. Determination of nine pyrethroid pesticide residues in tea by gas chromatography-tandem mass spectrometry combined with accelerated solvent extraction and solid phase extraction[J]. Chin J Chromatogr, 2018, 36(12):1303-1310.
[8]王秀丽,贾彦博,李玮,等.固相萃取-气相色谱质谱内标法测定茶叶中噻螨酮和喹螨醚[J].中国卫生检验杂志,2018, 28(15):1817-1820.Wang XL, Jia YB, Li W, et al. Determination of hexythiazox and fenazaquin in tea by solid phase extraction-gas chromatographic mass spectrometry with interal standard method[J]. Chin J Health Lab Technol,2018,28(15):1817-1820.
[9]李晔,郭蒙京,袁佗.气相色谱-质谱法测定茶叶中溴虫腈、啶虫脒、茚虫威、三氯杀螨醇及拟除虫菊酯等11种农药残留[J].中国卫生检验杂志,2016, 26(11):1579-1581,1584.Li Y, Guo MJ, Yuan T. Determination of 11 pesticide residues, such as chlorfenapyr, acetamiprid, indoxacarb, dicofol and synthetic pyrethroids in tea by gas chromatography-mass spectrometry[J]. Chin J Health Lab Technol, 2016, 26(11):1579-1581, 1584.
[10]褚能明,孟霞,康月琼,等.分散固相萃取-气相色谱-串联质谱法测定茉莉花茶中86种农药残留[J].食品科学,2016, 37(24):239-246.Chu NM, Meng X, Kang YQ, et al. Determination of 86 pesticide residues in jasmine tea by dispersive solid-phase extraction combined with gas chromatography-tandem mass spectrometry[J]. Food Sci, 2016, 37(24):239-246.
[11]黄田田,汤桦,董晓倩,等.多壁碳纳米管QuEChERS-气相色谱法测定茶叶中23种有机磷农药残留量[J].食品科学,2018, 39(06):315-321.Huang TT, Tang H, Dong XQ, et al. Determination of 23organophosphorus pesticide residues in tea by QuEChERS extraction with multi-walled carbon nanotubes(MWCNTs)coupled to gas chromatography[J]. Food Sci, 2018, 39(6):315-321.
[12]贾玮,黄峻榕,凌云,等.高效液相色谱-串联质谱法同时测定茶叶中290种农药残留组分[J].分析测试学报,2013, 32(01):9-22.Jia W, Huang JR, Ling Y, et al. Determination of 290 pesticide residues in tea by high performance liquid chromatography-tandem mass spectrometry[J]. J Instrum Anal, 2013, 32(1):9-22.
[13] Zhao CL, Ding RY, Huo LG, et al. Determination of pesticide residues in tea by gas chromatography/triple quadrupole mass spectrometry with solid-phase extraction[J]. J AOAC Int, 2014, 97(4):1001-1006.
[14] Xue H, Shao RL, Shi TQ, et al. A multi-residue method for the determination of pesticides in tea using multi-walled carbon nanotubes as a dispersive solid phase extraction absorbent[J]. Food Chem, 2014,153(15):121-129.
[15]刘腾飞,杨代凤,董明辉,等.分散固相萃取-气相色谱法测定茶鲜叶中7种拟除虫菊酯类农药残留[J].农药学学报,2015, 17(5):571-578.Liu TF, Yang DF, Dong MH, et al. Determination of pyrethroid residues in fresh tea leaves by dispersive solid phase extraction and gas chromatography[J]. Chin J Pest Sci, 2015, 17(5):571-578.
[16]蓝梦哲,林绪,刘雅琼,等.液相色谱-串联质谱法同时测定8种花草茶中77种农药残留[J].色谱,2018, 36(9):938-945.Lan MZ, Lin X, Liu YQ, et al. Simultaneous determination of 77 pesticide residues in eight kinds of herbal tea by liquid chromatography-tandem mass spectrometry[J]. Chin J Chromatogr, 2018, 36(9):938-945.
