毛细管柱气相色谱法测定食品中农药残留量的研究
摘要
化学农药使用后，在环境中受阳光、土壤微生物、植物体内酶系等的分解作用，以及
在水中的水解作用，农药逐渐降解而消失毒性。没有解毒的农药产生有毒的代谢物残留在
作物上或环境中，污染食品及生活环境，人畜长期少量吸入并在体内积累，可能发生毒害
作用，这就是人们关注的农药残毒问题。残毒农药进入人体的途径主要来自食品。因此，
世界各国都规定了食品中农药最大残留限量(MRL)，控制农药残留量，防止农药残毒。
在农药残留量分析中，样品中所含的农药量极少，前处理十分复杂，测定样品时对方法的
准确度和精密度要求并不是很高，如回收率达100％±20％即可，但要求方法的灵敏度高，
即能检出样品中的微量农药。本论文共分五章：
第一章，综述了近五年国内外食品、植物等中农药残留量的气相色谱分析方法，比较
了几种样品前处理方法的应用，以及在测定样品过程中，固定液和检测器的使用情况，并
对农药残留分析的发展趋势和要求进行了讨论。
第二章，研究了用弹性石英毛细管柱气相色谱-电子捕获检测器法测定水果、蔬菜中甲
氰菊酯残留量的试验方法，检测限为0.017mg／kg。
第三章，研究了用液-液分配萃取技术、采用火焰光度检测器测定粮食、蔬菜中9种
有机磷农药残留量的方法。对样品的前处理，尤其是水分的除去作了一定的探讨。结果表
明，9种有机磷农药分离好，且方法快速、灵敏，完全符合实际应用需要。
第四章，采用环己烷-丙酮混合溶剂提取、柱层析净化、环己烷-石油醚混合溶剂洗
脱，研究了用毛细管柱气相色谱-电子捕获检测器法测定水果、蔬菜中20种有机氯和拟除
虫菊酯农药残留量的试验方法。
第五章，采用高速匀浆法提取、柱层析法净化技术，研究了用毛细管柱气相色谱-火焰
光度检测器法测定银杏叶中12种有机磷农药残留量的分析方法。
Chemical pesticides will gradually degrade and their toxicity will disappear due to the decomposition reaction of sunlight in environment, microbe in soil, enzyme in plants and hydrolysis in water after their application. However, pesticide residues still remain in the crops, the soil and the groundwater and constitute a health risk because of their residual toxicity. To protect consumers' health, many countries have restricted the usage of these deleterious chemicals and have established maximum residue levels (MRLs) to control their levels in foods. In the process of analyzing pesticide residues, sample's preparation is very complicated because there is a very small amount pesticide residued in samples. Therefore, requirement of method's accuracy and precision are not very high, fortified sample recoveries can be between 80% and 120%. But the method's sensitivity must be very high in order to be able to determine trace pesticide. Five chapters are consisted of the paper:
In the first chapter, the new development was focused on the reports which were evolved over the last 5 years. The determinations of insecticides, herbicides, miticides, etc. in foods, plants, human body fluids were reviewed. The several methods used in sample preparation, the applications of fixed-fluids and detectors were compared. In the meantime, the developing trends of pesticides residual analysis were discussed.
In the second chapter, a simple, rapid, economical and efficient method was described for the determination of residues of fenpropathrin in apple and eggplant with spring quartz capillary column. The mixture of cyclohexane-acetone was used to extract samples, following by a cleanup technique on a column packed with Florisil using the mixture of cyclohexane-petroleum ether to elute the samples. The samples were analyzed by gas chrornatography-electron capture detector (GC-ECD) with detection limit of (LOD) 0.017mg /kg.
In the third chapter, a method based on liquid-liquid extraction following by gas chromatography with flame-photometric detector (FPD) was developed for determining 9 organophosphorus pesticide residues in cereal and kidney bean samples. The preparation of samples and the procedure of eliminating water were studied. It was shown that good separations were obtained using a fused-silica capillary column DB-1701 by the optimized temperature program. The process was rapid, and the method was sensitive and practical.
In the fourth chapter, a simple and rapid method was described for the determination of 20 kinds of organochlorine pesticide and pyrethroid residues in vegetable and fruit. The mixture of cyclohexane-acetone was used to extract the samples, followed by a cleanup technique on a column packed with Florisil using the mixture of cyclohexane-petroleum ether to elute the samples. The samples were concentrated by rotary vacuum evaporator and analyzed by gas chromatography-electron capture detector (GC-ECD).
