RESEARCH ARTICLE ZHONG Donglian,et al: Determination of 14 Pesticide Residues in Fresh Jujube relationship could be achieved for the detection of 14 p

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1 钟冬莲, 刘毅华, 沈丹玉, 莫润宏, 丁明, 汤富彬 * ( / ( ), ) : 选择强疏水性硅胶基质 tc18 柱为固相萃取净化柱, 以电喷雾 (ESI) 为离子源, 正离子多级反应离子监测 (MRM) 模式, 建立了固相萃取 - 液相色谱 - 串联质谱法 (HPLC-MS/MS) 测定鲜枣中 14 种农药 ( 包括有机磷杀虫剂杀菌剂, 有机杂环类杀虫剂和新型烟碱类杀虫剂 ) 残留的分析方法研究比较了不同提取溶剂的提取效果和不同固相萃取小柱的净化效果, 同时优化了色谱分离条件和质谱条件 14 种农药在 10~500 μg/l ( 或 1~50 μg/l) 范围内线性相关, 相关系数为 ~ , 方法的定量限为 0.10~9.50 μg/kg 14 种农药在鲜枣中 3 个水平添加质量浓度的的回收率在 67.4%~116.8%,RSD 为 0.8%~14.8% 之间该方法操作简便, 灵敏度准确度和精密度均符合农药多残留检测技术要求, 适用于鲜枣中 14 种农药多残留的检测 : 固相萃取 ; 鲜枣 ; 液相色谱 - 串联质谱法 ; 农药残留 :O :A : (2015) Determination of 14 Pesticide Residues in Fresh Jujube ZHONG Donglian, LIU Yihua, SHEN Danyu, MO Runhong, DING Ming, TANG Fubin * (Research Institute of Subtropial Foresty,Chinese Academy of Forestry / Quality Testing Center for Non-Wood Forest Products of State Forestry Administration,Fuyang ,China) Abstract: This study developed a method to identify 14 pesticides residues (including organic phosphorus insecticides,fungicides,organic heterocyclic pesticides and novel nicotine insecticide) in fresh jujube by solid-phase extraction and liquid chromatography coupled with electrospray ionization tandem (HPLC-MS/MS),in which a strong hydrophobic silica bonded tc18 column was selected as the solid-phase extraction,electrospray ionization (ESI) was used as the ion source and positive ion multiple reaction monitoring (MRM) was set as the detection mode. The effects of different extraction solvents and solid-phase extraction columns were compared for the determination of 14 pesticides residues,and at the meanwhile the separation and detection conditions for the multiresidue analysis by chromatography and mass spectrometry were also optimized. A good linear : : ( , ) : (1985 ),,,, zhongdonglian215@163.com * : (1972 ),,,, yalinsuozjzx@163.com

2 RESEARCH ARTICLE ZHONG Donglian,et al: Determination of 14 Pesticide Residues in Fresh Jujube relationship could be achieved for the detection of 14 pesticides in fresh jujube in the range of 10~500 μg/l (or 1~50 μg/l),with the correlation coefficients of ~ ,the quantitation limits of 0.10~9.50 μg/kg,the recoveries of 67.4% ~116.8% for 14 pesticides of three different concentrations,and RSD of 0.8% ~14.8%. The optimized method,which is applicable to determine 14 pesticide residues in fresh jujube,meets the requirements of the multiresidue analysis with simple operation,good sensitivity,and high accuracy. Keywords: solid phase extraction,fresh jujube,liquid chromatography tandem mass spectrometry (LC-MS/MS),pesticides residues (Ziziphus jujuba Mill.), 14 ( 100 μ, g/ml, μ g/ml): ; :HPLC, Merck, ; :, ;, :, Sigma ;tc18, (500mg) Carbon NH3 (1 000 mg) C18 (500 mg): Waters ;PSA :500 mg, [1], ;, Milli-Q [3-5],, 1.2, GC/FPD GC/ECD GC- MS, 10 ml, : IKA : 1.00 ml, 100 μg/ml(, 10 μg/ml), -20 [1,6-8] : 1.00 ml 10 ml,, ml, 10 μg/ [9,11-16,22-24] ml( 1 μg/ml),, -4, 14 (, ), , g 150 ml,, 50.0 ml, 2 min,,, 5~7 g NaCl 100 ml, 40~50 ml,, 2 min, 20 min, 1 5 ml, 100 ml 1.1, 40 Waters Quttro Premier : Waters ;IKAT18 : 100 ml 2 ml - IKA ; : Thermo ; ( 3 1), 10 ml - ( 3 1) 732 JOURNAL OF FOOD SCIENCE AND BIOTECHNOLOGY Vol.34 No

