Microsoft Word 史晓梅-二校

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1 6 4 Vol. 6 No Journal of Food Safety and Quality Apr., 2015 * 史晓梅, 陈士恒, 章晴, 高丁, 杨永坛 (,, ) 摘要 : 目的 - (GC-ECD) 16 方法, Florisil,, 结果 ~0.5 mg/l, R ; mg/kg 71.0%~103%, 1.28%~8.74%, 0.1~16 μg/kg 结论,,, 关键词 : ; ; ; ; Simultaneous determination of organic chlorine and pyrethroid pesticides residues in corn by solid phase extraction-gas chromatography SHI Xiao-Mei, CHEN Shi-Heng, ZHANG Qing, GAO Ding, YANG Yong-Tan * (Beijing Key Laboratory of Nutrition Health and Food Safety, COFCO Nutrition & Health Research Institute, Beijing , China) ABSTRACT: Objective To develop a method for the simultaneous determination of organic chlorine and pyrethroid pesticides residues in corn by gas chromatography with ECD detector. Methods Corn samples were extracted with acetonitrile by ultra-sonic, and the extracts were purified by solid phase extraction using Florisil, then samples were detected by GC-ECD after concentrated by nitrogen flushing. Results The method showed a good linearity in the range of 0.01~0.5 mg/l for organic chlorine and pyrethroid pesticides with R 2 >0.99. The recoveries were in the range of 71.0%~103% at 3 spiked levels of 0.02, 0.05, and 0.2 mg/kg for organic chlorine and pyrethroid pesticides, and the relative standard deviations (RSDs) were 1.28%~8.74%. The limit of detection was in the range of 0.1~16 μg/kg. Conclusion The method is suitable for quantitative and qualitative determination of organic chlorine and pyrethroid pesticides residues in a large number of corn samples with a sample and fast pretreatment procedure. Meanwhile, samples can be effectively cleaned up, and it could meet the requirements of daily inspection and supervision work. KEY WORDS: organic chlorine pesticides; pyrethroid pesticides; solid phase extraction; gas chromatography; corn * 通讯作者 :,, yangyongtan@cofco.com *Corresponding author: YANG Yong-Tan, Senior Engineer, Food Quality & Safety Center, COFCO Nutrition & Health Research Institute, Road No.4, Future Science and Technology Park South, Beiqijia, Changping, Beijing , China. yangyongtan@cofco.com

2 4, : 引言,,, [1,2], [3], 300, ( ),, [4-8], [9] - ( ),,,, [10-13],,,,,,, 2 材料与方法 2.1 仪器与材料 : 100 mg/l, 99.0% 99.6% ( ), 0.5 ml 5 ml,, 10 mg/l ; Florisil (1 g/6 ml, ); (, Fisher ) GC-2010 Plus ( ECD, ); TG 16-II ( ); BSA 224S-CW ( ); SB-3200 DTDN ( ); HGC-24A ( ); QL-902 ( ); ( ) 2.2 实验方法样品前处理 10.0 g, 50 ml, 20 ml, 2 min, 20 min, 8000 r/min 5 min 5 ml 5 ml - (90:10, v:v) Florisil,, 2 ml, 10 ml - (95:5, v:v),,, 1.0 ml, 仪器条件 : DB-35ms(30 m 0.25 mm, 0.25 μm, Agilent ) : min, 10 /min 300, 18 min; :,, 1.0 ml/min; : 220 ; :, : 10:1; : 1 μl; 结果和讨论 3.1 前处理条件的选择,,,,,,, 30 min, (Florisil),, Florisil 16 1

