乙基多杀菌素在杨梅果实和土壤中的残留消解特征及其安全性评价

doi:10.3785/j.issn.1008-9209.2020.07.151

浙江大学学报（农业与生命科学版）

2021, Vol. 47

Issue (1): 43-51 DOI: 10.3785/j.issn.1008-9209.2020.07.151

植物保护

乙基多杀菌素在杨梅果实和土壤中的残留消解特征及其安全性评价

王天玉¹(

),林媚¹,姚周麟¹,王鹏¹,平新亮¹,方华²(

)

^1.浙江省农业科学院浙江省柑橘研究所，浙江台州 318026
^2.浙江大学农业与生物技术学院农药与环境毒理研究所，杭州 310058

Dissipation characteristics and safety evaluation of spinetoram in red bayberry and soil

Tianyu WANG¹(

),Mei LIN¹,Zhoulin YAO¹,Peng WANG¹,Xinliang PING¹,Hua FANG²(

)

^1.Citrus Research Institute of Zhejiang Province, Zhejiang Academy of Agricultural Sciences, Taizhou 318026, Zhejiang, China
^2.Institute of Pesticide and Environmental Toxicology, College of Agriculture and Biotechnology, Zhejiang University, Hangzhou 310058, China

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摘要：

为明确乙基多杀菌素在杨梅园中使用后的环境安全性，建立了杨梅和土壤中乙基多杀菌素的残留分析方法，并在浙江和福建2地进行了为期2年的乙基多杀菌素在杨梅果实和土壤中的残留消解规律研究。植物样品采用乙腈作为提取剂，N-丙基乙二胺和无水硫酸镁作为分散净化剂；土壤样品用水和乙腈作为提取剂，用N-丙基乙二胺进行净化，利用超高效液相色谱-串联质谱法检测，通过外标法定量。结果表明：乙基多杀菌素在0.001～0.5 mg/L范围内的质量浓度和峰面积之间具有良好的线性关系（R²＞0.999）；在0.005～0.5 mg/kg 添加水平下，乙基多杀菌素在杨梅果实中的平均回收率为89.40%～101.85%，相对标准偏差为3.63%～7.25%；其在土壤中的平均回收率为95.09%～102.66%，相对标准偏差为3.05%～3.61%；在杨梅果实和土壤中其定量限均为5.0×10^－3 mg/kg，检测限均为5.2×10^－5 mg/kg。消解动态试验结果表明：按1.5倍的最高推荐剂量（60 mg/L）于杨梅刚开始转色时喷施1次，乙基多杀菌素在杨梅果实和土壤中的消解动态均符合一级动力学方程，其半衰期分别为4.4～5.2和1.2～1.9 d，属于易降解性农药。田间最终残留试验结果显示，7 d后，乙基多杀菌素在杨梅果实中的残留量为0.073～0.353 mg/kg，在土壤中的残留量为低于定量限～0.094 mg/kg。综上所述，采用该方法能够实现杨梅和土壤中乙基多杀菌素的残留检测，简便、准确、灵敏度高；按照田间试验推荐的使用浓度和次数后，乙基多杀菌素的降解半衰期短，其最终残留量远低于国标规定的在杨梅中的最大临时限量标准（1 mg/kg），说明乙基多杀菌素在安全间隔期内用于杨梅树上害虫防治是安全的。

关键词： 乙基多杀菌素; 超高效液相色谱-串联质谱法; 杨梅果实; 土壤; 残留; 消解动态

Abstract:

To assess the environmental safety of applications of insecticide spinetoram in red bayberry, the analytical method and residue dynamics as well as final residues in the red bayberry and soil were investigated in Zhejiang and Fujian for two years. The plant samples were extracted with acetonitrile, cleaned up with primary secondary amine (PSA) sorbent and anhydrous magnesium sulfate, and analyzed by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The soil samples were extracted with water-acetonitrile, cleaned up with PSA sorbent and analyzed by UPLC-MS/MS, and quantified by external standard method. The results showed good linearity (R²＞0.999) between concentration and peak area when the concentrations of spinetoram ranged from 0.001 to 0.5 mg/L. When the spiked levels ranged from 0.005 to 0.5 mg/kg, the average recoveries in the red bayberry were in the range of 89.40% to 101.85%, with relative standard deviations (RSDs) of 3.63%-7.25%; the average recoveries in the soil were in the range of 95.09% to 102.66%, with RSDs of 3.05%-3.61%; the limit of detection (LOD) was 5.2×10^－5 mg/kg, while the limits of quantification (LOQs) were 5.0×10^－3 mg/kg for the red bayberry and soil. When the red bayberry was sprayed with 60 mg/L spinetoram suspension concentrate at the 1.5 times of the recommended maximum dosage at fruit color-changed period (one time), the dissipation dynamics of spinetoram in the red bayberry and soil were in accordance with the first-order kinetic equation, and the dissipation half lives of spinetoram residues were 4.4-5.2 and 1.2-1.9 d in the red bayberry and soil, respectively, belonging to degradable pesticide. The final residues were 0.073-0.353 mg/kg in the red bayberry and less than the limit of quantification-0.094 mg/kg in the soil at 7 d after spraying. In conclusion, the methods are fast, accurate and sensitive for detection of spinetoram residues in the red bayberry and soil, and the dissipation half lives of spinetoram are short after using the concentration and times recommended by the field experiment, and the final residues are lower than the maximum residue limit of red bayberry stipulated by national standard (1 mg/kg). Therefore, it is safe to use spinetoram for the pest control of red bayberry tree in preharvest interval.

Key words: spinetoram ultra performance liquid chromatography-tandem mass spectrometry red bayberry soil residue dissipation dynamics

收稿日期: 2020-07-15 出版日期: 2021-03-09

CLC:

基金资助: 浙江省台州市科学技术局项目(162ny12);国家自然科学基金(31801642);浙江省自然科学基金重点项目(LZ21B070002)

通讯作者: 方华 E-mail: wangtianyu2011@163.com;agri@zju.edu.cn

作者简介: 王天玉（https://orcid.org/0000-0002-9365-2766），E-mail：wangtianyu2011@163.com

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引用本文:

王天玉,林媚,姚周麟,王鹏,平新亮,方华. 乙基多杀菌素在杨梅果实和土壤中的残留消解特征及其安全性评价[J]. 浙江大学学报（农业与生命科学版）, 2021, 47(1): 43-51.

Tianyu WANG,Mei LIN,Zhoulin YAO,Peng WANG,Xinliang PING,Hua FANG. Dissipation characteristics and safety evaluation of spinetoram in red bayberry and soil. Journal of Zhejiang University (Agriculture and Life Sciences), 2021, 47(1): 43-51.

链接本文:

http://www.zjujournals.com/agr/CN/10.3785/j.issn.1008-9209.2020.07.151 或 http://www.zjujournals.com/agr/CN/Y2021/V47/I1/43

表1 乙基多杀菌素的UPLC-MS/MS检测参数

表 2 乙基多杀菌素在杨梅果实和土壤中的添加回收率及相对标准偏差

图1 乙基多杀菌素在多反应监测模式下的提取离子流图谱

表 3 乙基多杀菌素在样品中的灵敏度对比

图 2 乙基多杀菌素在杨梅果实中的消解动态

图 3 乙基多杀菌素在土壤中的消解动态

表 4 乙基多杀菌素在杨梅果实和土壤中的消解动态方程及半衰期

表 5 浙江和福建2地土壤的理化指标

表6 乙基多杀菌素在杨梅果实中的最终残留量

表 7 乙基多杀菌素在土壤中的最终残留量

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