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QuEChERS-高效液相色谱-串联质谱法检测吡噻菌胺、肟菌酯及代谢物在番茄中的残留及长期膳食风险评估

李若同 胡继业

李若同, 胡继业. QuEChERS-高效液相色谱-串联质谱法检测吡噻菌胺、肟菌酯及代谢物在番茄中的残留及长期膳食风险评估[J]. 农药学学报, 2022, 24(3): 572-580. doi: 10.16801/j.issn.1008-7303.2021.0183
引用本文: 李若同, 胡继业. QuEChERS-高效液相色谱-串联质谱法检测吡噻菌胺、肟菌酯及代谢物在番茄中的残留及长期膳食风险评估[J]. 农药学学报, 2022, 24(3): 572-580. doi: 10.16801/j.issn.1008-7303.2021.0183
LI Ruotong, HU Jiye. Residue and chronic dietary risk assessment of penthiopyrad, trifloxystrobin and their metabolites in tomato by QuEChERS-high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Pesticide Science, 2022, 24(3): 572-580. doi: 10.16801/j.issn.1008-7303.2021.0183
Citation: LI Ruotong, HU Jiye. Residue and chronic dietary risk assessment of penthiopyrad, trifloxystrobin and their metabolites in tomato by QuEChERS-high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Pesticide Science, 2022, 24(3): 572-580. doi: 10.16801/j.issn.1008-7303.2021.0183

QuEChERS-高效液相色谱-串联质谱法检测吡噻菌胺、肟菌酯及代谢物在番茄中的残留及长期膳食风险评估

doi: 10.16801/j.issn.1008-7303.2021.0183
详细信息
    作者简介:

    李若同,729198725@qq.com

    通讯作者:

    胡继业,jyhu@ustb.edu.cn

  • 中图分类号: TQ450.263;O657.63

Residue and chronic dietary risk assessment of penthiopyrad, trifloxystrobin and their metabolites in tomato by QuEChERS-high performance liquid chromatography-tandem mass spectrometry

  • 摘要: 建立了吡噻菌胺及其主要代谢物1-甲基-3- (三氟甲基)-1H-吡唑-4-甲酰胺 (PAM)和肟菌酯及其代谢物肟菌酸在番茄中残留的分析方法。样品经乙酸-乙腈提取,无水硫酸镁、N-丙基乙二胺 (PSA)和石墨化碳黑 (GCB)净化,高效液相色谱-串联质谱 (HPLC-MS/MS)检测。结果表明:吡噻菌胺、PAM、肟菌酯和肟菌酸在0.025~2 mg/L范围内的线性关系良好,R2≥0.999 2。在不同添加水平下,4种化合物在番茄中的平均回收率在88%~97%之间,相对标准偏差 (RSD)小于3.9%,定量限 (LOQ)均为0.05 mg/kg。按照《农作物中农药残留试验准则》在全国12个地区开展规范残留试验,30%吡噻菌胺 • 肟菌酯悬浮剂以推荐剂量有效成分270 g/hm2,于番茄灰霉病发生初期喷雾施药2次,施药间隔7 d (推荐的安全间隔期为5 d)。在分别于末次施药后5和7 d采集的番茄样品中,吡噻菌胺的残留量均低于0.26 mg/kg,肟菌酯的均低于0.33 mg/kg,均未超出中国制定的吡噻菌胺和肟菌酯在番茄中的最大残留限量 (MRL)值。根据田间残留试验结果、膳食结构和毒理学数据进行了长期膳食风险评估。结果表明:普通人群吡噻菌胺和肟菌酯国家估算每日摄入量 (NEDI)分别为0.1382和0.2645 mg,膳食风险商 (RQ)均小于100%,说明在推荐的良好农业规范 (GAP)条件下施用30%吡噻菌胺 • 肟菌酯悬浮剂不会对人体健康产生不可接受的风险。
  • 1  吡噻菌胺 (a)、PAM (b)、肟菌酯 (c) 和肟菌酸 (d) 的化学结构式

    1.  The structural formula of penthiopyrad (a), PAM (b), trifloxystrobin (c) and trifloxystrobin acid (d)

    表  1  吡噻菌胺、PAM、肟菌酯和肟菌酸质谱检测条件

    Table  1.   Mass spectrometry parameters for penthiopyrad, PAM, trifloxystrobin and trifloxystrobin acid