3 钟冬莲, 等 : 固相萃取 - 液相色谱 - 电喷雾串联质谱法测定鲜枣中 14 种农药残留 Sep-pak Vac 6cc tc18, 0.3 ml/min; :0~5 min,90%~50% A;, 10 ml - ( 3 5~8 min,50%~20%a;8~10 min,20%~5% A;10~18 1), 15 ml, 40, 2 ml - ( 3 2), A 0.22 μm, 液相色谱条件 Atlantis T3 (2.1 mm 100 mm,5 μm); :35 ; :10 μl; A: 0.05% ; B: ;. /min /(m/z) 1 methamidophos ( ) acephate( ) omethoate( ) carbendazim( ) trichlorphon( ) imidacloprid( ) dimethoate( ) dichlorvos( ) isocarbophos( ) triadimefon( ) malathion( ) phoxim( ) chlorpyrifos( ) buprofezin( ) * Quantification ion 2 Table min,5% A;18 ~22 min,5% ~90% A;22 ~25 min,90% (ESI+); :3.0 kv; :80 ; 450 ; :550 L/h; :50 L/h; : MRM 1 14 Mass spectrometry detection conditions for 14 pesticides residues analysis /V /(m/z) 93.9* * * * * * * * * * * * * * /ev [9-14] [15-16] [16], 3 14, 2, 2,

4 RESEARCH ARTICLE ZHONG Donglian,et al: Determination of 14 Pesticide Residues in Fresh Jujube, 2.2,, -,, [17-18], (GPC) [16,19], (SPE) [11,13-14,20-22] ; Table 2 Effect of the recoveries of 14 spiked pesticides in, Sep-Pak Vac fresh jujube by 3 different extraction solvents % 6cc tc18 Sep-Pak Vac 6cc C18 Sep-Pak Vac 6cc CarbonNH3 Bond Elut -PSA 1 methamidophos , - ( 3 1) 2 acephate ,Sep-Pak Vac 6cc tc18,sep-pak Vac 6cc C18, 3 omethoate Sep-Pak Vac 6cc CarbonNH 3 Bond Elut-PSA 4 carbendazim trichlorphon ,Sep -pak vac 6 imidacloprid CarbonNH dimethoate ,, 8 dichlorvos , 4 9 isocarbophos % PSA,, 10 triadimefon malathion Sep-pak vac tc18 Sep-pak vac C18, 12 phoxim %~120%, Sep-pak 13 chlorpyrifos vac tc18, 14 buprofezin ,, Sep-pak vac C (n=3), Sep-pak vac tc18 14 Table 3 Statisticsof spiked recoveries of 14 pesticides in different extraction solvents (n=3) Sep-pak vac C18, Sep-pak vac tc <60% 0 0 5, 60%~120% >120% Fig. 1 1 Selection of solid phase extraction columns 734 JOURNAL OF FOOD SCIENCE AND BIOTECHNOLOGY Vol.34 No

