凝胶渗透色谱—气相色谱/质谱技术在农药多残留分析中的应用
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摘要
随着人们生活水平的日益提高,食品安全已经成为人们日益关注的问题,由于农药的大量使用,环境和食品中的农药残留问题已经引起了人们的广泛重视,并且成为制约我国商品出口的贸易壁垒。本文根据我国河豚鱼、鳗鱼和对虾等水产品中农药使用品种和我国及主要出口国农药残留量要求,对水产品中农药多残留的提取、净化技术和气相色谱-质谱检测条件进行了研究,建立了一种快速、准确、灵敏地测定河豚鱼、鳗鱼和对虾中191种农药残留的理想的方法,得到以下几个结论:
1.建立了简单、高效的样品前处理方法。使用乙酸乙酯-环己烷(1:1,体积比)作为河豚鱼、鳗鱼、对虾中191种农药残留分析的提取剂,同时作为凝胶渗透色谱的流动相,在优化后的条件下可有效地净化样品提取液中的蛋白、油脂等大分子杂质,并在线富集浓缩样品中的残留农药。同时,研究了173种农药的凝胶渗透色谱行为参数。
2.气相色谱-质谱检测方面,建立了191种农药残留气相色谱-质谱检测方法。结果表明,191种农药在相应的质量浓度范围内,各农药的响应值与其质量浓度均成良好的线性范围,相关系数均高于0.97,方法的最低检出限范围为0.002~0.3 mg/kg,最低定量限范围为0.007~1.2 mg/kg。
3.我们进行了方法精密度和准确度实验并得到了满意的结果。分别以最低定量限和4倍最低定量限为添加浓度对河豚鱼、鳗鱼和对虾样品进行了两个水平的添加回收率实验,方法的回收率范围为50.2%~120% (其中回收率在70%~120%的占89.5%),相对标准偏差范围为0.6%~21.6%。
With the rising of peoples’living standards, the question of food safety has attracted more and more attention. Due to large-scale use of pesticides, pesticide residues in food and environment has attracted extensive attention,which also became the technical trade barriers in China's merchandise exports. According to the kinds of pesticides used and the limits for pesticide residues in fugu, eel, prawn samples, this paper studied extraction, purification of sample pretreatments and GC-MS detection conditions of pesticide residues and also developed a new analytical procedure to determine 191 multiple pesticide residues in fugu, eel, prawn and other fishes in water. The details are as follows:
1. Building the simple, effective sample pretreatments. Using the ethyl acetate–cyclohexane(1:1,v:v) extracting residual pesticides in samples,and using the same solvent as the gel permeation chromatography mobile phase can remove macromolecule impurities such as proteins, lipids in sample efficiently, then extracting and concentrating the residual pesticides in samples on line,meanwhile investigating the 173 pesticides’gel permeation chromatography action parameters.
2. In this research, we established the GC-MS detection method for 191 pesticides. Linear regression in the corresponding concentration range was all over 0.97. The limits of detection and the limits of quantification were 0.002~0.3 mg/kg, 0.007~1.2 mg/kg respectively.
3. We took the precision and accuracy methodology test and got satisfied conclusion. The recovery was conducted at two spiked levels which is the LOQ concentration and 4 times of LOQ concentration, the validation results were as follows: the overall recoveries were from 50.2% to 120% (89.5% of the recoveries were from 70% to 120%), with the relative standard deviations (RSDS) of 0.6%-21.6%.
1.建立了简单、高效的样品前处理方法。使用乙酸乙酯-环己烷(1:1,体积比)作为河豚鱼、鳗鱼、对虾中191种农药残留分析的提取剂,同时作为凝胶渗透色谱的流动相,在优化后的条件下可有效地净化样品提取液中的蛋白、油脂等大分子杂质,并在线富集浓缩样品中的残留农药。同时,研究了173种农药的凝胶渗透色谱行为参数。
2.气相色谱-质谱检测方面,建立了191种农药残留气相色谱-质谱检测方法。结果表明,191种农药在相应的质量浓度范围内,各农药的响应值与其质量浓度均成良好的线性范围,相关系数均高于0.97,方法的最低检出限范围为0.002~0.3 mg/kg,最低定量限范围为0.007~1.2 mg/kg。
3.我们进行了方法精密度和准确度实验并得到了满意的结果。分别以最低定量限和4倍最低定量限为添加浓度对河豚鱼、鳗鱼和对虾样品进行了两个水平的添加回收率实验,方法的回收率范围为50.2%~120% (其中回收率在70%~120%的占89.5%),相对标准偏差范围为0.6%~21.6%。
With the rising of peoples’living standards, the question of food safety has attracted more and more attention. Due to large-scale use of pesticides, pesticide residues in food and environment has attracted extensive attention,which also became the technical trade barriers in China's merchandise exports. According to the kinds of pesticides used and the limits for pesticide residues in fugu, eel, prawn samples, this paper studied extraction, purification of sample pretreatments and GC-MS detection conditions of pesticide residues and also developed a new analytical procedure to determine 191 multiple pesticide residues in fugu, eel, prawn and other fishes in water. The details are as follows:
1. Building the simple, effective sample pretreatments. Using the ethyl acetate–cyclohexane(1:1,v:v) extracting residual pesticides in samples,and using the same solvent as the gel permeation chromatography mobile phase can remove macromolecule impurities such as proteins, lipids in sample efficiently, then extracting and concentrating the residual pesticides in samples on line,meanwhile investigating the 173 pesticides’gel permeation chromatography action parameters.
2. In this research, we established the GC-MS detection method for 191 pesticides. Linear regression in the corresponding concentration range was all over 0.97. The limits of detection and the limits of quantification were 0.002~0.3 mg/kg, 0.007~1.2 mg/kg respectively.
3. We took the precision and accuracy methodology test and got satisfied conclusion. The recovery was conducted at two spiked levels which is the LOQ concentration and 4 times of LOQ concentration, the validation results were as follows: the overall recoveries were from 50.2% to 120% (89.5% of the recoveries were from 70% to 120%), with the relative standard deviations (RSDS) of 0.6%-21.6%.
引文
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