CN106872604A - 一种同时检测食品中三氯杀螨醇和拟除虫菊酯农药的方法 - Google Patents
一种同时检测食品中三氯杀螨醇和拟除虫菊酯农药的方法 Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
一种同时检测食品中三氯杀螨醇和拟除虫菊酯农药的方法,所述方法包括:制作标准曲线;用提取液对样品进行超声离心提取得到上层清液;利用改性多壁碳纳米管对上层清液进行净化处理得到样品净化液;对样品净化液进行气相色谱‑质谱测定。本发明以改性多壁碳纳米管作为净化吸附剂,将改良QuEChERS法与气相色谱‑质谱联用仪结合应用于苹果、大米、香蕉、柑橘、陈皮、陈皮普洱茶样品中三氯杀螨醇和拟除虫菊酯农药的同时检测,操作简单,准确度高,稳定性好,满足痕量分析的要求。
Description
技术领域
本发明涉及农药残留量的检测方法,特别是涉及一种同时检测食品中三氯杀螨醇和拟除虫菊酯农药的方法。
背景技术
植食性螨类是危害农产品的主要害虫之一,使用三氯杀螨醇是防治螨害的主要手段,拟除虫菊酯类农药具有和天然除虫菊酯相似的化学结构,因其高效、广谱、低毒、低残留,具有击倒速度快、作用范围广、对人低毒等特点被广泛应用于农产品病害虫的预防工作中。因此,制定食品中三氯杀螨醇和拟除虫菊酯类农药残留的分析方法,具有积极的作用。
QuEChERS(Quick、Easy、Cheap、Effective、Rugged、Safe)方法是2003年美国农业部科学家开发的一种用于农产品检测的快速样品前处理技术,其步骤可以简单归纳为:(1)样品粉碎;(2)单一溶剂乙腈提取;(3)加入MgSO4等盐类除水;(4)加入乙二胺-N-丙基硅烷(PSA)等净化吸附剂净化;(5)对提取的上清液进行GC-MS、LC-MS检测。QuEChERS方法因操作简单、通用性强、成本低、环境友好、能满足性质差异较大的多种目标物的同时分析检测,被国内外广泛应用于农药残留检测,但是,用乙二胺-N-丙基硅烷(PSA)作为净化吸附剂,去除基质中干扰物的能力有限。
而多壁碳纳米管(MWNTs)因其准一维中空管结构加之大的比表面积,使其在净化吸附方面具有优异的性能。目前有文献报道其用于痕量组分样品前处理中的富集与净化。但未处理的多壁碳纳米管由于表面缺少活性官能基团,疏水性强,不溶不熔,会团聚成致密的网络,影响了其作为净化吸附剂的应用。
发明内容
基于此,本发明的目的在于,提供一种同时检测食品中三氯杀螨醇和拟除虫菊酯农药的方法,该方法以改性多壁碳纳米管作为净化吸附剂,将改良QuEChERS法与气相色谱-质谱联用仪结合应用于食品中三氯杀螨醇和拟除虫菊酯农药残留的检测,能有效除去基质干扰,方法准确、灵敏度高、操作简单快速。
本发明的技术方案如下:
一种同时检测食品中三氯杀螨醇和拟除虫菊酯农药的检测方法,该方法步骤包括:
(1)制作标准曲线:用提取液配制三氯杀螨醇和拟除虫菊酯农药混合标准溶液,对混合标准溶液进行气相色谱-质谱测定,以定量离子色谱峰面积为纵坐标,对应的质量浓度为横坐标作标准曲线;
(2)提取样品:将待测食品粉碎,加水充分浸润,然后用提取液对待测食品中的三氯杀螨醇和拟除虫菊酯农药进行提取,并进行振荡、离心处理,然后吸取上层清液;
