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1 6 4 Vol. 6 No 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.,, ; 2., ) 1* 摘要 : 目的 19 - (UPLC-MS/MS) 方法 1%, GCB PSA,, - 结果 ~0.10 mg/l, r>0.994; 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 , China; 2. Scientific Services Center, COFCO TunHe Co., Ltd, Xinjiang , 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 > 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 :,, 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 , China. yangyongtan@cofco.com.

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

2 4, : QuEChERS 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 实验方法标准溶液的配制 mg ( 0.1 mg), 10.0 ml, 1.0 mg/ml, -20 : µl 10 ml,, 10 mg/l :,

[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.

3 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 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% ()-, 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% () % 20% % 90% % 90% % 20% % 20% - :, ESI ; : 3.0 kv; (ESI) : 150 ; : 500 ; (): 1000 L/h; : 150 L/h; : 0.15 ml/min; : 535 V; : (MRM) 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 ± ± 50 :, 3 结果和讨论 3.1 质谱参数优化 Masslynx Quanpedia,, Quanpedia,, Masslynx IntelliStart, 3, 提取方式的选择,,,,,, min ;, ;

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.

4 4, : QuEChERS 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 / ESI >102.0/189.1> / ESI >126.2/223.2> / ESI >128.2/199.3> / ESI >89.0/215.3> / ESI >182.1/431.9> / ESI >220.1/280.1> / ESI >453.5/484.4> / ESI+ 3.98& >300.9/388.1> / ESI >372.0/404.1> / ESI >70.1/308.0> / ESI >315.8/362.2> / ESI >252.1/284.4> /26 噁 ESI >331.1/392.2> / ESI >163.0/388.1> / ESI >203.0/528.0> / ESI >316.1/376.0> / ESI >186.0/409.0> / ESI >164.3/360.0> / ESI >212.2/282.2> /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 mg/l, 19, 19, r S/N=3 19 (LOD), S/N=10 19 (LOQ), 4

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.

5 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

6 4, : QuEChERS 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, %~116.8%, (RSD) 13%, 实际样品分析, 19, 2, 0.05 mg/kg 0.06 mg/kg, 3 mg/kg,, 6 GB 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 Y= X Y= X Y= X Y= X Y= X Y= X Y= X Y= X Y= X Y= 32.6X Y= X 噁 Y= X Y= X Y= X Y= X Y= X Y= X Y= X

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)

7 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) mg/kg 0.05 mg/kg 0.10 mg/kg (RSD,%) (RSD,%) (RSD,%) (6.0) 79.5(5.5) 90.4(2.1) (3.6) 95.4(4.9) 105.7(1.1) (3.3) 90.5(10) 101(5) (8.3) 89.3(6.8) 99.6(2.1) (8.2) 93.1(12.1) 116.8(6.3) (4.2) 97.5(7.2) 110.5(3.6) (10.9) 76.5(6.6) 92.5(4.7) (2.2) 96.5(8.5) 115.3(4.8) (2.7) 88.3(9.8) 78.2(3.3) (4.9) 78.8(2.7) 94.2(3.6) (7.6) 72.2(6.1) 83.8(2.6) (3.2) 89.6(7.8) 106.7(3.1) 13 噁 92.7(10.3) 92.3(4.2) 93.4(10.9) (3.4) 72.8(7.2) 96.8(4.6) (2.9) 77.7(5.7) 98.8(5.5) (5.3) 73.1(7.5) 95.8(5.8) (5.1) 81.4(10.8) 110(4.5) (7.5) 73.5(6.7) 99.5(4.6) (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 mg/kg 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): Sun JL. Study on the current situation, problem and measure of Xinjiang's agricultural product trade [J]. J Anhui Agric Sci, 2010,

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.