In the fifth chapter, a method based on homogenized extraction at high speed and cleanup on column packed with Florisil was used to determine the residues of 12 organophosphorus pesticides in Ginkgo Biloba leaves by gas chromatography with flame-photometric detector (GC-FPD).
在水中的水解作用，农药逐渐降解而消失毒性。没有解毒的农药产生有毒的代谢物残留在
作物上或环境中，污染食品及生活环境，人畜长期少量吸入并在体内积累，可能发生毒害
作用，这就是人们关注的农药残毒问题。残毒农药进入人体的途径主要来自食品。因此，
世界各国都规定了食品中农药最大残留限量(MRL)，控制农药残留量，防止农药残毒。
在农药残留量分析中，样品中所含的农药量极少，前处理十分复杂，测定样品时对方法的
准确度和精密度要求并不是很高，如回收率达100％±20％即可，但要求方法的灵敏度高，
即能检出样品中的微量农药。本论文共分五章：
第一章，综述了近五年国内外食品、植物等中农药残留量的气相色谱分析方法，比较
了几种样品前处理方法的应用，以及在测定样品过程中，固定液和检测器的使用情况，并
对农药残留分析的发展趋势和要求进行了讨论。
第二章，研究了用弹性石英毛细管柱气相色谱-电子捕获检测器法测定水果、蔬菜中甲
氰菊酯残留量的试验方法，检测限为0.017mg／kg。
第三章，研究了用液-液分配萃取技术、采用火焰光度检测器测定粮食、蔬菜中9种
有机磷农药残留量的方法。对样品的前处理，尤其是水分的除去作了一定的探讨。结果表
明，9种有机磷农药分离好，且方法快速、灵敏，完全符合实际应用需要。
第四章，采用环己烷-丙酮混合溶剂提取、柱层析净化、环己烷-石油醚混合溶剂洗
脱，研究了用毛细管柱气相色谱-电子捕获检测器法测定水果、蔬菜中20种有机氯和拟除
虫菊酯农药残留量的试验方法。
第五章，采用高速匀浆法提取、柱层析法净化技术，研究了用毛细管柱气相色谱-火焰
光度检测器法测定银杏叶中12种有机磷农药残留量的分析方法。
Chemical pesticides will gradually degrade and their toxicity will disappear due to the decomposition reaction of sunlight in environment, microbe in soil, enzyme in plants and hydrolysis in water after their application. However, pesticide residues still remain in the crops, the soil and the groundwater and constitute a health risk because of their residual toxicity. To protect consumers' health, many countries have restricted the usage of these deleterious chemicals and have established maximum residue levels (MRLs) to control their levels in foods. In the process of analyzing pesticide residues, sample's preparation is very complicated because there is a very small amount pesticide residued in samples. Therefore, requirement of method's accuracy and precision are not very high, fortified sample recoveries can be between 80% and 120%. But the method's sensitivity must be very high in order to be able to determine trace pesticide. Five chapters are consisted of the paper:
In the first chapter, the new development was focused on the reports which were evolved over the last 5 years. The determinations of insecticides, herbicides, miticides, etc. in foods, plants, human body fluids were reviewed. The several methods used in sample preparation, the applications of fixed-fluids and detectors were compared. In the meantime, the developing trends of pesticides residual analysis were discussed.
In the second chapter, a simple, rapid, economical and efficient method was described for the determination of residues of fenpropathrin in apple and eggplant with spring quartz capillary column. The mixture of cyclohexane-acetone was used to extract samples, following by a cleanup technique on a column packed with Florisil using the mixture of cyclohexane-petroleum ether to elute the samples. The samples were analyzed by gas chrornatography-electron capture detector (GC-ECD) with detection limit of (LOD) 0.017mg /kg.
In the third chapter, a method based on liquid-liquid extraction following by gas chromatography with flame-photometric detector (FPD) was developed for determining 9 organophosphorus pesticide residues in cereal and kidney bean samples. The preparation of samples and the procedure of eliminating water were studied. It was shown that good separations were obtained using a fused-silica capillary column DB-1701 by the optimized temperature program. The process was rapid, and the method was sensitive and practical.
