40%多·溴·福可湿性粉剂在黄瓜和土壤中的残留分析及消解动态研究
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摘要
本文主要研究了农药溴菌腈和多菌灵在黄瓜和土壤中的残留分析方法、消解动态规律及其最终残留量,以期对40%多·溴·福可湿性粉剂在黄瓜上的安全性使用进行评价,为制定该药安全使用准则、产品登记及溴菌腈在黄瓜上的最大残留限量提供重要的理论及科学依据。主要研究结果如下:
1.分别建立了新型农药溴菌腈在黄瓜和土壤中的气相色谱和气相色谱-串联质谱连用分析方法。样品采用丙酮提取,二氯甲烷对提取液进行萃取。萃取液浓缩用丙酮定容,气相色谱(NPD)和气相色谱-串联质谱联用测定。气相色谱(NPD)的最小检出量为1×10-11 g,溴菌腈在黄瓜和土壤的最低检出浓度为0.1 mg/Kg,在0.1 mg/Kg、0.5 mg/Kg和1 mg/Kg三个添加水平,溴菌腈在黄瓜和土壤中的平均回收率分别为82.57%～87.69%和91.25%～93.09%,相对标准偏差分别为5.37%～6.04%和2.40%～4.32%。气相色谱-串联质谱联用的最小检出量为1×10-11 g,溴菌腈在黄瓜和土壤的最低检出浓度为0.1 mg/Kg,在0.1 mg/Kg、0.5 mg/Kg和1 mg/Kg三个添加水平,溴菌腈在黄瓜和土壤中的平均回收率分别为91.54%～108.93%和99.03%～110.87%,相对标准偏差分别为4.57%～5.85%和4.02%～8.68%。两种分析方法的灵敏度、准确度高,精密度好,均能够满足溴菌腈在黄瓜和土壤中的残留检测需要。
2.分别建立了农药多菌灵在黄瓜和土壤中超高效液相色谱-串联质谱联用和高效液相色谱分析方法。样品采用乙酸乙酯提取,超高效液相色谱-串联质谱联用测定,多反应监测技术确定多菌灵的两对离子m/z 191.2/ 132和m/z 191.2/ 160为定性离子,m/z 191.2/ 160为定量离子。仪器的最小检出量为3×10-12 g,多菌灵在黄瓜和土壤的最低检出浓度为0.01 mg/kg,在0.01 mg/kg、0.05 mg/kg和0.1 mg/kg三个添加水平,多菌灵在黄瓜和土壤中的平均回收率分别为96.75%～101.87%和98.15%～109.48%,相对标准偏差分别为2.77%～3.31%和2.99%～5.64%。两种方法的灵敏度、准确度、精密度等均符合农药残留检测的要求,但液相色谱-串联质谱联用测定的灵敏度更高。高效液相色谱测定多菌灵的最小检出量为2×10-10 g,多菌灵在黄瓜和土壤中的最低检出浓度均为0.1 mg/Kg,在0.1 mg/Kg、0.5 mg/Kg和1 mg/Kg三个添加水平,多菌灵在黄瓜和土壤中的平均回收率分别为86.09%～91.79%和95.30%～97.10%,相对标准偏差分别为2.50%～3.58%和2.13%～3.27%。
3.采用田间试验方法,研究了40%多·溴·福可湿性粉剂在黄瓜和土壤中残留消解动态规律及其最终残留量。通过在山东、河南、浙江和北京一年四地田间试验,对40%多·溴·福可湿性粉剂按推荐剂量2倍处理黄瓜及其土壤样品,残留消解动态规律表明,40%多·溴·福可湿性粉剂在黄瓜及其土壤中降解过程符合一级动力学数学模型。多菌灵在土壤中消解半衰期为4.9～6.9天,在黄瓜中消解半衰期为2.0～2.8天。溴菌腈在黄瓜中消解半衰期为1.1～1.5天。说明此农药属于易降解农药。
4.按照田间试验设计方案,2008年一年四地的试验结果显示,40%多·溴·福可湿性粉剂在黄瓜及其土壤中分别按照推荐剂量(150克制剂/亩),施药3次,在收获期距最后一次施药问隔为5天时,多菌灵和溴菌腈在黄瓜中的最高残留量分别为≤0.366 mg/Kg和<0.2mg/Kg。
In order to provide basic data for residual rule of 40%Carbendazim·Bromothalonil·Thiram, analysis methods of 40%Carbendazim·Bromothalonil·Thiram residue and degradation in cucumber and soil, and its final residues were studied. The results were shown as follows:
1.Residue analysis method of bromothalonil was established in cucumber and soil. The bromothalonil could be extracted with acetone, and then re-extracted with dichloromethane. After being concentrated by evaporation, the residue was reconstituded with acetone and detected in GC(NPD) and GC-MS. The limit of detection in GC(NPD) was 1×10-11 g, and limits of quantitation of bromothalonil in cucumber and soil were both 0.1 mg/Kg. In the three levels of 0.1 mg/Kg, 0.5 mg/Kg and 1 mg/Kg, the average recoveries in cucumber and soil were 82.57%～87.69% and 91.25%～93.09%, respectively, and the relative standard deviations were 25.37%～6.04% and 2.40%～4.32%, respectively. The minimum detectable limit of the GC-MS was 1×10-11 g, and the minumun detectable concentration of