蔬菜中农药多残留气相色谱—质谱法测定中的基质效应研究
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摘要
选择17种蔬菜基质对29种农药在气相色谱-质谱测定过程中的基质效应进行研究。通过比较不同的基质种类和浓度、不同农药种类和浓度、进样口和色谱柱活性点类型与数量、进样口温度、进样方式和进样体积等条件下的基质效应差别,阐述基质效应的产生原因及其影响因素。同时比较了不同净化方式的去杂能力,以及评价了分析物保护剂对基质效应的补偿效果。结果如下:
1.基质效应的产生根本原因是进样口和色谱系统本身存在的以及受到污染产生的活性点。活性点数量越多,基质效应越强。
2.几乎所有的基质都会产生基质效应,基质效应随基质含量的增大而增强;青椒和香菇的基质效应极显著,藕的基质效应不显著;基质中某些萜类和芳香取代物可能是引起基质增强效应的物质。
3.有机磷类(如甲胺磷、乙酰甲胺磷、氧乐果、久效磷、三唑磷和保棉磷等)和唑类(如氟菌唑、氟硅唑和多效唑)以及天然化合物嘧菌酯的基质效应较强;农药浓度越小受基质效应影响越大。
4.调整仪器条件以及采用适当的进样技术可以有效降低基质效应对测定结果的影响。如:对进样口及色谱系统进行有效的维护,适当提高进样口温度,脉冲进样,较大体积进样等。
5.采用分析物保护剂对敏感农药具有较好的补偿效果,可以改善峰形、提高灵敏度以及测定结果的准确性。
In this paper, 29 pesticides in 17 sorts of vegetable matrices were collected for the study of matrix effects by GC-MS. In order to illuminate the courses and factors of matrix effects, the differences of matrix effects of different sorts and concentrations of matrices and pesticides,number and type of active sites in the inlet and GC column,inlet temperature, injection technique and volume were compared .At the same time, the capabilities to eliminate matrix components of different clean-up methods and the analyte protectants compensation for matrix effects were evaluted. The main results were showed as follow.
1.The active sites in the inlet and GC column are essential causes which lead to matrix effects, those active sites exist originally and produced by contaminations are involved.
2. matrices with complicated components such as green pepper and mushroom produce higher matrix effect; Lotus root without obvious matrix effect; higher concentration of matrix can produces higher matrix effect; Some terpenes and ramifications of aromatic components can produce matrix effects probably
3. except for some organophosphoros pesticides(methamidophos, acephate,omethoate, monocrotophos, triazophos and azinphos-methyl) ,some zole pesticides (triflumizole, flusilazole, paclobutrazol)and some crudes such as azoxytrobin are much easier affected with matrix effect; pesticides with lower concentration produce lower matrix effect.
4.To adjust the instrument and let it at its best or use appropriate injection technology ,such as available maintenance of inlet and GC column, improveing the temperature of inlet,injection with pulsed splitless and using larger injection volumn.
5.Some susceptive pesticides can get better peak shape and higher sensitivity with An-alyte protectants,that means the analyte protectants can compensate matrix effect very we-ll.
1.基质效应的产生根本原因是进样口和色谱系统本身存在的以及受到污染产生的活性点。活性点数量越多,基质效应越强。
2.几乎所有的基质都会产生基质效应,基质效应随基质含量的增大而增强;青椒和香菇的基质效应极显著,藕的基质效应不显著;基质中某些萜类和芳香取代物可能是引起基质增强效应的物质。
3.有机磷类(如甲胺磷、乙酰甲胺磷、氧乐果、久效磷、三唑磷和保棉磷等)和唑类(如氟菌唑、氟硅唑和多效唑)以及天然化合物嘧菌酯的基质效应较强;农药浓度越小受基质效应影响越大。
4.调整仪器条件以及采用适当的进样技术可以有效降低基质效应对测定结果的影响。如:对进样口及色谱系统进行有效的维护,适当提高进样口温度,脉冲进样,较大体积进样等。
5.采用分析物保护剂对敏感农药具有较好的补偿效果,可以改善峰形、提高灵敏度以及测定结果的准确性。
In this paper, 29 pesticides in 17 sorts of vegetable matrices were collected for the study of matrix effects by GC-MS. In order to illuminate the courses and factors of matrix effects, the differences of matrix effects of different sorts and concentrations of matrices and pesticides,number and type of active sites in the inlet and GC column,inlet temperature, injection technique and volume were compared .At the same time, the capabilities to eliminate matrix components of different clean-up methods and the analyte protectants compensation for matrix effects were evaluted. The main results were showed as follow.
