QuEChERS法一色质联用技术在农药残留检测应用中的研究
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摘要
随着人民生活水平的日益提高,食品安全已经成为广泛关注的问题。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高度重视。为此,各国对农药在食品中的残留监控也越来越严格,很多国家先后制定了食品中多种农药的最高残留限量,已形成制约我国食品出口的贸易壁垒。食品中危及人身健康和环境安全的农药残留分析检测已成为广大分析工作者面临的重要研究内容之一。但因其体系复杂、组分痕量,给快速分离和准确测定带来了很大的困难。因此,建立快速、高效、灵敏的农药多残留检测方法是目前国际上的热点研究课题。
本文根据我国食品中农药使用品种和主要出口国农药残留限量的要求,对蔬菜、水果、茶叶及中药中农药多残留的提取、净化技术和色谱/质谱检测条件进行了研究,建立了一种快速、准确、灵敏、廉价的食品中农药残留的检测方法。主要包括以下内容：
1.建立蔬菜、水果及茶叶中多农残的QuEChERS/气相色谱/质谱(QuEChERS/GC/MS)检测方法。通过样品前处理各条件优选,建立了用乙腈提取,采用C18、PSA和GCB净化样品的前处理方法,气相色谱/质谱(GC/MS)的选择离子监测(SIM)模式分析了样品中的30种农药残留。方法检测限为0.015～6.5μg/L,回收率为70%～114%,RSD小于10.4%,在各自的线性范围内,峰面积Y与质量浓度X的线性关系良好,R2>0.994,符合多农残检测要求。
2.建立气相色谱/串联质谱(GC/MS/MS)同时检测黄芪中40种农药的多残留分析方法。采用QuEChERS样品前处理方法,从黄芪中提取净化残留农药,用气相色谱／三重四极杆串联质谱仪测定。在0.0025～1.0 mg/L范围内,各种农药基质标准溶液的峰面积与其浓度呈良好的线性关系,最低检测限在0.10～42 ng/L(S/N=3)范围内。在样品中添加40种农药的混合标准溶液,以环氧七氯为内标,各种农药的平均回收率75%～112%,RSD为2.02%～11.58%(n=6)。该方法的灵敏度、准确度和精密度均符合农药残留检测的技术要求。同时比较了单重四级杆和串联四级杆对相同样品的检测,结果表明,串联四级杆模式有更高的选择性及灵敏度,定性、定量更准确。
3.通过优化超高效液相色谱流动相、梯度洗脱程序和样品溶解液等条件,建立了43种农药的超高效液相色谱/串联质谱(UPLC/MS/MS)的检测方法。样品使用QuEChERS方法提取、净化。超高效液相色谱使用Waters ACQUITY UPLC HSS T3 (50 mm×2.1 mm,1.8μm)色谱柱,流动相为含0.05%甲酸的乙腈水溶液。串联质谱的离子源为电喷雾离子源,使用多反应监测模式监测。方法检测限为2.5～170 ng/L,回收率为73.23%～121.5%,RSD小于11.99%,在各自的线性范围内,峰面积Y与质量浓度X的线性关系良好,R2>0.995。该方法适用于农药残留分析的快速筛查及阳性样品的确证。以上所建立的分析方法,均已用于实际样品的分析。
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 have attracted extensive attention. Many countries have established residue monitoring system and MRLs of pesticides in food, so food export of our country are facing more and more technical barriers. The analysis of pesticide residues in food which harm human health and influence environment safety is one of the important research duties to chemical analysts. But it is great difficult to separate fastly and measure accurately, because of the complexity of the determination system and the ultratrace components. At present, development of the fast, effective, sensitive multi-residue detection methods for pesticides residues analysis is the focus of study in the world.
