固相萃取-气相色谱-质谱联用法检测啤酒中酰胺类除草剂及其中间体物质
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摘要
目的建立固相萃取-气相色谱-质谱联用法(gas chromatography-mass spectrometry,GC-MS)建立同时测定啤酒中8种酰胺类除草剂和2种芳香胺的分析方法。方法稀释过的样品,经活化后的C18固相萃取小柱吸附,用乙腈-甲苯(3:1,V:V)的混合溶液洗脱,DB-5 MS石英毛细管柱分离以及GC-MS的定性和定量分析。结果在线性范围0.1~20μg/L内,本方法的线性关系良好,检出限为2.37~10.28 ng/L。在3个加标浓度(0.1、1和10μg/L)下,回收率在92.1%~113.9%之间,相对标准偏差(relative standard deviation,RSD)在2.6%~5.4%之间。将所建立的方法对其他3种啤酒进行了检验,未检出10种目标物。结论本研究建立的方法操作简单、回收率高、准确度高,可以应用到检测啤酒中酰胺类除草剂及其中间体物质。
Objective To establish a method for simultaneous determination of 8 kinds of amide herbicides and 2 kinds of aromatic amines in beer by solid-phase extraction(SPE) combined with gas chromatography-mass spectrometry(GC-MS). Methods The diluted samples were absorbed by activated C18 solid-phase extraction column. Then they were eluted by a mixed solution of acetonitrile-toluene(3:1, V:V), and separated by DB-5 MS quartz capillary column. GC-MS was used for qualitative and quantitative analysis. Results In the range of 0.1-20 g/L, this method had good linear relationships and the limits of detection were 2.37-10.28 ng/L. At the spiked levels of 0.1, 1 and 10 μg/L, the average recoveries were 92.1%-113.9%, and relative standard deviations(RSDs) were 2.6%-5.4%. The developed method had been applied to detect another three brands of beer, but none of the targets had been detected. Conclusion The established method is simple, with high recovery and high accuracy, which can be applied to detect amide herbicides and their intermediates in beer.
Objective To establish a method for simultaneous determination of 8 kinds of amide herbicides and 2 kinds of aromatic amines in beer by solid-phase extraction(SPE) combined with gas chromatography-mass spectrometry(GC-MS). Methods The diluted samples were absorbed by activated C18 solid-phase extraction column. Then they were eluted by a mixed solution of acetonitrile-toluene(3:1, V:V), and separated by DB-5 MS quartz capillary column. GC-MS was used for qualitative and quantitative analysis. Results In the range of 0.1-20 g/L, this method had good linear relationships and the limits of detection were 2.37-10.28 ng/L. At the spiked levels of 0.1, 1 and 10 μg/L, the average recoveries were 92.1%-113.9%, and relative standard deviations(RSDs) were 2.6%-5.4%. The developed method had been applied to detect another three brands of beer, but none of the targets had been detected. Conclusion The established method is simple, with high recovery and high accuracy, which can be applied to detect amide herbicides and their intermediates in beer.
引文
[1]周蓓蕾,管文辰,章虎.高效液相色谱-串联质谱法检测多菌灵在啤酒加工过程中的残留量变化[J].农药学学报,2016,18(3):402-406.Zhou BL,Guan WC,Zhang H.Fate of carbendazim residue during beer brewing process by high performance liquid chromatography-tandem mass spectrometry[J].Chin J Pest Sci,2016,18(3):402-406.
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[20]胡贝贞,沈国军,邵铁锋.固相萃取-气质联用法测定啤酒中9种有机磷农药残留[J].化学分析计量,2008,17(1):35-37.Hu BZ,Shen GJ,Shao TF.Determination of nine organo phosphrous pesticides in beer by solid phase extraction and gas chromatography-mass spectrometry[J].Chem Anal Meterag,2008,17(1):35-37.
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[22]Bao X,Zhua Z,Li NQ,et al.Electrochemical studies of rutin interacting with hemoglobin and determination of hemoglobin[J].Talanta,2001,54(4):591-596.