1.The active sites in the inlet and GC column are essential causes which lead to matrix effects, those active sites exist originally and produced by contaminations are involved.
2. matrices with complicated components such as green pepper and mushroom produce higher matrix effect; Lotus root without obvious matrix effect; higher concentration of matrix can produces higher matrix effect; Some terpenes and ramifications of aromatic components can produce matrix effects probably
3. except for some organophosphoros pesticides(methamidophos, acephate,omethoate, monocrotophos, triazophos and azinphos-methyl) ,some zole pesticides (triflumizole, flusilazole, paclobutrazol)and some crudes such as azoxytrobin are much easier affected with matrix effect; pesticides with lower concentration produce lower matrix effect.
4.To adjust the instrument and let it at its best or use appropriate injection technology ,such as available maintenance of inlet and GC column, improveing the temperature of inlet,injection with pulsed splitless and using larger injection volumn.
5.Some susceptive pesticides can get better peak shape and higher sensitivity with An-alyte protectants,that means the analyte protectants can compensate matrix effect very we-ll.
引文
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3 洪振涛, 张卫锋等.应用固相萃取分析蔬菜水果中农药残留的研究. 广东化工,2005(7):8-10,18
4 郜红建 蒋新等. 叶类蔬菜有机氯农药残留测定过程中的提取和净化.环境化学,2004, 23(5):587-590
5 耿昱,郭寅龙. 固相微萃取/气相色谱/质谱联用技术在农药残留物分析中的应用. 分析测试技术与仪器,2001,7(4):230-235
6 金晓英,袁东星.动态液相微萃取-气相色谱法测定水样中有机磷农药残留.分析化学 2005,33(3):347-350
7 孔祥红,何学文.毛细管色谱法测定水果、蔬菜中 17 种有机氯农药的残留量.化学分析计量,2004,13(1):21-23
8 李永香,黄勇等.C/MS 内标法同时测定食品中 31 种有机磷农残的实验方法研究.中国卫生检疫杂志,2004,14(6):677-679
9 李金培.大口径毛细管柱气相色谱测定烟草中 6 种拟除虫菊脂农药残留量.分析化学,2001,29(7):793-795
10 李锋格,全晓盾.气相色谱-质谱法同时测定番茄制品中拟除虫菊酯类农药残留.分析化学,2005,33(6):838-842
11 刘凌,裴志国等.微波辅助溶剂提取法对土壤中残留苯并咪唑类农药的测定.分析试验室,2004,23(4):34-37
12 刘凡岩,马育松.固相萃取技术在农残分析中的应用.河北大学学报,2005,25(1):109-115
13 刘咏梅,王志华等.凝胶渗透色谱净化一气相色谱分离同时测定糙米中 50 种有机磷农药残留.分析化学,2005,33(6) :808-810
14 MengChin-Kai,Stephen L Werner 等.固相萃取和液相色谱/质谱/质谱在正离子和负离子模式下检测水中的农药残留.环境化学,2008,27(1):127-130
15 梅文泉,黎其万等.花椰菜中乙酰甲胺磷、氧化乐果两种农药残留的分离测定.云南农业大学学报,2004,19(6):681-684
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17 汤桦,孔祥虹. 浓缩苹果汁中多种拟除虫菊酯类农药残留量的气相色谱-质谱测定方法. 分析试验室,2004,23(8):25-27
18 万益群,李申杰等.中草药中有机磷及氨基甲酸酯类农药残留量的 GC-MS 测定.分析试验室,2007,26(6):81-84
19 武中平,高巍等.氨基甲酸酯类农药残留测定方法的研究进展.江苏化工,2004,32(5):24-27
20 谢文,丁慧瑛等.硅胶活性碳柱净化一气相色谱法测定茶叶中多种有机磷农药残留量. 理化检验,2005,41:232-234
21 赵海峰,刘永波.GC-MSD 法快速测定蔬菜中四种农药残留方法的改进.化学分析方法, 2004,13(5):25-27