    化合物
    Compound
    保留时间
    Retention time/min
    定量离子
    Quantitative ion
    定性离子
    Qualitative ion
    碎裂电压
    Cone voltage/V
    碰撞能量
    Collision energy/eV
    吡噻菌胺 penthiopyrad 1.22 360.1→276 360.1→177
    360.1→276
    55 276/12
    177/40
    PAM 0.59 194→134 194→174
    194→134
    40 134/20
    174/6
    肟菌酯 trifloxystrobin 1.63 409→186 409→206
    409→186
    76 186/15
    206/10
    肟菌酸 trifloxystrobin acid 1.01 395→186 395→148
    395→186
    114 186/10
    148/10
    下载: 导出CSV

    表  2  吡噻菌胺、PAM、肟菌酯和肟菌酸在番茄中的平均添加回收率和相对标准偏差

    Table  2.   The average recoveries and RSDs of penthiopyrad, PAM, trifloxystrobin and trifloxystrobin acid in tomato

    化合物
    Compound
    添加水平Spiked level/
    (mg/kg)
    平均回收率Average recovery/
    %
    相对标准偏差
    RSD/%
    吡噻菌胺
    penthiopyrad
    0.05 97 3.4
    0.7 90 2.7
    2 89 3.7
    PAM 0.05 95 1.7
    0.7 92 3.2
    2 88 3.5
    肟菌酯
    trifloxystrobin
    0.05 95 3.8
    0.3 90 2.6
    0.7 90 3.9
    肟菌酸
    trifloxystrobin acid
    0.05 94 3.6
    0.4 91 2.9
    0.7 89 3.6
    下载: 导出CSV

    表  3  吡噻菌胺、PAM、肟菌酯和肟菌酸在番茄中的线性方程、定量限、检出限及基质效应

    Table  3.   Linear equations, LOQ, LOD and matrix effects of penthiopyrad, PAM, trifloxystrobin and trifloxystrobin acid in tomato

    化合物
    Compound
    线性方程
    Linear equation
    R2定量限
    LOQ/(mg/kg)
    检出限
    LOD/(μg/kg)
    基质效应
    Me/%
    吡噻菌胺 penthiopyrad 基质 Matrix y = 96909x + 529.85 0.9999 0.05 0.105 −26
    溶剂 Solvent y = 130958x + 682.05  0.0998
    PAM 基质 Matrix y = 10703x + 38.251 1.0000 0.05 0.060 −24
    溶剂 Solvent y = 14082x + 59.53 0.0999
    肟菌酯 trifloxystrobin 基质 Matrix y = 221053x + 5059 0.9992 0.05 0.006 −18
    溶剂 Solvent y = 269576x + 7263 0.0994
    肟菌酸 trifloxystrobin acid 基质 Matrix y = 94378x + 272.03 0.9997 0.05 0.004 −20
    溶剂 Solvent y = 117972x + 493.97 0.0998
    下载: 导出CSV

    表  4  吡噻菌胺、肟菌酯、吡噻菌胺 (总量) 和肟菌酯 (总量) 在12个试验点番茄样品中的最终残留量 (n = 2)

    Table  4.   Terminal residues of penthiopyrad, total penthiopyrad (sum of penthiopyrad and PAM), trifloxystrobin and total trifloxystrobin (sum of trifloxystrobin and trifloxystrobin acid) in tomato samples from 12 test sites (n = 2)

    化合物  
    Compound  
    采收间隔期
    Harvest interval/d
    最终残留量
    Terminal residue/(mg/kg)
    残留试验中值
    STMR/(mg/kg)
    最高残留量
    HR/(mg/kg)
    吡噻菌胺
    penthiopyrad
    5 < 0.05 (14),0.055,0.060,0.067,0.069,0.070,
    0.072,0.099,0.13 (2),0.16
    0.05 0.16
    7 < 0.05 (18),0.063,0.078 (2),0.086,0.10, 0.26 0.05 0.26
    吡噻菌胺 (总量)
    total penthiopyrad
    5 < 0.1 (14),0.11(2),0.12 (4),0.15,0.18 (2),0.21 0.10 0.21
    7 < 0.1 (18),0.11,0.13 (2),0.14,0.15,0.31 0.10 0.31
    肟菌酯
    trifloxystrobin
    5 < 0.05 (20),0.060,0.080,0.11,0.13 0.05 0.13
    7 < 0.05 (22),0.078,0.33 0.05 0.33
    肟菌酯 (总量)
    total trifloxystrobin
    5 < 0.1 (20),0.11,0.13,0.16,0.18 0.10 0.18
    7 < 0.1 (22),0.13,0.38 0.10 0.38
    下载: 导出CSV