[17]楼正云,陈宗懋,罗逢健,等.固相萃取-气相色谱法测定茶叶中残留的92种农药[J].色谱,2008(05):568-576.Lou ZY, Chen ZM, Luo FJ, et al. Determination of 92 pesticide residues in tea by gas chromatography with solid-phase extraction[J]. Chin J Chromatogr, 2008,(5):568-576.
[18] Lehotay SJ, De KA, Hiemstra M. Validation of a fast and easy method for the determination of residues from 229 pesticides in fruits and vegetables using gas and liquid chromatography and mass spectrometric detection[J].J AOAC Int, 2005, 88(2):595-614.
[19] EU, Document No. SANCO/10476/2003. Quality control procedures for pesticide residues analysis. Guidelines for residues monitoring in the European Union[S].
[20]贺利民,刘祥国,曾振灵.气相色谱分析农药残留的基质效应及其解决方法[J].色谱,2008,(1):98-104.He LM, Liu XG, Zeng ZL. Solutions to matrix-induced response enhancement in pesticide residue analysis by gas chromatography[J].Chin J Chromatogr, 2008,(1):98-104.
[2] GB 2763-2016食品安全国家标准食品中农药残留限量标准[S].GB 2763-2016 National food safety standard-Maximum residue limits for pesticides in food[S].
[3]胡付照,陈正行,李鹤,等.茶叶中农药残留标准及检测方法研究进展[J].食品与生物技术学报,2018,37(10):1009-1014.Hu FZ, Chen ZX, Li H, et al. Research advance of pesticide residues standards and new detection methods in tea[J]. J Food Sci Biotechnol,2018, 37(10):1009-1014.
[4]李慧思,黄超群,蒋沁婷,等.在线净化-液相色谱-串联质谱法测定茶叶中5种烟碱类农药残留[J].色谱,2016, 34(3):263-269.Li HS, Huang CQ, Jiang QT, et al. Determination of five neonicotinoid pesticide residues in tea by online clean-up-liquid chromatography-tandem mass spectrometry[J]. Chin J Chromatogr, 2016, 34(3):263-269.
[5]鲍治帆,官兴丽,谢吉林,等.分散固相萃取-气相色谱法快速测定茶叶中27种常见含卤素农药残留[J].食品科学,2014, 35(10):174-178.Bao ZF, Guan XL, Xie JL, et al. Rapid Determination of 27 kinds of common halogen-containing pesticide residues in tea by dispersive solid-phase extraction and gas chromatography[J]. Food Sci, 2014, 35(10):174-178.
[6]王晓亮,毛卫中,汪新华,等.QuEchERS-高效液相色谱柱后衍生法测定茶叶中10种氨基甲酸酯类农药残留[J].食品工业科技,2018,39(14):190-193.Wang XL, Mao WZ, Wang XH, et al. Simultaneous determination of ten carbamate pesticide residues in tea by QuEChERS-HPLC with post-column derivatization[J]. Sci Technol Food Ind, 2018, 39(14):190-193.
[7]黄微,李娜,徐瑞晗,等.加速溶剂萃取-固相萃取净化-气相色谱-串联质谱法检测茶叶中9种拟除虫菊酯类农药残留[J].色谱,2018, 36(12):1303-1310.Huang H, Li N, Xu RH, et al. Determination of nine pyrethroid pesticide residues in tea by gas chromatography-tandem mass spectrometry combined with accelerated solvent extraction and solid phase extraction[J]. Chin J Chromatogr, 2018, 36(12):1303-1310.
[8]王秀丽,贾彦博,李玮,等.固相萃取-气相色谱质谱内标法测定茶叶中噻螨酮和喹螨醚[J].中国卫生检验杂志,2018, 28(15):1817-1820.Wang XL, Jia YB, Li W, et al. Determination of hexythiazox and fenazaquin in tea by solid phase extraction-gas chromatographic mass spectrometry with interal standard method[J]. Chin J Health Lab Technol,2018,28(15):1817-1820.