(3)净化样品:将步骤(2)中的上层清液进行蒸发处理,所得残留物用提取液溶解,然后加入改性多壁碳纳米管,进行净化处理,然后将净化后的上层清液过滤,得到样品净化液;
(4)样品检测:将步骤(3)中所得的样品净化液进行气相色谱-质谱测定,得到样品净化液的色谱峰面积,根据步骤(1)的标准曲线,计算得到样品中三氯杀螨醇和拟除虫菊酯农药的残留量。
本发明采用改性多壁碳纳米管作为净化剂,可有效除去待测食品样品中的水溶性和脂溶性杂质,得到的净化液几乎无色,杂质对三氯杀螨醇和拟除虫菊酯农药检测无影响且回收率高;此外,所述改性多壁碳纳米管能在广泛的pH值范围内保持稳定,保证了净化效果及方法的稳定性和通用性。
进一步地,所述的提取液为体积比为1:1的乙酸乙酯-正己烷混合溶液。采用体积比为1:1的乙酸乙酯-正己烷混合溶液作为食品中三氯杀螨醇和拟除虫菊酯农药残留物的提取液,可以获得较高的提取回收率;此外,乙酸乙酯-正己烷混合溶液毒性较小,提取液便于浓缩,对人体健康危害低。
进一步地,所述混合标准溶液是浓度梯度为0.010μg/mL、0.020μg/mL、0.050μg/mL、0.10μg/mL、0.40μg/mL、1.0μg/mL的三氯杀螨醇和拟除虫菊酯农药混合溶液。所述混合标准溶液中三氯杀螨醇和各拟除虫菊酯农药的浓度与所述混合标准溶液的浓度相对应。
进一步地,所述改性多壁碳纳米管是表面产生羟基、羧基活性官能基团的多壁碳纳米管。羟基、羧基化多壁碳纳米管在有机溶剂中的分散性好,净化吸附能力强。
进一步地,所述改性多壁碳纳米管的制备方法为:将多壁碳纳米管与浓硫酸混合进行超声处理,再加入浓硝酸,超声处理后静置,吸除上层混酸清液,然后利用超纯水稀释并过滤,将过滤液用水洗至滤液的pH值为7,所得黑色固体干燥后即得被氧化的改性多壁碳纳米管。通过对多壁碳纳米管进行衍生化化学修饰,用强氧化性酸对多壁碳纳米管进行氧化处理,使其表面产生一定量的羟基、羧基活性官能基团,有效提高了多壁碳纳米管在溶液介质中的分散性能和对有机化合物的吸附性能;另外,采用自制的改性多壁碳纳米管作为净化吸附剂,可大幅度降低样品前处理的成本。
进一步地,所述改性多壁碳纳米管的长度为100~200nm。
进一步地,在上述步骤(1)和(4)的气相色谱-质谱测定中,所采用的色谱条件为:色谱柱:毛细管色谱柱,规格为30m×0.25mm×0.25μm;载气:高纯氦气(纯度>99.999%);柱流速:1.0mL/min;进样量:1μl;进样口温度:275℃;进样方式:程序升温不分流进样;升温程序:初始50℃,保持1min,然后以15℃/min升至200℃,保持8min,再以5℃/min升至275℃,保持12min;所采用的质谱条件为:接口温度:275℃;离子源温度:200℃;电子轰击能:70eV;溶剂延迟:15.5min;采集方式:选择离子扫描;扫描间隔:0.3s。气相色谱-质谱联用综合了色谱高分离效能和质谱准确定性的特点,能通过保留时间和特征离子碎片及其丰度比可靠定性,又能准确定量,解决了气相色谱定性的局限性;采用上述色谱、质谱条件,使得食品中的三氯杀螨醇和拟除虫菊酯农药能够很好地分离,便于定量分析。
进一步地,所述食品是水果类及其制品或蔬菜类及其制品。