Bromothalonil in cucumber and soil was all 0.1mg/Kg. In the three level of 0.1 mg/Kg, 0.5 mg/Kg and 1 mg/Kg, the average recoveries in cucumber and soil were 91.54%～108.93% and 99.03%～110.87%, with the relative standard deviations were 4.57%～5.85% and 4.02%～8.68%, respectively. The sensitivity, accuracy and precision of the method well satisfied the essential rules of pesticide residue determination.
2. Residue analysis method of carbendazim was established in cucumber and soil. The sample was extracted with ethyl acetate and determined by UPLC-MS/MS. The precursor ion/product ion transitions were m/z 191.2/130 and m/z 191.2/160 at the mode of multi-reaction monitor and m/z 191.2/160 was used for quantification. The limit of detection in UPLC-MS was 3×10-12 g, and limits of quantitation of carbendazim in cucumber and soil were both 0.01 mg/Kg. In the three levels of 0.01 mg/Kg, 0.05 mg/Kg and 0.1 mg/Kg, the average recoveries in cucumber and soil were 96.75%～101.87% and 98.15%～109.48%, with the relative standard deviations were 2.77%～3.31% and 2.99%～5.64%, respectively. The sensitivity, accuracy and precision of the two methods well satisfied the essential rules of pesticide residue determination, but the sensitivity of UPLC-MS determination was better. The limit of detection in HPLC was 2×10-10 g, and limits of quantitation of carbendazim in cucumber and soil were both 0.1 mg/Kg. In the three levels of 0.1 mg/Kg, 0.5 mg/Kg and 1 mg/Kg, the average recoveries in cucumber and soil were 86.09%～91.79% and 95.30%～97.10%, with the relative standard deviations were 2.50%～3.58% and 2.13%～3.27%, respectively.
3. Degradation dynamic of 40%Carbendazim·Bromothalonil·Thiram in cucumbers and soil was studied by a one-year four fields (2008) experiments in Shandong, Zhejiang, Henan and Beijing. The cucumbers and soil were treated with the pesticides at recommended dosage and two times of the recommendation dosage. Samples of cucumber and soil were analysised at different time, then the degradation procedure was corresponding to the mathematic pattern: C=C0e-kt. The half lifes of carbendazim in soil were 4.9～6.9 d, and that in cucumber were 2.0～2.8 d. The half lifes of bromothalonil in cucumber were 1.1～1.5 d. The result showed that carbendazim and bromothalonil were degraded easily in cucumber and soil.
4. With sprayed 40%Carbendazim·Bromothalonil·Thiram on cucumbers and soil at recommended dosage by a one-year four fields (2008) experiment in Shandong, Zhejiang, Henan and Beijing, on the 5th day after the last application, the final residue of Carbendazim and Bromothalonil in cucumber was≤0.366 mg/Kg and <0.2 mg/Kg.
