Microsoft Word 张群-二校 出2020

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1 7 5 Vol. 7 No Journal of Food Safety and Quality May, 张 1, 群 2* 1,, 吴南村 2 1,, 张月 2, 刘春华 1, 2 (1., ; 2., ) 摘要 : 目的 3 - (gel permeation chromatography-gas chromatography-tandem mass spectrometry, GPC-GC-MS/MS) 方法,,, 结果 ~0.50 mg/l, ; mg/kg; mg/kg 3, %~104.8%, 2.9%~7.9% 结论, 3 关键词 : ; ; ; - Simultaneous determination of 3 kinds of pesticide residues in guava by gel permeation chromatography-gas chromatography-tandem mass spectrometry ZHANG Qun 1, 2*, WU Nan-cun 1, 2, ZHANG Yue 1, 2, LIU Chun-hua 1, 2 (1. Analysis and Testing Center, Chinese Academy of Tropical Agricultural Sciences, Haikou , China; 2. Hainan Provincial Key Laboratory of Quality and Safety for Tropical Fruits and Vegetables, Haikou , China) ABSTRACT: Objective To develop an analysis method for determination of 3 kinds of pesticide residues in guava by gel permeation chromatography-gas chromatography-tandem mass spectrometry (GPC-GC-MS/MS). Methods The guava samples were extracted by acetonitrile, followed by a cleanup procedure with GPC, and then separated by capillary gas chromatography column. Finally, the concentrated solution was analyzed by triple tandem quadrupole multiple reaction monitoring (MRM). Results The correlation coefficients (r 2 ) of 3 kinds of tested pesticides were greater than within their respective linear ranges of 0.05~0.50 mg/l. The limits of quantitation (LOQ) for chlorpyrifos, propargite and cyfluthrin were 0.002, and 0.01 mg/kg, respectively. The average recoveries of three pesticides were 83.3%~104.8% when the spiked levels were 0.05, 0.10 and 0.50 mg/kg, with relative standard deviations (RSDs) in the range of 2.9%~7.9%. Conclusions The method is easy, and can satisfy for detection of 基金项目 : ( ) ( ) Fund: Supported by Risk Assessment of National Agricultural Products Quality and Safety Program ( ) and Natural Science Foundation of Hainan Province ( ) * 通讯作者 :,,, zhangqun123@zju.edu.cn *Corresponding author: ZHANG Qun, Doctor, Research Associate, Analysis and Testing Center, Chinese Academy of Tropical Agricultural Sciences & Hainan Provincial Key Laboratory of Quality and Safety for Tropical Fruits and Vegetables, No. 4, Xueyuan Road, Haikou , China. zhangqun123@zju.edu.cn

2 5, : chlorpyrifos, propargite and cyfluthrin residues in guava. KEY WORDS: guava; pesticide residues; gas chromatography-tandem mass spectrometry; gel permeation chromatography 1 引言 (Psidium guajava L.),,, 17,, 1.5 hm 2, 25, 20 [1],,, [2],, mg/kg [3-5] mg/kg, ; [6] [7], 3,,, (gel permeation chromatography, GPC),,, [8] GPC,, [9-11] [12,13] [14] ( ) [15,16] GPC, - (gas chromatography-tandem mass spectrometry, GC-MS/MS), 3 GPC-GC-MS/MS,, 3 2 材料与方法 2.1 试剂与材料 (HPLC, Fisher ); (, ), 99%( ),, 94.5%( Dr Ehrenstorfer ) 2.2 仪器与设备 Agilent 7890A/7000A ( Agilent ); GPC VARIO ( LC Tech ); T25 basic ( ); RE52CS-1 ( ); EB ( ); QL-901 ( ); SLB-5ms ( SUPELCO ); ( )(25 mm 0.45 µm, ) 2.3 试验方法 样品前处理 25.0 g( 0.01g) 150 ml, 50.0 ml, 2 min, 5 g 100 ml,,, 2 min, 30 min, 100 ml ml, 50 ml, 40, 10 ml / (1:1, V:V),, GPC GPC,, 2 ml,, 添加回收率与精密度测定 3 3, 5, mg/kg,, 标准溶液及基质标准溶液的配制 : 100 mg/l, 18 : ( ),, 气相色谱 - 串联质谱条件 : SLB-5ms(30 m 0.25 mm, 0.25 µm); : 100, 40 /min 230, 5 /min 260, 1 min, 5 /min 280, 5 min; : min; :, %;,, 1.00 ml/min; : 260 ; : 1 µl; :

3 : : 1.50 ml/min, 2.25 ml/min; : : 70 Ev; : ; : 230 ; : 4.00 min;, 3,, GPC 条件 GPC : 25 mm 400 mm; : Bio-Beads S-X3( Mesh); : / (1:1, V:V); (GPC Flow Rate): 5 ml/min; (GPC Fore Run): 1040 s; (GPC Main faction): 600 s; 5 ml 3 结果与讨论 3.1 凝胶渗透色谱净化条件的选择 GPC,,,, 153~664, 5%~13% [17] GPC GPC,,,, 1040 s, 1040~1640 s, 1040~1640 s 3, 75% 3.2 待测农药定量和定性离子的选择 3, ( 1) ( 1),,,,,, (MRM) 1 3 (0.50 mg/l) 1 2,, MRM, 线性方程 定量限 回收率和精密度 线性方程, 2.3,,,, 0.05~0.50 mg/kg ( 2) 表 1 串联质谱多反应监测模式下待测农药的检测条件 Table 1 MS/MS conditions /min (m/z) (m/z) /ev / / / / / / > > > >95 15

