CN112834647A - 高油复杂基质样品前处理技术结合gc-msms测定297种农药残留的方法 - Google Patents
高油复杂基质样品前处理技术结合gc-msms测定297种农药残留的方法 Download PDFInfo
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- CN112834647A CN112834647A CN202011641110.8A CN202011641110A CN112834647A CN 112834647 A CN112834647 A CN 112834647A CN 202011641110 A CN202011641110 A CN 202011641110A CN 112834647 A CN112834647 A CN 112834647A
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Abstract
本发明提供一种高油复杂基质样品前处理技术结合GC‑MSMS测定297种农药残留的方法,称取适量高油复杂基质样品于离心管外萃取管中,加入超纯水、乙酸酸化乙腈、陶瓷均质子和萃取盐,内插管中加入萃取盐、净化剂和陶瓷均质子,把内插管嵌套入外萃取管中拧好,置于全自动样品处理设备,经反复震荡、多次离心处理后,取内插管中适量上清液,氮吹至近干,加入1ml乙酸乙酯超声复溶,过0.22μm滤膜,利用GC‑MS/MS实现297种农药残留的检测。各农药组分在色谱柱下分离效果好,所测得的检出限、定量限等各项指标满足农药的多残留分析,可以应用于高油复杂基质样品的多农药残留检测中。
Description
技术领域
本发明属于农药残留分析技术领域,具体涉及高油复杂基质样品前处理技术结合GC-MSMS测定297种农药残留的方法。
背景技术
目前,农药残留问题已经成为食品安全问题中亟待解决和国际社会共同关注的食品安全重大问题之一。我国各类农作物的产量逐年提高,但是农药的使用也存在较为严重的问题,农药的滥用以及不正确的使用方式,不仅危害我国人民的身体健康且造成环境的污染,更会使我国的经济在进出口贸易时受挫。我国出口到国外的农副产品也时常有超标情况的检出,如何有效的控制农药残留超标现象,保证我国人民的健康饮食,打破国际贸易的壁垒,已经变得十分重要。我国在去年发布的GB2763-2019《食品安全国家标准食品中农药最大残留限量》中,进一步增加了2967项农药残留限量标准,面对新标准的实施,相关的检测技术也应该得到发展和提升。
农药残留检测技术目前已经在普通果蔬基质发展较为完善,但在一些复杂基质的检测方法和技术相关发展仍然存在挑战,特别是高油复杂基质样品,含油量高、色素含量大,还含有多糖、蛋白质等成分,基质成分复杂,目标农药与基质分离难度大,在前处理的过程中如果无法有效的去除基质所带来的干扰,则会在仪器检测过程中无法实现准确的定性和定量。
目前对于高油复杂基质农药残留检测技术的研究,仅针对某一类检测对象。由于不同的高油复杂基质样品中基质种类差别较大,现有样品前处理技术中,针对不同种样品采用不同的样品前处理方法,需要准备不同的检测试剂、不同的处理流程,不利于降低检测成本和提高检测人员的熟练程度,目前没有一种通用的、标准化的样品前处理技术可以针对高油复杂基质样品进行有效地处理。
