杨梅中灭蝇胺及其代谢物检测方法与风险评估

doi:10.3969/j.issn.1004-1524.2021.03.19

浙江农业学报 ›› 2021, Vol. 33 ›› Issue (3): 534-540.DOI: 10.3969/j.issn.1004-1524.2021.03.19

杨梅中灭蝇胺及其代谢物检测方法与风险评估

田培¹^,², 赵慧宇¹^,²^,^*(), 刘之炜¹^,², 王娇¹^,², 狄珊珊¹^,², 徐浩¹^,², 汪志威¹^,³, 王新全¹^,²^,⁴, 齐沛沛¹^,⁴

1.浙江省农业科学院农产品质量安全与营养研究所,浙江杭州 310021
2.浙江省农药残留检测与控制研究重点实验室,浙江杭州 310021
3.农业农村部农药残留检测重点实验室,浙江杭州 310021
4.农业农村部农产品质量安全风险评估实验室(杭州),浙江杭州 310021;

收稿日期:2020-11-04 出版日期:2021-04-02 发布日期:2021-03-25
通讯作者: 赵慧宇
作者简介:*, 赵慧宇,E-mail: zhaohuiyu64@163.com
田培(1988—),女,湖北天门人,学士,助理工程师,主要从事农产品质量安全检测。E-mail: 544599749@qq.com
基金资助:
浙江省农业农村厅农业重大科研专项(“一县一品一策”)(ZJNY2020001)

Analysis and risk assessment of cyromazine and its metabolites in bayberry

TIAN Pei¹^,², ZHAO Huiyu¹^,²^,^*(), LIU Zhiwei¹^,², WANG Jiao¹^,², DI Shanshan¹^,², XU Hao¹^,², WANG Zhiwei¹^,³, WANG Xinquan¹^,²^,⁴, QI Peipei¹^,⁴

1. Institute of Quality Safety and Nutrition For Agricultural Products, Zhejiang Academy of Agricultural Sciences, Hangzhou 310021, China
2. Key Laboratory of Detection for Pesticide Residue and Control of Zhejiang, Hangzhou 310021, China
3. Key Laboratory for Pesticide Residue Detection, Ministry of Agriculture and Rural Affairs, Hangzhou 310021, China
4. Risk Assessment Laboratory for Agricultural Products, Ministry of Agriculture and Rural Affairs, Hangzhou 310021, China

Received:2020-11-04 Online:2021-04-02 Published:2021-03-25
Contact: ZHAO Huiyu

摘要/Abstract

摘要：

杨梅是我国南方地区重要经济作物,因其登记农药种类少,裸果食用的质量安全问题备受关注。果蝇是杨梅果实成熟期最为重要的虫害,对于果蝇防治药剂的残留风险评估十分必要。生产调研中发现,灭蝇胺在生产中被用于防治果蝇,但灭蝇胺及其代谢产物三聚氰胺有较强的水溶性,为其检测方法的开发带来了困难。本研究采用固相萃取-高效液相串联质谱仪(LC-MS/MS)多反应监测的检测模式,建立了杨梅基质中灭蝇胺及其代谢产物三聚氰胺的残留分析方法,通过1%三氯乙酸溶剂提取,MCX固相萃取柱净化等前处理,结合超高效液相色谱-串联质谱法进行残留检测。结果表明,该方法灭蝇胺和三聚氰胺的添加回收率均在88%~110%,相对标准偏差小于10%,灭蝇胺和三聚氰胺方法的检出限(LOD)均为0.01 mg·kg ^-1;方法的定量限(LOQ)均为0.05 mg·kg ^-1,在0.01~0.10 mg·L ^-1具有良好线性关系;基质效应评价结果为基质抑制效应。经过风险评估,杨梅中的灭蝇胺和三聚氰胺的慢性和急性风险商均小于1,说明杨梅中灭蝇胺和三聚氰胺的急慢性风险均在可接受范围内,一般情况下,不会对人体健康产生风险。该检测方法具有灵敏、有机溶剂使用少等优势,适用于我国杨梅中灭蝇胺及其代谢产物三聚氰胺的风险检测。

关键词: 杨梅, 残留, 灭蝇胺, 三聚氰胺, 风险评估

Abstract:

Bayberry is an important economic fruit in south China. Its quality and safety are highly concerned because of lacking registered pesticides and direct consumption habit with bare fruit without washing. Drosophila melanogaster is the most important insect which harm bayberry fruit during harvest time. Therefore, it is necessary to evaluate the residual risk of its control agents such as cyromazine, which has been widely used for preventing Drosophila melanogaster on bayberry. Cyromazine and its metabolite melamine were not easy to be analysed becaused of highly solubable property in water. In this study, an analytical method had been developed for analyzing cyromazine and its metabolite melamine using solid phase extraction coupled with high performance liquid phase tandem mass spectrometer (LC-MS/MS) under multi-reaction monitoring mode. The sample was extracted by 1% trichloroacetic acid solution, followed by purification with MCX SPE, and then detected by LC-MS/MS. The results showed that recoveries of cyromazine and melamine were in the range of 88%-110%. The relative standard deviations were less than 10%. The detection limit (LOD) for both cyromazine and melamine methods were 0.01 mg·kg ^-1. The quantitative limits (LOQ) of the methods were all 0.05 mg·kg ^-1, with good linear relationship in the range of 0.01-0.10 mg·L ^-1. The evaluation result of matrix effect showed matrix inhibition impact. Risk assessment results showed that both chronic and acute risk quotients for cyromazine and melamine were less than 1, indicating that their acute and chronic risks were negligible or within the acceptable range according to the monitoring data. In general, there was no risk protentical for bayberry consumers. This method had the advantages of good sensitivity, friendly to people and environment with less solvent usage. It could be applied for future risk monitoring of cyromazine and its metabolite melamine on bayberry.

