5 9 Vol. 5 No. 9 2014 9 Journal of Food Safety and Quality Sep., 2014-13 * 袁烁, 赵建庄, 蔡慧敏, 贾临芳, 梁丹, 魏朝俊 (, 102206) 摘要 : 目的 -, 13, 7, 4 2 方法 20 g, 50 ml, NH 2, HP-5, GC-ECD 结果 13, 0.996, 0.01 mg/kg~0.5 mg/kg 13 0.01 mg/kg~2 mg/kg, 70.5%~114.5%, 2.17%~6.85% 结论, 50, 6 关键词 : ; ; ; Simultaneous determination for the residue of thirteen pesticides in strawberry with solid phase extraction and gas chromatography YUAN Shuo, ZHAO Jian-Zhuang, CAI Hui-Min, JIA Lin-Fang, LIANG Dan, WEI Chao-Jun * (Beijing University of Agriculture, Beijing 102206, China) ABSTRACT: Objective To established a solid phase extraction-capillary gas chromatography method for the determination of 13 pesticides multi-residues in strawberry, including seven fungicides such as chlorothalonil, procymidone, flutriafol, myclobutanil, kresoxim-methyl, difenoconazole and dimethomorph; four insecticides such as chlorpyrifos, cyhalothrin, pyridaben and fenvalerate; two herbicides such as atrazine and acetochlor. Methods After the homogenized strawberry samples with 20 g were extracted with acetonitrile by 50 ml and purified with NH 2 solid-phase extraction column, the samples were separated by HP-5 gas chromatography column and detected with GC-ECD. Results A good separation for 13 pesticides was achieved using the established method, with correlation coefficients above 0.996. The detection limit of the method was 0.01~0.5 mg/kg. Shown as the addition recovery experiments, the method average recoveries of the 13 pesticides ranged from 70.5% to 114.5% in the range of 0.01 mg/kg~2 mg/kg. The relative standard 基金项目 : (KM201210020014, PXM2014_014207_000001); (2077516003) Fund: Supported by General Program of Science and Technology Development Project of Beijing Municipal Education Commission (KM201210020014, PXM2014_014207_000001); Youth Fund of Beijing University of Agriculture (2077516003) * 通讯作者 :,, E-mail:chaojunwei@sina.com *Corresponding author: WEI Chao-Jun, Technician, Beijing University of Agriculture, No.7, Huilongguan, Changping District, Beijing 102206, China. E-mail:chaojunwei@sina.com
2870 5 deviation was 2.17%~6.85%. Conclusion The method showed simple, rapid, and sensitive, with good purifying effect and high recovery rate, and was suitable for the detection and security monitoring of pesticide residues in strawberry. Six kinds of pesticides, chlorothalonil, chlorpyrifos, acetochlor, flutriafol, kresoxim methyl, and dimethomorph, were found through the detection in 50 strawberry samples. KEY WORDS: strawberry; solid-phase extraction; gas chromatography; pesticide residues. 