目前全球已注册的农药超2000余种,其中常用的约500种,而且不断有新的农药被研发和应用。高油复杂基质样品涉及的农药种类也越来越多,但是已有的农药残留检测技术仅能针对少数农药种类进行检测。CN111521709A一种花椒中25种农药残留的气质联用检测方法,样品采用乙腈提取,结合涡旋振荡和超声提取的方式,再利用固相萃取柱(在Carb/NH2复合柱基础上加入100mg中性氧化铝、100mgC18)净化,实现了花椒中25种农药残留的检测。目前的检测技术已经不能适应样品种类众多、农药品种日益增加的现状,不能满足进出口商品对于农药残留检测的需求。
为了解决上述问题,本发明提供一种高油复杂基质样品通用的前处理技术,适用于花生、花椒、芝麻、八角、桂皮、胡椒、孜然、香叶、陈皮等,能够实现297种目标农药与基质的有效分离,结合气相色谱-串联质谱(GC-MS/MS),能够对297种农药实现气相色谱分离,检出限(LOD)范围为1-5μg/kg,定量限(LOQ)范围为2-10μg/kg,在10μg/kg、50μg/kg和100μg/kg 3个添加水平下,平均回收率分别为72.7%-116.0%、73.2%-111.5%和71.5%-119.7%,相对标准偏差(RSDs)分别为0.9%-14.9%、0.6%-14.4%和0.4%-14.7%。对于填补高油复杂基质样品多农药残留研究现状的空白,打破进出口贸易壁垒,具有十分重要的意义。
发明内容
针对上述问题,本发明提供了高油复杂基质样品前处理技术结合GC-MSMS测定297种农药残留的方法。
本发明的技术方案是:高油复杂基质样品前处理技术结合GC-MSMS测定297种农药残留的方法,其特征是,包括以下步骤:
1.高油复杂基质样品前处理过程:
称取适量样品于离心管外萃取管中,加入超纯水、乙酸酸化乙腈、陶瓷均质子和萃取盐,内插管中加入萃取盐、净化剂和陶瓷均质子,把内插管嵌套入外萃取管中拧好,置于全自动样品处理设备,经反复震荡、离心多次处理后,取内插管中适量上清液,氮吹至近干,加入1ml乙酸乙酯超声复溶,过0.22μm滤膜,待上机检测。
所述高油复杂基质样品为花生、花椒、芝麻、八角、桂皮、胡椒、孜然、香叶、陈皮中的一种。
所述外萃取管所加提取剂为1%乙酸酸化乙腈和超纯水,按体积比计,1%乙酸酸化乙腈:超纯水=15:2。高油复杂基质样品、水、1%乙酸酸化乙腈提取液与萃取盐的质量体积比为2g:2ml:15ml:5g。
所述萃取盐为:无水硫酸镁和氯化钠、乙酸钠、柠檬酸钠、柠檬酸氢二钠的一种或多种。优选无水硫酸镁和乙酸钠,无水硫酸镁:乙酸钠=4:1,在有效除水的同时,与提取剂形成乙酸-乙酸钠缓冲体系,更加有助于农药的萃取;或优选无水硫酸镁、柠檬酸钠和柠檬酸氢二钠,无水硫酸镁:柠檬酸钠:柠檬酸氢二钠=4:1:1,在有效去除水分的同时,对碱敏感性农药起到保护作用;或优选无水硫酸镁和氯化钠,无水硫酸镁:氯化钠=2:1在有效去除水分的同时,使水相与有机相进一步分离。
所述净化剂为乙二胺-N-丙基硅烷(PSA)、十八烷基硅烷键合硅胶(C18)、石墨化无孔碳(ENVI-Carb)、石墨化碳黑(GCB)、多壁碳纳米(Cleaner NANO-carb)、二氧化锆胶(Z-Sep)、碳十八键合锆胶(Z-Sep+)、弗罗里硅土(Florisil)、增强型脂质去除剂(EMR-Lipid)的一种或多种。
全自动样品处理程序为①振荡频率1100转振荡10分钟;②4200转离心5分钟;③振荡频率1100转振荡5分钟;4200转离心5分钟。
2.GC-MS/MS检测过程:
色谱柱:HP-5MS石英毛细管柱(30m×0.25mm×0.25μm,美国Agilent公司);恒流模式流速为1.2mL/min;载气:氦气,99.999%;柱温:初始温度40℃,保持1min,以30℃/min升温至130℃,再以5℃/min升温至250℃,以10℃/min升温至300℃,保持8min;进样口温度:250℃;进样方式:不分流进样;溶剂延迟:4min;EI离子源温度:270℃;EI源能量:70eV;传输线温度:280℃;四极杆温度:150℃;碰撞气:高纯氮气(99.999%);扫描模式:多重反应监测(MRM)模式。
297种农药为:甲胺磷、敌敌畏、敌草腈、2,4,6-三氯苯酚、茵草敌、联苯、氟酰脲、灭草敌、苯胺灵、邻苯二甲酰亚胺、速灭威、克草敌、威杀灵、氯苯甲醚、丁噻隆、五氯苯、庚烯磷、燕麦酯、氧乐果、氟啶虫酰胺、残杀威、毒草胺、二苯胺、环草敌、灭线磷、磷酸三丁酯、甲基苯噻隆、去乙基阿特拉津、百治磷、噁虫威、氟乐灵、久效磷、乙丁氟灵、硫线磷、治螟磷、牧草胺、猛杀威、α-六六六、西玛通、氯硝胺、五氯甲氧基苯、乐果、乙氧喹啉、西玛津、扑灭通、绿谷隆、莠去津、异噁草酮、扑灭津、特丁通、丁咪酰胺、灭害威、β-六六六、五氯硝基苯、五氯苯甲腈、特丁硫磷、特丁津、咯喹酮、草达津、地虫硫磷、胺丙畏、炔苯酰草胺、嘧霉胺、二嗪磷、δ-六六六、甲呋酰胺、仲丁通、兹克威、野麦畏、ε-六六六、氯唑磷、异稻瘟净、丁基嘧啶磷、解草嗪、庚酰草胺、五氯苯胺、拌种胺、抗蚜威、氯硫酰草胺、呋草黄、敌稗、环丙津、除线磷、二甲草胺、嗪草酮、二甲吩草胺、溴丁酰草胺、呋嘧醇、乙草胺、甲基对硫磷、甲基毒死蜱、乙烯菌核利、特草灵、西草净、甲萘威、甲基立枯磷、马拉氧磷、七氯、四氟苯菊酯、甲草胺、莠灭净、敌蝇威、异丙草胺、灭草环、扑草净、甲霜灵、八氯二丙醚、苄草丹、萘乙酰胺、砜吸磷、2,4'-三氯杀螨醇、坪草丹、特丁净、氟硫草定、杀螟硫磷、除草定、灭藻醌、戊草丹、甲基嘧啶磷、乙氧呋草黄、抑芽唑、烯丙苯噻唑、草完隆、绿麦隆、禾草丹、艾氏剂、异丙净、马拉硫磷、枯莠隆、异丙甲草胺、烯虫炔酯、乙霉威、倍硫磷、毒死蜱、对硫磷、氰草津、丁嗪草酮、三唑酮、呋菌胺、异氯磷、氯酞酸甲酯、碳氯灵、氟噻草胺、仲草丹、水胺硫磷、芬螨酯、四氟醚唑、增效胺、噻唑磷、仲丁灵、异艾氏剂、双苯酰草胺、嘧菌环胺、嘧啶磷、异丙乐灵、吡唑草胺、氧化氯丹、二甲戊灵、戊菌唑、异戊乙净、啶斑肟、氟虫腈亚砜、地胺磷、异柳磷、喹硫磷、三唑醇、氟虫腈、稻丰散、呋霜灵、腐霉利、整形醇、反式氯丹、氟菌唑、炔丙菊酯、杀扑磷、o,p'-滴滴伊、乙基溴硫磷、丙虫磷、多效唑、氟吡甲禾灵、α-硫丹、乙拌磷砜、杀虫威、顺式氯丹、嘧菌胺、清菌噻唑、丁草胺、反式九氯、粉唑醇、咪草酸、杀螨酯、敌草胺、己唑醇、啶氧菌酯、氟酰胺、抑霉唑、丙硫磷、稻瘟灵、丙溴磷、狄氏剂、烯效唑、p,p'-滴滴伊、丙草胺、噁草酮、o,p'-滴滴滴、腈菌唑、苄氯三唑醇、氟硅唑、氧环唑、甲氧丙净、氟虫腈砜、乙嘧酚磺酸酯、醚菌酯、除草醚、环丙唑醇、环丙嘧啶醇、乙滴滴、吡氟禾草灵、β-硫丹、乙酯杀螨醇、丙酯杀螨醇、倍硫磷亚砜、烯唑醇、乙环唑、酯菌胺、p,p'-滴滴滴、麦草氟异丙酯、倍硫磷砜、o,p'-滴滴涕、噁霜灵、乙硫磷、灭锈胺、三唑磷、氯杀螨砜、呋酰胺、苯霜灵、苯虫醚、敌瘟磷、苯腈磷、丙环唑、环酰菌胺、氟草敏、滴滴涕、环嗪酮、戊唑醇、氟苯嘧啶醇、禾草灵、炔螨特、磷酸三苯酯、增效醚、氟环唑、氟吡乙禾灵、吡唑解草酯、新燕灵、螺甲螨酯、糠菌唑、胺菊酯、溴螨酯、丁硫克百威、苯氧威、氟吡酰草胺、氟唑菌酰胺、联苯菊酯、甲氧滴滴涕、乙螨唑、咪唑菌酮、叶菌唑、吡螨胺、喹螨醚、莎稗磷、三氯杀螨砜、灭菌唑、呋线威、伏杀硫磷、吡丙醚、苯噻酰草胺、氯氟氰菊酯、杀螺吗啉、益棉磷、吡菌磷、丙硫克百威、噁唑禾草灵、联苯三唑醇、哒螨灵、氟喹唑、咪鲜胺、氟丙嘧草酯、唑草胺、腈苯唑、啶酰菌胺、氟氰戊菊酯、醚菊酯、三氟甲吡醚、苯醚甲环唑、茚虫威、烯酰吗啉和唑虫酰胺。
