基质固相分散—气相色谱—质谱联用技术在农药多残留分析中的应用研究
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摘要
农药在蔬菜上的残留以及对人类健康和环境造成的毒害越来越为人们所关注。为此各国对农药在蔬菜中的残留监控也越来越严格,很多国家先后制定了蔬菜中多种农药的最高残留限量,使我国蔬菜出口面临越来越多的技术壁垒。本文对蔬菜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,建立了基质固相分散-气相色谱-质谱检测蔬菜中249种农药残留的方法,并利用所建立的方法对市售蔬菜进行检测,本文的主要研究结果如下:
1.在气相色谱-质谱检测方面,对柱温等色谱条件进行了研究,从而建立了蔬菜中249种农药残留气相色谱-质谱检测方法。结果表明,249种农药在0.05-1.0 mg/L浓度范围内,相关系数都在0.99以上;最小检出限为0.5~28.8μg/kg,低于国家规定的最大允许残留量。
2.采用基质固相分散法从蔬菜中提取净化多种农药残留,对固相萃取材料、洗脱剂、填料比等影响农药提取、净化效率的因素进行研究,建立了以2 g C18为固相萃取材料,石墨化炭黑为净化剂,30mL丙酮:正己烷(1:1)为洗脱剂,填料比为1:2的基质固相分散前处理方法,并利用此方法对249种农药进行添加回收率实验,221种有机磷农药的加标回收率范围为70~130%,相对标准偏差小于20%。
3.采用本研究建立的方法对市售蔬菜进行检测,四种蔬菜中共检出毒死蜱、甲霜灵、多菌灵、敌百虫、氯氰菊酯、氰戊菊酯和百菌清七种农药,参照GB2763-2005-《食品中农药最大残留限量》,这七种农药并未超出国家标准最大残留限量(MRL);但日本肯定列表制度规定,毒死蜱在蔬菜中的MRL值为0.01 mg/kg,由此可以看出,菠菜和黄瓜样品的毒死蜱残留量超出了这一标准。
People pay more attention to pesticides residue on vegetables and harm on health and Environment. Many countries have established residue monitoring system and MRLs of pesticides on vegetables, so vegetables export of our country are facing more and more technical barriers. This paper studied extraction, purification and GC-MS detection conditions of pesticide residues and developed a new analytical procedure based on MSPD coupled to GC-MS for the determination of 249 pesticides in vegetables.The method was successfully used in detecting the vegetables in the market. The main results were as follows:
1 In this research, we optimized the column tempreture and established GC-MS detection method for 249 pesticides. Linear regression in the concentration range of 0.05~1 mg/L (>0.99) was fine and the detection limit was 0.5~28.8μg/kg which was lower than MRLs.
2 In this research, we optimized the asorbent, eluent and the rate of sample and asorbent, established a preparation method which used 2 g C18 as absorbent, GCB as purificant, 30 mL hexane:acetone(1:1) as eluent and the rate of sample and absorbent was 1:2. The recovery range was 70~130% of 221 pesticides and 28 out of the range and the relative standard deviations is below 20%.
3 Samples was collected from local markets and detected using the established method. 7 pesticides (Chlorpyrifos, Metalaxyl, Carbendazim, Dipterex, Cypermethrin, Fenvalerate and Chlorothalonil) were detected in four vegetables and the contents of the 7 pesticides was lower than MRLs. Chlorpyrifos on spinach and cucumber exceeded the standard(0.01 mg/kg)of Positive List System of Japan.
1.在气相色谱-质谱检测方面,对柱温等色谱条件进行了研究,从而建立了蔬菜中249种农药残留气相色谱-质谱检测方法。结果表明,249种农药在0.05-1.0 mg/L浓度范围内,相关系数都在0.99以上;最小检出限为0.5~28.8μg/kg,低于国家规定的最大允许残留量。
2.采用基质固相分散法从蔬菜中提取净化多种农药残留,对固相萃取材料、洗脱剂、填料比等影响农药提取、净化效率的因素进行研究,建立了以2 g C18为固相萃取材料,石墨化炭黑为净化剂,30mL丙酮:正己烷(1:1)为洗脱剂,填料比为1:2的基质固相分散前处理方法,并利用此方法对249种农药进行添加回收率实验,221种有机磷农药的加标回收率范围为70~130%,相对标准偏差小于20%。
3.采用本研究建立的方法对市售蔬菜进行检测,四种蔬菜中共检出毒死蜱、甲霜灵、多菌灵、敌百虫、氯氰菊酯、氰戊菊酯和百菌清七种农药,参照GB2763-2005-《食品中农药最大残留限量》,这七种农药并未超出国家标准最大残留限量(MRL);但日本肯定列表制度规定,毒死蜱在蔬菜中的MRL值为0.01 mg/kg,由此可以看出,菠菜和黄瓜样品的毒死蜱残留量超出了这一标准。
People pay more attention to pesticides residue on vegetables and harm on health and Environment. Many countries have established residue monitoring system and MRLs of pesticides on vegetables, so vegetables export of our country are facing more and more technical barriers. This paper studied extraction, purification and GC-MS detection conditions of pesticide residues and developed a new analytical procedure based on MSPD coupled to GC-MS for the determination of 249 pesticides in vegetables.The method was successfully used in detecting the vegetables in the market. The main results were as follows:
1 In this research, we optimized the column tempreture and established GC-MS detection method for 249 pesticides. Linear regression in the concentration range of 0.05~1 mg/L (>0.99) was fine and the detection limit was 0.5~28.8μg/kg which was lower than MRLs.
2 In this research, we optimized the asorbent, eluent and the rate of sample and asorbent, established a preparation method which used 2 g C18 as absorbent, GCB as purificant, 30 mL hexane:acetone(1:1) as eluent and the rate of sample and absorbent was 1:2. The recovery range was 70~130% of 221 pesticides and 28 out of the range and the relative standard deviations is below 20%.
3 Samples was collected from local markets and detected using the established method. 7 pesticides (Chlorpyrifos, Metalaxyl, Carbendazim, Dipterex, Cypermethrin, Fenvalerate and Chlorothalonil) were detected in four vegetables and the contents of the 7 pesticides was lower than MRLs. Chlorpyrifos on spinach and cucumber exceeded the standard(0.01 mg/kg)of Positive List System of Japan.
引文
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