Microsoft Word 二校

Size: px

Start display at page:

Download "Microsoft Word 二校"

佃阮
5 years ago
Views:

1 7 9 Vol. 7 No Journal of Food Safety and Quality Sep., 2016 袁龙飞 1*, 李薇 1, 李莉 1, 许瑞翔 1, 石凯威 (1., ; 2., ) 1, 2 摘要 : 目的, 方法 3,, - (gas chromatography-election capture detector, GC-ECD), 结果 0.01~2 mg/kg, 91.6%~104.6%, 1.4%~4.2%; 0.01 mg/kg 3,, 11~19 d, 1.4~4.1 d , d, mg/kg 结论 0.8 mg/kg,, 30 d 关键词 : ; ; ; ; Degradation dynamics and residues analysis of spirodiclofen in apple and soil YUAN Long-Fei 1*, LI Wei 1, LI Li 1, XU Rui-Xiang 1, SHI Kai-Wei 1, 2 (1. State Key Laboratory of Integrated Management of Pest Insects and Rodents, Institute of Zoology, Chinese Academy of Sciences, Beijing , China; 2. College of Science, China Agricultural University, Beijing , China) ABSTRACT: Objective To formulate the scientific basis for the reasonable dosage and the pre-harvest interval (PHI) on controlling apple red mite with spraying application based on the investigation of the degradation dynamics of spirodiclofen in apple and soil. Methods The residual trials of spirodiclofen in apple were carried out in Beijing, Anhui and Shandong Province. The samples were extracted with acetonitrile, purified by florisil solid-phase extraction (SPE) column and determined by gas chromatography equipped with electron capture detector (GC-ECD). The external standard method was used for quantitation. Results The average recoveries spiked at the levels of 0.01~2 mg/kg were 91.6%~104.6% in apple and soil with the relative standard deviations (RSD) of 1.4%~4.2%. The limit of quantification of this method was 0.01 mg/kg. The degradation dynamic equations of spirodiclofenin apple and soil were fitted the first order reaction dynamic equations, and the 基金项目 : ( ) Fund: Supported by the National Natural Science Foundation of China ( ) * 通讯作者 :,,, yuanlongfei@ioz.ac.cn *Corresponding author: YUAN Long-Fei, Ph.D, Assistant Professor, State Key Laboratory of Integrated Management of Pest Insects and Rodents, Institute of Zoology, Chinese Academy of Sciences, Beijing , China. yuanlongfei@ioz.ac.cn

2 degradation half-lives of spirodiclofen were 11~19 d in apple and 1.4~4.1 d in soil. The final residues of spirodiclofen in apple were below mg/kg at the end of the time interval of 30, 40, 50 d after the last application with the 1 and 1.5 times of high level of recommend does. Conclusions Considering about the maximum residue limit (MRL) of 0.8 mg/kg set by Codex Alimentarius Commission, United States of America and European Union, it is suggested that apple is safe for human after spraying spirodiclofen for 30 d under the application dosage and times of spirodiclofen. KEY WORDS: spirodiclofen; dissipation dynamics; residue; apple; soil 1 引言, spirodiclofen, 3-(2, 4-)-2--1-[4, 5] , 2-, (Envidor), [1], [2-7],,, [8, 9] (maximum residue limits, MRLs), (Codex Alimentarius Commission, CAC) [10] [11] [12] MRL 0.8 mg/kg, GB [13] MRL,,,, -(gas chromatographyelection capture detector, GC-ECD) [14-17] - (high performance liquid chromatographydiode array detector, HPLC-DAD) [18] - (gas chromatography-quadrupole mass spectrometry, GC-MS) [19], GC-MS 8 [19], GC-ECD, [14-17], [20-23],, GC-ECD,, MRL 2 材料与方法 2.1 仪器与试剂 Agilent7890A (, ); KQ-600 ( ); EYELA OSB-2000 ( ); Sartorius MA150 ( ); SC-3612 ( ); Thermo Scientific Heraeus Pico 17 ( ); MaxSignal MTV-100 Multi-Tube Vortexer ( ); FOSS HM 294 Homogeniser ( ); OHAUS SE2020d=0.01g ( ); METTLER TOLEDO AL204-1Cd=0.001g ( - ); CNW-CA g/6 ml ( ) 98%, Dr. Ehrenstorfer GmbH ;, : 45% : 田间试验试验地点 NY/T [24], 2, 3,,, 消解动态, 2500 (180 mg a.i./kg) 1, 2 h d, 3,, 12 ( 2 kg)