Key words: bayberry, residues, cyromazine, melamine, risk assessment

中图分类号:

S667.6

田培, 赵慧宇, 刘之炜, 王娇, 狄珊珊, 徐浩, 汪志威, 王新全, 齐沛沛. 杨梅中灭蝇胺及其代谢物检测方法与风险评估[J]. 浙江农业学报, 2021, 33(3): 534-540.

TIAN Pei, ZHAO Huiyu, LIU Zhiwei, WANG Jiao, DI Shanshan, XU Hao, WANG Zhiwei, WANG Xinquan, QI Peipei. Analysis and risk assessment of cyromazine and its metabolites in bayberry[J]. Acta Agriculturae Zhejiangensis, 2021, 33(3): 534-540.

图/表 6

参考文献 13

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农药 Pesticide	定量与定性离子对 Ions pair(m/z)	碰撞能量 Collision energy/eV	去簇电压 DP/V
灭蝇胺Cyromazine	167.0/125.0^*,167.0/108	25,29	46,41
三聚氰胺Melamine	127.0/85.0^*,127.0/68.0	23,37	86,86

农药 Pesticide	定量与定性离子对 Ions pair(m/z)	碰撞能量 Collision energy/eV	去簇电压 DP/V
灭蝇胺Cyromazine	167.0/125.0^*,167.0/108	25,29	46,41
三聚氰胺Melamine	127.0/85.0^*,127.0/68.0	23,37	86,86

溶剂 Solution	回收率Recovery rate/%
溶剂 Solution	灭蝇胺 Cyromazine	三聚氰胺 Melamine
1%三氯乙酸	93.3	79.0
1% Trichloroacetic acid solution
1%三氯乙酸-乙腈(3+2)	84.3	61.6
1% Trichloroacetic acid solution- Acetonitrile(3+2)
乙酸铵-乙腈(1+4)	61.2	41.1
Ammonium acetate-Acetonitrile(1+4)
乙腈Acetonitrile	56.8	9.7

溶剂 Solution	回收率Recovery rate/%
溶剂 Solution	灭蝇胺 Cyromazine	三聚氰胺 Melamine
1%三氯乙酸	93.3	79.0
1% Trichloroacetic acid solution
1%三氯乙酸-乙腈(3+2)	84.3	61.6
1% Trichloroacetic acid solution- Acetonitrile(3+2)
乙酸铵-乙腈(1+4)	61.2	41.1
Ammonium acetate-Acetonitrile(1+4)
乙腈Acetonitrile	56.8	9.7

农药 Pesticide	溶剂标线性方程 Linear equation of solvent standard	R²	基质标线性方程 Matrix standard linear equation	R²	检出限 LOD/(μg·g^-1)	定量限 LOQ/(μg·g^-1)
灭蝇胺 Cyromazine	y=5×10⁷x+29185	0.999 5	y=3×10⁶x+13877	0.998 4	0.01	0.05
三聚氰胺Melamine	y=6×10⁷x+66347	0.994 9	y=5×10⁶x+23142	0.997 6	0.01	0.05

杨梅中灭蝇胺及其代谢物检测方法与风险评估

Analysis and risk assessment of cyromazine and its metabolites in bayberry

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农药 Pesticide	添加水平 Add level/ (mg·kg^-1)	回收率 Recovery rate/%	相对标准偏差 RSD/%
灭蝇胺	0.05	77.6	2.5
Cyromazine	0.10	84.6	5.2
	0.20	88.2	2.9
	0.40	90.8	7.5
三聚氰胺	0.05	71.6	2.0
Melamine	0.10	78.6	4.2
	0.20	80.3	2.3
	0.40	84.7	8.8

农药 Pesticide	检出率 Detection rate/%	残留量Residue/(mg·kg^-1)
农药 Pesticide	检出率 Detection rate/%	平均残留量 Average	最小残留量 Min	最大残留量 Max	残留中值 Median residue
灭蝇胺Cyromazine	2.4	0.06	<0.01	0.13	0.05
三聚氰胺Melamine	21.7	0.02	<0.01	0.08	0.02

农药 Pesticide	每日摄入量 EDI/(10^-5 mg·kg^-1·d^-1)	慢性风险商 RQc	短期摄入量的估计值 ESTI/(10^-3 mg·kg^-1·d^-1)	急性风险商 RQa
灭蝇胺Cyromazine	7.3	0.001 2	2.3	0.024
三聚氰胺Melamine	2.5	0.000 1	1.4	0.006

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