22 张伟国,陶传江等.GC/MS/AMDIS 技术用于韭菜中残留农药的确证.质谱学报,2004.8,25(3):141-144,171
23 张亚莉,阎正.中药中农药残留分析技术进展.河北工业科技,2004,21(5):56-59
24 Amirav , S Dagan.A Direct Sample Introduction Device for Mass Spectrometry Studies and GC-MS Analysis.Europ Mass Spectrom,1997 (3):105-111
25 Anastassiades M,S J Lehotay,et al.Fast and Easy Multiresidue Method Employing Acetonitrile Extraction/Partitioning and Dispersive Solid-Phase Extraction for the Determination of Pesticide Residues in Produce. J AOAC intern,2003,86(2):412-431
26 Anastassiades M,Kterina Mastovska,et al.Application of Gas Chromatography in Food Analysis.J Chromatography A,2003,1015:163-184
27 Anastassiades M, K Mastovska, et al.Evaluation of analyte protectants to improve gas chromatographic analysis of pesticides. J Chromatogr A,2003,1015:163-184
28 Cajka T,Mastovska K,et al..Use of automated direct sample introduction with analyte protectants in the gc-ms analysis of pesticide resides.Journal of Separation Science,2005,28:1048-1060
29 Chars G C-Y,Chars W T.Plasma-related matrix effects in inductively coupled plasma-atomic emissionspectrometry by group I and group II matrix-elements.Spectrochimica Acta Part B, 58 (2003):1301-1317
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31 Ding W H, C H Liu,et al.Analysis of chlorophenoxy acid herbicides in water by large-volume on-line derivatization and gas chromatography-mass spectrometry.J Chromatog A,2000,896:111-116
32 Eike Kleine-Benne,Dirk Brmer,et al.Automated Liner-Exchange for GC-Injectors-New Concepts for Handling Dirty Samples.2004
33 Erney D R,Gillespie A M,et al..Explanation of the matrix-induced chromatographic response enhancement of organophosphorus pesticides during open tubular column gas chromatography with splitless or hot on-column injection and flame photometric detection.J Chromatogr,1993,638(1):57-63
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2 丁毅,徐光曙.气相色谱-二级质谱联用技术测定有机磷农药.现代农药, 2006,5(1):17-19
3 洪振涛, 张卫锋等.应用固相萃取分析蔬菜水果中农药残留的研究. 广东化工,2005(7):8-10,18
4 郜红建 蒋新等. 叶类蔬菜有机氯农药残留测定过程中的提取和净化.环境化学,2004, 23(5):587-590
5 耿昱,郭寅龙. 固相微萃取/气相色谱/质谱联用技术在农药残留物分析中的应用. 分析测试技术与仪器,2001,7(4):230-235
6 金晓英,袁东星.动态液相微萃取-气相色谱法测定水样中有机磷农药残留.分析化学 2005,33(3):347-350
7 孔祥红,何学文.毛细管色谱法测定水果、蔬菜中 17 种有机氯农药的残留量.化学分析计量,2004,13(1):21-23
8 李永香,黄勇等.C/MS 内标法同时测定食品中 31 种有机磷农残的实验方法研究.中国卫生检疫杂志,2004,14(6):677-679
9 李金培.大口径毛细管柱气相色谱测定烟草中 6 种拟除虫菊脂农药残留量.分析化学,2001,29(7):793-795
10 李锋格,全晓盾.气相色谱-质谱法同时测定番茄制品中拟除虫菊酯类农药残留.分析化学,2005,33(6):838-842