5 钟冬莲, 等 : 固相萃取 - 液相色谱 - 电喷雾串联质谱法测定鲜枣中 14 种农药残留 2, 67.4%~116.8%,RSD 0.8%~ 78%, 100%~150%, 10(S/N=10),, ~9.5 μg/kg 14.8% 3 Fig. 2 2 Distribution of matrix effects intensity on the response of pesticides 2.4, MRM (Y) (X,μg/L) 14 4, ~ , 20, μg/kg( 1.0~50 μg/l 3 (a) (b), 2.0, μg/kg), Fig. 3 6 ( 4), 14 Total ion chromatogram of 14 pesticides residues standards(a) and spiked fresh jujube samples (b) Table Characteristic indexes for the determination of 14 pesticides residues /(μg/l) R (n=18,%) RSD/% LOD/(μg/kg) methamidophos 10~500 Y= ~ ~ acephate 10~500 Y= ~ ~ omethoate 10~500 Y= ~ ~ carbendazim 1~50 Y= X ~ ~ trichlorphon 10~500 Y= ~ ~ imidacloprid 10~500 Y= ~ ~ dimethoate 10~500 Y= X ~ ~ dichlorvos 10~500 Y= X ~ ~ isocarbophos 10~500 Y= ~ ~ triadimefon 10~500 Y= X ~ ~ malathion 10~500 Y= ~ ~ phoxim 10~500 Y= ~ ~ chlorpyrifos 10~500 Y= ~ ~ buprofezin 1~50 Y= ~ ~

6 RESEARCH ARTICLE ZHONG Donglian,et al: Determination of 14 Pesticide Residues in Fresh Jujube 2.5,, 26, 53.84%;26 3 2, (9 ), [3] (10 ),,Sep-Pak Vac tc18,, NY/, T ,,,,,, : [ 1 ],. [J].,2007,6(2): JIN Zengjun,CAO Keqiang. Determination of cypermethrin,fenvalerate and triadimefon pesticide residues in Jujube by GC[J]. Modern Agrochemicals,2007,6(2):36-38.(in Chinese) [ 2 ],. [M]. :,2002. [ 3 ] GB [S]. [ 4 ] LY/T [S]. [ 5 ] GB [S]. [ 6 ],,,. [J].,2009,25(15): MA Qinhua,XU Jiuru,WANG Guixi,et al. Determination of chlorothalonil,cypermethrin and fenvalerate pesticide residues in Dongzao[J]. Chinese Agricultural Science Bulletin,2009,25(15):51. (in Chinese) [ 7 ],, [J].,2011,3 (238): (in Chinese) ZHAO Xiaotian,SHI Huijuan,YUAN Chao,et al. Analysis and detection 9 mycotoxins and 77 pesticides residue in jujube dates [J]. Academia Periodical of Farm Products Processing,2011,3(238):61. (in Chinese) [ 8 ],,,. [J].,2012,11(3): QIAN Zongyao,ZHOU Xiaolong,LIU Hejiang,et al. Determination of difenoconazole residue in red jujube by Gas chromatography-mass spectrometry[j]. Mordern Agrochemicals,2012,11(3):37.(in Chinese) [ 9 ],,,. / - [J].,2014,33(6): ZHOU Li,LUO Fengjiang,ZHANG Xinzhong,et al. Determination of multi-pesticide residues in green tea by nano bamboo charcoal-dspe/ultra high performance lliquid chromatography-tandem mass spectrometry [J]. Journal of Instrumental Analysis,2014,33(6): (in Chinese) [10],,,. RP-HPLC 9 [J].,2014,33(6): LUO Chong,WANG Kai,DING Chenhong,et al. Simultaneous determination of nine pesticide residues in vegetables,fruit and edible fungi by reverse phase high performance liquid chromatography [J]. Journal of Instrumental Analysis,2014,3 (6): (in Chinese) [11],,, [J].,2013,41 (8): YU Yanbin,TAN Pigong,LIU Zongxing,et al. Determination of 22 pesticides residues in domestic fungus by solid phase extraction and LC/MS/MS with matrix correction [J]. Chinese Journal of Analytical Chemistry,2013,41 (8): (in Chinese) [12],,, [J]., 2013,41(4): JOURNAL OF FOOD SCIENCE AND BIOTECHNOLOGY Vol.34 No