1.分别建立了新型农药溴菌腈在黄瓜和土壤中的气相色谱和气相色谱-串联质谱连用分析方法。样品采用丙酮提取,二氯甲烷对提取液进行萃取。萃取液浓缩用丙酮定容,气相色谱(NPD)和气相色谱-串联质谱联用测定。气相色谱(NPD)的最小检出量为1×10-11 g,溴菌腈在黄瓜和土壤的最低检出浓度为0.1 mg/Kg,在0.1 mg/Kg、0.5 mg/Kg和1 mg/Kg三个添加水平,溴菌腈在黄瓜和土壤中的平均回收率分别为82.57%～87.69%和91.25%～93.09%,相对标准偏差分别为5.37%～6.04%和2.40%～4.32%。气相色谱-串联质谱联用的最小检出量为1×10-11 g,溴菌腈在黄瓜和土壤的最低检出浓度为0.1 mg/Kg,在0.1 mg/Kg、0.5 mg/Kg和1 mg/Kg三个添加水平,溴菌腈在黄瓜和土壤中的平均回收率分别为91.54%～108.93%和99.03%～110.87%,相对标准偏差分别为4.57%～5.85%和4.02%～8.68%。两种分析方法的灵敏度、准确度高,精密度好,均能够满足溴菌腈在黄瓜和土壤中的残留检测需要。
2.分别建立了农药多菌灵在黄瓜和土壤中超高效液相色谱-串联质谱联用和高效液相色谱分析方法。样品采用乙酸乙酯提取,超高效液相色谱-串联质谱联用测定,多反应监测技术确定多菌灵的两对离子m/z 191.2/ 132和m/z 191.2/ 160为定性离子,m/z 191.2/ 160为定量离子。仪器的最小检出量为3×10-12 g,多菌灵在黄瓜和土壤的最低检出浓度为0.01 mg/kg,在0.01 mg/kg、0.05 mg/kg和0.1 mg/kg三个添加水平,多菌灵在黄瓜和土壤中的平均回收率分别为96.75%～101.87%和98.15%～109.48%,相对标准偏差分别为2.77%～3.31%和2.99%～5.64%。两种方法的灵敏度、准确度、精密度等均符合农药残留检测的要求,但液相色谱-串联质谱联用测定的灵敏度更高。高效液相色谱测定多菌灵的最小检出量为2×10-10 g,多菌灵在黄瓜和土壤中的最低检出浓度均为0.1 mg/Kg,在0.1 mg/Kg、0.5 mg/Kg和1 mg/Kg三个添加水平,多菌灵在黄瓜和土壤中的平均回收率分别为86.09%～91.79%和95.30%～97.10%,相对标准偏差分别为2.50%～3.58%和2.13%～3.27%。
3.采用田间试验方法,研究了40%多·溴·福可湿性粉剂在黄瓜和土壤中残留消解动态规律及其最终残留量。通过在山东、河南、浙江和北京一年四地田间试验,对40%多·溴·福可湿性粉剂按推荐剂量2倍处理黄瓜及其土壤样品,残留消解动态规律表明,40%多·溴·福可湿性粉剂在黄瓜及其土壤中降解过程符合一级动力学数学模型。多菌灵在土壤中消解半衰期为4.9～6.9天,在黄瓜中消解半衰期为2.0～2.8天。溴菌腈在黄瓜中消解半衰期为1.1～1.5天。说明此农药属于易降解农药。
4.按照田间试验设计方案,2008年一年四地的试验结果显示,40%多·溴·福可湿性粉剂在黄瓜及其土壤中分别按照推荐剂量(150克制剂/亩),施药3次,在收获期距最后一次施药问隔为5天时,多菌灵和溴菌腈在黄瓜中的最高残留量分别为≤0.366 mg/Kg和<0.2mg/Kg。
In order to provide basic data for residual rule of 40%Carbendazim·Bromothalonil·Thiram, analysis methods of 40%Carbendazim·Bromothalonil·Thiram residue and degradation in cucumber and soil, and its final residues were studied. The results were shown as follows:
1.Residue analysis method of bromothalonil was established in cucumber and soil. The bromothalonil could be extracted with acetone, and then re-extracted with dichloromethane. After being concentrated by evaporation, the residue was reconstituded with acetone and detected in GC(NPD) and GC-MS. The limit of detection in GC(NPD) was 1×10-11 g, and limits of quantitation of bromothalonil in cucumber and soil were both 0.1 mg/Kg. In the three levels of 0.1 mg/Kg, 0.5 mg/Kg and 1 mg/Kg, the average recoveries in cucumber and soil were 82.57%～87.69% and 91.25%～93.09%, respectively, and the relative standard deviations were 25.37%～6.04% and 2.40%～4.32%, respectively. The minimum detectable limit of the GC-MS was 1×10-11 g, and the minumun detectable concentration of Bromothalonil in cucumber and soil was all 0.1mg/Kg. In the three level of 0.1 mg/Kg, 0.5 mg/Kg and 1 mg/Kg, the average recoveries in cucumber and soil were 91.54%～108.93% and 99.03%～110.87%, with the relative standard deviations were 4.57%～5.85% and 4.02%～8.68%, respectively. The sensitivity, accuracy and precision of the method well satisfied the essential rules of pesticide residue determination.