所述净化剂优选乙二胺-N-丙基硅烷(PSA)、十八烷基硅烷键合硅胶(C18)、石墨化无孔碳(ENVI-Carb)和碳十八键合锆胶(Z-Sep+)组合使用,乙二胺-N-丙基硅烷(PSA):十八烷基硅烷键合硅胶(C18):石墨化无孔碳(ENVI-Carb):碳十八键合锆胶(Z-Sep+)=0.8-1.2:1.8-2.2:0.8-1.2:0.3-0.8,优选乙二胺-N-丙基硅烷(PSA):十八烷基硅烷键合硅胶(C18):石墨化无孔碳(ENVI-Carb):碳十八键合锆胶(Z-Sep+)=1:2:1:0.5;或优选乙二胺-N-丙基硅烷(PSA)、弗罗里硅土(Florisil)和碳十八键合锆胶(Z-Sep+)组合使用,乙二胺-N-丙基硅烷(PSA):弗罗里硅土(Florisil):碳十八键合锆胶(Z-Sep+)=0.8-1.2:0.8-1.2:0.8-1.2,优选乙二胺-N-丙基硅烷(PSA):弗罗里硅土(Florisil):碳十八键合锆胶(Z-Sep+)=1:1:1;或优选十八烷基硅烷键合硅胶(C18)和多壁碳纳米(Cleaner NANO-carb)组合使用,十八烷基硅烷键合硅胶(C18):多壁碳纳米(Cleaner NANO-carb)=3.8-4.2:0.8-1.2,优选十八烷基硅烷键合硅胶(C18):多壁碳纳米(Cleaner NANO-carb)=4:1。
在高油复杂基质样品前处理过程中,为了提高对各类样品的适用范围,有效的降低基质干扰,在提取时加入萃取溶剂、萃取盐和均质子,净化时加入净化剂,实现目标农药和基质的有效分离,从而减小高油复杂基质样品的基质干扰,提高检测结果的准确性。极性溶剂乙腈有较高的提取效率,尤其适用于多残留分析。萃取盐中无水硫酸镁可以有效去除样品提取时的水分,氯化钠可以起到盐析作用,而乙酸钠、柠檬酸钠、柠檬酸氢二钠可以形成一种酸性的缓冲体系,其一种或多种缓冲盐的使用,有助于农药的提取。均质子的加入,可以通过其产生的剪切力,防止硫酸镁结块并进一步增大高油复杂基质样品与提取液的接触面积,提高提取效率。净化剂的加入可以有效的减少测定过程中同系物、异构体、降解产物的影响,乙二胺-N-丙基硅烷(PSA)可以有效的去除提取物内的脂肪酸和糖类共萃物;十八烷基硅烷键合硅胶(C18)、二氧化锆胶(Z-Sep)、碳十八键合锆胶(Z-Sep+)、弗罗里硅土(Florisil)和增强型脂质去除剂(EMR-Lipid)可以有效去除体系内的脂类干扰,能够有效降低提取物中的含油量;石墨化无孔碳(ENVI-Carb)、石墨化碳黑(GCB)和多壁碳纳米(Cleaner NANO-carb)可以有效去除高油复杂基质样品色素所带来的干扰,具有极优的吸附性。一种或多种净化填料的联用,可以有效的减少高油复杂基质样品的干扰,使前处理的方法对所有高油复杂基质样品具有普遍适用性。
本发明的有益效果是:
1)本发明提出的高油复杂基质样品前处理技术结合GC-MSMS测定297种农药残留的方法,通过优化萃取溶剂、萃取盐、净化剂的组合方式,能够提高样品前处理的通用性,实现对多种高油复杂基质样品的提取净化处理,有效的降低了高油复杂基质样品农药残留检测过程中所带来的基质干扰,进一步减小了对仪器的损害,有利于降低检测成本和提高检测人员的熟练程度。
2)本发明提出的前处理方法将样品和提取剂、均质子、萃取盐和净化剂一次性放入全自动萃取管中,与传统前处理方法相比,避免了多次转移提取液、净化液等步骤所造成的损失,使用全自动样品制备系统,震荡、离心步骤能在同一个装置中反复进行多次,无需人工转移,能够实现多个样品快速处理,大大节省了样品制备时间,进一步解放了劳动力,对于高油复杂基质样品的提取及净化提供了一种切实可行的方案。
3)本发明提出的高油复杂基质样品前处理技术结合GC-MSMS测定297种农药残留的方法,能够填补高油复杂基质样品农药多残留的空白,完成高油复杂基质样品中297种农药残留的检测,,各农药组分在色谱柱下分离效果好,所测得的检出限、定量限等各项指标满足农药的多残留分析,可以应用于高油复杂基质样品的多农药残留检测中,对于打破贸易壁垒,促进进出口贸易具有重要意义。
附图说明
图1为297种农药GC/MS/MS总离子流图
具体实施方式
实施例1
1实验部分
1.1仪器与试剂
Agilent 7890A-7000B气相色谱-三重四极杆串联质谱仪(美国Agilent公司);全自动样品制备系统(北京本立科技公司);N-112氮吹浓缩仪(美国OrganomationAssociates公司),TRIOTM-1N涡旋搅拌器(日本ASONE公司),Milli-Q超纯水机(美国Millipore公司),PL602-L电子天平(瑞士Mettler-Toledo公司),超声波清洗器(中国江苏昆山超声仪器有限公司)。
297种农药标准品:纯度≥95%(天津阿尔塔公司);乙腈为色谱纯(美国Honeywell公司);吸附剂:PSA、Florisil吸附剂(天津Bonna-Agela公司);Z-Sep+(美国Supelco公司);实验用水均为高纯水(经Milli-Q超纯水器纯化)。
1.2标准溶液的配制
各称取10mg标准品于10ml容量瓶中,用甲醇准确定容至刻度线,配制成浓度为1000mg/L的单标储备液,于-18℃下保存。从浓度为1000mg/L的单标储备液中,各取100μL于10ml棕色容量瓶中,配制成浓度为10mg/L的混标贮备液,于-18℃下保存。按需取适量的标准储备液,配制成需要浓度的标准工作液,于4℃避光储存。
1.3.样品制备与提取净化
将花生仁用料理机粉碎,混匀,备用。准确称取2.00g样品于配套试管的外萃取管中,加入2ml超纯水浸润30min,后加入15ml的1%乙酸酸化乙腈,4g硫酸镁和1g乙酸钠,12颗陶瓷均质子,内插管中加入400mg无水硫酸镁、100mg PSA,100mg Z-Sep+,100mg Florisil,6颗陶瓷均质子,把内插管嵌套入外萃取管中拧好,放入全自动前处理设备,提取震荡转速1100rpm,时长10min,离心转速4500rpm,时长5min,净化转速1100rpm,离心转速4500rpm,各5min。取内插管净化液2ml,氮气吹干,1ml乙酸乙酯定容,过0.22μm滤膜,供GC-MS/MS测定。
1.4色谱-质谱条件