进一步地,所述食品是苹果、大米、香蕉、柑橘、陈皮及其制品。
进一步地,所述的拟除虫菊酯农药包括:联苯菊酯、甲氰菊酯、三氟氯氰菊酯、氯菊酯、氯氰菊酯、氟氰戊菊酯、氰戊菊酯和溴氰菊酯。
为了更好地理解和实施,下面结合附图详细说明本发明。
附图说明
图1为本发明多壁碳纳米管氧化改性前后的透射电镜图,其中图a为氧化改性前,图b为氧化改性后;
图2为本发明多壁碳纳米管氧化改性前后的红外光谱图,其中曲线a为氧化改性前,曲线b为氧化改性后;
图3为本发明浓度为0.01μg/mL的混合标准溶液的总离子流图;
图4为本发明具体实施例中的陈皮样品的总离子流图;
图5为本发明具体实施例中的陈皮普洱茶样品的总离子流图;
图6为本发明具体实施例中的苹果样品的总离子流图;
图7为本发明具体实施例中的大米样品的总离子流图;
图8为本发明乙腈、乙酸乙酯、正己烷和不同配比的乙酸乙酯-正己烷混合溶液对三氯杀螨醇、甲氰菊酯和氰戊菊酯3种农药的提取回收率的影响;
图9为本发明提取样品时超声时间对三氯杀螨醇、甲氰菊酯和氰戊菊酯3种农药的提取回收率的影响;
图10为本发明改性多壁碳纳米管用量对三氯杀螨醇、甲氰菊酯和氰戊菊酯3种农药回收率的影响;
图11为本发明氯菊酯和氰戊菊酯的提取离子流图;
图12为本发明具体实施例中在陈皮普洱茶样品中添加浓度为0.02μg/mL的混合标准溶液的总离子流图;
其中,1为三氯杀螨醇;2为联苯菊酯;3为甲氰菊酯;4为三氟氯氰菊酯;5为氯菊酯;6为氯氰菊酯;7为氟氰戊菊酯;8为氰戊菊酯;9为溴氰菊酯。
具体实施方式
(一)仪器与试剂
QP 2010 Ultar气相色谱-质谱联用仪(日本岛津公司),配AOC-20si自动进样系统;H-800-1型透射电子显微镜(日本日立公司);Nexus 670型傅立叶变换红外光谱扫描仪(美国Thermo公司);KQ 2200DB型超声振荡器(昆山超声仪器有限公司);DZF-6050真空干燥机(上海精密仪表公司);2-16型通用台式高速离心机(德国Sigma公司);LAB DANCER涡旋混合器(德国IKA公司);DN-12W氮吹仪(上海比郎公司);Milli-Q超纯水系统(美国Millipore公司);50mm×0.22μm聚四氟乙烯微孔滤膜(美国蜜理博公司)。
三氯杀螨醇、联苯菊酯、甲氰菊酯、三氟氯氰菊酯、氯菊酯、氯氰菊酯、氟氰戊菊酯、氰戊菊酯、溴氰菊酯9种农药标准品:规格为1mL,浓度为100μg/mL,购自农业部环境保护科研检测所;正己烷、乙腈、乙酸乙酯为色谱纯,购自德国默克公司;多壁碳纳米管纯度>95%,直径10~20nm,长度300~800nm,购自深圳纳米港有限公司;弗洛里(Florisil)净化吸附剂,规格为80~100目,购自上海博势公司;N-丙基乙二胺(PSA)净化吸附剂,平均粒度45μm,孔体积0.8m3/g,购自山东奥秘公司;硅胶,规格为60~100目,购自青岛海洋化工;实验用水为超纯水。
(二)实施例
1、实施例1:改性多壁碳纳米管的制备
称取50g多壁碳纳米管置于500mL的烧瓶中,加入50mL浓硫酸,超声30min,再向烧瓶中加入30mL浓硝酸,超声30min,静置,用吸管吸除上层混酸清液,然后加入1000mL超纯水进行稀释,将稀释液过0.22μm的聚四氟乙烯微孔滤膜过滤,将过滤液用水洗至滤液的pH值为7,所得黑色固体经真空烘箱50℃干燥即得被氧化的改性多壁碳纳米管。