2. Residue analysis method of carbendazim was established in cucumber and soil. The sample was extracted with ethyl acetate and determined by UPLC-MS/MS. The precursor ion/product ion transitions were m/z 191.2/130 and m/z 191.2/160 at the mode of multi-reaction monitor and m/z 191.2/160 was used for quantification. The limit of detection in UPLC-MS was 3×10-12 g, and limits of quantitation of carbendazim in cucumber and soil were both 0.01 mg/Kg. In the three levels of 0.01 mg/Kg, 0.05 mg/Kg and 0.1 mg/Kg, the average recoveries in cucumber and soil were 96.75%～101.87% and 98.15%～109.48%, with the relative standard deviations were 2.77%～3.31% and 2.99%～5.64%, respectively. The sensitivity, accuracy and precision of the two methods well satisfied the essential rules of pesticide residue determination, but the sensitivity of UPLC-MS determination was better. The limit of detection in HPLC was 2×10-10 g, and limits of quantitation of carbendazim in cucumber and soil were both 0.1 mg/Kg. In the three levels of 0.1 mg/Kg, 0.5 mg/Kg and 1 mg/Kg, the average recoveries in cucumber and soil were 86.09%～91.79% and 95.30%～97.10%, with the relative standard deviations were 2.50%～3.58% and 2.13%～3.27%, respectively.
3. Degradation dynamic of 40%Carbendazim·Bromothalonil·Thiram in cucumbers and soil was studied by a one-year four fields (2008) experiments in Shandong, Zhejiang, Henan and Beijing. The cucumbers and soil were treated with the pesticides at recommended dosage and two times of the recommendation dosage. Samples of cucumber and soil were analysised at different time, then the degradation procedure was corresponding to the mathematic pattern: C=C0e-kt. The half lifes of carbendazim in soil were 4.9～6.9 d, and that in cucumber were 2.0～2.8 d. The half lifes of bromothalonil in cucumber were 1.1～1.5 d. The result showed that carbendazim and bromothalonil were degraded easily in cucumber and soil.
4. With sprayed 40%Carbendazim·Bromothalonil·Thiram on cucumbers and soil at recommended dosage by a one-year four fields (2008) experiment in Shandong, Zhejiang, Henan and Beijing, on the 5th day after the last application, the final residue of Carbendazim and Bromothalonil in cucumber was≤0.366 mg/Kg and <0.2 mg/Kg.