[9]李晔,郭蒙京,袁佗.气相色谱-质谱法测定茶叶中溴虫腈、啶虫脒、茚虫威、三氯杀螨醇及拟除虫菊酯等11种农药残留[J].中国卫生检验杂志,2016, 26(11):1579-1581,1584.Li Y, Guo MJ, Yuan T. Determination of 11 pesticide residues, such as chlorfenapyr, acetamiprid, indoxacarb, dicofol and synthetic pyrethroids in tea by gas chromatography-mass spectrometry[J]. Chin J Health Lab Technol, 2016, 26(11):1579-1581, 1584.
[10]褚能明,孟霞,康月琼,等.分散固相萃取-气相色谱-串联质谱法测定茉莉花茶中86种农药残留[J].食品科学,2016, 37(24):239-246.Chu NM, Meng X, Kang YQ, et al. Determination of 86 pesticide residues in jasmine tea by dispersive solid-phase extraction combined with gas chromatography-tandem mass spectrometry[J]. Food Sci, 2016, 37(24):239-246.
[11]黄田田,汤桦,董晓倩,等.多壁碳纳米管QuEChERS-气相色谱法测定茶叶中23种有机磷农药残留量[J].食品科学,2018, 39(06):315-321.Huang TT, Tang H, Dong XQ, et al. Determination of 23organophosphorus pesticide residues in tea by QuEChERS extraction with multi-walled carbon nanotubes(MWCNTs)coupled to gas chromatography[J]. Food Sci, 2018, 39(6):315-321.
[12]贾玮,黄峻榕,凌云,等.高效液相色谱-串联质谱法同时测定茶叶中290种农药残留组分[J].分析测试学报,2013, 32(01):9-22.Jia W, Huang JR, Ling Y, et al. Determination of 290 pesticide residues in tea by high performance liquid chromatography-tandem mass spectrometry[J]. J Instrum Anal, 2013, 32(1):9-22.
[13] Zhao CL, Ding RY, Huo LG, et al. Determination of pesticide residues in tea by gas chromatography/triple quadrupole mass spectrometry with solid-phase extraction[J]. J AOAC Int, 2014, 97(4):1001-1006.
[14] Xue H, Shao RL, Shi TQ, et al. A multi-residue method for the determination of pesticides in tea using multi-walled carbon nanotubes as a dispersive solid phase extraction absorbent[J]. Food Chem, 2014,153(15):121-129.
[15]刘腾飞,杨代凤,董明辉,等.分散固相萃取-气相色谱法测定茶鲜叶中7种拟除虫菊酯类农药残留[J].农药学学报,2015, 17(5):571-578.Liu TF, Yang DF, Dong MH, et al. Determination of pyrethroid residues in fresh tea leaves by dispersive solid phase extraction and gas chromatography[J]. Chin J Pest Sci, 2015, 17(5):571-578.
[16]蓝梦哲,林绪,刘雅琼,等.液相色谱-串联质谱法同时测定8种花草茶中77种农药残留[J].色谱,2018, 36(9):938-945.Lan MZ, Lin X, Liu YQ, et al. Simultaneous determination of 77 pesticide residues in eight kinds of herbal tea by liquid chromatography-tandem mass spectrometry[J]. Chin J Chromatogr, 2018, 36(9):938-945.
[17]楼正云,陈宗懋,罗逢健,等.固相萃取-气相色谱法测定茶叶中残留的92种农药[J].色谱,2008(05):568-576.Lou ZY, Chen ZM, Luo FJ, et al. Determination of 92 pesticide residues in tea by gas chromatography with solid-phase extraction[J]. Chin J Chromatogr, 2008,(5):568-576.
[18] Lehotay SJ, De KA, Hiemstra M. Validation of a fast and easy method for the determination of residues from 229 pesticides in fruits and vegetables using gas and liquid chromatography and mass spectrometric detection[J].J AOAC Int, 2005, 88(2):595-614.
[19] EU, Document No. SANCO/10476/2003. Quality control procedures for pesticide residues analysis. Guidelines for residues monitoring in the European Union[S].
[20]贺利民,刘祥国,曾振灵.气相色谱分析农药残留的基质效应及其解决方法[J].色谱,2008,(1):98-104.He LM, Liu XG, Zeng ZL. Solutions to matrix-induced response enhancement in pesticide residue analysis by gas chromatography[J].Chin J Chromatogr, 2008,(1):98-104.