食品中农药残留分析方法研究
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摘要
食品中农药残留量是世界各国关注的重要的食品安全问题，与人类健康和食品国际贸易密切相关。WHO／FAO-CAC对食品中农药残留作了相应的最高残留限量(MRL)规定。一些发达国家利用食品中的农药残留限量及其检测技术作为食品国际贸易的技术壁垒，设置贸易障碍。食品中农药残留量的检测技术成为了食品安全执法和国际贸易的关键问题。为了保护消费者健康，消除发达国家的技术壁垒，提高我国食品的国际市场竞争力，开发针对我国食品的农药残留问题和国际食品贸易要求的快速检测技术显得十分重要。开发简单、快速、有效的样品前处理技术，以及具有高灵敏度和高选择性的多残留同时检测方法是农药残留检测技术的发展趋势。本研究采用微量化学样品前处理技术、固相萃取技术等样品前处理技术和食品中农药残留量气相色谱检测方法，建立了食品中多种农药的多残留快速检测方法，以满足食品安全管理和食品国际贸易对农药残留量检测技术的需要。
本论文共分为三个部分：第一章是第一部分，为相关的背景及文献综述；第二部分包括第二、三、四、五章四种分析方法，分别为气相色谱法测定荞头中甲胺磷农药残留量、低温提取气相色谱法测定荞头中13种有机磷农药残留量、气相色谱法测定茶叶中20种有机磷农药残留量以及气相色谱法测定茶叶中8种氨基甲酸酯类农药残留量；第六章是最后一部分，为食品中杀虫双农药残留量测定方法的初步研究结果。
第一章 样品的前处理方法和气相色谱分析技术及其在农药残留分析中的应用。主要介绍了微量化学法及其在农药残留分析中的应用，并对气相色谱法等分析检测方法进行了简单的概述。
第二章 荞头中甲胺磷农药残留检测方法。利用丙酮改变甲胺磷农药在有机相和水相的分配比，提高了甲胺磷农药的提取率，消除了荞头中含硫化合物的干扰。该方法的回收率为87.4-109％，精密度为0.5-2.5％，检测低限为0.02mg／kg，满足荞头中甲胺磷农药残留分析测定的要求。
第三章 低温提取气相色谱法测定荞头中13种弱极性有机磷农药残留量。采用2℃低温条件提取，建立了荞头中有机磷农药残留分析的前处理方法，基本克服了荞头中含硫化合物对有机磷农药残留量测定的干扰。方法回收率为61.5-135％，精密度为2.6-15％，检测低限达到0.005-0.04mg／kg，符合荞头中多种有机磷农药残留分析要求。
第四章茶叶中20种有机磷农药的气相色谱分析方法。方法的添加标样回
收率为60一120%，精密度为0.3一10.2%，检测低限为0.018一0.04m岁kg，快速、
简单、灵敏，消除了复杂化合物干扰，完全适用于茶叶样品的农药残留的快速
分析。
第五章茶叶中8种氨基甲酸酷类农药残留量的分析方法。根据欧盟新的
农残限量标准和我国茶园使用氨基甲酸醋农药的情况，采用微量化学法和固相
萃取技术，建立了同时测定茶叶中8种氨基甲酸酷农药残留量的方法。方法回
收率为70一104%，精密度为2.4一s%，检测低限达0.01一0.lmg/kg。
第六章食品中杀虫双农药残留的气相色谱分析方法初步研究。采用微量
化学方法，改进样品衍生条件，利用气相色谱法测定大米和荞头中杀虫双农药
残留量。研究结果表明，添加浓度相当于1.om眺g一5.0m眺g的杀虫双农药
标准能够定量衍生，衍生产物通过气相色谱分析，峰面积的对数与浓度的对数
呈良好线性关系，满足分析方法要求。
The pesticide residues are the critical food safety question concerned by every nation, relative to persons' healthy and international trade in food. So the maximum residue levels (MRL) in food were constituted by WHO/FAO-CAC. Some developed county created difficulties for our foreign trade by the detection technologies of pesticide residues in food, therefore it is the critical problem in executing the law about food safety and international trade. In order to protect consumers' healthy, avoid handicapping by the developed country in international trade, improve the competitive ability of our food in the international market, it is very important to exploit the prompt detection technologies based on pesticide residues in food and the requirement for international trade on food. It is the trend to exploit simply, fast, efficient pre-treatment technologies for samples and high sensitive, high selective methods in multi-pesticide residues detections. Focused on the study on micro-chemical method and solid-phas
e extraction technology used in the sample pre-treatment and the detection methods by gas chromatography, fast methods on the multi-pesticide residues in food has been established. The methods are significant for the management on food safety and international trade.
