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超高效液相色谱-串联质谱同时检测水稻中3种农药及2种代谢物残留

张斌斌 董丰收 潘兴鲁 吴小虎 徐军 郑永权

张斌斌, 董丰收, 潘兴鲁, 吴小虎, 徐军, 郑永权. 超高效液相色谱-串联质谱同时检测水稻中3种农药及2种代谢物残留[J]. 农药学学报. doi: 10.16801/j.issn.1008-7303.2022.0047
引用本文: 张斌斌, 董丰收, 潘兴鲁, 吴小虎, 徐军, 郑永权. 超高效液相色谱-串联质谱同时检测水稻中3种农药及2种代谢物残留[J]. 农药学学报. doi: 10.16801/j.issn.1008-7303.2022.0047
ZHANG Binbin, DONG Fengshou, PAN Xinglu, WU Xiaohu, XU Jun, ZHENG Yongquan. Determination of the residues of three pesticides and two metabolites in rice by ultra-high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Pesticide Science. doi: 10.16801/j.issn.1008-7303.2022.0047
Citation: ZHANG Binbin, DONG Fengshou, PAN Xinglu, WU Xiaohu, XU Jun, ZHENG Yongquan. Determination of the residues of three pesticides and two metabolites in rice by ultra-high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Pesticide Science. doi: 10.16801/j.issn.1008-7303.2022.0047

超高效液相色谱-串联质谱同时检测水稻中3种农药及2种代谢物残留

doi: 10.16801/j.issn.1008-7303.2022.0047
基金项目: 国家自然科学基金(31901922)
详细信息
    作者简介:

    张斌斌,zbb35387@163.com

    通讯作者:

    董丰收,dongfengshou@caas.cn

  • 中图分类号: TQ450.2;O657.63

Determination of the residues of three pesticides and two metabolites in rice by ultra-high performance liquid chromatography-tandem mass spectrometry

Funds: National Nature Science Foundation of China (31901922)
  • 摘要: 建立并优化了基于超高效液相色谱-串联质谱 (UPLC-MS/MS) 同时检测水稻中甲氨基阿维菌素苯甲酸盐、氯虫苯甲酰胺、氟唑菌酰胺及其代谢物M700F008、M700F048的分析方法。稻壳和糙米经0.2%甲酸-乙腈提取后用C18净化,稻秆经1%甲酸-乙腈提取后用N-丙基乙二胺 (PSA) 和石墨化碳黑 (GCB) 净化,流动相为甲醇和0.2%甲酸水溶液,梯度洗脱,采用T3色谱柱进行分离。电喷雾正离子模式 (ESI+) 采集,多反应监测 (MRM),外标法定量。结果表明:5种供试化合物的质量浓度与峰面积间线性关系良好,决定系数均大于0.9955;5种化合物在水稻稻壳、糙米及稻秆3种基质中的平均回收率均在71%~119%之间,相对标准偏差 (RSD) 在1%~11%之间,满足残留分析的要求。在3地供试糙米样品中,甲氨基阿维菌素苯甲酸盐、氯虫苯甲酰胺和氟唑菌酰胺的残留量均低于中国规定的最大残留限量标准。
  • 1  甲维盐、氯虫苯甲酰胺、氟唑菌酰胺及其代谢物M700F008及M700F048结构式

    1.  The structural formula of emamectin benzoate, chlorantraniliprole, fluxapyroxad, M700F008 and M700F048

    图  1  甲维盐、氯虫苯甲酰胺、氟唑菌酰胺、M700F008和M700F048的质谱图及其在不同基质中的空白样品添加色谱图

    A-甲维盐 emamectin benzoate;B-氯虫苯甲酰胺 chlorantraniliprole;C-氟唑菌酰胺 fluxapyroxad;D-M700F008;E-M700F048。0-标准溶液 standard solution;1-糙米添加 brown rice (1 mg/kg);2-稻壳添加 rice husk (1 mg/kg);3-稻秆添加 rice straw (1 mg/kg)。

    Figure  1.  Mass spectrogram of emamectin benzoate, chlorantraniliprole, fluxapyroxad, M700F008 and M700F048 and chromatogram of different blank matrix samples spiked with the five compounds

    图  2  甲维盐、氯虫苯甲酰胺、氟唑菌酰胺、M700F008及M700F048在不同基质和提取溶剂中的平均回收率

    Figure  2.  Average recovery of emamectin benzoate, chlorantraniliprole, fluxapyroxad, M700F008 and M700F048 in different matrices and extraction solvents