8 4, : QuEChERS (23): [3] Amvrazi EG, Tsiropoulos NG. Application of single-drop microextraction coupled with gas chromatography for the determination of multiclass pesticides in vegetables with nitrogen phosphorus and electron capture detection [J]. J Chromatogr A, 2009, 1216(14) : [4],, [J]., 2013, 4: Zhang Q, Chen SH, Yang YT. Determination of 25 organochlorine and pyrethroid pesticide residues in tea by dispersive solid phase extraction-gas chromatography [J]. Anal Instrum, 2013, 4: [5],,. -- [J]., 2014, 32(5): Chen SH, Zhang Q, Shi XM, et al. Determination of 13 organophosphorus pesticides residues in green tea by ultrasonic assisted extraction-dispersive solid phase extraction-gas chromatography [J]. J Food Sci Technol, 2014, 32(5): [6],,,. [J]., 2014, 5(8): Yang YT, Chen SH, Shi XM, et al. Rapid determination of multi-residues of organochlorine, pyrethroid and organophosphorus in tea by gas chromatography [J]. J Food Saf Qual, 2014, 5(8): [7],,,. - [J]., 2009, 34(10): Zhou JK, Sun MC, Liu RY, et al. Determination of carbamate insecticides in the tomato jam by high performance liquid chromatography [J]. China Cond, 2009, 34(10): [8],,,. DSPE-GC/MS 52 [J]., 2014, 32(3): Chen SH, Zhang Q, Shi XM, et al. Fast determination of 52 pesticide residues in grape wine by DSPE-GC/MS [J]. J Food Sci Technol, 2014, 32(3): [9],,. / 72 [J]., 2013, 34(12): Shang DJ, Wei S, Li SY. Determination of 72 pesticide residues in tomato paste by TSQ Quantumn-GC [J]. Food Sci, 2013, 34(12): [10] Kong ZQ, Dong FS, Xu J, et al. Determination of difenoconazole residue in tomato during home canning by UPLC-MS/MS [J]. Food Control, 2012, 23(2): [11] Andrade GCRM, Monteiroa SH, Franciscoa JG, et al. Liquid chromatography electrospray ionization tandem mass spectrometry and dynamic multiple reaction monitoring method for determining multiple pesticide residues in tomato [J]. Food Chem, 2015, 175(1): [12] Ozgur G, Bulent K. Evaluation of QuEChERS sample preparation and liquid chromatography triple-quadrupole mass spectrometry method for the determination of 109 pesticide residues in tomatoes [J]. Food Chem, 2015, 176(1): [13],,,. - 6 [J]., 2011, 29(11): Su M, Li SY, Li FG, et al. Rapid determination of 6 pesticide residues in tomato paste by ultra performance liquid chromatography-tandem mass spectrometry [J]. Chin J Chromatogr, 2011, 29(11): [14],,,. - [J]., 2007, 17(3): Li FG, Quan XD, Dou H, et al. Determination of metalaxyl, benalaxyl and oxadixyl residues in tomato sauce by gas chromatography mass spectrometry [J]. Chin J Health Lab Technol, 2007, 17(3): [15] EU Pesticides database [DB/OL]. pesticides/public/index.cfm?event=pesticide.residue.selection&la nguage=en [16] Zhang X, Mobley N, Zhang JG, et al. Analysis of agricultural residues on tea using d-spe sample preparation with GC-NCI-MS and UHPLC-MS/MS [J]. J Agric Food Chem, 2010, 58(22): [17] Charlène P, Mikaël T, Nadia Q, et al. Multi-residue analysis of free and conjugated hormones and endocrine disruptors in rat testis by QuEChERS-based extraction and LC-MS/MS [J]. Anal Bioanal Chem, 2012, 402(9): [18] Oscar N, Héctor G, Imma F, et al. Strategies for the multi-residue analysis of 100 pesticides by liquid chromatography triple quadrupole mass spectrometry [J]. J Chromatogr A, 2012, 1249(1): ( 责任编辑 : 李振飞 )

J Chromatogr A, 2009, 1216(14) :2789 2797. [4],,. - 25 [J]., 2013, 4: 16 22. Zhang Q, Chen SH, Yang YT.

9 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 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 yangyongtan@cofco.com 食品化学与营养专题征稿函, ; ; ; ;,,,,,,,,,,,,,,,, ,,, 投稿方式 : : jfoodsq@126.com 食品安全质量检测学报编辑部

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.

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