7 钟冬莲, 等 : 固相萃取 - 液相色谱 - 电喷雾串联质谱法测定鲜枣中 14 种农药残留 LIU Xiaoliang,LI Xuesheng,LIU Shaowen,et al. Determination of 13 representative pesticides in chinese herbal medicine plants by dispersive solid-phase cleanup and Gas chromatography-tandem mass spetrometry [J]. Chinese Journal of Analytical Chemistry,2013,41(4): (in Chinese) [13],, [J].,2013,32(1): 9-22 JIA Wei,HUANG Junrong,LING Yun,et al. Determination of 290 pesticide residues in tea by high performance liquid chromatography-tandem mass spectrometry[j]. Journal of Instrumental Analysis,2013,32(1):9-22.(in Chinese) [14],,,. 11 [J].,2010,29(1): LIU Qinbin,ZHANG Rui,WANG haitao,et al. Determation of multi-residues of organophosphorus pesticides in gardenia jasminoides ellis by HPLC tandem MS/MS[J]. Journal of Instrumental Analysis,2010,29(1): (in Chinese) [15],,, [J].,2011,29 (10): HUANG Jiangrui,KONG Xiang hong,yao Binghua,et al. Detemination of 88 pesticide residues in cranberry plant extract by gas chromatography-triple quadrupole tandem mass spectrometry [J]. Chinese Journal of Chromatography,2011,29 (10): (in Chinese) [16],,. - - [J].,2012,30(7): OUYANG Yunfu,TANG Hongbin,WU Ying,et al. Rapid determination of pesticide multiresidues in vegetables and fruits by accelerated solvent extraction coupled with online gel permeation chromatography-gas chromatography-mass spectrometry [J]. Chinese Journal of Chromatography,2012,30(7): (in Chinese) [17],. [J].,2007(10): ZHANG Qi,LI Da. Determination of chlorpyrifos pesticide residues in ginger by GC [J]. Chemical Engineer,2007(10): (in Chinese) [18],,,. 11 [J]. - ),2009,45(7): PAN Yuxiang,DONG Jing,XUN Jun,et al. GC determination of residual amounts of 11 pesticides in vegetable of complex matrixes[j]. Physical Testing and Chemical analysis Part B:Chemical analysis,2009,45(7): (in Chinese) [19],, [J].,2010,28(8): YANG Ruzhen,WANG Jinhua,ZHANG Rong,et al. Determination of 11 carbamate pesticide residues in Glycyrrhizae radis et rhizama and its extracts using ultra performance liquid chromatography-tandem mass spectrometry with gel permeation chromatographic clean-up[j]. Chinese Journal of Chromatography,2010,28(8): (in Chinese) [20],,, [J].,2013,31 (2): DING Ming,ZHONG Donglian,TANG Fubin,et al. Determination of seven pesticide residues in bamboo shoots by high performance liquid chromatography-tandem mass spectrometry coupled with solid-phase extraction [J]. Chinese Journal of Chromatography,2013,31(2): (in Chinese) [21],,, [J].,2011,30(2): WANG Jin,YUE Yongde,TANG feng,et al. Simultaneous Derterminatiion of 40 pesticides residue in Bamboo Shoots by GC- MS method with solid Phase extracton[j]. Journal of Instrumental Analysis,2011,30(2): (in Chinese) [22],,, [J].,2010,28(6): WANG Jin,PANG Guofang,WANG Minglin,et al. Determination of 215 pesticide residues in ginger using liquid chromatography coupled with electrospray ionization tandem mass spectrometry [J]. Chinese Journal of Chromatography,28 (6): (in Chinese)

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