    图  3  不同净化剂对糙米、稻壳和稻秆中甲维盐、氯虫苯甲酰胺、氟唑菌酰胺、M700F008及M700F048回收率的影响

    Figure  3.  Effects of different cleanup sorbents on recoveries of emamectin benzoate, chlorantraniliprole, fluxapyroxad, M700F008 and M700F048 in brown rice, rice husk and rice straw

    表  1  甲维盐、氯虫苯甲酰胺、氟唑菌酰胺、M700F008和M700F048主要质谱检测参数

    Table  1.   Mass spectrometric parameters for the detection of emamectin benzoate, chlorantraniliprole, fluxapyroxad, M700F008 and M700F048

    化合物
    Compound
    保留时间
    Retention time/min
    母离子
    Precursor ion
    子离子
    Product ion
    去簇电压
    Declustering potential/V
    碰撞能
    Collision energy/eV
    甲维盐 emamectin benzoate 2.44 886.5 158.1* 110.00 40.00
    126.1 110.00 75.00
    氯虫苯甲酰胺 chlorantraniliprole 2.42 483.9 452.9* 80.00 28.00
    285.9 80.00 28.00
    氟唑菌酰胺 fluxapyroxad 2.46 382.2 342.0 125.03 33.85
    314.0* 104.89 36.30
    M700F008 2.47 368.2 348.1* 93.44 23.22
    328.1 109.01 34.35
    M700F048 2.40 530.1 368.1* 82.29 21.79
    348.0 82.29 39.00
    注:* 为定量离子。Note: * represents quantitative ion.
    下载: 导出CSV

    表  2  甲维盐、氯虫苯甲酰胺、氟唑菌酰胺、M700F008和M700F048的线性回归方程、决定系数和基质效应

    Table  2.   Linear equation, determination coefficients, and matrix effects of emamectin benzoate, chlorantraniliprole, fluxapyroxad, M700F008 and M700F048

    化合物
    Compound
    基质
    Matrix
    线性回归方程
    Linear regression equation
    决定系数
    R2
    斜率比值
    k
    线性范围
    Linear range/(mg/kg)
    甲维盐 emamectin benzoate 乙腈 Acetonitrile y = 35248600x + 427415 0.9978 0.01~1
    糙米 Brown rice y = 46968500x + 420911 0.9982 1.33
    稻壳 Rice husk y = 21927591x + 221375 0.9996 0.62
    稻秆 Rice straw y = 30013600x + 320622 0.9990 0.85
    氯虫苯甲酰胺 chlorantraniliprole 乙腈 Acetonitrile y = 13607100x-37150 0.9985 0.02~1
    糙米 Brown rice y = 18372800x + 23839 0.9985 1.35
    稻壳 Rice husk y = 7352155x + 31114 0.9997 0.54
    稻秆 Rice straw y = 8747939x + 224273 0.9992 0.64
    氟唑菌酰胺 fluxapyroxad 乙腈 Acetonitrile y = 22437160x + 28345 0.9955 0.02~1
    糙米 Brown rice y = 25435816x + 20798 0.9981 1.13
    稻壳 Rice husk y = 5488118x + 12804 0.9998 0.24
    稻秆 Rice straw y = 11379354x + 25084 0.9996 0.51
    M700F008 乙腈 Acetonitrile y = 31321500x-24314 0.9998 0.02~1
    糙米 Brown rice y = 28296164x + 15514 0.9994 0.90
    稻壳 Rice husk y = 3299129x + 19778 0.9998 0.11
    稻秆 Rice straw y = 12350021x + 15281 0.9994 0.39 0.05~1
    M700F048 乙腈 Acetonitrile y = 20029051x-84841 0.9978 0.02~1
    糙米 Brown rice y = 22392939x + 14154 0.9993 1.12
    稻壳 Rice husk y = 3825229x + 19778 0.9991 0.19
    稻秆 Rice straw y = 7487584x + 12745 0.9996 0.37 0.05~1
    下载: 导出CSV

    表  3  甲维盐、氯虫苯甲酰胺、氟唑菌酰胺、M700F008及M700F048在糙米、稻壳和稻秆中的添加回收率及RSD

    Table  3.   Recovery and RSDs of emamectin benzoate, chlorantraniliprole, fluxapyroxad, M700F008 and M700F048 in three matrices at 3 spiked levels