In the fourth chapter, a simple and rapid method was described for the determination of 20 kinds of organochlorine pesticide and pyrethroid residues in vegetable and fruit. The mixture of cyclohexane-acetone was used to extract the samples, followed by a cleanup technique on a column packed with Florisil using the mixture of cyclohexane-petroleum ether to elute the samples. The samples were concentrated by rotary vacuum evaporator and analyzed by gas chromatography-electron capture detector (GC-ECD).
In the fifth chapter, a method based on homogenized extraction at high speed and cleanup on column packed with Florisil was used to determine the residues of 12 organophosphorus pesticides in Ginkgo Biloba leaves by gas chromatography with flame-photometric detector (GC-FPD).
引文
[1] 刘虎威．气相色谱方法及应用[M]．北京：化学工业出版社，2000．127
[2] 金军，赵国栋，崔云，等．高效液相色谱／大气压电离质谱(HPLC／APIMS)在农药残留分析中的应用[J]．化学通报，1999(6)：25
[3] 仲维科，郝戬，樊耀波，等．食品农药残留分析进展[J]．分析化学．2000，28(7)：904～910
[4] Song H, Kim J, Ann T L, et al. Analytical method development for 18 pesticides in house dust and settled residues using SEC, SPE, TMS methylation, and GC-MS[J]. J Chromatogr Sci, 2001, 39(3): 101
[5] 李金培．大口径毛细竹柱气相色谱测定烟草中6种拟除虫菊酯农药残留量[J]．分析化学，2001，29(7)：793-795
[6] Navickiene S, Polese L, Minellie V, et al. A simplified method for the determination of fenpropathrin residues in fruits[J]. Chromatogr, 1999, 49(3-4): 212
[7] Yoon H R, Cho S Y, Kim J M, et al. Analysis of multi-component pesticide residues in herbal medicines by GC-MS with electron impact ionization and with positive-and negative-ion chemical ionization[J]. Chromatogr, 1999, 49(9-10): 525
[8] Russo M V. Fast solid phase extraction of polychlorobiphenyls and chlorinated pesticide residues from mussels using sep-pak catridges[J]. Chromatogr, 2000, 51(1-2): 71-76
[9] Nunes M J, Cam(?)es M F, Fournier[J]. Analysis of organophosphorus, organochlorine and pyrethroid insecticides in medicinal plants[J].chromatogr, 1997, 44(9-10): 505
[10] Szymezyk K, Malalczewska M. Gas chromatography analysis of organophosphorous pesticides in plant samples[J]. Chromatogr, 1998, 48(1-2): 156
[11] Colum(?) A, C(?)rdenass S, Gallego M, et al. Semiautomatic method for the screening and determination of 23 organochlorine pesticides in horticultural samples by gas chromatography with electron-capture detection[J]. J Chromatogr A, 1999, 849(1): 235-243
[12] Norman K N T, Panton S H W. Supercritical fluid extraction and quantitative determination of organophosphorus pesticide residues in wheat and maize using gas chromatography with flame photometric and mass spectrometric detection[J]. J Chromatogr A, 2001, 907(1-2): 247-255
[13] Fem(?)ndez M, Padr(?)n C, Marconi L, et al. Determination of organophosphorus pesticides in honeybees after solid-phase microextraction[J]. J Chromatogr A, 2001, 922(1-2): 257-265
[14] Kim D H, Heo G S, Lee D W. Determination of organophosphorus pesticides in wheat flour by supercritical fluid extraction and gas chromatohraphy with nitrogen-phosphorus detection[J]. J Chromatogr A, 1998, 824(1): 63-70
[15] Stan H J. Pesticide residue analysis in foodstuffs applying capillary gas chromatography with mass spectrometric detection/State-of-the-art use of modified DEG-multimethod S19 and automated data evaluation[J]. J Chromatogr A, 2000, 892(1-2): 347-377
[16] Kaushik N, Handa S K. New clean-up method for gas chromatographic analysis of pyrethroid residues[J]. Chromatogr, 1997, 46(3-4): 209
[17] 朱梦栩，王勇．大口径毛细竹气相色谱柱测定茶叶中三氯杀螨醇的残留量[J]．色谱，2000，18(1)：64-66
[18] Paoli M D, Barbina M T, Damiano V, et al. Simplified determination of combined residues of prochloraz and its metabolities in vegetable, fruit and wheat samples by gas chromatography[J]. J Chromatogr A, 1997, 765(1): 127-131
