6 4 Vol. 6 No. 4 2015 4 Journal of Food Safety and Quality Apr., 2015 QuEChERS 19 陈 士 恒 1, 史 晓 梅 1, 吕 岳 文 2, 刘 超 2, 章 晴 1, 孙 屏 2, 杨 永 坛 (1.,, 102209; 2., 831100) 1* 摘 要 : 目 的 19 - (UPLC-MS/MS) 方 法 1%, GCB PSA,, - 结 果 19 0.001~0.10 mg/l, r>0.994; 0.010 0.050 0.10 mg/kg 72.2%~116.8%, 13%, 0.016~3.96 μg/kg 结 论,,, 19 关 键 词 : QuEChERS; -; ; ; Simultaneous determination of 19 common pesticides residues in tomato paste by QuEChERS-ultra performance liquid chromatography-tandem mass spectrometry CHEN Shi-Heng 1, SHI Xiao-Mei 1, LV Yue-Wen 2, LIU Chao 2, ZHANG Qing 1, SUN Ping 2, YANG Yong-Tan 1* (1. Beijing Key Laboratory of Nutrition Health and Food Safety, COFCO Nutrition & Health Research Institute, Beijing 102209, China; 2. Scientific Services Center, COFCO TunHe Co., Ltd, Xinjiang 831100, China.) ABSTRACT: Objective To develop a fast and accurate method for simultaneous determination of 19 pesticide residues in tomato paste by ultra performance liquid chromatography-tandem mass spectrometry. Methods Tomato paste was firstly dispersed by water and extracted with acetonitrile containing 1% acetic acid by ultra-sonic, and the extracts were purified by dispersive solid phase extraction using GCB and PSA as the sorbents. After centrifugation and concentrated by nitrogen flushing, samples were detected by UPLC-MS/MS. Results The method showed a good linearity in the range of 0.001~0.10 mg/l for 19 pesticides with r >0.994. The recoveries were in the range of 72.2%~116.8% at 3 spiked levels of 0.010, 0.050, and 0.10 mg/kg for 19 pesticides, and the relative standard deviations (RSDs) were less than 13%. The limits of detections were in the range of 0.016~3.96 μg/kg. Conclusion The method is simple, fast and reliable, with a good repeatability, which could meet the detection requirements of these 19 pesticide residues in tomato paste 基 金 项 目 : (2012-C2-F013) Fund: Supported by the Fundamental Research Project of COFCO Corporation (2012-C2-F013) * 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, No.4 Road, Future Science and Technology Park South, Beiqijia, Changping, Beijing 102209, China. E-mail: yangyongtan@cofco.com.
4, : QuEChERS- - 19 1129 at home and abroad. The method is suitable for quality control and food safety risk control in factory. KEY WORDS: QuEChERS; ultra performance liquid chromatography-tandem mass spectrometry; tomato paste; multiple pesticide residues; fast detection 1 引 言 70%,, [1],,, [2] [3-6], [7], - [8,9] - [10] [4] [5],,, -, [11,12] -, (multiple reaction monitoring, MRM), [13,14] [7] QuEChERS [9], ;,, ; QuEChERS,, QuEChERS - (UPLC-MS/MS) QuEChERS, UPLC-MS/MS, 19, ; ;,, 10 min,, 2 材 料 与 方 法 2.1 仪 器 与 试 剂 ACQU ITY Ultra Performance (Waters ), Xevo TQ (Waters, Masslynx 4.1); Allegra 64R ( ); BSA 224S-CW ( 0.1 mg, ); SB-3200 DTDN ( ); HGC-24A (); QL-902 (), (HPLC, Acros Organics ); (HPLC, Fisher ); (GCB) N- (PSA)( ); (, ); (Millipore ); : 噁, Dr Ehrenstorfer GmbH 2.2 实 验 方 法 2.2.1 标 准 溶 液 的 配 制 19 10.0 mg ( 0.1 mg), 10.0 ml, 1.0 mg/ml, -20 : 19 100 µl 10 ml,, 10 mg/l :,