    化合物
    Compound
    糙米
    Brown rice
    稻壳
    Rice husk
    稻秆
    Rice straw
    添加水平
    Spiked level/
    (mg/kg)
    回收率
    Recovery/
    %
    相对标准
    偏差
    RSD/%
    添加水平
    Spiked level/
    (mg/kg)
    回收率
    Recovery/
    %
    相对标准
    偏差
    RSD/%
    添加水平
    Spiked level/
    (mg/kg)
    回收率
    Recovery/
    %
    相对标准
    偏差
    RSD/%
    甲维盐
    emamectin benzoate
    0.01 85 3.0 0.01 98 3.7 0.01 107 2.5
    0.02 92 1.4 0.02 94 5.0 0.02 97 1.5
    1 85 2.8 1 97 4.2 1 102 2.4
    氯虫苯甲酰胺
    chlorantraniliprole
    0.02 105 3.9 0.02 106 4.0 0.02 93 4.1
    0.5 92 1.9 0.5 106 1.9 0.5 104 6.2
    1 95 2.7 1 107 2.8 1 97 8.8
    氟唑菌酰胺
    fluxapyroxad
    0.02 103 5.0 0.02 119 3.7 0.02 99 5.0
    1 97 6.1 1 104 4.7 1 102 7.0
    5 97 3.0 5 107 1.7 5 108 4.4
    M700F008 0.02 104 4.4 0.02 112 5.7 0.05 79 4.7
    1 92 2.3 1 98 5.3 1 83 4.2
    5 96 1.4 5 107 1.1 5 87 4.3
    M700F048 0.02 88 2.4 0.02 104 10.7 0.05 73 2.0
    1 83 2.3 1 78 9.5 1 71 1.1
    5 87 1.7 5 81 5.9 5 74 4.3
    下载: 导出CSV

    表  4  甲维盐、氯虫苯甲酰胺、氟唑菌酰胺、M700F008及M700F048在糙米、稻壳和稻秆中的最终残留量(mg/kg)

    Table  4.   The terminal residues of emamectin benzoate, chlorantraniliprole, fluxapyroxad, M700F008 and M700F048 in rice samples (mg/kg)

    化合物
    Compound
    样品采收地
    Sample collection site
    糙米
    Brown rice
    稻壳
    Rice husk
    稻秆
    Rice straw
    21 d28 d21 d28 d21 d28 d
    甲维盐
    emamectin benzoate
    湖北 Hubei <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ
    广西 Guangxi <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ
    广东 Guangdong <LOQ <LOQ <LOQ <LOQ <LOQ <LOQ
    氯虫苯甲酰胺
    chlorantraniliprole
    湖北 Hubei <LOQ 0.02 3.12 1.29 1.15 0.29
    广西 Guangxi <LOQ <LOQ 2.40 2.56 0.17 0.23
    广东 Guangdong 0.03 <LOQ 3.11 1.29 0.36 0.16
    氟唑菌酰胺a fluxapyroxada 湖北 Hubei 0.08 0.07 2.50 1.36 3.64 1.48
    广西 Guangxi 0.07 0.06 4.09 3.60 0.56 0.24
    注:a为总残留量 (氟唑菌酰胺总残留量 = 氟唑菌酰胺残留量 + M700F008残留量 × 1.038 + M700F048残留量 × 0.72[15],残留量小于定量限以定量限计)。Note: a represents the total residues (total residue of fluxapyroxad = fluxapyroxad residue + M700F008 residue × 1.038 + M700F048 residue × 0.72, the limit of quantification was used for the calculation when the residue was lower than the limit of quantification).
    下载: 导出CSV
  • [1] ANE N U, HUSSAIN M. Diversity of insect pests in major rice growing areas of the world[J]. J Entomol Zool Stud, 2015, 4(1): 36-41.
    [2] MEW T W, LEUNG H, SAVARY S, et al. Looking ahead in rice disease research and management[J]. Crit Rev Plant Sci, 2004, 23(2): 103-127. doi: 10.1080/07352680490433231
    [3] 蒲小明, 王爱臣, 林壁润, 等. 5%甲维盐水分散粒剂防治鳞翅目害虫田间效果[J]. 广东农业科学, 2021, 48(4): 106-110.

    PU X M, WANG A C, LIN B R, et al. Control effect of 5% emamectin benzoate water dispersible granule against Lepidoptera pests in field[J]. Guangdong Agric Sci, 2021, 48(4): 106-110.
    [4] 林炳松. 甲氨基阿维菌素苯甲酸盐和氯虫苯甲酰胺环保剂型研制[D]. 保定: 河北农业大学, 2020.