引文
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王静,金芬. 2007.农药多残留检测样品前处理技术研究进展.农业质量标准. (1): 28～31
吴艳华,冒乃和,刘波,C. Sengonca. 2002.越筑越高的绿色壁垒-残留物最高限量标准.中国农业科技导报. (40): 40～41
王运浩. 2003.食品农药残留与分析控制技术展望.现代科学仪器. 87(1): 8～12
吴旭刚,袁旭,庞宏宇. 2008. RP-HPLC法测定葱、蒜类蔬菜中多菌灵的残留.食品科学. 29(5):367～368
王登飞,陈练洪,游俊,等. 2008.固相萃取-HPLC法同时测定果蔬中多菌灵和噻菌灵残留量.农药. 47(6):443～447
吴刚,吴俭俭,赵珊红. 2008.加速溶剂萃取-固相萃取结合液相色谱分析茶叶中多菌灵残留量.中国食品学报. 8(4): 165～168
王骏,钟青. 2008.烟草中“多菌灵”残留量的液相色谱-质谱测定.烟草化学.(11):44～47
许艇,李季. 2003.农产品中的农药残留及其分析技术的发展趋向.大学化学. 18(6):5～11
许人骥. 2003.蔬菜水果中乙烯利残留量的测定.沈阳农业大学硕士论文. 10～11
余向阳,骆爱兰,刘贤进. 2004.小麦中多菌灵残留量HPLC分析方法研究.现代农药. 3(1): 17～19
游静,王国俊,余维乐. 1999.超临界流体萃取在环晚分析中的应用.色谱. 17(1): 30～34
于维森,郝文,于卫红,等. 2008.食品中42种农药残留的气相色谱-质谱选择离子测定法.职业与健康. 24(23):2506～2510
郑亚辉. 2006.技术在食品安全分析中的应用.现代科学仪器. (1): 31～35
朱静,周欣,付春梅. 2004.固相萃取一气相色谱/质谱联用测定环境水中噻唑硫磷农药残留.色谱. 22 (6): 655～657
周井刚,郭正元,梁菁,等. 2008. 6%甲萘威·四聚乙醛在小白菜及土壤中残留分析方法及消解动态.农药. (11): 62～65
章虎,吴俐勤,谢磊,等. 2006.高效液相色谱法测定甘蓝、青菜和番茄中虫酰肼、甲氧虫酰肼和呋喃虫酰肼残留.现代科学仪器. ( 3 ): 55～58
张大弟,张晓红. 2001.农药污染与防治.化学工业出版社. 28～32
Paul Zavitsannos, Paul Yang, Lorna Grey. 2002.安捷伦(Agilent)环境科学专栏:液相/质谱(LC/MS)技术用于有机磷农药分析.环境化学. 21(1): 92～95
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Barker S. A., Long A. R., Short C. R.. 1989. Chromatogr A. 475(1): 353～361
Christer Jansson, Tui Ja Pihlstrom, Bengt-goran Osterdahl, et al. 2004. A new multiresidue method for analysis of pesicide reside in fruit and vegetable using liquid chromatogrophy with tandem mass Spectrometric Detectioon. Journal of Chromatography A, 1023 (2004): 93～104
Debriun L. S. 1998. Solid-phase microextraction of monocyclic aromatic from biological fluids. Anal Chem. 70(9):1986～1988
Dimuccio A., Barbini D.A., Generali T., et al. 1997. Clean-up of aqueous acetone vegetable extracts by partition for pyrethroid residue determination by gas detection. Jounal of Chromatography A. 765 (1): 39～49
Fanggui Ye, Zenghong Xie, Xiaoping Wu, et al. 2006. Determination of pyrethroid pesticide residues in vegetables by pressurized capillary electrochromatography. Talanta. 69(9): 97～102
Felix Hernandez, Carmen Hidalgo, Juan V. Sancho. 2003. Determination of Glyphosate residues in plants by precolumn derivatization and coupled-column liquid chromatography with fluorescence detection. Journal of AOAC INTERNATIONAL. 83(3): 728-734
Granby K, Johannesen S, VahL M. J.. 2003. Analysis of glyphosate residues in cereals using liquid chromatography-mass spectrometry. Food Addit Contam. 20(8): 692～695
Graoiela Palma, Alejandra Sbncihez, Yohana O Lave, et al. 2004. Pesticide levels in surface waters in an agrictultural-forestry basin in Southern Chile. Chanosphere. (57): 763～770
Hogendoorn E A, Ossendrijver F M, Dijkman E, et al. 1999. Rapid determination of glyphosate in cereal samples by means of pre-colum derivatisation with 9-fluorenylmethyl choroformate and coupled-colum liquid chromatograp with fluorescence detection.Chromatography. 833(1): 67～73
Hoffman M. R.. 1995. Environment app1ication of semiconduct photocataLysis. Chemistry. 95:69～96
Hwang B. H., Lee M. R.. 2000. Solid-phase Microextraction for Organ Chlorine Pesticide Residues Analysis in Chinese Herbal Formulations. Journal of Chromatography A. 898(1): 245～256
Inoue T., Sasaki S., Uchikawa S., et al. 2003. Determination of low-level pesticide residues in agricultural products by ion-trap GC/MS/MS. Journal of the Food Hygienic Society of Japan. 44 (6): 310～315