3 9, : 3451, 500 g,,, 最终残留 45% 5000~7500 (60~90 mg a.i./kg), 1, 30 d,,,, 5000 (90 mg a.i./kg), 1.5, 3333 (135 mg a.i./kg), 1 2, 30 d, 3, 2 ; d, 2.3 分析方法样品前处理 10 g, 20 ml, 1 min, 15 min 5 g 1 min, 3000 r/min 3 min 10 ml 100 ml, 35, 5 ml Florisil-SPE (1 g/6 ml), 20 ml /(9:1, V:V) 4, 5 ml, 100 ml, ml, GC 色谱条件 Agilent HP-5 (30 m 0.32 mm, 0.25 μm); 1 μl: 80, 1 min, 30 /min 270, 10 min, 20 / min 280, 6 min 280 ;, 1.5 ml/min; 290, : 25 ml/min,, 10.6 min 标准溶液的配制 98% 10.9 mg, 25 ml, mg/l, mg/l 2.3.2,,, 添加回收, mg/kg,, 5, 计算公式 (1), (2) C=C 0 e -KT (1) T 1/2 =ln2/k (2) (1) C, C 0, T ; (2) T 1/2, K 3 结果与讨论 3.1 线性范围, 0.01~2 mg/l, (Y) (X, mg/l), Y= X , r=0.9984; Y= X , r=0.9997; Y= X , r= S /S =1.63, S /S =1.52,,,, 3.2 回收率及定量限 1, mg/kg, 92.0%~104.6%, 1.4%~4.2%, 91.6%~99.6%, 1.7%~3.9%, 1 表 1 螺螨酯在苹果和土壤中的加标回收率 (n=5) Table 1 Recoveries of spirodiclofen in apple and soil (n=5) (mg/kg) (%) (%)

4 Fig. 1 Gas chromatograms of spirodiclofen (A); (B); (C) 0.02 mg/l; (D) 0.02 mg/l; (E) 0.01 mg/kg; (F) 0.01 mg/kg (A) blank of apple; (B) blank of soil; (C) 0.02 mg/l standard of spirodiclofen in apple matrix; (D) 0.02 mg/l standard of spirodiclofen in soil matrix; (E) spirodiclofen spiked in apple at 0.01 mg/kg; (F) spirodiclofen spiked in soil at 0.01 mg/kg NY/T [24] (limit of quantification, LOQ) ( mg/kg ), 0.01 mg/kg,, 0.01 mg/kg 3.3 消解动态 2 2,, 11~19 d, 1.4~4.1 d, 3,,, [25], 3.4 最终残留, 5000 (90 mg a.i./kg), 3333 (135 mg a.i./kg), 1 2, 30 d 3, d, mg/kg, CAC MRL 0.8 mg/kg,, 30 d

5 9, : 3453 表 2 螺螨酯在苹果和土壤中的消解动态 Table 2 Dissipation of spirodiclofen in apple and soil (r) (d) C=0.12e T C=0.31e T C=0.06 e T C=0.45e -0.18T C=0.55e -0.50T C=0.04e -0.17T Table 3 表 3 螺螨酯在苹果和土壤中的最终残留 The terminal residues of spirodiclofen in apple and soil (d) (mg/kg) (mg/kg) 结论 GC-ECD,,,, 11~19 d 1.4~4.1 d 45% 90 mg a.i./kg , d, CAC MRL 0.8 mg/kg, 30 d 参考文献 [1] Feng XG, Xu LZ, Kong FR, et al. Spirodiclofen derivatives as highly potential acaricides: Synthesis, structure and bioactivity [J]. Chem Res Chin U, 2011, 27(6): [2],,,. [J]., 2008, (3): Zhang HJ, Qiu GS, Run WT, et al. The new acaricide spirodiclofen apple mite prevention efficacy trials [J]. Chin Fruit Trees, 2008, (3): [3],,,. 240g/L [J]., 2013, 17(5): Tao B, Yuan ST, Wang JZ, et al. Effect of 240 g/l Spirodiclofen SC to control European red mite in field [J]. J Hebei Agr Sci, 2013, 17(5): [4],,,. [J]., 2010, 39(5): Lu H, Chen BX, Dong YZ, et al. Activity and efficacy evaluation of a new acaricide Spirodiclofen Citrus mite [J]. South China Fruits, 2010, 39(5): [5]. 6 [J]., 2015, 14: Mao TX. Efficacy of 6 kinds of acaricideto control Citrus red mite in field [J]. Anhui Agric Sci, 2015, 14: [6],,,. [J]., 2015, 09: Wei H, Li YH, Zhang KZ, et al. Different concentration of spirodiclofen SC prevention efficacy trials to control apple Tetranychus urticae [J]. Chin Garden Abstract, 2015, 09: [7],,,. 24% [J]., 2016, 15 (1): Ju GX, Xu SS, Chen GX, et al. Formulation and control effect of Spirodiclofen Sulfonester 24% OD [J]. Mod Agrochem, 2016, 15(1): [8] Marcic D, Ogurlic I, Peric P. Effects of spirodiclofen on the reproductive potential of two-spotted spider mite (acari: Tetranychidae) ovipositing females [J]. Arch Biol Sci, 2009, 61(4): [9] Seyed-Talebi FS, Kheradmand K, Talaei-Hassanloui R, et al. Synergistic effect of beauveria bassiana and spirodiclofen on the two-spotted spider

3454 7 mite (tetranychus urticae) [J]. Phytoparasitica, 2014, 42(3): 405 412. [10] CodexAlimentarius. Codex alimentarius pesticide detail [EB/OL]. http://www.fao.