1 引言,,, [1-2],, [3], ; ; [4-6] 13, (MRLs) [7] Bolanos [8], - (GC/QqQ-MS/MS) ;, (GC HPLC GC-MS LC-MS) [9-14],, 13,,, [15], [16], [17] ; [18-20] QuEChERs(Quick Easy Cheap Effective Rugged Safe) QuEChERs, GC, 13,, 2 材料与方法 2.1 试剂耗材与农药标准品 : (, ), 3 ; (, Tedia Fairfieldoh, USA); NH 2 C 18 Florisil, 1000 mg/6 ml( Agilent ); 0.45 µm ( Membrana ); ( ) : 13 ( ) 100 µg/ml,, ( ) 2.2 实验仪器与设备 (Agilent 6890 N, µ-ecd, Agilent ); (Laborota 4001, Heidolph ); (SC-8 L-150, ); (Kubota 6200, Kubota );
9, : - 13 2871 (KQ-600, ); (XW-80 A, ); (CP-225 D, Sartorius ); (EPS-502, ); (SHB-Ⅲ, ); (FW-100, ); (MDF-U 3286 S, Sanyo ) ; (G72X-9070 MBE, ); ( Eppendorf ); ( ) 2.3 色谱条件 : HP-5 (30 m 0.32 mm i.d., 0.25 µm); 280 ; : 170, 5 /min 210, 5 min, 10 /min 265, 11.5 min; (µecd) 300 ;, 2.0 ml/min, 93.3 kpa, N 2 40.0 ml/min; 1 µl; : 2.4 标准曲线的制作 13 :, 2 ml,, 4 ( 1) 1.0 µl,, 2.5 样品预处理 2.5.1 样品提取 (, 50, 1 kg), 20 g 250 ml, 50 ml 10 ml, 30 min, 100 ml ( 7.0 g ), 3 min,,, 10 ml 15 ml ( 5 g ), 3 min, 5000 r/min 10 min, 5 ml 25 ml, 1~2 ml, 2.5.2 样品净化 NH 2, 5 ml 5 ml 5 ml / ( 80/20),,, 5 ml / (80/20), 25 ml, 30, 1.0 ml, 0.45 µm, Table 1 表 1 13 种农药保留时间及标准系列浓度 The retention time and standard concentration of 13 pesticides /min µg/ml 1 atrazine 4.696 0.2 0.5 1 2 5 10 2 chlorothalonil 5.569 0.02 0.05 0.1 0.2 0.5 1 3 acetochlor 6.213 0.1 0.25 0.5 1 2.5 5 4 chlorpyrifos 7.467 0.02 0.05 0.1 0.2 0.5 1 5 procymidone 8.876 0.1 0.25 0.5 1 2.5 5 6 flutriafol 9.725 0.2 0.5 1 2 5 10 7 myclobutanil 10.758 0.1 0.25 0.5 1 2.5 5 8 kresoxim-methyl 11.145 0.02 0.05 0.1 0.2 0.5 1 9 cyhalothrin 18.067 0.01 0.025 0.05 0.1 0.25 0.5 10 pyridaben 19.126 0.02 0.05 0.1 0.2 0.5 1 11 fenvalerate 22.399 0.02 0.05 0.1 0.2 0.5 2 12 difenoconazole 23.57 0.1 0.25 0.5 1 2.5 5 13 dimethomorph 25.301 0.2 0.5 1 2 5 10
2872 5 3 结果与分析 3.1 色谱柱的选择 HP-5 DB-17, : HP-5,,, 30 min 13, ( 1) 3.2 提取溶剂的选择 [21],,, 40.7%~86.6%;, 59.3%~ 98.1%,,,,,,, 70.5%~114.5%, 3.3 固相萃取柱的选择 [22] NH 2, C 18 Florisil,, C 18, Florisil, NH 2,, ( 2), NH 2 95%, Florisil C 18 90% 85%, NH 2 1 13 Fig. 1 The chromatogram of thirteen pesticides 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 1. atrazine 2. chlorothalonil 3. acetochlor 4. chlorpyrifos 5. procymidone 6. flutriafol 7. myclobutanil 8. kresoxim-methyl 9. cyhalothrin 10. pyridaben 11. fenvalerate 12. difenoconazole 13.dimethomorph Fig. 2 2 13 3 The recoveries of thirteen pesticides by NH 2, Florisil, C 18 solid-phase extraction column