Jimenez J.J., Bernal J.L., Del Nozal M.J., et al. 1998. Gas chromatography with electron-capture and nitrogen-phosphorus detection in the analysis of pesticides in honey after elution from a florisil column-influence of the honey matrix on the quantitative results. Jounal of Chromatography A. 823 (1～2): 381～387
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Louch D., Motlagh S., Pawliszyn J. 1992. Dynamics of oragnic compound extraction from water using liquid-coated fused silica fibers. Analytical Chemistry. 64(10): 1187
Arthur C. L., Killam L. M., Buchbolz K. D., et al. 1992. Automation and optimization of solid-phase microextraction. Analytical Chemistry. 64(17): 1960～1966
Lopez F. J., Pitarch E, Egea S, et al. 2001. Gas chromatographic determination of organochlorine and organophosphorus pesticides in human fluids using solid phase microextraction. Analytica Chimica Acta. (433): 217～226
Lou Ping, Zhong Shao hua,Cai Shengning, et al. 1994. Emination of buprofezin residues in tea and soil by HPLC. Pesticide China. 33(2): 18～19
Nerin C., Battle R., Gacbo J.. 1998. Determination of pesticides in high-water-content samples by off-line supercritical fluid extraction-gas chromatography-electron capture detection. Cbromatogr.A. 795 (1): 117～124
Nunes JM., Camoes MF., Foumier J.. 1997. Progress on sample preparation techniques for analysis of pesticide residues in food stuffs. Journal of Chromatogram A. 44(9～10): 505～513
Popp P., Karsten K., Gudrun O. 1994. Application of solid-phase microextraction and gas chromatography with electron-capture and mass spectrometric detection for the determination of hexachlorocychohexanes in soil solutions. Journal of Chromatography A. 687: 133～140
R.Rodriguez, Y. Pico, C. Font, et al. 2002. Analysis of thiabendazole and procymidone in fruits and vegetables bycapillary electrophoresis-electrospray mass spectrometry. Journal of Chromatography A. 949(5 ): 359～366
Steven J. Lebotay. 2000. Analysis of pesticide residues in mixed fruit and vegetable extracts by direct sample Introduction gas chromatography tandem mass spectrometry. Journal of AOAC International. 83(3): 680～697
Sancho J V, Carmen Hidalgo, Juan V Sancho. 1996. Rapid determination of glufosinate, glyphsate and amino methyl phosphoric acid in environmental water samples using precolumn fluorogenic labling and coupled-column liquid chromatography. Journal of Chromatography A. 737(1): 75～83
Shashi B. Singh, Gregory D. Foster, Shahamat U. Khan. 2007. Determination of thiophanate methyl and carbendazim residues in vegetable samples using microwave-assisted extraction. Journal of Chromatography A. 1148(2): 152～157
Scheyer A., Morville S., Mirabel P, et al. 2005. A multi residue method using ion-trap gas chromatography-tandem mass spectrometry with or without derivatisation with pentafluorobenzylbromide for the analysis of pesticides in the atmosphere. Analytical and Bisanalytical Chemistry. 381(6): 1226～1233
Zuin V.G, Yariwake J.H., Bicchi C. 2003. Fast supercritical fluid extraction and high-esolution gas chromatography with electron-capture and flame photometric detection for multiresidue screening of organochlorine and organophosphorus pesticides in Brazil's medicinal plants. Jounal of Chromatography A. 85 (1～2): 159～166
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吴艳华,冒乃和,刘波,C. Sengonca. 2002.越筑越高的绿色壁垒-残留物最高限量标准.中国农业科技导报. (40): 40～41