[19] Lino C M, Silveira M I N D. Extraction and clean-up methods for the determination of organochlorine pesticide residues in medicinal plants[J]. J Chromatogr A, 1997, 769(2): 275-283
[20] Haj(?)lov(?) J, Holadov(?) K, Kocoureak V, et al. Matrx-induced effects: a critical point in the gas chromatographic analysis of pesticide residues[J]. J Chromatogr A, 1998, 800(2): 283-295
[21] Font J, Marsal A. Determination of organochlorine pesticides in skins and leather by gas chromatography[J]. J Chromatogr A, 1998, 811(1-2): 256-260
[22] Wang J H, Qiang X, Kui J. Supercritical fluid extraction and off-line clean-up for the analysis of organochlorine pesticide residues in garlic[J]. J Chromatogr A, 1998, 818(1): 138-143
[23] Jim(?)nez J J, Bernal J L, Nozal M J D, et al. Gas chromatography with electron-capture and nitrogen-phosphorus detection in the analysis of pesticides in honey after elution from a Florisil column[J]. J Chromatogr A, 1998, 823(1-2): 381-387
[24] Jim(?)nez J J, Bernal J L, Nozal M J D, et al. Solid-phase microextraction applied to the analysis of pesticide residues in honey using gas chromatography with electron-capture detection[J]. J Chromatogr A, 1998, 829(1-2): 269-277
[25] Oliva J, Navarro S, Barba A, et al. Determination of chlorpyrifos, penconazole, fenarimol, vinclozolin and metalaxyl in grapes, must and wine by on-line microextraction and gas chromatography[J]. J Chromatogr A, 1999, 833(1): 43-51
[26] Lentza-Rizos CH, Avaramides E J. Inclusion of the fungicide chlozolinate in a multiresidue method[J]. J Chromatogr A, 1999, 858(1): 123-131
[27] Saikia N, Kulshrestha G. New gas chromatographic method for residue determination of dithiopyr in soil, wheat grain and straw[J]. J Chromatogr A, 1999, 864(2): 351-353
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[29] Jim(?)nez J J, Bernal J L, Nozal M J D, et al. Analysis of pesticide residues in wine by solidphase extraction and gas chromatography with electron capture and nitrogen-phosphorus detection[J]. J Chromatogr A, 2001, 919(1): 147-156
[30] Lentza-Rizos CH, Avramides E J, Visi E. Determination of residues of endosulfan and five pyrethroid insecticides in virgin olive oil using gas chromatography with electron-capture detection[J]. J Chromatogr A, 2001, 921(2): 297-304
[31] 张莹，黄克强，李拥军．气相色谱法测定茶叶中多种有机磷农药残留量[J]．色谱，2001，19(3)：273-275
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[43] Dubey J.K, Heberer T, Stan H J. Determination of ethylenethiourea in food commodities by a two-step derivatization method and gas chromatography with electron-capture and nitrogenphosphorus Detection. J. Chromatogr A. [J], 1997, 765(1): 31-38
[44] Amirav A, Jing H W. Simultaneous pulsed flame photometric and mass spectrometric detection for enhanced pesticide analysis capabilities. J Chromatogr A.[J]. 1998, 814(1): 133-150
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[46] 刘虎威．气相色谱方法及应用[M]．北京：化学工业出版社，2001．251
[47] 梁文平，郑斐能，王仪，等．21世纪农药发展的趋势：绿色农药与绿色农药制剂[J]．农药，1999，38(9)：1-2
[48] 汪正范．色谱定性与定量[M]．北京：化学工业出版社，2001．27-28
[2] 金军，赵国栋，崔云，等．高效液相色谱／大气压电离质谱(HPLC／APIMS)在农药残留分析中的应用[J]．化学通报，1999(6)：25
[3] 仲维科，郝戬，樊耀波，等．食品农药残留分析进展[J]．分析化学．2000，28(7)：904～910
[4] Song H, Kim J, Ann T L, et al. Analytical method development for 18 pesticides in house dust and settled residues using SEC, SPE, TMS methylation, and GC-MS[J]. J Chromatogr Sci, 2001, 39(3): 101
[5] 李金培．大口径毛细竹柱气相色谱测定烟草中6种拟除虫菊酯农药残留量[J]．分析化学，2001，29(7)：793-795
[6] Navickiene S, Polese L, Minellie V, et al. A simplified method for the determination of fenpropathrin residues in fruits[J]. Chromatogr, 1999, 49(3-4): 212
