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

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

李若同,
胡继业^,

1.
北京科技大学化学与生物工程学院，北京 100083

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
计量
- 文章访问数: 132
- HTML全文浏览量: 39
- PDF下载量: 23
- 被引次数: 0
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

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

LI Ruotong,
HU Jiye^,

1.
School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing 100083, China

摘要

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。
- QuEChERS /
- 高效液相色谱-串联质谱 /
- 吡噻菌胺 /
- 肟菌酯 /
- 代谢物 /
- 番茄 /
- 残留 /
- 膳食风险评估
Abstract: A method was established for the simultaneous determination of penthiopyrad, its main metabolite 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide (PAM), trifloxystrobin and its metabolite trifloxystrobin acid in tomato. The samples were extracted with acetic acid and acetonitrile, cleaned-up with anhydrous MgSO₄, primary secondary amine (PSA) and GCB, and detected by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The linearities of penthiopyrad, PAM, trifloxystrobin and trifloxystrobin acid ranged from 0.025 to 2 mg/L, with R²≥ 0.9992. The average recoveries of the four compounds in tomato at different spiked levels were 88%-97%, with the relative standard deviations (RSD) less than 3.9%. The limits of quantification (LOQs) of the analytes were all 0.05 mg/kg. The supervised residue trials were carried out in 12 farm regions in China according to "Guideline for the Testing of Pesticide Residues in Crops". The 30% suspension concentrate of penthiopyrad and trifloxystrobin was sprayed twice with an interval of 7 days at the recommended dosage of 270 g a.i./hm² at the early stage of Botrytis cinerea in tomato, and the recommended pre-harvest interval was 5 days. On the 5th and 7th day after the last application, the residues of penthiopyrad in tomato samples were below 0.26 mg/kg, and the residues of trifloxystrobin were below 0.33 mg/kg, which were lower than the corresponding MRLs set in China. The dietary risk assessment was carried out according to the results of residue field trials, dietary structure and toxicological data. The results showed that the national estimated daily intake (NEDI) of penthiopyrad and trifloxystrobin were 0.1382 mg and 0.2645 mg, respectively. The dietary risk quotient (RQ) of penthiopyrad and trifloxystrobin in tomato were less than 100%, which indicated that the application of the 30% suspension concentrate of penthiopyrad and trifloxystrobin under recommended Good Agricultural Practice (GAP) conditions would not pose an unacceptable risk to human health.
- QuEChERS /
- high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) /
- penthiopyrad /
- trifloxystrobin /
- metabolite /
- tomato /
- residue /
- dietary risk assessment

HTML全文

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)

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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
吡噻菌胺 penthiopyrad	1.22	360.1→276	360.1→177 360.1→276	55	177/40
PAM	0.59	194→134	194→174 194→134	40	134/20
PAM	0.59	194→134	194→174 194→134	40	174/6
肟菌酯 trifloxystrobin	1.63	409→186	409→206 409→186	76	186/15
肟菌酯 trifloxystrobin	1.63	409→186	409→206 409→186	76	206/10
肟菌酸 trifloxystrobin acid	1.01	395→186	395→148 395→186	114	186/10
肟菌酸 trifloxystrobin acid	1.01	395→186	395→148 395→186	114	148/10

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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

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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 M_e/%
吡噻菌胺 penthiopyrad	基质 Matrix　y = 96909x + 529.85	0.9999	0.05	0.105	−26
吡噻菌胺 penthiopyrad	溶剂 Solvent　y = 130958x + 682.05	0.0998	0.05	0.105	−26
PAM	基质 Matrix　y = 10703x + 38.251	1.0000	0.05	0.060	−24
PAM	溶剂 Solvent　y = 14082x + 59.53	0.0999	0.05	0.060	−24
肟菌酯 trifloxystrobin	基质 Matrix　y = 221053x + 5059	0.9992	0.05	0.006	−18
肟菌酯 trifloxystrobin	溶剂 Solvent　y = 269576x + 7263	0.0994	0.05	0.006	−18
肟菌酸 trifloxystrobin acid	基质 Matrix　y = 94378x + 272.03	0.9997	0.05	0.004	−20
肟菌酸 trifloxystrobin acid	溶剂 Solvent　y = 117972x + 493.97	0.0998	0.05	0.004	−20

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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
吡噻菌胺 penthiopyrad	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
吡噻菌胺 (总量) total penthiopyrad	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
肟菌酯 trifloxystrobin	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
肟菌酯 (总量) total trifloxystrobin	7	< 0.1 (22)，0.13，0.38	0.10	0.38

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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)
化合物　　　　　　 Compound	采收间隔期 Harvest interval/d	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

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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

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