王运浩. 2003.食品农药残留与分析控制技术展望.现代科学仪器. 87(1): 8～12
吴旭刚,袁旭,庞宏宇. 2008. RP-HPLC法测定葱、蒜类蔬菜中多菌灵的残留.食品科学. 29(5):367～368
王登飞,陈练洪,游俊,等. 2008.固相萃取-HPLC法同时测定果蔬中多菌灵和噻菌灵残留量.农药. 47(6):443～447
吴刚,吴俭俭,赵珊红. 2008.加速溶剂萃取-固相萃取结合液相色谱分析茶叶中多菌灵残留量.中国食品学报. 8(4): 165～168
王骏,钟青. 2008.烟草中“多菌灵”残留量的液相色谱-质谱测定.烟草化学.(11):44～47
许艇,李季. 2003.农产品中的农药残留及其分析技术的发展趋向.大学化学. 18(6):5～11
许人骥. 2003.蔬菜水果中乙烯利残留量的测定.沈阳农业大学硕士论文. 10～11
余向阳,骆爱兰,刘贤进. 2004.小麦中多菌灵残留量HPLC分析方法研究.现代农药. 3(1): 17～19
游静,王国俊,余维乐. 1999.超临界流体萃取在环晚分析中的应用.色谱. 17(1): 30～34
于维森,郝文,于卫红,等. 2008.食品中42种农药残留的气相色谱-质谱选择离子测定法.职业与健康. 24(23):2506～2510
郑亚辉. 2006.技术在食品安全分析中的应用.现代科学仪器. (1): 31～35
朱静,周欣,付春梅. 2004.固相萃取一气相色谱/质谱联用测定环境水中噻唑硫磷农药残留.色谱. 22 (6): 655～657
周井刚,郭正元,梁菁,等. 2008. 6%甲萘威·四聚乙醛在小白菜及土壤中残留分析方法及消解动态.农药. (11): 62～65
章虎,吴俐勤,谢磊,等. 2006.高效液相色谱法测定甘蓝、青菜和番茄中虫酰肼、甲氧虫酰肼和呋喃虫酰肼残留.现代科学仪器. ( 3 ): 55～58
张大弟,张晓红. 2001.农药污染与防治.化学工业出版社. 28～32
Paul Zavitsannos, Paul Yang, Lorna Grey. 2002.安捷伦(Agilent)环境科学专栏:液相/质谱(LC/MS)技术用于有机磷农药分析.环境化学. 21(1): 92～95
Anastassiades M., Scbwack W.. 1998. Analysis of carbcndazim. bcnomyl. tbiopbanate methyl and 2.4-dicbloropbenoiyacetic acid in fruits and vegetables after supercritical fluid eitraction Cbromatogr. 825 (1): 45～54
Barker S. A., Long A. R., Short C. R.. 1989. Chromatogr A. 475(1): 353～361
Christer Jansson, Tui Ja Pihlstrom, Bengt-goran Osterdahl, et al. 2004. A new multiresidue method for analysis of pesicide reside in fruit and vegetable using liquid chromatogrophy with tandem mass Spectrometric Detectioon. Journal of Chromatography A, 1023 (2004): 93～104
Debriun L. S. 1998. Solid-phase microextraction of monocyclic aromatic from biological fluids. Anal Chem. 70(9):1986～1988
Dimuccio A., Barbini D.A., Generali T., et al. 1997. Clean-up of aqueous acetone vegetable extracts by partition for pyrethroid residue determination by gas detection. Jounal of Chromatography A. 765 (1): 39～49
Fanggui Ye, Zenghong Xie, Xiaoping Wu, et al. 2006. Determination of pyrethroid pesticide residues in vegetables by pressurized capillary electrochromatography. Talanta. 69(9): 97～102
Felix Hernandez, Carmen Hidalgo, Juan V. Sancho. 2003. Determination of Glyphosate residues in plants by precolumn derivatization and coupled-column liquid chromatography with fluorescence detection. Journal of AOAC INTERNATIONAL. 83(3): 728-734
Granby K, Johannesen S, VahL M. J.. 2003. Analysis of glyphosate residues in cereals using liquid chromatography-mass spectrometry. Food Addit Contam. 20(8): 692～695
Graoiela Palma, Alejandra Sbncihez, Yohana O Lave, et al. 2004. Pesticide levels in surface waters in an agrictultural-forestry basin in Southern Chile. Chanosphere. (57): 763～770
Hogendoorn E A, Ossendrijver F M, Dijkman E, et al. 1999. Rapid determination of glyphosate in cereal samples by means of pre-colum derivatisation with 9-fluorenylmethyl choroformate and coupled-colum liquid chromatograp with fluorescence detection.Chromatography. 833(1): 67～73
Hoffman M. R.. 1995. Environment app1ication of semiconduct photocataLysis. Chemistry. 95:69～96
Hwang B. H., Lee M. R.. 2000. Solid-phase Microextraction for Organ Chlorine Pesticide Residues Analysis in Chinese Herbal Formulations. Journal of Chromatography A. 898(1): 245～256
Inoue T., Sasaki S., Uchikawa S., et al. 2003. Determination of low-level pesticide residues in agricultural products by ion-trap GC/MS/MS. Journal of the Food Hygienic Society of Japan. 44 (6): 310～315