According to the kinds of pesticides used and the limits for pesticide residues in vegetables, fruits, tea and traditional Chinese medicine samples, this paper studied extraction, purification of sample pretreatments and chromatography/mass spectrometry detection conditions of pesticide residues and also developed a rapid, accurate, sensitive, cheap analytical procedure to determine multi-pesticide residues in food. The details are as follows:
1. A rapid detection QuEChERS/GC/MS method was developed, which could detect 30 pesticides in vegetables、fruits and tea. Pesticides were extracted from samples with acetonitrile and clean up by C18、PSA and GCB. The collected solution was analyzed by the GC/MS and quantified by internal standard method. The 30 pesticides were separated efficiently from impurity in high sensitivity and reproducibility. The limits of detection (LODs) ranged from 0.015μg/L to 6.5μg/L. The recoveries ranged from 70% to 114%, and the relative standard deviations (RSD) were 0.49%～10.38%(n=6). The sensitivity、accuracy and precision of the method all satisfy the requirement of pesticide residue analysis.
2. A GC/MS/MS method was developed for the simultaneous determination of 40 pesticides residues in radix astragal. Samples were extracted and cleaned up by QuEChERS, then determined by a triple quadrupole mass spectrometer with select reaction monitoring (SRM). There were good linear relationships between the peak area and concentration in the linear ranges of 0.0025～1.0 mg/L for the 40 pesticides, the limits of detection (LODs) ranged from 0.10 ng/L to 42 ng/L (S/N=3). The recoveries of those pesticides were 74.9%-112.2%, and the relative standard deviations (RSD) were 2.024%-11.582% (n=6), those quantified by internal standard method. The sensitivity、accuracy and precision of the method all satisfy the requirement of pesticide residue analysis.
3. A UPLC/MS/MS method was developed for the simultaneous determination of 43 pesticide residues in rhizoma gastrodiae. Samples were extracted and cleaned up by QuEChERS. The UPLC was performed on a Waters ACQUITY UPLC HSS T3 (50 mm×2.1 mm,1.8μm) column. Using 0.05% formic acid and acetonitrile as mobile phase, the flow rate is 0.3mL/min. The analyte were detected by ESI (+) under multiple reaction monitoring (MRM). There were good linear relationships between the peak area and concentration in the linear ranges for the 43 pesticides, the limits of detection (LODs) ranged from 2.5μg/L to 170 ng/L (S/N=3). The recoveries of those pesticides were 73.23%～121.5%, and the relative standard deviations (RSD) were 1.23%～11.99% (n=6), those quantified by internal standard method. The method is simple, sensitive and suitable for preliminary screening and corroboration the corroboration samples.
All the methods above were applied to analysis the real samples.
本文根据我国食品中农药使用品种和主要出口国农药残留限量的要求,对蔬菜、水果、茶叶及中药中农药多残留的提取、净化技术和色谱/质谱检测条件进行了研究,建立了一种快速、准确、灵敏、廉价的食品中农药残留的检测方法。主要包括以下内容：
1.建立蔬菜、水果及茶叶中多农残的QuEChERS/气相色谱/质谱(QuEChERS/GC/MS)检测方法。通过样品前处理各条件优选,建立了用乙腈提取,采用C18、PSA和GCB净化样品的前处理方法,气相色谱/质谱(GC/MS)的选择离子监测(SIM)模式分析了样品中的30种农药残留。方法检测限为0.015～6.5μg/L,回收率为70%～114%,RSD小于10.4%,在各自的线性范围内,峰面积Y与质量浓度X的线性关系良好,R2>0.994,符合多农残检测要求。
2.建立气相色谱/串联质谱(GC/MS/MS)同时检测黄芪中40种农药的多残留分析方法。采用QuEChERS样品前处理方法,从黄芪中提取净化残留农药,用气相色谱／三重四极杆串联质谱仪测定。在0.0025～1.0 mg/L范围内,各种农药基质标准溶液的峰面积与其浓度呈良好的线性关系,最低检测限在0.10～42 ng/L(S/N=3)范围内。在样品中添加40种农药的混合标准溶液,以环氧七氯为内标,各种农药的平均回收率75%～112%,RSD为2.02%～11.58%(n=6)。该方法的灵敏度、准确度和精密度均符合农药残留检测的技术要求。同时比较了单重四级杆和串联四级杆对相同样品的检测,结果表明,串联四级杆模式有更高的选择性及灵敏度,定性、定量更准确。
3.通过优化超高效液相色谱流动相、梯度洗脱程序和样品溶解液等条件,建立了43种农药的超高效液相色谱/串联质谱(UPLC/MS/MS)的检测方法。样品使用QuEChERS方法提取、净化。超高效液相色谱使用Waters ACQUITY UPLC HSS T3 (50 mm×2.1 mm,1.8μm)色谱柱,流动相为含0.05%甲酸的乙腈水溶液。串联质谱的离子源为电喷雾离子源,使用多反应监测模式监测。方法检测限为2.5～170 ng/L,回收率为73.23%～121.5%,RSD小于11.99%,在各自的线性范围内,峰面积Y与质量浓度X的线性关系良好,R2>0.995。该方法适用于农药残留分析的快速筛查及阳性样品的确证。以上所建立的分析方法,均已用于实际样品的分析。
