7 5 Vol. 7 No. 5 2016 5 Journal of Food Safety and Quality May, 2016-3 张 1, 群 2* 1,, 吴南村 2 1,, 张月 2, 刘春华 1, 2 (1., 571101; 2., 571101) 摘要 : 目的 3 - (gel permeation chromatography-gas chromatography-tandem mass spectrometry, GPC-GC-MS/MS) 方法,,, 结果 3 0.05~0.50 mg/l, 0.9990; 0.002 0.005 0.01 mg/kg; 0.05 0.10 0.50 mg/kg 3, 3 83.3%~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 571101, China; 2. Hainan Provincial Key Laboratory of Quality and Safety for Tropical Fruits and Vegetables, Haikou 571101, 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 0.9990 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, 0.005 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 : (201500202) (0104932035) Fund: Supported by Risk Assessment of National Agricultural Products Quality and Safety Program (201500202) and Natural Science Foundation of Hainan Province (0104932035) * 通讯作者 :,,, E-mail: 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 571101, China. E-mail: zhangqun123@zju.edu.cn
5, : - 3 2021 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],, 0.05 0.01 0.02 mg/kg [3-5] 0.05 0.02 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-280-12 ( ); QL-901 ( ); SLB-5ms ( SUPELCO ); ( )(25 mm 0.45 µm, ) 2.3 试验方法 2.3.1 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 10.00 ml, 50 ml, 40, 10 ml / (1:1, V:V),, GPC GPC,, 2 ml,, - 2.3.2 添加回收率与精密度测定 3 3, 5, 0.05 0.10 0.50 mg/kg,, 2.3.3 标准溶液及基质标准溶液的配制 : 100 mg/l, 18 : ( ),, 2.3.4 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; : 19.25 min; :, 99.999%;,, 1.00 ml/min; : 260 ; : 1 µl; :
2022 7 : : 1.50 ml/min, 2.25 ml/min; : : 70 Ev; : ; : 230 ; : 4.00 min;, 3,, 1 2.3.5 GPC 条件 GPC : 25 mm 400 mm; : Bio-Beads S-X3(200-400 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, 3 3.3 线性方程 定量限 回收率和精密度 3.3.1 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 6.143 314/258 9.706 135/107 1 14.465 226/206 2 14.656 226/206 3 14.765 226/206 4 14.856 226/206 314>258 15 314>286 12 135>107 17 135>95 15
5, : - 3 2023 3.3.2 定量限 3 (S/N) 3 (LOD) 9 10 5 mg/kg; 10 (LOQ) 3 10 4 mg/kg, 0.002 0.005 0.01 mg/kg, 5 72.5% 74.1% ' 77.4%, (RSD) 8.0% 7.4% 5.2% 3.3.3 回收率和精密度 0.05 0.10 0.50 mg/kg 3, 3 83.3%~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)
2024 7 : A. MRM ; B. MRM. : a. ; b. ; c1. 1; c2. 2; c3. 3; c4. 4. 2 (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 2 0.05~0.50 Y=1.347 10 4 X 338.7 0.9993 0.05~0.50 Y=2.539 10 4 X 815.1 0.9994 0.05~0.50 Y=4.489 10 3 X 119.8 0.9995 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) /% /% 0.05 0.10 0.50 0.05 0.10 0.50 0.05 0.10 0.50 92.6 91.6 104.8 87.8 88.9 102.2 83.3 97.6 99.7 7.6 7.9 6.6 7.0 5.4 4.9 3.9 6.9 2.9
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