Microsoft Word 袁烁二校2871

Size: px

Start display at page:

Download "Microsoft Word 袁烁二校2871"

铜乐
5 years ago
Views:

1 5 9 Vol. 5 No Journal of Food Safety and Quality Sep., * 袁烁, 赵建庄, 蔡慧敏, 贾临芳, 梁丹, 魏朝俊 (, ) 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 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 , 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 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 : (KM , PXM2014_014207_000001); ( ) Fund: Supported by General Program of Science and Technology Development Project of Beijing Municipal Education Commission (KM , PXM2014_014207_000001); Youth Fund of Beijing University of Agriculture ( ) * 通讯作者 :,, chaojunwei@sina.com *Corresponding author: WEI Chao-Jun, Technician, Beijing University of Agriculture, No.7, Huilongguan, Changping District, Beijing , China. chaojunwei@sina.com

2 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 );

3 9, : (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 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, 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 chlorothalonil acetochlor chlorpyrifos procymidone flutriafol myclobutanil kresoxim-methyl cyhalothrin pyridaben fenvalerate difenoconazole dimethomorph

4 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 Fig. 1 The chromatogram of thirteen pesticides 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 The recoveries of thirteen pesticides by NH 2, Florisil, C 18 solid-phase extraction column

5 9, : 洗脱剂体积优化,, / (80:20), mL,,, 10 ml, 90%, 10 ml 3.5 方法的线性关系和检出限 6,,, 方法的回收率和精密度,, 5,,, 3 3, %~114.5%, 2.17%~6.85%, 3.7 样品测定 50,,, , 2.8, 结论 - 13,, 70.5%~114.5 %, 2.17%~6.85%, 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 ~1 Y=6117.2X ~5 Y=39263X ~1 Y=51433X ~5 Y=63892X ~10 Y=2544.4X ~5 Y=24555X ~1 Y=99512X ~0.5 Y=9192.6X a 0.02~1 Y=35386X ~1 Y=2619.5X ~5 Y=12882X ~10 Y=4464.4X * ; a, mg/kg

6 / 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 %

7 9, : ,, 参考文献 [1],,,. [J]., 2006, 1: Lai SC, Wang FH, Deng YC, et al. Analysis of present research situation and development of residual pesticides at home and abroad [J]. Guangdong Agri Sci, 2006, 1: [2]. [J]., 2000, 21(2): Qiao XW. Oversea pesticide residue monitoring in food [J]. Pestic Sci Admin, 2000, 21(2): [3],,,. SPE-GC 7 [J]., 2012, 31(11): Yang ZH, Wei CJ, Zhao JZ, et al. Simultaneous determination of the residue of seven commonly -used pesticides in strawberry with solidphase extraction and gas chromatography [J]. J Agro-Environ Sci, 2012, 31(11): [4],,. [J]., 2011, 14: Liang LJ, Li QK, Yang X J. Status analysis of pesticide residues in strawberry samples based on laboratory [J].Guangdong Agri Sci, 2011, 14: [5],,, [J]., 2011, 50(5): Yang JC, WuQ, Li XJ, et al. New active ingredients registered or launched in 2010 [J]. Agrochemicals, 2011, 50(5): [6] Fernandes VC, Domingues VF, Mateus N, et al. Organochlorine pesticide residues in strawberries from integrated pest management and organic farming[j]. J Agric Food Chem, 2011, 59(14): [7] Hirahara Y, Kimura M, Inoue T, et al. Validation of multiresiduescreening methods for the determination of 186 pesticides in agricultural products using gas chromatography(gc) [J]. J Health Sci, 2005, 51(5): [8] Bolanos PP, Moreno JL F, Shtereva DD, et al. Development and validation of a multiresidue method for the analysis of 151 pesticide residues in strawberry by gas chromatography coupled to a triple quadrupole mass analyzer [J]. Rapid Commun Mass SP, 2007, 21(14): [9],. - [J]., 2013, 29(6): Zhai SL, Zhang XF. Determination of organophosphorus pesticides in strawberry by GC-SPE [J]. Mod Food Sci Tech, 2013, 29(6): [10],,,. MSPD/UPLC-TOFMS 4 [J]., 2012, 51(5): Lu H, Wu GJ, Liang SQ, et al. Determination of 4 pesticide residues in strawberry using MSPD/UPLC-TOFMS [J]. Agrochemicals, 2012, 51(5): [11],,,. - 5 [J]., 2009, 30(14): Li RY, Yuan XR, Li H, et al. Headspace solid-phase microextraction and gas chromatography-mass spectrometry for the rapid detection of 5 organophosphorus pesticide residues in strawberries [J]. Food Sci, 2009, 30(14): [12],,,. MAE/GC [J]., 2008, 1: 76 78, 83. Yu Y, Meng H, Du CL, et al. Analysis of organophosphorous pesticide residue in strawberry by MAE/GC Method [J]. Henan Agri Sci, 2008, 1: 76 78, 83. [13],,,. SPE-HPLC 10 [J]., 2013, 29(10): Shao JL, Wang LX, Mei WQ, et al. Determination of 10 pesticide residues in fruits by HPLC with SPE and UV double wavelength [J]. Mod Food Sci Tech, 2013, 29(10): [14],,. QuEChERs-UPLC-MS/MS 7 [J]., 2013, 34(2): Guo CJ, Wang JZ, Hao XL. The condition optimization determination of multi-reside of pesticides in cabbage and strawberry by QuEChERs-UPLC-MS/MS [J]. J Chi Mass Spect Soci, 2013, 34(2): [15]. - [J]., 2010, 22(6) : Liu Z. Determination of pesticide residues in tea by accelerated solvent extraction-gas chromatography [J]. Chin J Food Hygi, 2010, 22(6): [16],,,. [J]., 2009,11(14): Zhang ZH, Li HY, Wu M, et al. Residue and risk assessment of chlorothalonil,myclobutanil and pyraclostrobin in greenhouse

