6 4 Vol. 6 No. 4 2015 4 Journal of Food Safety and Quality Apr., 2015 * 史晓梅, 陈士恒, 章晴, 高丁, 杨永坛 (,, 102209) 摘要 : 目的 - (GC-ECD) 16 方法, Florisil,, 结果 16 0.01~0.5 mg/l, R 2 0.99; 0.02 0.05 0.2 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 102209, 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 :,, E-mail: 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 102209, China. E-mail: yangyongtan@cofco.com
4, : - 1123 1 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 2.2.1 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, 2.2.2 仪器条件 : DB-35ms(30 m 0.25 mm, 0.25 μm, Agilent ) : 100 2 min, 10 /min 300, 18 min; :,, 1.0 ml/min; : 220 ; :, : 10:1; : 1 μl; 320 3 结果和讨论 3.1 前处理条件的选择,,,,,,, 30 min, (Florisil),, Florisil 16 1
1124 6 1 16 (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 0.500 0.200 0.050 0.020 0.010 mg/l,, 3, 6, RSD, S/N=3 (LOD), S/N=10 (LOQ), 1 3.3 不确定度评价,, A B [14,15], : 3.3.1 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) =0.0006 3.3.2 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 =0.0577 mg, u m rel =0.0577 mg/10000 mg= 0.00000577, 3.3.3 体积引入的不确定度, : A, u v rel =0.0136 3.3.4 标准曲线引入的不确定度 6 ( ), 2,,, Y=734188X-1958 ( 1) 1, S=6768.47, n j 1 1 0 [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 0.00562, u cc rel xx = B1 p n Sxx x 0.301 3.3.5 重复性引入的不确定度 6, 2
4, : - 1125 u rep n k 1 ( xk x ) n 1 2, u rep rel = 0.0277 3.5.6 合成不确定度 =0.0006, =0.0136, =0.301, =0.0277 2 2 2 2 rel c rel v rel cc rel rep rel u u u u u =0.303 3.4 实际样品分析 5, 2 (MRL) GB 2763-2014, 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 2 0.02 mg/kg 0.05 mg/kg 0.2 mg/kg LOD (μg/kg) (RSD, %) (RSD, %) (RSD, %) 1 α- Y=1812514X+2537 0.999 75.0 (5.58) 86.6 (5.84) 90.0 (3.31) 0.1 2 β- Y=1091017X+15578 0.996 75.7 (4.05) 103 (4.78) 101 (2.03) 0.2 3 γ- Y=1902430X+10791 0.998 79.0 (6.31) 92.0 (6.24) 94.0 (3.23) 0.5 4 δ- Y=2056740X+10386 0.999 75.5 (7.09) 92.0 (4.38) 95.0 (2.31) 0.5 5 p,p - Y=1820116X+12702 0.999 79.5 (5.52) 95.4 (3.50) 93.5 (1.31) 1.0 6 p,p - Y=1724179X+9043 0.998 72.0 (4.94) 94.8 (2.99) 95.5 (2.10) 1.0 7 p,p - Y=2132893X+10123 0.999 71.5 (5.50) 92.2 (4.15) 92.0 (1.84) 0.8 8 o,p - Y=1569531X+18968 0.997 76.0 (5.74) 99.2 (3.73) 96.5 (1.63) 1.0 9 Y=1886718X+20616 0.998 82.5 (3.11) 90.2 (6.13) 93.5 (2.84) 0.8 10 Y=2077708X+11210 0.999 71.0 (5.92) 91.0 (5.30) 93.0 (2.72) 0.8 11 Y=592013X+9495 0.996 78.0 (4.49) 103 (2.82) 98.0 (1.37) 3.0 12 Y=1195973X+332 0.999 85.5 (2.11) 93.0 (2.22) 94.0 (2.84) 0.8 13 Y=326012X + 2846 0.997 71.5 (2.64) 96.2 (2.73) 89.5 (1.28) 16 14 Y=734188X-1958 0.999 75.0 (4.44) 94.6 (8.22) 95.5 (1.61) 5.0 15 Y=1072571X+2148 1.000 94.5 (2.14) 93.4 (2.55) 83.0 (1.76) 3.0 16 Y=553264X+6228 0.999 83.5 (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) 0.003 0.004 n.d. 0.006 n.d. 0.05 n.d. n.d. n.d. n.d. n.d. 0.05 n.d. n.d. n.d. n.d. n.d. 0.02 n.d. n.d. n.d. n.d. n.d. 0.02 n.d. n.d. n.d. n.d. n.d. 0.1 n.d. n.d. n.d. n.d. n.d. 0.02 n.d. n.d. n.d. n.d. n.d. 2.0 n.d. n.d. n.d. n.d. n.d. 0.05 n.d. n.d. n.d. n.d. n.d. 0.02 n.d. n.d. n.d. n.d. n.d. 0.2 : n.d.
1126 6 4 结论 -, Florisil,,, 0.02~0.20 mg/kg, 16 71.0%~103%, (n=6) 1.28%~8.74%, 0.1~16 μg/kg,, 参考文献 [1],,,. [J]., 2013, 34(14): 95 98. 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): 95 98. [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): 219 231. [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): 385 391. [4],,,. - 50 [J]., 2007, 17(5): 84 88. 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): 84 88. [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): 1366 1408. [6],,,. - 20 [J]., 2009, 27(2): 176 180. 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): 176 180. [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: 372 380. [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): 9776 9781. [9],,,. - [J]., 2013, 32(3): 487 494. 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): 487 494. [10],,. - [J]., 2006, 25(6): 84 87. Shao H, Liu S, Qian YZ. Evaluation on uncertainty of determination of dimethoate by GC-MS [J]. Chin J Anal Lab, 2006, 25(6): 84 87. [11],. [J]., 2006, 25(12): 54 57. Jiang YX, Ye L. Uncertainty evaluation of determination of organophosphorus pesticide multi-residues in tea [J]. Chin J Anal Lab, 2006, 25(12): 54 57. [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: 106 113. [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): 3 13. [14] JJF 1135-2005 [S]. JJF 1135-2005 Evaluation of uncertainty in chemical analysis measurement [S]. [15],,,. - [J]., 2014, 35(12): 200 203. 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): 200 203. ( 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: 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 E-mail: yangyongtan@cofco.com 鲜切果蔬 专题征稿,,,,,, 2015 7,,, 2015 6 20 E-mail 投稿方式 : : www.chinafoodj.com E-mail: jfoodsq@126.com 食品安全质量检测学报 编辑部