3 (0.01 mg/kg) Fig. 1 Chromatogram of the 16 organ chlorine pesticides matrix-match standard solutions (0.01 mg/kg) ( : 1: α- ; 2: γ- ; 3: β- ; 4: ; 5: δ- ; 6: ; 7: p, p - ; 8: o, p - ; 9: p, p - ; 10: p, p - 11: ; 12: ; 13: 1; 14: 2; 15: -1; 16: -2; 17: -3; 18: -1; 19: -2; 20: ) (1: α-hch; 2: γ-hch; 3: β-hch; 4: Heptachlor; 5: δ-hch; 6: aldrin; 7: p, p -DDE; 8: o, p -DDT; 9: p, p -DDD; 10: p, p -DDT; 11: fenpropathrin; 12: cyhalothrin; 13: permethrin-1; 14: permethrin-2; 15: cypermethrin-1; 16: cypermethrin-2; 17: cypermethrin-3; 18: esfenvalerate-1; 19: esfenvalerate-2; 20: deltamethrin) 3.2 线性范围方法回收率与检出限, 10 mg/l mg/l,, 3, 6, RSD, S/N=3 (LOD), S/N=10 (LOQ), 不确定度评价,, A B [14,15], : 标准品纯度引入的不确定度 100 mg/l, u c ±0.06 mg/l, : u c rel = (0.06 mg/l)/ (100 mg/l) = 样品称重质量引入的不确定度 10 g ( 0.1 mg), k= 3, u m( )=a/k=0.1 mg/ 3 = mg, u m rel = mg/10000 mg= , 体积引入的不确定度, : A, u v rel = 标准曲线引入的不确定度 6 ( ), 2,,, Y=734188X-1958 ( 1) 1, S= , n j [A (B C B )] S n 2 2, S xx n j 1 j (C C) 0.322, 2 S 1 1 (C C) u ucc , u cc rel xx = B1 p n Sxx x 重复性引入的不确定度 6, 2

4 4, : u rep n k 1 ( xk x ) n 1 2, u rep rel = 合成不确定度 =0.0006, =0.0136, =0.301, = rel c rel v rel cc rel rep rel u u u u u = 实际样品分析 5, 2 (MRL) GB , α- β- γ- δ-, p, p - o, p - p, p - p, p - 2 5, 3, 0.05 mg/kg Table 1 表 1 16 种有机氯拟除虫菊酯农药的线性范围相关系数回收率检出限 (n=6) Linear equations, correlation coefficients, recoveries, LOD of 16 organic chlorine and pyrethroid pesticides matrix-match standard solutions (n=6) R mg/kg 0.05 mg/kg 0.2 mg/kg LOD (μg/kg) (RSD, %) (RSD, %) (RSD, %) 1 α- Y= X (5.58) 86.6 (5.84) 90.0 (3.31) β- Y= X (4.05) 103 (4.78) 101 (2.03) γ- Y= X (6.31) 92.0 (6.24) 94.0 (3.23) δ- Y= X (7.09) 92.0 (4.38) 95.0 (2.31) p,p - Y= X (5.52) 95.4 (3.50) 93.5 (1.31) p,p - Y= X (4.94) 94.8 (2.99) 95.5 (2.10) p,p - Y= X (5.50) 92.2 (4.15) 92.0 (1.84) o,p - Y= X (5.74) 99.2 (3.73) 96.5 (1.63) Y= X (3.11) 90.2 (6.13) 93.5 (2.84) Y= X (5.92) 91.0 (5.30) 93.0 (2.72) Y=592013X (4.49) 103 (2.82) 98.0 (1.37) Y= X (2.11) 93.0 (2.22) 94.0 (2.84) Y=326012X (2.64) 96.2 (2.73) 89.5 (1.28) Y=734188X (4.44) 94.6 (8.22) 95.5 (1.61) Y= X (2.14) 93.4 (2.55) 83.0 (1.76) Y=553264X (8.74) 95.6 (5.34) 94.0 (3.09) 1.6 Table 2 表 2 实际玉米样品检测结果 (mg/kg) Determination results of real corn samples (mg/kg) Corn 1 Corn 2 Corn 3 Corn 4 Corn 5 MRL (mg/mg) n.d n.d n.d. n.d. n.d. n.d. n.d n.d. n.d. n.d. n.d. n.d n.d. n.d. n.d. n.d. n.d n.d. n.d. n.d. n.d. n.d. 0.1 n.d. n.d. n.d. n.d. n.d n.d. n.d. n.d. n.d. n.d. 2.0 n.d. n.d. n.d. n.d. n.d n.d. n.d. n.d. n.d. n.d n.d. n.d. n.d. n.d. n.d. 0.2 : n.d.