2876 5 strawberry [J]. Chi J Pesti Sci, 2009, 11(14): 449 455. [17],,,. 54 QuEChERS/GC-MS [J]., 2008, 27(1): 66 69. DongJ, Pan YX, Zhu LP, et al.

Gao WH, Wang FC, Guo CM. Simultaneous determination of 7 herbicides in strawberry by gas chromatography-mass spectrometry [J]. Food Sci, 2008, 29(2): 359 361. [19],,,. - 9 [J]., 2011, 32(2): 44 47.

8 strawberry [J]. Chi J Pesti Sci, 2009, 11(14): [17],,,. 54 QuEChERS/GC-MS [J]., 2008, 27(1): DongJ, Pan YX, Zhu LP, et al. Improvements and applications of the QuEChERS method in multi-residueanalysis of 54 pesticides in vegetables and fruits[j]. J Instrum Ana, 2008, 27(1): [18],,. - 7 [J]., 2008, 29(2): Gao WH, Wang FC, Guo CM. Simultaneous determination of 7 herbicides in strawberry by gas chromatography-mass spectrometry [J]. Food Sci, 2008, 29(2): [19],,,. - 9 [J]., 2011, 32(2): Sun DL, HuQ B, Yang F, et al. Determination of nine pesticide residues in fruits by dispersive-spe-gas chromatography[j]. J South Chi Agri Uni. 2011, 32(2): [20] Li HP, LinCH, Jen JF. Analysis of aqueous pyrethroid residualsby one-step microwave-assisted headspace solid-phasemicroextraction and gas chromatography with electron capture detection [J]. Talanta, 2009, 79(2): [21] Tuan SJ, Tsai HM, Hsu SM, et al. Multiresidueanalysis of 176 pesticides and metabolites in pre-harvested fruits and vegetables for ensuring food safety by gas chromatography and high performance liquid chromatography[j]. J Food Drug Ana, 2009, 17(3): [22] TaoCJ, Hu JY, Li JZ, et al. Multi-residue determination of pesticides in vegetables by gas chromatography/ion trap mass spectrometry [J]. B Environ Contam Tox, 2009, 82: 作者简介 ( 责任编辑 : 白洪健 ) 袁烁, 硕士研究生, 主要研究方向为农药残留分析 @qq.com 魏朝俊, 实验师, 主要研究方向为仪器分析及农产品安全检测技术 chaojunwei@sina.com

DOI /j.issn Food Research And Development UPLC-MS/MS 5 0.

DOI /j.issn Food Research And Development UPLC-MS/MS 5 0. 118 217 5 38 1 DOI 1.3969/j.issn.5-6521.217.1.28 Food Research And Development 1 2 1 2 1 2 1 2 1 2 1 2 1. 731 2. 731 - UPLC-MS/MS 5. 1 mol/l ProElut PXC 5 % - Thermo Hypersil Gold mm 2.1 mm 1.9 μm ESI

Microsoft Word 袁 烁二校2871

Microsoft Word 袁烁二校2871