    LIN B S. Development of environmental friendly formulations of emamectin benzoate and chlorantraniliprole[D]. Baoding: Hebei Agricultural University, 2020.
    [5] 伏荣桃, 王剑, 陈诚, 等. 氯虫苯甲酰胺防控水稻二化螟的应用效果评价[J]. 中国植保导刊, 2020, 40(1): 78-81. doi: 10.3969/j.issn.1672-6820.2020.01.015

    FU R T, WANG J, CHEN C, et al. Effect evaluation of chlorantraniliprole applied in rice Chilo suppressalis Walker control[J]. China Plant Prot, 2020, 40(1): 78-81. doi: 10.3969/j.issn.1672-6820.2020.01.015
    [6] 路彩红, 杨林, 申流柱, 等. 超高效液相色谱-串联质谱法检测水稻和土壤中氟唑菌酰胺的残留及消解动态[J]. 植物保护, 2016, 42(4): 132-136. doi: 10.3969/j.issn.0529-1542.2016.04.021

    LU C H, YANG L, SHEN L Z, et al. Residues and degradation determination of fluxapyroxad in rice and soil by UPLC-MS/MS[J]. Plant Prot, 2016, 42(4): 132-136. doi: 10.3969/j.issn.0529-1542.2016.04.021
    [7] 王刚, 吕亮, 刘吉永, 等. 氟唑菌酰胺的合成与生物活性[J]. 现代农药, 2017, 16(4): 12-14. doi: 10.3969/j.issn.1671-5284.2017.04.003

    WANG G, LV L, LIU J Y, et al. Synthesis and bioactivity of fluxapyroxad[J]. Mod Agrochem, 2017, 16(4): 12-14. doi: 10.3969/j.issn.1671-5284.2017.04.003
    [8] 国家食品安全标准 食品中农药最大残留限量: GB 2763—2021. [S]. 北京: 中国农业出版社, 2021.

    National Food Safety Standard−Maximum residue limits for pesticides in food: GB 2763—2021. [S]. Beijing: China Agriculture Press, 2021.
    [9] DONG F S, CHEN X, LIU X G, et al. Simultaneous determination of five pyrazole fungicides in cereals, vegetables and fruits using liquid chromatography/tandem mass spectrometry[J]. J Chromatogr A, 2012, 1262: 98-106. doi: 10.1016/j.chroma.2012.08.100
    [10] CHEN X X, DONG F S, XU J, et al. Effective monitoring of fluxapyroxad and its three biologically active metabolites in vegetables, fruits, and cereals by optimized QuEChERS treatment based on UPLC-MS/MS[J]. J Agric Food Chem, 2016, 64(46): 8935-8943. doi: 10.1021/acs.jafc.6b03253
    [11] 农作物中农药残留试验准则: NY/T 788—2018[S]. 北京: 中国农业出版社, 2018.

    Guideline for the testing of pesticide residues in crops: NY/T 788—2018[S]. Beijing: China Agriculture Press, 2018.
    [12] 齐晓雪, 董崭, 冯义志, 等. 超高效液相色谱串联质谱法检测水稻中五氟磺草胺、吡嘧磺隆和丙草胺的残留量[J]. 农药, 2021, 60(4): 290-293. doi: 10.16820/j.cnki.1006-0413.2021.04.015

    QI X X, DONG Z, FENG Y Z, et al. Determination of the residues of penoxsulam, pyrazosulfuron-ethyl and pretilachlor in rice by ultra high performance liquid chromatography-tandem mass spectrometry[J]. Agrochemicals, 2021, 60(4): 290-293. doi: 10.16820/j.cnki.1006-0413.2021.04.015
    [13] 刘亚伟, 董一威, 孙宝利, 等. QuEChERS在食品中农药多残留检测的应用研究进展[J]. 食品科学, 2009, 30(9): 285-289. doi: 10.3321/j.issn:1002-6630.2009.09.067

    LIU Y W, DONG Y W, SUN B L, et al. Summary of application of QuEChERS method in multi-residue determination of pesticides in food[J]. Food Sci, 2009, 30(9): 285-289. doi: 10.3321/j.issn:1002-6630.2009.09.067
    [14] LI S S, LIU X G, ZHU Y L, et al. A statistical approach to determine fluxapyroxad and its three metabolites in soils, sediment and sludge based on a combination of chemometric tools and a modified quick, easy, cheap, effective, rugged and safe method[J]. J Chromatogr A, 2014, 1358: 46-51. doi: 10.1016/j.chroma.2014.06.088
    [15] 郭亚歌, 徐军, 董丰收, 等. 关于JMPR植物源产品残留定义中含有代谢产物的农药在进行膳食风险评估时残留数据计算的介绍[J]. 植物保护, 2021, 47(2): 169-178. doi: 10.16688/j.zwbh.2020401

    GUO Y G, XU J, DONG F S, et al. Conversion of residue data for pesticide residue definition containing metabolites in dietary risk assessment for plant commodities of JMPR[J]. Plant Prot, 2021, 47(2): 169-178. doi: 10.16688/j.zwbh.2020401
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  • 收稿日期:  2022-01-16
  • 录用日期:  2022-04-19
  • 网络出版日期:  2022-08-23

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