The thesis includes three parts: the background and literature summarize (Chapter I), four Methods of determination for pesticide residues in food (Chapter II to V), and the primary study on analysis method on the Hope pesticide residues in food (Chapter VI).
Sample pre-treatment technologies and their application to pesticide residues analysis were introduced in Chapter I. It is mainly in the micro-chemical technology and gas chromatography method.
In Chapter II, the method of analysis on methamidophos in Allium Chinense has been established. And high recoveries (87.4-109%) have been obtained by changing the quantity of acetone in organic and water phase. Relative standard deviations (RSDs) were from 0.5% to 2.5% and the detection limit was 0.02 mg/kg, according with the requirement of MRLs.
In Chapter III, It is method of determination for 13 OPPs with weak polarity in Allium Chinense. Multi-organophosphorus pesticides were extracted under 2 and
detected by gas chromatography. The interference of the chemical substance in Allium Chinense was eliminated. The recoveries were from 61.5% to 135%. RSDs were from 2.6% to 15% and the detection limits were from 0.005 mg/kg to 0.04 mg/kg, according with the requirement of MRLs on the organophosphorus pesticide residues in Allium Chinense.
In Chapter IV, twenty organophosphorus pesticides in tea have been analyzed using gas chromatography. The most kinds of organophosphorus pesticides in tea can be detected with the same program in domestic. The recoveries were from 60% to 120%. RSDs were from 0.3% to 10.2% and the detection limits were 0.018-0.04 mg/kg, according with the requirement of MRLs by European Union (EU) on the analysis of organophosphorus pesticide residues in tea.
In Chapter V, the method has been established for determination 8 Carbamate pesticide residues in tea using gas chromatography with micro-chemical and solid phase extraction technology based on the new pesticide residues regulated by EU and the practice in our tea gardens. The recoveries ranged from 70% to 104%. RSDs were 2.4%-8% and the detection limits were 0.01-0.1 mg/kg. This method is rapid, sensitive and suitable for pesticide residues analysis. It can also be applied to the determination of Carbamate pesticide multi- residues in other plant samples such as vegetables, fruits and so on.
In Chapter VI, the analysis method for Hope in food using gas chromatography was primarily investigated. Hope pesticide residues in rice and Allium Chinense were detected using micro-chemical method and improved sample pre-treatment technology. The research results indicated that the standard pesticides added in blank samples can be derived quantitatively and can be detected with good linearity by gas chromatography. And this method can b
本论文共分为三个部分：第一章是第一部分，为相关的背景及文献综述；第二部分包括第二、三、四、五章四种分析方法，分别为气相色谱法测定荞头中甲胺磷农药残留量、低温提取气相色谱法测定荞头中13种有机磷农药残留量、气相色谱法测定茶叶中20种有机磷农药残留量以及气相色谱法测定茶叶中8种氨基甲酸酯类农药残留量；第六章是最后一部分，为食品中杀虫双农药残留量测定方法的初步研究结果。
第一章 样品的前处理方法和气相色谱分析技术及其在农药残留分析中的应用。主要介绍了微量化学法及其在农药残留分析中的应用，并对气相色谱法等分析检测方法进行了简单的概述。
第二章 荞头中甲胺磷农药残留检测方法。利用丙酮改变甲胺磷农药在有机相和水相的分配比，提高了甲胺磷农药的提取率，消除了荞头中含硫化合物的干扰。该方法的回收率为87.4-109％，精密度为0.5-2.5％，检测低限为0.02mg／kg，满足荞头中甲胺磷农药残留分析测定的要求。
第三章 低温提取气相色谱法测定荞头中13种弱极性有机磷农药残留量。采用2℃低温条件提取，建立了荞头中有机磷农药残留分析的前处理方法，基本克服了荞头中含硫化合物对有机磷农药残留量测定的干扰。方法回收率为61.5-135％，精密度为2.6-15％，检测低限达到0.005-0.04mg／kg，符合荞头中多种有机磷农药残留分析要求。
第四章茶叶中20种有机磷农药的气相色谱分析方法。方法的添加标样回
收率为60一120%，精密度为0.3一10.2%，检测低限为0.018一0.04m岁kg，快速、
简单、灵敏，消除了复杂化合物干扰，完全适用于茶叶样品的农药残留的快速
分析。
第五章茶叶中8种氨基甲酸酷类农药残留量的分析方法。根据欧盟新的
农残限量标准和我国茶园使用氨基甲酸醋农药的情况，采用微量化学法和固相
萃取技术，建立了同时测定茶叶中8种氨基甲酸酷农药残留量的方法。方法回
收率为70一104%，精密度为2.4一s%，检测低限达0.01一0.lmg/kg。
第六章食品中杀虫双农药残留的气相色谱分析方法初步研究。采用微量
化学方法，改进样品衍生条件，利用气相色谱法测定大米和荞头中杀虫双农药
残留量。研究结果表明，添加浓度相当于1.om眺g一5.0m眺g的杀虫双农药
标准能够定量衍生，衍生产物通过气相色谱分析，峰面积的对数与浓度的对数
呈良好线性关系，满足分析方法要求。