色谱柱:HP-5MS UI气相色谱柱(30m×0.25mm×0.25μm,美国Agilent公司);载气流速为1.2mL/min;载气:氦气,99.999%;柱温:初始温度40℃,保持1min,以30℃/min升温至130℃,再以5℃/min升温至250℃,以10℃/min升温至300℃,保持8min;进样口温度:250℃;进样方式:不分流进样;溶剂延迟:4min;EI离子源温度:270℃;EI源电离能量:70eV;传输线温度:280℃;四极杆温度:150℃;碰撞气:高纯氮气(99.999%);扫描模式:多重反应监测(MRM)模式。
表1 297种农药化合物质谱参数
2方法学验证-标准曲线、检出限、定量限、回收率和精密度的测定
选花生阴性样品为空白基质,每种农药选取7个浓度(5、10、20、40、60、80、100μg/L)制备基质匹配标准溶液,并测定其线性范围,各种农药在其各自线性范围内,呈良好线性关系,相关系数(R2)>0.995。采用信噪比法测定其检出限与定量限,以信噪比S/N=3确定方法的检出限(LOD),S/N=10确定方法的定量限(LOQ)。按照实验方法,进行添加回收实验,选取低(10μg/kg)、中(50μg/kg)、高(100μg/kg)三个浓度为添加回收水平,每个添加水平进行6组实验,结果表明297种农药其平均回收率范围为71.5-119.7%,相对标准偏差<14.7%。
表2 297种化合物检出限、定量限和线性相关系数及回收率
3结论
本发明实现了自动样品制备与气相色谱-串联质谱法相结合,建立了高油复杂基质样品中297种农药残留检测方法,实现了前处理过程的全自动,该方法定量准确,灵敏度、准确度、精密度和线性关系良好,能够满足市售花生、芝麻、孜然、香叶等样品中的农药残留检测。
实施例2
采用本发明方法实测市售花生20批次,共11批检出农药残留,检出农药20种,其中反式九氯检出农药检出浓度最高为36.51ug/kg,第9批次样品检出农药数量最多为6种,分别检出反式九氯、茵草敌、乙氧呋草黄、甲呋酰胺、氟乐灵和敌蝇威。
表3花生实测样品农药种类及含量
Claims (10)
1.一种高油复杂基质样品前处理技术结合GC-MSMS测定297种农药残留的方法,其特征是,包括以下步骤:
(1)高油复杂基质样品前处理过程:
称取适量样品于离心管外萃取管中,加入超纯水、乙酸酸化乙腈、陶瓷均质子和萃取盐,内插管中加入萃取盐、净化剂和陶瓷均质子,把内插管嵌套入外萃取管中拧好,置于全自动样品处理设备,经反复震荡、离心多次处理后,取内插管中适量上清液,氮吹至近干,加入1ml乙酸乙酯超声复溶,过0.22μm滤膜,待上机检测;
所述萃取盐为:无水硫酸镁和氯化钠、乙酸钠、柠檬酸钠、柠檬酸氢二钠的一种或多种;
所述净化剂为乙二胺-N-丙基硅烷(PSA)、十八烷基硅烷键合硅胶(C18)、石墨化无孔碳(ENVI-Carb)、石墨化碳黑(GCB)、多壁碳纳米(Cleaner NANO-carb)、二氧化锆胶(Z-Sep)、碳十八键合锆胶(Z-Sep+)、弗罗里硅土(Florisil)、增强型脂质去除剂(EMR-Lipid)的一种或多种;
(2)GC-MS/MS检测过程:
色谱柱:HP-5MS石英毛细管柱(30m×0.25mm×0.25μm);恒流模式流速为1.2mL/min;载气:氦气,99.999%;柱温:初始温度40℃,保持1min,以30℃/min升温至130℃,再以5℃/min升温至250℃,以10℃/min升温至300℃,保持8min;进样口温度:250℃;进样方式:不分流进样;溶剂延迟:4min;EI离子源温度:270℃;EI源能量:70eV;传输线温度:280℃;四极杆温度:150℃;碰撞气:高纯氮气(99.999%);扫描模式:多重反应监测(MRM)模式;