6 mite (tetranychus urticae) [J]. Phytoparasitica, 2014, 42(3): [10] CodexAlimentarius. Codex alimentarius pesticide detail [EB/OL]. -detail/en/?p_id= [11] United States Government Publishing Office. ecfr-code of Federal Regulations [EB/OL]. fd0e1bc4042ba51eda540b8b2&mc=true&node=se _1608&rgn=d iv [12] European Commission. EU Pesticides database [EB/OL]. eu/food/plant/pesticides/eu-pesticides-database/public/?event=pesticide.res idue.currentmrl&language=en [13] GB [S]. GB National Food Safety Standard-Maximum residue limits for pesticides in food [S]. [14],,,. [J]., 2007, 26: Liu JN, Han ZH, Wu GQ, et al. Gas Chromatographic determ ination of Spirodiclofen residues in orange and soil [J]. J Agro-Environ Sci, 2007, 26: [15],,,. [J]., 2009, 25(2): Bai Y, Xu PJ, Gao xs, et al. Determination of residual Spirodiclofen in apple and soil [J]. J Anal Sci, 2009, 25(2): [16],,,. [J]., 2012, 24(2): Xie L, Yang RB, Fu Q, et al. Determination for Spirodiclofen residues in orange and soil [J]. Environ Monit Manag Technol, 2012, 24(2): [17],,,. [J]., 2014, 5(8): Li D, Li WB, Zhu ZT, et al. Determination of Spirodiclofen in orange by gas chromatography [J]. J Food Saf Qual, 2014, 5(8): [18],,,. [J]., 2014, 53(7): Zhao YZ, Tan H, Xi peiyu, et al. Residue analysis of spirodiclofen in soil [J]. Pesticides 2014, 53(7): [19],,,. - 9 [J]., 2008, 11: Xu PJ, Gao XS, Tao B, et al. Determination of spirodiclofen residue in nine fruits by gas chromatography-quadrupole mass spectrometry with dispersive soild phase extraction [J]. J Anal Sci, 2008, 11: [20],,,. [J]., 2012, 28(31): Xie L, Yang RB, Fu Q, et al.residueand dissipation dynamics of spirodiclofen in orangeand soil [J]. Chin Agric Sci Bull, 2012, 28(31): [21] Sun H, Liu C, Wang S, et al. Dissipation, residues, and risk assessment of spirodiclofen in citrus [J]. Environ Monit Assess, 2013, 185(12): [22] Sun D, Zhu Y, Pang J, et al. Residue level, persistence and safety of spirodiclofen-pyridaben mixture in citrus fruits [J]. Food Chem, 2016, 194: [23],,,. [J]., 2016, 8 (43): Ou YJ, Peng XC, Wu YY, et al. Degradation of spirodiclofen and bifenazate residue in citrus and its risk [J]. Guangdong Chem, 2016, 8(43): [24] NY/T [S]. NY/T Guideline on pesticide residue trials [S]. [25],. 1 [J]. ( ), 2016, 1: Jia HF, Zhu YZ. Screening and removal efficiency of a spirodiclofen degrading bacterium [J]. J Qingdao Agric Univ (NatSci), 2016, 1: 作者简介 ( 责任编辑 : 姚菲 ) 袁龙飞, 博士, 助理研究员, 主要研究方向为农药残留分析与食品安全 yuanlongfei@ioz.ac.cn

g ml 10% ph 色谱条件 kinetex C μm 100 A 4. 6 mm 150 mm 25 5 μl A B 10 mmol /L ml /min

g ml 10% ph 色谱条件 kinetex C μm 100 A 4. 6 mm 150 mm 25 5 μl A B 10 mmol /L ml /min 25 4 2013 8 监测技术 5 1 2 1 ( 1. 江苏省疾病预防控制中心, 江苏南京 210009; 2. 南京医科大学第二附属医院, 江苏南京 210029) 5 Phenomenex kinetex C 18 2. 6 μm 4. 6 mm 150 mm 10 mmol /L ph 2. 5 + 60 40 DAD 280 nm 5 20. 0 mg /L ~ 100 mg /L 0.