1130 6 2.2.2 样 品 前 处 理 1: 500 g, ; 2: 5 g ( 0.01 g)50 ml, 5 ml, ; 20 ml 1%- 3 g, 2 min, 1 g ; 30 min,, ; 5 g,, ; 5000 r/min 5 min 3: 1.3 g( 50 mg GCB 250 mg PSA 1000 mg ) 50 ml, 15 ml; 3 min, ; 5000 r/min 5 min, 1 ml 2.2.3 仪 器 条 件 : Waters ACQUITY UPLC CSH C 18 (2.1 mm 100 mm.i d., 1.7 μm ); 40 ; 20 ; 2 μl A 0.1% ()-, B 0.1% ()-, 1 0.2 ml/min Table 1 Time (min) 表 1 UPLC 流 动 相 梯 度 条 件 Gradient mobile phase for ultra performance liquid chromatography 0. 1% 0. 1% () - 0 80% 20% - 4 10% 90% 6 7 10% 90% - 7.5 80% 20% 6 15 80% 20% - :, ESI ; : 3.0 kv; (ESI) : 150 ; : 500 ; (): 1000 L/h; : 150 L/h; : 0.15 ml/min; : 535 V; : (MRM) 2.2.4 定 性 与 定 量 : 1 2,,, 2, 表 2 定 性 时 与 离 子 的 相 对 丰 度 相 对 应 的 最 大 允 许 偏 差 Table 2 Corresponding maximum permitted tolerances at different relative abundances of the qualitative ion for qualitative analysis /% /% > 50 ± 20 > 20~50 ± 25 > 10~20 ± 30 10 ± 50 :, 3 结 果 和 讨 论 3.1 质 谱 参 数 优 化 Masslynx Quanpedia,, Quanpedia,, Masslynx IntelliStart, 3, 19 1 3.2 提 取 方 式 的 选 择,,,,,, 40 60 min ;, ;
4, : QuEChERS- - 19 1131 Table 3 表 3 19 种 农 药 在 MRM 模 式 下 UPLC-MS/MS 分 析 的 质 谱 参 数 Mass spectrometry parameters for the 19 pesticides by UPLC-MS /MS in MRM mode () * mg/kg Min / 10 188.3 ESI+ 1.26 189.1>102.0/189.1>144 22 12/17 0.15 222.7 ESI+ 2.70 223.2>126.2/223.2>90.1 32 20/35 0.2 198.2 ESI+ 2.93 199.3>128.2/199.3>111.1 17 9/18 0.1 214.3 ESI+ 3.46 215.3>89.0/215.3>131.0 50 18/20 0.05 410.4 ESI+ 3.48 431.9>182.1/431.9>325.1 20 10/35 0.2 279.3 ESI+ 3.77 280.1>220.1/280.1>192.1 15 17/13 0.60 483.4 ESI+ 4.05 484.4>453.5/484.4>286.3 20 20/10 1 387.3 ESI+ 3.98&4.07 388.1>300.9/388.1>165.0 28 20/30 3 403.4 ESI+ 4.31 404.1>372.0/404.1>329.0 35 19/44 0.5 307.0 ESI+ 4.56 308.0>70.1/308.0>125.0 31 22/40 0.05 361.5 ESI+ 4.58 362.2>315.8/362.2>91.0 20 30/18 0.05 283.8 ESI+ 4.78 284.4>252.1/284.4>176.1 21 13/26 噁 1 374.4 ESI+ 4.96 392.2>331.1/392.2>238.0 38 18/21 0.3 387.8 ESI+ 5.08 388.1>163.0/388.1>193.9 20 12/25 0.5 527.8 ESI+ 5.18 528.0>203.0/528.0>150.0 40 17/23 0.05 375.7 ESI+ 5.2 376.0>316.1/376.0>91.1 25 32/18 0.5 408.4 ESI+ 5.27 409.0>186.0/409.0>145.0 25 40/16 1 359.9 ESI+ 5.51 360.0>164.3/360.0>268.1 36 19/28 0.05 281.3 ESI+ 5.77 282.2>212.2/282.2>194.1 25 10/15 * [15] ( 30 min),, 3.3 净 化 剂 的 选 择 QuEChERS,,, GCB PSA C 18 [16-18], GCB, PSA, C 18,, GCB PSA, PSA 19, 250 mg PSA GCB 噁, [8] 2 GCB 噁, GCB 50 mg 60%, GCB 50 mg 3.4 方 法 的 线 性 范 围 与 检 出 限 2.2,, 10 mg/l 0.001 0.005 0.010 0.025 0.05 0.10 mg/l, 19, 19, r 0.994 S/N=3 19 (LOD), S/N=10 19 (LOQ), 4
1132 食品安全质量检测学报 图 1 19 种常见农药的液相色谱-串联四级杆质谱 MRM Fig. 1 MRM chromatogram of 19 kinds of carbamate pesticides 第6卷
