论文总字数：25888字

摘 要

螺虫乙酯是一种新型季酮酸类杀虫剂，有关螺虫乙酯的环境行为及其降解影响因子方面的研究较少报道。本研究以螺虫乙酯为研究对象，主要研究螺虫乙酯在土壤，柑橘中的超高效液相色谱-串联质谱检测方法；并运用该方法螺虫乙酯在柑橘及探究其在福州、苏州和重庆三地土壤中的消解规律。

本文的前处理方法是用乙腈提取，N-丙基乙二胺(PSA)和石墨化碳黑(GCB)作为净化剂的QuEChERS方法，并利用超高效液相色谱-串联质谱(UPLC-MS/MS)检测。结果表明：螺虫乙酯及4种代谢产物在0.002~0.500mg/L质量浓度范围内有较好的线性关系(r²≥0.989)；在0.01~1.00mg/kg添加水平范围内平均回收率为71.6%~104.0%；相对标准偏差为1.0%~7.3%；方法检出限(LOD)在0.12~1.4μg/kg范围内；定量限(LOQ)在0.4~4.9μg/kg范围内。

运用上述所建立的检测方法定量检测调福州，苏州，重庆三地土壤中螺虫乙酯及其代谢产物的动态消解状况。土壤样品的动态消解结果如下。结果显示，螺虫乙酯在土壤中的初始沉积量为157.7 μg/kg(重庆)、188.3μg/kg(苏州)、148.7μg/kg(福州)，在重庆试验点的消解半衰期为8.0d，在福州的消解半衰期为5.6d，在苏州的消解半衰期为2.3 d，可见螺虫乙酯在土壤中的降解速度较快，三地土壤消解试验中螺虫乙酯的代谢产物S1,代谢产物S2，代谢产物S3，代谢产物S4均无检出。

结论表明：此方法分析速度快，灵敏度高，重现性好，适用于柑橘和土壤中螺虫乙酯及其代谢产物的残留的快捷检测和验证。

关键词：螺虫乙酯 代谢产物 柑橘 超高效液相色谱-串联质谱

A Study on the Detection of Spirotetramat and its Metabolites in Environmental Matrix

ABSTRACT

Spirotetramat is a new type of tetronic acid insecticide. The current domestic reports are limited to a small amount of residue analysis methods. Studies on the environmental behavior of spirotetramat and its degradation influencing factors have not been reported.In this study, spirotetramat was used as the research object, and the method was mainly used to detect spirotetramat in soil and citrus by ultra performance liquid chromatography-tandem mass spectrometry; external standard method was used for quantification, and spirotetramat in citrus and soil. Dispel the law.

The pretreatment method in this paper is the QuEChERS method with acetonitrile extraction, N-propyl ethylenediamine (PSA) and graphitized carbon black (GCB) as the dispersive scavenger, and UPLC MS/MS. ) Detection in multiple reaction ion monitoring mode (MRM), external standard method.

The results showed that the spirotetramat and the four metabolites had a good linear relationship within the range of 0.002~0.500mg/L (r2≥0.989); the average recovery rate was between 0.01 and 1.00mg/kg. 71.6%~104.0%; the relative standard deviation was 1.0%~7.3%; the method detection limit (LOD) was in the range of 0.12~1.4μg/kg; the limit of quantitation (LOQ) was in the range of 0.4~4.9μg/kg. The results show that this method is rapid, sensitive and reproducible, and it is suitable for rapid detection and verification of residues of spirotetramat and its metabolites in citrus and soil.

Quantitative detection of dynamic elimination of spirotetramat and its metabolites in the soils of Fuzhou, Suzhou, and Chongqing was conducted using the above-mentioned established detection methods. The results of dynamic digestion of soil samples are as follows. The results showed that the initial deposition of spirotetramat in the soil was 157.7 μg/kg (Chongqing), 188.3 μg/kg (Suzhou), and 148.7 μg/kg (Fuzhou). The half-life of the solution at the Chongqing test site was 8.0d. The half-life of digestion in Fujian was 5.6d, and the halflife of digestion in Suzhou was 2.3d. The degradation rate of spirotetramat in soil was faster, and the metabolite S1 of spirotetramat was not detected in soil digestion test in the three soils.

Key words: spirotetramat; metabolites; citrus; ultra performance liquid chrom

目录

摘要 I

ABSTRACT II

第一章 文献综述 1

1.1螺虫乙酯及其代谢产物的基本信息 1

1.2检测方法 5

1.2.1高效液相色谱法(HPLC) 5

1.2.2气相色谱法(GC) 5

1.2.3联用技术 5

1.3螺虫乙酯检测方法研究进展 6

1.4本文的研究内容，目的及意义 7

第二章 螺虫乙酯及其代谢产物在多种介质中的分析方法 8

2.1实验部分 8

2.1.1实验试剂 8

2.1.2实验仪器 10

2.1.3样品处理 10

2.2仪器条件 12

2.2.1液相色谱测定条件 12

2.2.2质谱条件 13

2.3 溶液配制 14

2.3.1储备液配制 14

2.3.2标曲配制 15

2.3.3基质标曲配制 15

2.4 回收率实验 16

2.4.1土壤 16

2.4.2果肉 16

2.4.3果皮 16

2.4.4全果 16

2.5结果与讨论 17

2.5.1质谱条件 17

2.5.2色谱条件 17

2.5.3提取时间 18

2.5.4净化条件 19

2.5.5线性范围 20

2.5.6回收率和精密度 23

2.5.7最小检出限(LOD)和最小检测浓度(LOQ) 29

2.6总结 30

第三章 螺虫乙酯及其代谢产物在重庆，苏州，福州三地土壤中的消解动态实例应用 31

3.1实验所需试剂 31

3.2实验仪器 31

3.3实验方法 31

3.3.1样品采集 31

3.3.2样品预处理 32

3.3.3仪器条件 32

3.3.4实验结果与分析 32

第四章 结语 35

4.1结论 35

4.2 展望 35

参考文献 37

致谢 39

第一章 文献综述

回顾人类的农业史，不难发现农药在农业中发挥着不可磨灭的作用。但是凡事都有两面性，农药在解决人类粮食产量问题的同时，也带来了不可忽视的农药残留污染等问题。^[3]本文旨在研究螺虫乙酯及其代谢产物在环境介质中的代谢残留，为螺虫乙酯的推广提供安全数据。

1.1螺虫乙酯及其代谢产物的基本信息

螺虫乙酯(spirotetramat)，分子式为C21H27NO5，结构式见图1,1-1，化学名为顺式-4-(乙基羰氧基)-8原甲氧基-3-(2，5-二甲苯基)-1-氮杂螺[4.5]癸-3-烯-2-酮，是由拜耳公司研制的季酮酸类杀虫剂。

螺虫乙酯进入动植物体内后，很快被代谢为各种主要代谢产物BYI08330-enol-glucoside、BYI08330-ketohydroxy、BYI08330-enol和BYI08330-monohydroxy，^[5]这些代谢产物不仅与螺虫乙酯的生物活性关系密切，更有研究表明他们可能对雄性生物的生殖器官造成伤害。^[15]螺虫乙酯主要用于防治各种刺吸式口器害虫，作用与大豆，棉花，柑橘等作物。

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