Jimenez J.J., Bernal J.L., Del Nozal M.J., et al. 1998. Gas chromatography with electron-capture and nitrogen-phosphorus detection in the analysis of pesticides in honey after elution from a florisil column-influence of the honey matrix on the quantitative results. Jounal of Chromatography A. 823 (1～2): 381～387
Kandenczki L, Arpad Z, Gardi I.. 1992. Assoc. Off. Anal. Chem. 75 (1): 53～61
Louch D., Motlagh S., Pawliszyn J. 1992. Dynamics of oragnic compound extraction from water using liquid-coated fused silica fibers. Analytical Chemistry. 64(10): 1187
Arthur C. L., Killam L. M., Buchbolz K. D., et al. 1992. Automation and optimization of solid-phase microextraction. Analytical Chemistry. 64(17): 1960～1966
Lopez F. J., Pitarch E, Egea S, et al. 2001. Gas chromatographic determination of organochlorine and organophosphorus pesticides in human fluids using solid phase microextraction. Analytica Chimica Acta. (433): 217～226
Lou Ping, Zhong Shao hua,Cai Shengning, et al. 1994. Emination of buprofezin residues in tea and soil by HPLC. Pesticide China. 33(2): 18～19
Nerin C., Battle R., Gacbo J.. 1998. Determination of pesticides in high-water-content samples by off-line supercritical fluid extraction-gas chromatography-electron capture detection. Cbromatogr.A. 795 (1): 117～124
Nunes JM., Camoes MF., Foumier J.. 1997. Progress on sample preparation techniques for analysis of pesticide residues in food stuffs. Journal of Chromatogram A. 44(9～10): 505～513
Popp P., Karsten K., Gudrun O. 1994. Application of solid-phase microextraction and gas chromatography with electron-capture and mass spectrometric detection for the determination of hexachlorocychohexanes in soil solutions. Journal of Chromatography A. 687: 133～140
R.Rodriguez, Y. Pico, C. Font, et al. 2002. Analysis of thiabendazole and procymidone in fruits and vegetables bycapillary electrophoresis-electrospray mass spectrometry. Journal of Chromatography A. 949(5 ): 359～366
Steven J. Lebotay. 2000. Analysis of pesticide residues in mixed fruit and vegetable extracts by direct sample Introduction gas chromatography tandem mass spectrometry. Journal of AOAC International. 83(3): 680～697
Sancho J V, Carmen Hidalgo, Juan V Sancho. 1996. Rapid determination of glufosinate, glyphsate and amino methyl phosphoric acid in environmental water samples using precolumn fluorogenic labling and coupled-column liquid chromatography. Journal of Chromatography A. 737(1): 75～83
Shashi B. Singh, Gregory D. Foster, Shahamat U. Khan. 2007. Determination of thiophanate methyl and carbendazim residues in vegetable samples using microwave-assisted extraction. Journal of Chromatography A. 1148(2): 152～157
Scheyer A., Morville S., Mirabel P, et al. 2005. A multi residue method using ion-trap gas chromatography-tandem mass spectrometry with or without derivatisation with pentafluorobenzylbromide for the analysis of pesticides in the atmosphere. Analytical and Bisanalytical Chemistry. 381(6): 1226～1233
Zuin V.G, Yariwake J.H., Bicchi C. 2003. Fast supercritical fluid extraction and high-esolution gas chromatography with electron-capture and flame photometric detection for multiresidue screening of organochlorine and organophosphorus pesticides in Brazil's medicinal plants. Jounal of Chromatography A. 85 (1～2): 159～166