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 have attracted extensive attention. Many countries have established residue monitoring system and MRLs of pesticides in food, so food export of our country are facing more and more technical barriers. The analysis of pesticide residues in food which harm human health and influence environment safety is one of the important research duties to chemical analysts. But it is great difficult to separate fastly and measure accurately, because of the complexity of the determination system and the ultratrace components. At present, development of the fast, effective, sensitive multi-residue detection methods for pesticides residues analysis is the focus of study in the world.
According to the kinds of pesticides used and the limits for pesticide residues in vegetables, fruits, tea and traditional Chinese medicine samples, this paper studied extraction, purification of sample pretreatments and chromatography/mass spectrometry detection conditions of pesticide residues and also developed a rapid, accurate, sensitive, cheap analytical procedure to determine multi-pesticide residues in food. The details are as follows:
1. A rapid detection QuEChERS/GC/MS method was developed, which could detect 30 pesticides in vegetables、fruits and tea. Pesticides were extracted from samples with acetonitrile and clean up by C18、PSA and GCB. The collected solution was analyzed by the GC/MS and quantified by internal standard method. The 30 pesticides were separated efficiently from impurity in high sensitivity and reproducibility. The limits of detection (LODs) ranged from 0.015μg/L to 6.5μg/L. The recoveries ranged from 70% to 114%, and the relative standard deviations (RSD) were 0.49%～10.38%(n=6). The sensitivity、accuracy and precision of the method all satisfy the requirement of pesticide residue analysis.
2. A GC/MS/MS method was developed for the simultaneous determination of 40 pesticides residues in radix astragal. Samples were extracted and cleaned up by QuEChERS, then determined by a triple quadrupole mass spectrometer with select reaction monitoring (SRM). There were good linear relationships between the peak area and concentration in the linear ranges of 0.0025～1.0 mg/L for the 40 pesticides, the limits of detection (LODs) ranged from 0.10 ng/L to 42 ng/L (S/N=3). The recoveries of those pesticides were 74.9%-112.2%, and the relative standard deviations (RSD) were 2.024%-11.582% (n=6), those quantified by internal standard method. The sensitivity、accuracy and precision of the method all satisfy the requirement of pesticide residue analysis.
3. A UPLC/MS/MS method was developed for the simultaneous determination of 43 pesticide residues in rhizoma gastrodiae. Samples were extracted and cleaned up by QuEChERS. The UPLC was performed on a Waters ACQUITY UPLC HSS T3 (50 mm×2.1 mm,1.8μm) column. Using 0.05% formic acid and acetonitrile as mobile phase, the flow rate is 0.3mL/min. The analyte were detected by ESI (+) under multiple reaction monitoring (MRM). There were good linear relationships between the peak area and concentration in the linear ranges for the 43 pesticides, the limits of detection (LODs) ranged from 2.5μg/L to 170 ng/L (S/N=3). The recoveries of those pesticides were 73.23%～121.5%, and the relative standard deviations (RSD) were 1.23%～11.99% (n=6), those quantified by internal standard method. The method is simple, sensitive and suitable for preliminary screening and corroboration the corroboration samples.
All the methods above were applied to analysis the real samples.
引文
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