4, : QuEChERS- - 19 1133 2 GCB 噁 Fig. 2 The effect of different dosage about GCB on the azoxystrobin and famoxadone recoveries 3.5 回 收 率 和 精 密 度 实 验, 2.2,, 5, 19 72.2%~116.8%, (RSD) 13%, 5 3.6 实 际 样 品 分 析, 19, 2, 0.05 mg/kg 0.06 mg/kg, 3 mg/kg,, 6 GB 2763-2014 Table 4 表 4 19 种 农 药 化 合 物 的 基 质 匹 配 标 准 溶 液 工 作 曲 线 相 关 系 数 检 出 限 和 定 量 限 Equations, correlation coefficients, limit of detection (LOD) and limit of quantity (LOQ) of 19 pesticides matrix-match standard solutions r LOD (μg/kg) LOQ (μg/kg) 1 Y=479.24X-43.3479 0.999 0.12 0.396 2 Y= 601.298X+59.7931 0.998 0.008 0.026 3 Y= 25.1038X-7.37849 0.999 1.20 3.96 4 Y= 437.618X+161.298 0.994 0.096 0.317 5 Y= 26.5429X-0.0241273 0.996 1.20 3.96 6 Y= 739852X+67.002 0.998 0.005 0.016 7 Y= 225.862X+12.9233 0.994 0.024 0.079 8 Y= 785.531X+181.225 0.995 0.24 0.792 9 Y= 1436.57X+848.443 0.997 0.005 0.016 10 Y= 637.346X+ 14.7831 0.999 0.012 0.04 11 Y= 32.6X-4.23691 0.999 0.24 0.792 12 Y= 1115.85X+111.602 0.997 0.005 0.016 13 噁 Y= 12.7241X-23.8085 0.997 1.20 3.96 14 Y= 770.61X+130.065 0.995 0.006 0.02 15 Y= 1190.37X+23.2334 0.996 0.007 0.023 16 Y= 163.895X+47.4037 0.996 0.012 0.04 17 Y= 1621.77X+284.864 0.995 0.12 0.396 18 Y= 130.706X-50.0195 0.999 0.08 0.264 19 Y= 146.207X-50.1244 0.995 0.24 0.792
1134 6 Table 5 表 5 19 种 农 药 的 平 均 加 标 回 收 率 和 相 对 标 准 偏 差 (n=5) Average spiked recoveries and relative standard deviations (RSD) of 19 pesticides (n=5) 0.010 mg/kg 0.05 mg/kg 0.10 mg/kg (RSD,%) (RSD,%) (RSD,%) 1 72.4(6.0) 79.5(5.5) 90.4(2.1) 2 88.7(3.6) 95.4(4.9) 105.7(1.1) 3 103.8(3.3) 90.5(10) 101(5) 4 74.3(8.3) 89.3(6.8) 99.6(2.1) 5 84.0(8.2) 93.1(12.1) 116.8(6.3) 6 93.2(4.2) 97.5(7.2) 110.5(3.6) 7 87.4(10.9) 76.5(6.6) 92.5(4.7) 8 88.4(2.2) 96.5(8.5) 115.3(4.8) 9 95.4(2.7) 88.3(9.8) 78.2(3.3) 10 82.0(4.9) 78.8(2.7) 94.2(3.6) 11 74.0(7.6) 72.2(6.1) 83.8(2.6) 12 84.9(3.2) 89.6(7.8) 106.7(3.1) 13 噁 92.7(10.3) 92.3(4.2) 93.4(10.9) 14 84.1(3.4) 72.8(7.2) 96.8(4.6) 15 81.8(2.9) 77.7(5.7) 98.8(5.5) 16 75.3(5.3) 73.1(7.5) 95.8(5.8) 17 88.1(5.1) 81.4(10.8) 110(4.5) 18 90.8(7.5) 73.5(6.7) 99.5(4.6) 19 93.9(3.8) 74.7(4.3) 92(4.5) Table 6 表 6 实 际 番 茄 酱 品 检 测 结 果 Determination results of real tomato paste TP-1 mg/kg TP-2 mg/kg mg/kg GB 2763-2014 mg/kg 0.05 0.06 3-4 结 论 QuEChERS- - 19, 72.2~116.8%, 13%, 0.016~3.96 µg/kg,,,, 参 考 文 献 [1],,. [M]. :, 2010 Li SY, Yu Q, Shang DJ. Inspection of tomato products for export [M]. Beijing: Chinese metrology press, 2010 [2]. [J]., 2010, 38(23): 12824 12826. Sun JL. Study on the current situation, problem and measure of Xinjiang's agricultural product trade [J]. J Anhui Agric Sci, 2010,
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1136 6 作 者 简 介 陈 士 恒, 研 发 专 员, 主 要 研 究 方 向 为 食 品 质 量 与 安 全 E-mail: chenshiheng@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 食 品 化 学 与 营 养 专 题 征 稿 函, ; ; ; ;,,,,,,,,,,,,,,,, 2015 7,,, 2015 6 10 6 30 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