超声辅助-漂浮固化分散液液微萃取-气相色谱法测定茶叶中5种拟除虫菊酯类农药残留

茶叶科学 ›› 2017, Vol. 37 ›› Issue (3): 243-250.

超声辅助-漂浮固化分散液液微萃取-气相色谱法测定茶叶中5种拟除虫菊酯类农药残留

高玉玲^1,2, 郭秀娟³, 乔石³, 孙鹏^1,*

1. 黑龙江八一农垦大学,黑龙江大庆 163319;
2. 黑龙江八一农垦大学牡丹江食品与生物技术创新研究院,黑龙江牡丹江157000;
3. 威海海洋职业学院,山东荣成 264300

收稿日期:2016-12-26 修回日期:2017-02-22 出版日期:2017-06-15 发布日期:2019-08-22
通讯作者: *
作者简介:高玉玲,女,助理研究员,主要从事食品、农产品农药残留和兽药残留检测技术研究。
基金资助:
牡丹江市科技计划指导项目（Z2016n0017）、大庆市科技计划指导项目（szdfy-2015-50）、校内培育课题资助计划（XZR2014-17）

Ultrasound-assisted Dispersive Liquid-liquid Microextraction Based on the Solidification of a Floating Organic Droplet Followed by Gas Chromatography for the Determination of Five Pyrethroid Pesticides in Tea Samples

GAO Yuling^1,2, GUO Xiujuan³, QIAO Shi³, SUN Peng^1,*

1. Heilongjiang Bayi Agricultural University, Daqing 163319, China;
2. Heilongjiang Bayi Agricultural University of Mudanjiang Food and Bio Technology Innovation Institute, Mudanjiang 157000, China;
3. Weihai Ocean Vocational College, Rongcheng 264300, China

Received:2016-12-26 Revised:2017-02-22 Online:2017-06-15 Published:2019-08-22

摘要/Abstract

摘要： 建立了超声辅助-漂浮固化分散液液微萃取（UA-DLLME-SFO）-气相色谱法（GC）测定茶叶中甲氰菊酯、氟氯氰菊酯、氯氟氰菊酯、氰戊菊酯、溴氰菊酯5种拟除虫菊酯类农药残留的方法。获得最佳试验条件为20βμL十六烷（萃取剂）和800βμL丙酮（分散剂）,质量分数为4%的氯化钠,水相pH为4,35℃超声30βmin,–3℃、10β000βr·min^-1离心5βmin后,去除水相后经气相色谱测定。结果表明：在1~150βμg·kg^-1范围内,5种拟除虫菊酯类农药呈良好的线性关系,相关系数均大于0.9994,在1~5βμg·kg^-1添加水平下,平均回收率为92.3%~99.6%,日内相对标准偏差（RSD）均低于3.5%（n=6）,日间相对标准偏差（RSD）均低于5.9%（n=3）,5种农药在茶叶中的检出限为0.11~0.24βμg·kg^-1,定量限为0.36~0.81βμg·kg^-1。该方法操作简便、快速、安全、成本低、重现性好,适用于茶叶样品中拟除虫菊酯类农药残留的分析。

关键词: 超声辅助, 漂浮固化分散液液微萃取, 气相色谱, 拟除虫菊酯

Abstract: A novel ultrasound-assisted dispersive liquid-liquid microextraction based on solidification of floating organic droplet method (UA-DLLME-SFO) which combined with gas chromatography coupled with ECD detector was developed for the determination of five pyrethroid pesticides (fenpropathrin, cyfluthrin, cyhalothrin, fenvalerate, deltamethrin) in tea. The optimal liquid-liquid microextraction experiment conditions were as follows: 20βμL hexadecane was used as extraction solvent. After ultrasound for 30 min under 35℃, 800βμL of acetone (disersive solvent) were rapidly transferred. The NaCl Mass Fraction was 4% and pH was adjusted to 4. The sample solution was then centrigugated at 10 000 r·min^-1 for 5 min under －3℃ and then injected for gas chromatography analysis. It was shown that a good linearity for these pyrethroids was obtained at concentrations of 1.0 to 150.0 μg·kg^-1 with correlation coefficients higher than 0.9994. The average recoveries of the 5 pesticides in liquid milk were in the range of 92.3% to 99.6% at spiked levels between 1 to 5 μg·kg^-1, with intra-day relative standard deviations lower than 3.5%（n=6）and inter-day relative standard deviations lower than 5.9% (n=3). The limits of detection and quantification were 0.11-0.24 μg·kg^-1 and 0.36-0.81 μg·kg^-1 , respectively. The proposed method is simple, fast, safe, reliable and applicable for analyzing pyrethroid pesticides in tea samples.

Key words: ultrasound-assisted, DLLME-SFO, gas chromatography, pyrethroid pesticides

中图分类号:

TS272
S482

高玉玲, 郭秀娟, 乔石, 孙鹏. 超声辅助-漂浮固化分散液液微萃取-气相色谱法测定茶叶中5种拟除虫菊酯类农药残留[J]. 茶叶科学, 2017, 37(3): 243-250.