297种农药为:甲胺磷、敌敌畏、敌草腈、2,4,6-三氯苯酚、茵草敌、联苯、氟酰脲、灭草敌、苯胺灵、邻苯二甲酰亚胺、速灭威、克草敌、威杀灵、氯苯甲醚、丁噻隆、五氯苯、庚烯磷、燕麦酯、氧乐果、氟啶虫酰胺、残杀威、毒草胺、二苯胺、环草敌、灭线磷、磷酸三丁酯、甲基苯噻隆、去乙基阿特拉津、百治磷、噁虫威、氟乐灵、久效磷、乙丁氟灵、硫线磷、治螟磷、牧草胺、猛杀威、α-六六六、西玛通、氯硝胺、五氯甲氧基苯、乐果、乙氧喹啉、西玛津、扑灭通、绿谷隆、莠去津、异噁草酮、扑灭津、特丁通、丁咪酰胺、灭害威、β-六六六、五氯硝基苯、五氯苯甲腈、特丁硫磷、特丁津、咯喹酮、草达津、地虫硫磷、胺丙畏、炔苯酰草胺、嘧霉胺、二嗪磷、δ-六六六、甲呋酰胺、仲丁通、兹克威、野麦畏、ε-六六六、氯唑磷、异稻瘟净、丁基嘧啶磷、解草嗪、庚酰草胺、五氯苯胺、拌种胺、抗蚜威、氯硫酰草胺、呋草黄、敌稗、环丙津、除线磷、二甲草胺、嗪草酮、二甲吩草胺、溴丁酰草胺、呋嘧醇、乙草胺、甲基对硫磷、甲基毒死蜱、乙烯菌核利、特草灵、西草净、甲萘威、甲基立枯磷、马拉氧磷、七氯、四氟苯菊酯、甲草胺、莠灭净、敌蝇威、异丙草胺、灭草环、扑草净、甲霜灵、八氯二丙醚、苄草丹、萘乙酰胺、砜吸磷、2,4'-三氯杀螨醇、坪草丹、特丁净、氟硫草定、杀螟硫磷、除草定、灭藻醌、戊草丹、甲基嘧啶磷、乙氧呋草黄、抑芽唑、烯丙苯噻唑、草完隆、绿麦隆、禾草丹、艾氏剂、异丙净、马拉硫磷、枯莠隆、异丙甲草胺、烯虫炔酯、乙霉威、倍硫磷、毒死蜱、对硫磷、氰草津、丁嗪草酮、三唑酮、呋菌胺、异氯磷、氯酞酸甲酯、碳氯灵、氟噻草胺、仲草丹、水胺硫磷、芬螨酯、四氟醚唑、增效胺、噻唑磷、仲丁灵、异艾氏剂、双苯酰草胺、嘧菌环胺、嘧啶磷、异丙乐灵、吡唑草胺、氧化氯丹、二甲戊灵、戊菌唑、异戊乙净、啶斑肟、氟虫腈亚砜、地胺磷、异柳磷、喹硫磷、三唑醇、氟虫腈、稻丰散、呋霜灵、腐霉利、整形醇、反式氯丹、氟菌唑、炔丙菊酯、杀扑磷、o,p'-滴滴伊、乙基溴硫磷、丙虫磷、多效唑、氟吡甲禾灵、α-硫丹、乙拌磷砜、杀虫威、顺式氯丹、嘧菌胺、清菌噻唑、丁草胺、反式九氯、粉唑醇、咪草酸、杀螨酯、敌草胺、己唑醇、啶氧菌酯、氟酰胺、抑霉唑、丙硫磷、稻瘟灵、丙溴磷、狄氏剂、烯效唑、p,p'-滴滴伊、丙草胺、噁草酮、o,p'-滴滴滴、腈菌唑、苄氯三唑醇、氟硅唑、氧环唑、甲氧丙净、氟虫腈砜、乙嘧酚磺酸酯、醚菌酯、除草醚、环丙唑醇、环丙嘧啶醇、乙滴滴、吡氟禾草灵、β-硫丹、乙酯杀螨醇、丙酯杀螨醇、倍硫磷亚砜、烯唑醇、乙环唑、酯菌胺、p,p'-滴滴滴、麦草氟异丙酯、倍硫磷砜、o,p'-滴滴涕、噁霜灵、乙硫磷、灭锈胺、三唑磷、氯杀螨砜、呋酰胺、苯霜灵、苯虫醚、敌瘟磷、苯腈磷、丙环唑、环酰菌胺、氟草敏、滴滴涕、环嗪酮、戊唑醇、氟苯嘧啶醇、禾草灵、炔螨特、磷酸三苯酯、增效醚、氟环唑、氟吡乙禾灵、吡唑解草酯、新燕灵、螺甲螨酯、糠菌唑、胺菊酯、溴螨酯、丁硫克百威、苯氧威、氟吡酰草胺、氟唑菌酰胺、联苯菊酯、甲氧滴滴涕、乙螨唑、咪唑菌酮、叶菌唑、吡螨胺、喹螨醚、莎稗磷、三氯杀螨砜、灭菌唑、呋线威、伏杀硫磷、吡丙醚、苯噻酰草胺、氯氟氰菊酯、杀螺吗啉、益棉磷、吡菌磷、丙硫克百威、噁唑禾草灵、联苯三唑醇、哒螨灵、氟喹唑、咪鲜胺、氟丙嘧草酯、唑草胺、腈苯唑、啶酰菌胺、氟氰戊菊酯、醚菊酯、三氟甲吡醚、苯醚甲环唑、茚虫威、烯酰吗啉和唑虫酰胺。