[7] Yoon H R, Cho S Y, Kim J M, et al. Analysis of multi-component pesticide residues in herbal medicines by GC-MS with electron impact ionization and with positive-and negative-ion chemical ionization[J]. Chromatogr, 1999, 49(9-10): 525
[8] Russo M V. Fast solid phase extraction of polychlorobiphenyls and chlorinated pesticide residues from mussels using sep-pak catridges[J]. Chromatogr, 2000, 51(1-2): 71-76
[9] Nunes M J, Cam(?)es M F, Fournier[J]. Analysis of organophosphorus, organochlorine and pyrethroid insecticides in medicinal plants[J].chromatogr, 1997, 44(9-10): 505
[10] Szymezyk K, Malalczewska M. Gas chromatography analysis of organophosphorous pesticides in plant samples[J]. Chromatogr, 1998, 48(1-2): 156
[11] Colum(?) A, C(?)rdenass S, Gallego M, et al. Semiautomatic method for the screening and determination of 23 organochlorine pesticides in horticultural samples by gas chromatography with electron-capture detection[J]. J Chromatogr A, 1999, 849(1): 235-243
[12] Norman K N T, Panton S H W. Supercritical fluid extraction and quantitative determination of organophosphorus pesticide residues in wheat and maize using gas chromatography with flame photometric and mass spectrometric detection[J]. J Chromatogr A, 2001, 907(1-2): 247-255
[13] Fem(?)ndez M, Padr(?)n C, Marconi L, et al. Determination of organophosphorus pesticides in honeybees after solid-phase microextraction[J]. J Chromatogr A, 2001, 922(1-2): 257-265
[14] Kim D H, Heo G S, Lee D W. Determination of organophosphorus pesticides in wheat flour by supercritical fluid extraction and gas chromatohraphy with nitrogen-phosphorus detection[J]. J Chromatogr A, 1998, 824(1): 63-70
[15] Stan H J. Pesticide residue analysis in foodstuffs applying capillary gas chromatography with mass spectrometric detection/State-of-the-art use of modified DEG-multimethod S19 and automated data evaluation[J]. J Chromatogr A, 2000, 892(1-2): 347-377
[16] Kaushik N, Handa S K. New clean-up method for gas chromatographic analysis of pyrethroid residues[J]. Chromatogr, 1997, 46(3-4): 209
[17] 朱梦栩，王勇．大口径毛细竹气相色谱柱测定茶叶中三氯杀螨醇的残留量[J]．色谱，2000，18(1)：64-66
[18] Paoli M D, Barbina M T, Damiano V, et al. Simplified determination of combined residues of prochloraz and its metabolities in vegetable, fruit and wheat samples by gas chromatography[J]. J Chromatogr A, 1997, 765(1): 127-131
[19] Lino C M, Silveira M I N D. Extraction and clean-up methods for the determination of organochlorine pesticide residues in medicinal plants[J]. J Chromatogr A, 1997, 769(2): 275-283
[20] Haj(?)lov(?) J, Holadov(?) K, Kocoureak V, et al. Matrx-induced effects: a critical point in the gas chromatographic analysis of pesticide residues[J]. J Chromatogr A, 1998, 800(2): 283-295
[21] Font J, Marsal A. Determination of organochlorine pesticides in skins and leather by gas chromatography[J]. J Chromatogr A, 1998, 811(1-2): 256-260
[22] Wang J H, Qiang X, Kui J. Supercritical fluid extraction and off-line clean-up for the analysis of organochlorine pesticide residues in garlic[J]. J Chromatogr A, 1998, 818(1): 138-143
[23] Jim(?)nez J J, Bernal J L, Nozal M J D, et al. Gas chromatography with electron-capture and nitrogen-phosphorus detection in the analysis of pesticides in honey after elution from a Florisil column[J]. J Chromatogr A, 1998, 823(1-2): 381-387
[24] Jim(?)nez J J, Bernal J L, Nozal M J D, et al. Solid-phase microextraction applied to the analysis of pesticide residues in honey using gas chromatography with electron-capture detection[J]. J Chromatogr A, 1998, 829(1-2): 269-277
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