图1为多壁碳纳米管氧化改性前后的透射电镜图,由图1可见,氧化改性后所得多壁碳纳米管分散均匀,有一定的长径比、长度分布均匀,经氧化改性后的多壁碳纳米管的长度为100~200nm,说明本发明所采用的氧化改性多壁碳纳米管的方法效果好。图2为多壁碳纳米管氧化改性前后的红外光谱图,由图2可见,氧化改性后的多壁碳纳米管在3414cm-1波数处出现较宽的吸收峰,该吸收峰是由羟基伸缩振动所引起的,在1704cm-1处的吸收峰是羧基中的羰基伸缩振动引起的,说明经强酸氧化后多壁碳纳米管的表面产生了羟基和羧基活性官能基团。
2、实施例2:陈皮、陈皮普洱茶样品中三氯杀螨醇和拟除虫菊酯农药残留的检测
本实施例是基于改良的QuEChERS法与气相色谱-质谱联用仪测定陈皮及其制品中三氯杀螨醇和拟除虫菊酯农药的残留量。具体步骤如下:
(1)分别吸取适量浓度为100μg/mL的三氯杀螨醇、联苯菊酯、甲氰菊酯、三氟氯氰菊酯、氯菊酯、氯氰菊酯、氟氰戊菊酯、氰戊菊酯和溴氰菊酯农药标准品,用体积比为1:1的乙酸乙酯-正己烷混合溶液稀释定容,分别制备得到浓度为0.010μg/mL、0.020μg/mL、0.050μg/mL、0.10μg/mL、0.40μg/mL、1.0μg/mL的混合标准溶液,然后对混合标准溶液进行气相色谱-质谱测定,以定量离子色谱峰面积为纵坐标(y),对应的质量浓度为横坐标(x)作标准曲线。
(2)称取粉碎陈皮、陈皮普洱茶样品各2.00g于50mL具塞离心管中,加入4mL超纯水,振荡1min,超声5min,加入5mL体积比为1:1的乙酸乙酯-正己烷混合溶液,超声5min,3000r/min离心5min,吸取上层清液,再加入5mL体积比为1:1乙酸乙酯-正己烷混合溶液重复提取,合并上层清液合并混匀。
(3)将上述上层清液用氮吹仪吹干,所得残留物用2mL体积比为1:1的乙酸乙酯-正己烷混合溶液溶解,然后将其转移至装有200mg改性多壁碳纳米管的离心管中,振荡1min,3000r/min离心5min,吸取上清液,过0.22μm有机相滤膜过滤,得到样品净化液。
(4)将步骤(3)中所得的样品净化液进行气相色谱-质谱测定,得到样品净化液色谱峰面积,根据步骤(1)的标准曲线,计算得到样品中三氯杀螨醇、联苯菊酯、甲氰菊酯、三氟氯氰菊酯、氯菊酯、氯氰菊酯、氟氰戊菊酯、氰戊菊酯和溴氰菊酯的残留量。
其中,在进行GC-MS检测中,
所采用的色谱条件为:色谱柱:毛细管色谱柱,规格为30m×0.25mm×0.25μm;载气:高纯氦气(纯度>99.999%);柱流速:1.0mL/min;进样量:1μl;进样口温度:275℃;进样方式:程序升温不分流进样;升温程序:初始50℃,保持1min,然后以15℃/min升至200℃,保持8min,再以5℃/min升至275℃,保持12min。
所采用的质谱条件为:接口温度:275℃;离子源温度:200℃;电子轰击能:70eV;溶剂延迟:15.5min;采集方式:选择离子扫描;扫描间隔:0.3s。其他质谱条件见表1。
表1 9种农药残留测定方法的检测条件