4 5, : 定量限 3 (S/N) 3 (LOD) mg/kg; 10 (LOQ) mg/kg, mg/kg, % 74.1% ' 77.4%, (RSD) 8.0% 7.4% 5.2% 回收率和精密度 mg/kg 3, %~104.8%; 5 2.9%~7.9%,, 3 Fig. 1 a. ; b. ; c. 1 (1.0 mg/l) Full-scan MS spectrums of the tested pesticides in standard samples (1.0 mg/l)

5 : A. MRM ; B. MRM. : a. ; b. ; c1. 1; c2. 2; c3. 3; c (MRM) (0.50 mg/l) Fig. 2 MRM spectrums (0.50 mg/l) Table 2 表 2 待测农药的线性方程及线性相关系数 Linear equations and correlation coefficients for the tested pesticides (mg/l) r ~0.50 Y= X ~0.50 Y= X ~0.50 Y= X Table 3 表 3 待测农药的加标回收率及其相对标准偏差 (RSDs)(n=5) Average recoveries and the relative standard variations for the tested pesticides(n=5) (mg/kg) /% /%

6 5, : 结论 GPC-GC-MS/MS GPC,,,, 参考文献 [1],,. [J]., 2014, 34(12): Wu G, Chen HP, Tan LH. Status of tropical fruit industry in China and development countermeasures [J]. Chin J Trop Agric, 2014, 34(12): [2],,,. [J]., 2009, 48(3): Wen YJ, You WJ, Luo YZ, et al. Residual distribution regularity of chlorpyrifos in guavas [J]. Agrochemicals, 2009, 48(3): [3] Commission Regulation (EU) No 839/2008 [S]. [4] Commission Regulation (EU) 2015/400 [S]. [5] Commission Regulation (EU) No 737/2014 [S]. [6] The Japan food chemical research foundation. table of MRLs in Guava [EB/OL] [7] GB [S]. GB National food safety standard-maximum residue limits for pesticides in food [S]. [8] Henk K, Mol HGJ, Bart VDN. Volume overload cleanup: an approach for on-line SPE-GC, GPC-GC, and GPC-SPE-GC [J]. Anal Chem, 2007, 79(21): [9],,,. GPC-GC-MS [J]., 2009, 28(1): Guo L, Xie YM, Yan AP, et al. Simultaneous determination of multi-types of pesticide residues in edible vegetable oils by GPC-GC-MS method [J]. J Instrum Anal, 2009, 28(1): [10] Chen R, Shu T, Ma M, et al. Determination of 17 kinds of phthalates in oil by GPC-GC /MS and the uncertainty evaluation of the method [J]. Chemistry, 2014, 77(5): [11] Wang H, Zhao L, Yang HM, et al. Determination of benzo(a)pyrene and aflatoxins (B1, B2, G1, G2) in vegetable oil by GPC-HPLC-FLD [J]. Anal Methods, 2014, 6(5): [12],,,. GPC-GC 10 [J]., 2014, 53(3): Sun HQ, Li YQ, Xu GJ, et al. Simultaneous determination of 10 herbicides residue in tobacco by GPC-GC [J]. Agrochemicals, 2014, 53(3): [13] Qi DW, Fei T, Sha YF, et al. A novel fully automated on-line coupled liquid chromatography-gas chromatography technique used for the determination of organochlorine pesticide residues in tobacco and tobacco products [J]. J Chromatogr A, 2014, 1374: [14],,,. / - / - 33 [J]., 2008, 26(1): Hu BZ, Song WH, Xie LP, et al. Determination of 33 pesticides in tea by accelerated solvent extraction-gel permeation and solid-phase extraction purification-gas chromatography-mass spectrometry [J]. Chin J Chromatogr, 2008, 26(1): [15],,,. QuEChERS GPC/GC-MS 15 [J]., 2015, 34(12): Li HF, Nie JY, Xu GF, et al. Evaluation of QuEChERS method for the analysis of 15 triazole pesticides residues in fruits by online gel permeation chromatography gas chromatography mass spectrometer [J]. J Instrum Anal, 2015, 34(12): [16] Lu D, Qiu X, Feng C, et al. Simultaneous determination of 45 pesticides in fruit and vegetable using an improved QuEChERS method and on-line gel permeation chromatography gas chromatography/mass spectrometer [J]. J Chromatogr B, 2012, 895: [17],,. [J]., 2005, (6): Liu JL, Xia MZ, Yuan Y. Psidium guajava integrated utilization and its development prospects in China [J]. Forest By-Prod Special China, 2005, (6): 作者简介 ( 责任编辑 : 金延秋 ) 张群, 博士, 助理研究员, 主要研究方向为农药等有机污染物检测及污染修复 zhangqun123@zju.edu.cn