11 刘凌,裴志国等.微波辅助溶剂提取法对土壤中残留苯并咪唑类农药的测定.分析试验室,2004,23(4):34-37
12 刘凡岩,马育松.固相萃取技术在农残分析中的应用.河北大学学报,2005,25(1):109-115
13 刘咏梅,王志华等.凝胶渗透色谱净化一气相色谱分离同时测定糙米中 50 种有机磷农药残留.分析化学,2005,33(6) :808-810
14 MengChin-Kai,Stephen L Werner 等.固相萃取和液相色谱/质谱/质谱在正离子和负离子模式下检测水中的农药残留.环境化学,2008,27(1):127-130
15 梅文泉,黎其万等.花椰菜中乙酰甲胺磷、氧化乐果两种农药残留的分离测定.云南农业大学学报,2004,19(6):681-684
16 王建华,张艺兵等.微波处理-气相色谱法测定含硫蔬菜中的多类农药残留.分析测试学报,2005,24(1):100-102
17 汤桦,孔祥虹. 浓缩苹果汁中多种拟除虫菊酯类农药残留量的气相色谱-质谱测定方法. 分析试验室,2004,23(8):25-27
18 万益群,李申杰等.中草药中有机磷及氨基甲酸酯类农药残留量的 GC-MS 测定.分析试验室,2007,26(6):81-84
19 武中平,高巍等.氨基甲酸酯类农药残留测定方法的研究进展.江苏化工,2004,32(5):24-27
20 谢文,丁慧瑛等.硅胶活性碳柱净化一气相色谱法测定茶叶中多种有机磷农药残留量. 理化检验,2005,41:232-234
21 赵海峰,刘永波.GC-MSD 法快速测定蔬菜中四种农药残留方法的改进.化学分析方法, 2004,13(5):25-27
22 张伟国,陶传江等.GC/MS/AMDIS 技术用于韭菜中残留农药的确证.质谱学报,2004.8,25(3):141-144,171
23 张亚莉,阎正.中药中农药残留分析技术进展.河北工业科技,2004,21(5):56-59
24 Amirav , S Dagan.A Direct Sample Introduction Device for Mass Spectrometry Studies and GC-MS Analysis.Europ Mass Spectrom,1997 (3):105-111
25 Anastassiades M,S J Lehotay,et al.Fast and Easy Multiresidue Method Employing Acetonitrile Extraction/Partitioning and Dispersive Solid-Phase Extraction for the Determination of Pesticide Residues in Produce. J AOAC intern,2003,86(2):412-431
26 Anastassiades M,Kterina Mastovska,et al.Application of Gas Chromatography in Food Analysis.J Chromatography A,2003,1015:163-184
27 Anastassiades M, K Mastovska, et al.Evaluation of analyte protectants to improve gas chromatographic analysis of pesticides. J Chromatogr A,2003,1015:163-184
28 Cajka T,Mastovska K,et al..Use of automated direct sample introduction with analyte protectants in the gc-ms analysis of pesticide resides.Journal of Separation Science,2005,28:1048-1060
29 Chars G C-Y,Chars W T.Plasma-related matrix effects in inductively coupled plasma-atomic emissionspectrometry by group I and group II matrix-elements.Spectrochimica Acta Part B, 58 (2003):1301-1317
30 Cook J,Beckett M P et al.Multiresidue analysis of pesticides in fresh fruits and vegetables using procedures developed by the Florida Department of Agriculture and Consumer Services.J AOAC intern ,1999 82(6):1419-1435
31 Ding W H, C H Liu,et al.Analysis of chlorophenoxy acid herbicides in water by large-volume on-line derivatization and gas chromatography-mass spectrometry.J Chromatog A,2000,896:111-116
32 Eike Kleine-Benne,Dirk Brmer,et al.Automated Liner-Exchange for GC-Injectors-New Concepts for Handling Dirty Samples.2004
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