3、实施例3:苹果,大米,香蕉,柑橘样品中三氯杀螨醇和拟除虫菊酯农药残留的检测
本实施例与实施例2的区别在于:在步骤2中,称取粉碎苹果,大米,香蕉,柑橘样品各2.00g于50mL具塞离心管中,加入2mL超纯水,振荡1min,超声5min,加入5mL体积比为1:1的乙酸乙酯-正己烷混合溶液,超声5min,3000r/min离心5min,吸取上层清液,再加入3mL体积比为1:1乙酸乙酯-正己烷混合溶液重复提取,合并上清液并混匀。
其中,0.01μg/mL的混合标准溶液的总离子流图如图3所示;实施例1中陈皮样品的总离子流色谱图和陈皮普洱茶样品的总离子流图分别如图4和图5所示;实施例2中的苹果和大米样品的总离子流图分别如图6和图7所示。
(三)检测条件的筛选
1、提取液的选择
三氯杀螨醇和拟除虫菊酯农药化学结构和理化性质差异大,将其从样品中有效提取是多残留分析必须解决的首要问题。三氯杀螨醇和拟除虫菊酯农药极性与溶解性存在差异,依据提取溶剂与目标分析物之间“相似相溶”的原则,以三氯杀螨醇、甲氰菊酯和氰戊菊酯作为提取目标化合物,以加标回收率作为考察指标,在陈皮空白样品中添加25μg/kg的混合标准溶液,重复6次,考察乙腈、乙酸乙酯、正己烷和不同配比的乙酸乙酯-正己烷混合溶液等萃取体系的提取效率,结果如图8所示。
发现,乙腈作为提取溶剂时,亲脂性化合物如蜡质物、脂肪等不被提取,而且由于其毒性较强沸点高以致对提取液的蒸发浓缩困难;正己烷由于其极性低,亲酯性杂质干扰大,提取效率较差;乙酸乙酯作为单一提取溶剂,对三氯杀螨醇提取回收效率较低,而乙酸乙酯-正己烷混合溶液对三氯杀螨醇,甲氰菊酯和氰戊菊酯的提取回收率都较高,且乙酸乙酯-正己烷混合溶液体系毒性较小,提取液便于蒸发浓缩;从图8中不同有机溶剂提取的加标回收率对比分析可知,体积比为1:1的乙酸乙酯-正己烷混合溶液对三氯杀螨醇,甲氰菊酯和氰戊菊酯的提取回收率较高,最适宜用于提取本发明食品样品中的三氯杀螨醇和拟除虫菊酯农药残留。
2、提取样品时超声时间的优化
超声可以加速三氯杀螨醇和拟除虫菊酯农药在样品和提取液之间平衡的过程,因此超声时间是提取样品的重要影响因素。实验考察了超声时间分别为2min、5min、10min、15min时对样品中三氯杀螨醇、甲氰菊酯和氰戊菊酯的提取效率的影响,结果见图9。结果显示,随着超声时间的延长,三氯杀螨醇、甲氰菊酯和氰戊菊酯的回收率增大,超声5min时,三氯杀螨醇、甲氰菊酯和氰戊菊酯的回收率达到最高,继续延长超声时间,由于超声提取过程中产生热量造成农药分解,导致回收率降低,因此本发明实施例中提取样品时选择的超声时间为5min。
3、净化吸附剂的选择
本发明考察了改性多壁碳纳米管、未改性多壁碳纳米管、弗洛里、N-丙基乙二胺、硅胶5种净化吸附剂对陈皮样品中提取液的净化作用,以三氯杀螨醇、甲氰菊酯和氰戊菊酯为提取目标化合物,以三种目标化合物的回收率作为考察指标,结果见表2。由表可见,三种目标化合物在改性多壁碳纳米管、未改性多壁碳纳米管、弗洛里、N-丙基乙二胺、硅胶作为净化吸附剂条件下的回收率分别为84%~102%、16%~35%、55%~72%、48%~62%、27%~55%。
表2不同净化吸附剂下三氯杀螨醇、甲氰菊酯和氰戊菊酯在陈皮样品中的回收率