2.根据权利要求1所述的方法,其特征在于:所述高油复杂基质样品为花生、花椒、芝麻、八角、桂皮、胡椒、孜然、香叶、陈皮中的一种。
3.根据权利要求1所述的方法,其特征在于:所述外萃取管所加提取剂为1%乙酸酸化乙腈和超纯水,按体积比计,1%乙酸酸化乙腈:超纯水=15:2。
4.根据权利要求1所述的方法,其特征在于:所述萃取盐为无水硫酸镁:乙酸钠=4:1。
5.根据权利要求1所述的方法,其特征在于:所述萃取盐为无水硫酸镁:柠檬酸钠:柠檬酸氢二钠=4:1:1。
6.根据权利要求1所述的方法,其特征在于:所述萃取盐为无水硫酸镁:氯化钠=2:1。
7.根据权利要求1所述的方法,其特征在于:所述净化剂为乙二胺-N-丙基硅烷(PSA):十八烷基硅烷键合硅胶(C18):石墨化无孔碳(ENVI-Carb):碳十八键合锆胶(Z-Sep+)=0.8-1.2:1.8-2.2:0.8-1.2:0.3-0.8,或乙二胺-N-丙基硅烷(PSA):弗罗里硅土(Florisil):碳十八键合锆胶(Z-Sep+)=0.8-1.2:0.8-1.2:0.8-1.2,或十八烷基硅烷键合硅胶(C18):多壁碳纳米(Cleaner NANO-carb)=3.8-4.2:0.8-1.2。
8.根据权利要求1所述的方法,其特征在于:所述净化剂为乙二胺-N-丙基硅烷(PSA):十八烷基硅烷键合硅胶(C18):石墨化无孔碳(ENVI-Carb):碳十八键合锆胶(Z-Sep+)=1:2:1:0.5,或乙二胺-N-丙基硅烷(PSA):弗罗里硅土(Florisil):碳十八键合锆胶(Z-Sep+)=1:1:1,或十八烷基硅烷键合硅胶(C18):多壁碳纳米(Cleaner NANO-carb)=4:1。
9.根据权利要求1所述的方法,其特征在于:全自动样品处理程序为:①振荡频率1100rpm、振荡10分钟;4200rpm、离心5分钟;②振荡频率1100rpm、振荡5分钟;4200rpm、离心5分钟。
10.根据权利要求1所述的方法,其特征在于,高油复杂基质样品、水、1%乙酸酸化乙腈提取液与萃取盐的质量体积比为2g:2ml:15ml:5g。
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CN113945656A (zh) * | 2021-09-29 | 2022-01-18 | 中国农业科学院农产品加工研究所 | 一种检测中药材中农药及其代谢物残留的方法 |
CN113945655A (zh) * | 2021-09-29 | 2022-01-18 | 中国农业科学院农产品加工研究所 | 一种检测粮谷及其油料制品中杀虫剂残留的方法 |
CN114460204A (zh) * | 2022-02-15 | 2022-05-10 | 诺安实力可商品检验(青岛)有限公司 | 同时检测植物源性食品中环螨酯和烯虫炔酯农残的方法 |
CN114624365A (zh) * | 2022-04-18 | 2022-06-14 | 中国测试技术研究院 | 同时测定茶叶中三种烯虫酯类保幼激素类似物残留的方法 |
CN114624365B (zh) * | 2022-04-18 | 2023-08-08 | 中国测试技术研究院 | 同时测定茶叶中三种烯虫酯类保幼激素类似物残留的方法 |
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