The pesticide residues are the critical food safety question concerned by every nation, relative to persons' healthy and international trade in food. So the maximum residue levels (MRL) in food were constituted by WHO/FAO-CAC. Some developed county created difficulties for our foreign trade by the detection technologies of pesticide residues in food, therefore it is the critical problem in executing the law about food safety and international trade. In order to protect consumers' healthy, avoid handicapping by the developed country in international trade, improve the competitive ability of our food in the international market, it is very important to exploit the prompt detection technologies based on pesticide residues in food and the requirement for international trade on food. It is the trend to exploit simply, fast, efficient pre-treatment technologies for samples and high sensitive, high selective methods in multi-pesticide residues detections. Focused on the study on micro-chemical method and solid-phas
e extraction technology used in the sample pre-treatment and the detection methods by gas chromatography, fast methods on the multi-pesticide residues in food has been established. The methods are significant for the management on food safety and international trade.
The thesis includes three parts: the background and literature summarize (Chapter I), four Methods of determination for pesticide residues in food (Chapter II to V), and the primary study on analysis method on the Hope pesticide residues in food (Chapter VI).
Sample pre-treatment technologies and their application to pesticide residues analysis were introduced in Chapter I. It is mainly in the micro-chemical technology and gas chromatography method.
In Chapter II, the method of analysis on methamidophos in Allium Chinense has been established. And high recoveries (87.4-109%) have been obtained by changing the quantity of acetone in organic and water phase. Relative standard deviations (RSDs) were from 0.5% to 2.5% and the detection limit was 0.02 mg/kg, according with the requirement of MRLs.
In Chapter III, It is method of determination for 13 OPPs with weak polarity in Allium Chinense. Multi-organophosphorus pesticides were extracted under 2 and
detected by gas chromatography. The interference of the chemical substance in Allium Chinense was eliminated. The recoveries were from 61.5% to 135%. RSDs were from 2.6% to 15% and the detection limits were from 0.005 mg/kg to 0.04 mg/kg, according with the requirement of MRLs on the organophosphorus pesticide residues in Allium Chinense.
In Chapter IV, twenty organophosphorus pesticides in tea have been analyzed using gas chromatography. The most kinds of organophosphorus pesticides in tea can be detected with the same program in domestic. The recoveries were from 60% to 120%. RSDs were from 0.3% to 10.2% and the detection limits were 0.018-0.04 mg/kg, according with the requirement of MRLs by European Union (EU) on the analysis of organophosphorus pesticide residues in tea.
In Chapter V, the method has been established for determination 8 Carbamate pesticide residues in tea using gas chromatography with micro-chemical and solid phase extraction technology based on the new pesticide residues regulated by EU and the practice in our tea gardens. The recoveries ranged from 70% to 104%. RSDs were 2.4%-8% and the detection limits were 0.01-0.1 mg/kg. This method is rapid, sensitive and suitable for pesticide residues analysis. It can also be applied to the determination of Carbamate pesticide multi- residues in other plant samples such as vegetables, fruits and so on.
In Chapter VI, the analysis method for Hope in food using gas chromatography was primarily investigated. Hope pesticide residues in rice and Allium Chinense were detected using micro-chemical method and improved sample pre-treatment technology. The research results indicated that the standard pesticides added in blank samples can be derived quantitatively and can be detected with good linearity by gas chromatography. And this method can b
引文
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