结果表明,未改性多壁碳纳米管由于相互间强的比表面和范德华作用,并且由于表面缺少带羟基和羧基的官能基团,在有机溶剂和水溶液中的分散尤其差,在样品浓缩液中加入未改性多壁碳纳米管,未改性多壁碳纳米管团聚成致密的网络沉积在离心管底部,不能起到净化作用;弗洛里虽然能有效地吸附极性化合物,但其净化液呈浅黄色、浅绿色或绿色,N-丙基乙二胺能有效去除提取液中的有机酸、脂肪酸、糖类,但去除生物碱、色素、维生素、黄酮化合物等的作用不大,所以用弗洛里和N-丙基乙二胺做净化吸附剂,杂质对目标化合物的提取有干扰;硅胶对蛋白质、脂肪、维生素等杂质有较高的吸附能力,但也能牢固吸附目标化合物,对三氯杀螨醇、甲氰菊酯和氰戊菊酯的回收率低;而改性多壁碳纳米管可有效除去样品中的水溶性和脂溶性杂质,净化液几乎无色,杂质对目标化合物检测无影响且回收率最高。此外,改性多壁碳纳米管能在广泛的pH值范围内保持稳定,保证了净化效果及方法的通用性,所以本发明实施例采用改性多壁碳纳米管对提取液进行净化。
此外,还考察了改性多壁碳纳米管的用量对添加25μg/kg的混合标准溶液的空白样品中的三氯杀螨醇、甲氰菊酯和氰戊菊酯三种目标化合物回收率的影响,其中改性多壁碳纳米管的用量分别为0.1g、0.2g、0.4g、0.8g,结果见图10。相对于其他杂质,三氯杀螨醇、甲氰菊酯和氰戊菊酯农药含的π电子少,随着改性多壁碳纳米管用量增加,杂质与改性多壁碳纳米管能形成更强的π-π吸附而减少了对三种目标化合物的干扰,使得三种目标化合物回收率增大,当改性多壁碳纳米管用量为0.2g时回收率最高,继续增加改性多壁碳纳米管用量,三种目标化合物回收率没有明显变化,结果见图10。因此,本发明实施例选择改性多壁碳纳米管的最佳用量为0.2g。
4、质谱条件优化
首先配制9种农药的混合标准溶液,然后通过全扫描方式得到总离子流图,再根据每种农药在PESTEI、NIST谱库中的碎片离子质荷比和丰度比信息,对每一种农药标准物质进行质谱解析确认,通过试验选择6个时间段进行选择离子方式检测,每种农药分别选择1个定量离子外标法定量,2个定性离子和丰度比为定性依据,质谱参数见表1,部分目标化合物的提取离子流图见图11。
(四)实施例的试验结果
1、基质效应
基质效应指样品中被分析物以外的组分,对分析过程及结果准确性的影响和干扰。不同农药在同一基质中具有不同的基质效应,同一农药在不同基质中基质效应也不同,同时基质效应与浓度具有一定的关系,随着浓度增加,基质效应逐渐减弱。本发明对苹果,大米,香蕉,柑橘,陈皮和陈皮普洱茶的基质效应进行了研究。
分别用体积比为1:1的乙酸乙酯-正己烷混合溶液和基质空白提取液作为溶剂,配制浓度分别为0.010μg/mL、0.020μg/mL、0.050μg/mL、0.10μg/mL、0.40μg/mL、1.0μg/mL的三氯杀螨醇和拟除虫菊酯农药有机溶剂混合标准溶液和基质匹配混合标准溶液,在上述优化的色谱和质谱条件下,对两种混合标准溶液进行气相色谱-质谱测定,分别绘制有机溶剂标准曲线和基质匹配标准曲线,采用基质匹配标准曲线斜率和有机溶剂标准曲线斜率之比(K)来评价基质效应:若K值介于0.9~1.1之间,基质效应不明显,K大于1.1时为基质增强效应,小于0.9则是基质抑制效应。所述基质空白提取液是取与实际用于检测的量相等的空白样品,按照实施例2中的步骤(2)和(3)制备得到的样品净化液。