9, : - 13 2873 3.4 洗脱剂体积优化,, / (80:20), 5 10 15 20mL,,, 10 ml, 90%, 10 ml 3.5 方法的线性关系和检出限 6,,, 2 3.6 方法的回收率和精密度,, 5,,, 3 3, 13 70.5%~114.5%, 2.17%~6.85%, 3.7 样品测定 50,,, 3 1.4 5.9 1.7, 2.8, 2 1.1 3.8 4 结论 - 13,, 70.5%~114.5 %, 2.17%~6.85%, 13 0.01 mg/kg~0.5 mg/kg, Table 2 表 2 13 种农药的线性回归方程 相关系数 方法检出限和残留限量标准 The liner range, correlation coefficient, method detection limits and residue limits of 13 pesticides µg/ml mg/kg * mg/kg 0.2~10 Y=2835.8X 164.13 0.9987 0.025 0.05 0.02~1 Y=6117.2X+79.658 0.9975 0.5 3 0.1~5 Y=39263X 1912.7 0.9992 0.01 0.02 0.02~1 Y=51433X 121.31 0.9967 0.1 0.2 0.1~5 Y=63892X 5575.0 0.9988 0.01 0.02 0.2~10 Y=2544.4X 102.59 0.9981 0.25 0.5 0.1~5 Y=24555X 368.77 0.9998 0.5 1 0.02~1 Y=99512X+265.85 0.9996 0.5 1 0.01~0.5 Y=9192.6X 66.517 0.9979 0.01 0.02 a 0.02~1 Y=35386X 386.91 0.9996 0.5 1 0.02~1 Y=2619.5X 28.484 0.9978 0.01 0.02 0.1~5 Y=12882X 909.16 0.9981 0.05 0.1 0.2~10 Y=4464.4X 276.71 0.9990 0.025 0.05 * ; a, 13 0.02 mg/kg
2874 5 / mg kg 1 表 3 13 种农药在草莓中的添加回收率 (n=5) Table 3 Recoveries of 13 pesticides in strawberry(n=5) /% I II III IV V % 0.025 108.3 103.9 104.6 95.9 102.1 102.9 3.17 0.05 105.2 101.7 102.5 94.6 100.8 100.9 2.61 0.1 102.4 99.5 98.1 92.4 97.2 97.9 2.50 0.5 80.1 76.3 77.8 70.9 75.4 76.1 2.36 1 79.8 74.7 75.3 68.6 73.1 74.3 2.76 2 76.4 71.7 72.2 65.4 70.5 71.2 2.63 0.01 119.9 114.7 116.1 104.6 110.8 113.2 4.42 0.02 112.6 107.2 108.7 99.3 105.5 106.6 3.41 0.04 108.4 102.3 103.6 94.8 101.7 102.2 3.13 0.1 100.1 98.4 98.8 89.3 94.2 96.2 3.53 0.2 99.3 95.5 96.2 86.6 92.6 94.0 3.55 0.4 94.8 90.7 91.1 82.4 85.7 88.9 3.91 0.01 87.6 85.6 86.1 78.9 84.5 84.5 2.27 0.02 83.8 80.3 81.2 74.7 79.8 79.9 2.17 0.04 79.9 76.8 78.4 69.6 73.4 75.6 3.30 0.25 119.9 117.6 108.6 101.5 114.3 112.4 5.86 0.5 117.3 115.9 106.6 97.8 102.6 108.0 6.85 1 110.7 104.5 103.8 94.7 104.1 103.6 3.54 0.5 81.3 80.6 80.8 70.4 79.1 78.4 3.22 1 78.8 77.2 76.6 68.9 74.6 75.2 2.78 2 76.1 74.3 74.4 65.8 70.7 72.3 3.21 0.5 78.5 77.4 78.0 70.3 75.8 76.0 2.36 1 75.3 74.6 75.2 67.9 72.6 73.1 2.30 2 73.9 72.1 72.4 64.0 70.3 70.5 2.71 0.01 90.5 86.6 88.2 78.8 85.9 86.0 2.92 0.02 84.4 81.1 83.0 73.3 82.2 80.8 3.00 0.04 80.9 77.4 78.7 69.5 76.6 76.6 2.86 0.5 106.1 100.3 101.7 91.9 98.8 99.8 3.53 1 101.6 96.8 97.3 87.6 92.4 95.1 4.11 2 99.7 93.0 93.9 82.7 88.5 91.6 4.77 0.01 120.6 116.3 117.4 104.4 113.6 114.5 4.39 0.02 108.5 103.8 104.7 95.6 102.5 103.0 3.18 0.04 97.4 91.3 91.8 80.4 90.7 90.3 3.97 0.05 106.0 101.7 103.1 93.7 100.6 101.0 3.09 0.1 97.3 95.9 96.3 85.3 95.8 94.1 3.53 0.2 91.6 90.0 90.4 79.5 88.4 87.9 3.39 0.025 120.7 116.5 115.3 101.3 113.2 113.4 4.92 0.05 111.9 106.4 104.8 93.8 105.3 104.4 4.26 0.1 104.5 99.8 98.9 85.1 97.9 97.2 4.86
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