GAO Yuling, GUO Xiujuan, QIAO Shi, SUN Peng. Ultrasound-assisted Dispersive Liquid-liquid Microextraction Based on the Solidification of a Floating Organic Droplet Followed by Gas Chromatography for the Determination of Five Pyrethroid Pesticides in Tea Samples[J]. Journal of Tea Science, 2017, 37(3): 243-250.

参考文献 21

[1]	孙成玲, 汪付星, 颜冬云, 等. 拟除虫菊酯类农药残留检测前处理技术研究进展[J]. 农药, 2010, 49(1): 11-15.
[2]	黄海凤, 周炳, 赵美蓉, 等. 拟除虫菊酯类农药对哺乳动物神经毒理的研究进展[J]. 农药学学报, 2007, 9(3): 209-214.
[3]	邬新荣, 王岳飞, 张士康, 等. 茶多酚保健功能研究进展与保健食品开发[J]. 茶叶科学, 2010, 30(S1): 501-505.
[4]	苏建峰, 钟茂生, 陈晶, 等. 气相色谱-质谱法与气相色谱法测定茶叶及茶叶加工品中295种农药多残留[J]. 分析测试学报, 2015, 34(6): 625-638.
[5]	王波, 李贤良, 张雷, 等. 气相色谱法测定火锅底料中的多种有机氯农药和拟除虫菊酯农药残留[J]. 分析化学, 2010, 38(10): 1433-1438.
[6]	陈湘艺, 李小玲, 黄华伟, 等. 气相色谱法测定养殖水体及水产品组织中的拟除虫菊酯[J]. 安徽农业科学, 2015, 43(14): 96-98, 114.
[7]	F Hernández, M I Cervera, k T Portolés, et al. The role of GC-MS/MS with triple quadrupole in pesticide residue analysis in food and the environment[J]. Anal Methods, 2013, 5: 5875-5894.
[8]	李俊, 王震, 庞宏宇. 白酒中多种拟除虫菊酯类农药残留检测方法[J]. 酿酒科技, 2013(11): 98-100.
[9]	成昊, 张丽君, 张磊, 等. 基质固相分散萃取-分散液相微萃取-气相色谱质谱法测定土壤中拟除虫菊酯类农药[J]. 分析化学, 2015, 43(1): 137-140.
[10]	赫彩霞, 王姣姣, 高文惠. 高效液相色谱-DAD法检测粮谷作物中多种菊酯类农药残留[J]. 粮食与油脂, 2015, 28(4): 58-60.
[11]	CHANG Q Y, Fan C L, Chen H, et al.Determination of 187 pesticide residues in edible fungi by liquid chromatography-tandem mass spectrometry[J]. Anal Methods, 2014, 6: 4288-4304.
[12]	王东, 侯传金, 赵尔成. 分散液液微萃取/气相色谱-质谱法测定蜂蜜中六六六和滴滴涕类农药残留[J]. 色谱, 2015, 33(1): 40-45.
[13]	WANG W P, ZHU H L, CUI S M, et al.Ultrasound-assisted dispersive liquid-liquid microextraction based on solidification of floating organic droplets coupled with gas chromatography for the determination of pesticide residues in water samples[J]. Anal Methods, 2014, 6: 3388-3394.
[14]	Mir A F, LEILA K, ALI A A N. Determination of pyrethroid pesticides residues in vegetable oils using liquid-liquid extraction and dispersive liquid-liquid microextraction followed by gas chromatography-flame ionization detection[J]. Journal of Food Composition and Analysis, 2014, 34(2): 128-135.
[15]	孙鹏, 高玉玲, 王金梅, 等. 漂浮固化分散液-液微萃取-气相色谱法测定液态奶中5种拟除虫菊酯类农药残留[J]. 农药学学报, 2016, 18(4): 497-502.
[16]	孙鹏, 高玉玲, 王爽. 超声辅助-离子液体分散液液微萃取-高效液相色谱法测定液态奶中3种四环素类抗生素残留[J]. 化学试剂, 2016, 38(10): 999-1002.
[17]	孙鹏, 乔石, 郭秀娟, 等. 离子液体分散液相微萃取-HPLC法测定液态奶中恩诺沙星和环丙沙星[J]. 药物分析杂志, 2017, 37(1): 116-122.
[18]	毕欢, 郑鑫, 伦小文, 等. 漂浮固化分散液液微萃取/气相色谱法测定化妆水中4种增塑剂[J]. 分析测试学报, 2013, 32(7): 823-828.
[19]	崔淑华, 郭庆龙, 张峰, 等. 气相色谱-质谱法测定花生及制品中17种菊酯类农药残留[J]. 分析化学, 2013, 41(6): 944-948.
[20]	章晴, 陈士恒, 杨永坛. 分散固相萃取-气相色谱法测定茶叶中25种有机氯与拟除虫菊酯农药残留[J]. 分析仪器, 2013(4): 16-22.
[21]	林竹光, 金珍, 刘勇, 等. GC-NCI-MS分析茶叶中17种有机氯和拟除虫菊酯农药残留[J]. 高等学校化学学报, 2005, 26(12): 2218-2222.