结果表明:苹果,大米,香蕉,柑橘,陈皮和陈皮普洱茶作为基质,计算得出9种农药的标准曲线斜率比值K值在0.9236~1.0866之间,表明基质效应对本发明定量结果的影响可以忽略,因此本发明可避免使用基质匹配标准曲线,定量方法更简便。
2、线性范围和检出限
在上述优化的色谱和质谱条件下,对上述浓度为0.010μg/mL、0.020μg/mL、0.050μg/mL、0.10μg/mL、0.40μg/mL、1.0μg/mL的混合标准溶液进行气相色谱-质谱测定,以定量离子色谱峰面积为纵坐标(y),对应的质量浓度为横坐标(x)作标准曲线,结果见表3。从表3可见,三氯杀螨醇和8种拟除虫菊酯农药在0.010~1.0μg/mL范围内呈良好的线性关系,相关系数为0.9840~0.9977,以信噪比S/N=3计算检出限(LOD),9种农药的检出限在2.2~6.2μg/kg之间。
3、回收率和精密度
在上述最优色谱和质谱条件下,在柑橘,陈皮,陈皮普洱茶净化样品中分别添加0.010mg/kg、0.020mg/kg和0.10mg/kg 3种浓度水平的混合标准溶液,每个浓度水平重复测定6次,考察本发明的准确度和精密度,结果见表3。从表3看出,9种农药的平均加标回收率为76.7%~107%,相对标准偏差(RSD)为3.1%~9.5%。其中,陈皮普洱茶样品添加浓度为0.020μg/mL的混合标准溶液的总离子流图如图12所示。
表3 9种农药残留的相关系数、检出限、平均回收率及相对标准偏差(n=6)
4、实际样品检测
在上述最优条件下将所建立的方法对苹果、大米、香蕉、柑橘、陈皮、陈皮普洱茶等送检100批次样品进行检测,采用实验室空白、空白加标和平行样进行质量控制,其中2份陈皮普洱茶中检出三氯杀螨醇含量分别为0.048mg/kg,0.027mg/kg,其余样品均未检出三氯杀螨醇和拟除虫菊酯农药。
本发明以改性多壁碳纳米管作为净化吸附剂,将改良QuEChERS法与气相色谱-质谱联用仪结合应用于苹果、大米、香蕉、柑橘、陈皮、陈皮普洱茶样品中三氯杀螨醇和拟除虫菊酯农药的同时检测。目标检测物在0.010~1.0μg/mL范围内呈良好的线性关系,相关系数为0.9840~0.9977,检出限(S/N=3)为2.2~6.2μg/kg,平均加标回收率为76.7%~107%,相对标准偏差(RSD)为3.1%~9.5%,本发明方法简便快速,准确度高,稳定性好,成本低,能够满足国内外的残留限量要求,应用于实际样品的检测,得到满意的结果,符合食品农药残留分析从繁琐的传统方法向快速、简便的方法发展的趋势,具有一定的实际应用参考价值。
以上所述实施例仅表达了本发明的具体实施方式,其描述较为具体和详细,但并不能因此而理解为对发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。
Claims (10)
1.一种同时检测食品中三氯杀螨醇和拟除虫菊酯农药的方法,其特征在于:包括以下步骤:
(1)制作标准曲线:用提取液配制三氯杀螨醇和拟除虫菊酯农药混合标准溶液,对混合标准溶液进行气相色谱-质谱测定,以定量离子色谱峰面积为纵坐标,对应的质量浓度为横坐标作标准曲线;