    表  5  吡噻菌胺、肟菌酯、吡噻菌胺 (总量) 和肟菌酯(总量) 在4个试验点番茄样品中的残留消解动态 (n = 2)

    Table  5.   Dissipation of penthiopyrad, total penthiopyrad (sum of penthiopyrad and PAM), trifloxystrobin and total trifloxystrobin (sum of trifloxystrobin and trifloxystrobin acid) in tomato (n = 2)

    化合物      
    Compound      
    采收间隔期
    Harvest interval/d
    残留量 Residue/(mg/kg)
    北京
    Beijing City
    宁夏银川Yinchuan City of
    Ningxia Hui Autonomous Region
    山东济南Jinan City of
    Shandong Province
    贵州贵阳Guiyang City of
    Guizhou Province
    吡噻菌胺 penthiopyrad 0 0.12 1.0 0.16 0.47
    1 0.13 0.70 0.074 0.17
    3 0.054 <0.05 0.051 0.16
    5 <0.05 <0.05 0.065 0.11
    7 <0.05 <0.05 <0.05 0.17
    10 <0.05 <0.05 <0.05 0.053
    吡噻菌胺 (总量) total penthiopyrad 0 0.13 1.1 0.21 0.52
    1 0.054 0.75 0.13 0.22
    3 0.11 <0.1 0.10 0.21
    5 <0.1 <0.1 0.12 0.17
    7 <0.1 <0.1 <0.1 0.22
    10 <0.1 <0.1 <0.1 0.11
    肟菌酯 trifloxystrobin 0 0.062 0.076 0.14 0.26
    1 0.080 0.05 <0.05 0.15
    3 <0.05 <0.05 <0.05 0.15
    5 <0.05 <0.05 <0.05 0.12
    7 <0.05 <0.05 <0.05 0.20
    10 <0.05 <0.05 <0.05 0.054
    肟菌酯 (总量) total trifloxystrobin 0 0.12 0.13 0.19 0.31
    1 0.13 0.10 <0.1 0.20
    3 <0.1 <0.1 <0.1 0.20
    5 <0.1 <0.1 <0.1 0.17
    7 <0.1 <0.1 <0.1 0.26
    10 <0.1 <0.1 <0.1 0.1
    下载: 导出CSV

    表  6  吡噻菌胺和肟菌酯的膳食风险评估

    Table  6.   Dietary risk assessment of penthiopyrad and trifloxystrobin

    化合物
    Compound
    登记作物Registration
    crop
    食物种类Food
    classification
    膳食量Dietary intake/
    (kg/d)
    参考限量或残留试验中值Reference MRL
    or STMR/(mg/kg)
    来源
    Source
    国家估算每日摄入量
    NEDI/mg
    风险商
    RQ/%
    吡噻菌胺 penthiopyrad 番茄 Tomato 深色蔬菜 Dark-color vegetables 0.0915 0.10 残留中值 STMR 0.1382 2.2
    黄瓜 Cucumber 浅色蔬菜 Light-color vegetables 0.1837 0.7 欧盟 European Union
    葡萄 Grape 水果 Fruits 0.0457 0.01 欧盟 European Union
    肟菌酯 trifloxystrobin 水稻 Rice 米及其制品 Rice and its products 0.2399 0.1 中国 China 0.2645 10.5
    小麦 Wheat 面及其制品 Flour and its products 0.1385 0.2 中国 China
    玉米 Corn 其它谷类 Other cereals 0.0233 0.02 中国 China
    马铃薯 Potato 薯类 Tubers 0.0495 0.2 中国 China
    番茄 Tomato 深色蔬菜 Dark-color vegetables 0.0915 0.1 残留中值 STMR
    黄瓜 Cucumber 浅色蔬菜 Light-color vegetables 0.1837 0.3 中国 China
    樱桃 Cherry 水果 Fruits 0.0457 3 中国 China
    山核桃 Pecans 坚果 Nut 0.0039 0.02 中国 China
    咖啡 Coffee 饮料类 Drink 0.0120 0.05 欧盟 European Union
    人参 Ginseng 药用植物 Medicinal plant 0.0090 0.05 欧盟 European Union
    下载: 导出CSV
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出版历程
  • 收稿日期:  2021-09-10
  • 录用日期:  2021-11-19
  • 网络出版日期:  2021-12-28
  • 刊出日期:  2022-06-10

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