5 结论 -, Florisil,,, 0.02~0.20 mg/kg, %~103%, (n=6) 1.28%~8.74%, 0.1~16 μg/kg,, 参考文献 [1],,,. [J]., 2013, 34(14): Wang ZL, An J, Wang XH, et al. Method research of multi organochlorine pesticides determination technology in corn and soybean [J]. Chin J Food Res Dev, 2013, 34(14): [2] Stanisław W, Dariusz D. Improvement and extension to new analytes of a multi-residue method for the determination of pesticides in cereals and dry animal feed using gas chromatography tandem quadrupole mass spectrometry revisited [J]. J Chromatogr A, 2012, 1251(16): [3] Zhang YP, Yang J, Shi RH. Development of an analytical method based on accelerated solvent extraction, solid-phase extraction clean-up, then GC ECD for analysis of fourteen organochlorine pesticides in cereal crops [J]. Chin J Chromatogr, 2011, 73(3): [4],,, [J]., 2007, 17(5): Lu XY, Han S, Wang JH, et al. Mulresidue deterrnination of 50 pesticides in corn by gas chromatography/mass spectrometry [J]. Chin J Mod Sci Instrum, 2007, 17(5): [5] Pang GF, Liu YM, Fan CL, et al. Simultaneous determination of 405 pesticide residues in grain by accelerated solvent extraction then gas chromatography-mass spectrometry or liquid chromatography-tandem mass spectrometry [J]. Anal Bioanal Chem, 2006, 384(6): [6],,, [J]., 2009, 27(2): Li CF, Shen WJ, Jiang Y, et al. Determination of 20 kinds of pesticide residues in soybeans and corn using gas chromatography-negative chemical ionization mass spectrometry coupled with offline disperse solid-phase extraction [J]. Chin J Chromatogr, 2009, 27(2): [7] He ZY, Wang L, Peng Y, et al. Multiresidue analysis of over 200 pesticides in cereals using a QuEChERS and gas chromatography tandem mass spectrometry-based method [J]. Food Chem, 2015, 169: [8] Kang S, Chang N, Zhao Y, et al. Development of a method for the simultaneous determination of six sulfonylurea herbicides in wheat, rice, and corn by liquid chromatography-tandem mass spectrometry [J]. J Agric Food Chem, 2011, 59(18): [9],,,. - [J]., 2013, 32(3): Yang JJ, Tong L, WU SQ, et al. Determination of organochlorine pesticides and polychlorinated biphenyls in grains using gas chromatography with accelerated solvent extraction [J]. Chin J Rock Miner Anal, 2013, 32(3): [10],,. - [J]., 2006, 25(6): Shao H, Liu S, Qian YZ. Evaluation on uncertainty of determination of dimethoate by GC-MS [J]. Chin J Anal Lab, 2006, 25(6): [11],. [J]., 2006, 25(12): Jiang YX, Ye L. Uncertainty evaluation of determination of organophosphorus pesticide multi-residues in tea [J]. Chin J Anal Lab, 2006, 25(12): [12] Stanisław W. Validation and use of a QuEChERS-based gas chromatographic tandem mass spectrometric method for multiresidue pesticide analysis in black currants including studies of matrix effects and estimation of measurement uncertainty [J]. Talanta, 2014, 120: [13] Jordi Q, Isabel M, Francesc V. Monitoring of pesticides in drinking and related waters in NE Spain with a multiresidue SPE-GC MS method including an estimation of the uncertainty of the analytical results [J]. J Chromatogr A, 2001, 938(1): [14] JJF [S]. JJF Evaluation of uncertainty in chemical analysis measurement [S]. [15],,,. - [J]., 2014, 35(12): Wang JX, Zhang XZ, Wang YQ, et al. Uncertainty evaluation for the determination of bifenthrin in tea by gas chromatography and gas chromatography-mass spectrometry [J]. Food Sci, 2014, 35(12): ( 责任编辑 : 李振飞 )

4, : - 1127 作者简介史晓梅, 研发专员, 主要研究方向为食品质量与安全 E-mail:

com 杨永坛, 高级工程师, 主要研究方向为食品质量与安全 E-mail: yangyongtan@cofco.

6 4, : 作者简介史晓梅, 研发专员, 主要研究方向为食品质量与安全 shi_xiaomei@cofco.com 杨永坛, 高级工程师, 主要研究方向为食品质量与安全 yangyongtan@cofco.com 鲜切果蔬专题征稿,,,,,, ,,, 投稿方式 : : jfoodsq@126.com 食品安全质量检测学报编辑部

Microsoft Word 陈啟荣-二校

Microsoft Word 陈啟荣-二校 7 4 Vol. 7 No. 4 2016 4 Journal of Food Safety and Quality Apr., 2016-26 陈啟荣 *, 杨明, 梁颖, 朱琳娜, 邵鹏, 范筱京 (,, 100089) 摘要 : 目的 - 26 方法,, 结果,, 26 0.04~1.6 µg/ml 0.005~0.05 mg/kg, 0.015~0.15 mg/kg, 66.6%~125.5%,