(2)提取样品:将待测食品粉碎,加水充分浸润,然后用提取液对待测食品中的三氯杀螨醇和拟除虫菊酯农药进行提取,并进行振荡、离心处理,然后吸取上层清液;
(3)净化样品:将步骤(2)中的上层清液进行蒸发浓缩,所得残留物用提取液溶解,然后加入改性多壁碳纳米管,进行净化处理,然后将净化后的上层清液过滤,得到样品净化液;
(4)样品检测:将步骤(3)中所得的样品净化液进行气相色谱-质谱测定,得到样品净化液的色谱峰面积,根据步骤(1)的标准曲线,计算得到样品中三氯杀螨醇和拟除虫菊酯农药的残留量。
2.根据权利要求1所述的同时检测食品中三氯杀螨醇和拟除虫菊酯农药的方法,其特征在于:所述的提取液为体积比为1:1的乙酸乙酯-正己烷混合溶液。
3.根据权利要求1所述的同时检测食品中三氯杀螨醇和拟除虫菊酯农药的方法,其特征在于:所述混合标准溶液是浓度梯度为0.010μg/mL、0.020μg/mL、0.050μg/mL、0.10μg/mL、0.40μg/mL、1.0μg/mL的三氯杀螨醇和拟除虫菊酯农药混合溶液。
4.根据权利要求1所述的同时检测食品中三氯杀螨醇和拟除虫菊酯农药的方法,其特征在于:所述改性多壁碳纳米管是表面产生羟基、羧基活性官能基团的多壁碳纳米管。
5.根据权利要求4所述的同时检测食品中三氯杀螨醇和拟除虫菊酯农药的方法,其特征在于:所述改性多壁碳纳米管的制备方法为:将多壁碳纳米管与浓硫酸混合进行超声处理,再加入浓硝酸,超声处理后静置,吸除上层混酸清液,然后利用超纯水稀释并过滤,将过滤液用水洗至滤液的pH值为7,所得黑色固体干燥后即得被氧化的改性多壁碳纳米管。
6.根据权利要求5所述的同时检测食品中三氯杀螨醇和拟除虫菊酯农药的方法,其特征在于:所述改性多壁碳纳米管的长度为100~200nm。
7.根据权利要求1所述的同时检测食品中三氯杀螨醇和拟除虫菊酯农药的方法,其特征在于:在步骤(1)和(4)的气相色谱-质谱测定中,采用的色谱条件为:色谱柱:毛细管色谱柱,规格为30m×0.25mm×0.25μm;载气:高纯氦气(纯度>99.999%);柱流速:1.0mL/min;进样量:1μl;进样口温度:275℃;进样方式:程序升温不分流进样;升温程序:初始50℃,保持1min,然后以15℃/min升至200℃,保持8min,再以5℃/min升至275℃,保持12min;采用的质谱条件为:接口温度:275℃;离子源温度:200℃;电子轰击能:70eV;溶剂延迟:15.5min;采集方式:选择离子扫描;扫描间隔:0.3s。
8.根据权利要求1所述的同时检测食品中三氯杀螨醇和拟除虫菊酯农药的方法,其特征在于:所述的食品是水果类及其制品或蔬菜类及其制品。
9.根据权利要求1所述的同时检测食品中三氯杀螨醇和拟除虫菊酯农药的方法,其特征在于:所述的食品是苹果、大米、香蕉、柑橘或陈皮及其制品。
10.根据权利要求1所述的同时检测食品中三氯杀螨醇和拟除虫菊酯农药的方法,其特征在于:所述的拟除虫菊酯农药包括:联苯菊酯、甲氰菊酯、三氟氯氰菊酯、氯菊酯、氯氰菊酯、氟氰戊菊酯、氰戊菊酯和溴氰菊酯。
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