[23]Xie JQ,Zhang LJ,Zhao L,et al.Metolachlor stereoisomers:Enantioseparation,identification andchiral stability[J].J Chromatogr A,2016,1463:42-48.
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[28]Zhao RS,Diao CP,Chen QF,et al.Sensitive determination of amide herbicides in environmental water samples by a combination of solid-phase extraction and dispersive liquid-liquid microextraction prior to GC-MS[J].J Sep Sci,2009,32(7):1069-1074.
[29]侯颖.芳氧苯氧丙酸类和氯乙酰胺类除草剂降解菌的分离鉴定、降解基因克隆表达及其代谢途径研究[D].南京:南京农业大学,2011.Hou Y.Isolation,identification of aryloxyphenoxypropionate and chlopoacetamide herbicides-degrading bacteria,cloning and expression of metabolic pathway[D].Nanjing:Nanjing Agricultural University,2011.
[30]Vandana S,Manju G,Archana J,et al.Determination of aromatic primary amines atμg-llevel in environmental waters by gas chromatography–mass spectrometry involving N-allyl-N’-arylthiourea formation and their on-line pyrolysis to aryl isothiocyanates[J].J Chromatogr A,2003,1010:243-253.
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[2]林茂发.啤酒中有机氯及拟除虫菊酯残留检测方法研究[J].广州化工,2011,39(10):125-129.Lin MF.Study on determination of organochlorines and pyrethroids residues in beer[J].Guangzhou Chem Ind,2011,39(10):125-129.
[3]And MJH,Shibamoto T.Method development and fate Determination of pesticide-treated hops and their subsequent usage in the production of beer[J].J Agric Food Chem,2002,50:3412-3418.
[4]Navarro S,Perez G,Navarro G,et al.Decay of dinitroaniline herbicides and organophosphorus insecticides during brewing of lager beer[J].J Food Protect,2006,69(7):1699-1706.
[5]Vela N,Perez G,Navarro G,et al.Gas chromatographie determination of pestieide residues in malt,spent grains,wort,and beer with electron capture detection and mass spectrometry[J].J AOAC Int,2007,90(2):544-549.
[6]刘少伟,阮赞林.啤酒与草甘膦残留[J].质量与标准化,2017,4:39-40.Liu SW,Ruan ZL.Beer with the residues of glyphosate[J].Qual Stand,2017,4:39-40.
[7]李颖.最受欢迎的14种德国啤酒检出农药残留[J].消费警示,2016,4:44-45.Li Y.Herbicide residues were found in 14 of the most popular brands of German beers[J].Consumer Warning,2016,4:44-45.
[8]江伟,胡京奕,孙志伟,等.啤酒大麦中十五种农药残留检测方法的建立及应用[J].浙江农业学报,2010,22(6):795-801.Jiang W,Hu JY,Sun ZW,et al.Establishment and application of detection methods for 15 pesticide residues in beer barlry[J].Acta Agric Zhejiangensis,2010,22(6):795-801.
[9]刘志聪,谷方红,王德良,等.固相萃取-气相色谱-质谱联用法测定啤酒大麦中抗蚜威、乙草胺、三唑酮的残留量[J].食品与发酵工业,2009,135(4):158-162.Liu ZC,Gu FH,Wang DL,et al.Determination of pirimicarb,acetochlor and triadimefon residuals in barley by SPE and GC-MS[J].Food Ferment Ind,2009,135(4):158-162.
[10]秦瑞香.酰胺类除草剂、杀菌剂合成新工艺的研究[D].青岛:青岛科技大学,2004.Qin RX.Study on a new synthesis process of amide herbicide and fungicides[D].Qingdao:Qingdao University of Science and Technology,2004.
[11]王忠,郑朝晖.2-甲基-6-乙基苯胺和2,6-二乙基苯胺的合成技术及应用[J].石化技术,2000,7(1):53-58.Wang Z,Zheng CH.Synthesis technology and application of2-methyl-6-ethyl aniline and 2,6-diethyl aniline[J].Petro Ind Technol,2000,7(1):53-58.
[12]石昌富,刘巧云.丙草胺中间体2,6-二乙基苯胺基乙基丙基醚的合成[J].辽宁化工,2016,45(6):690-692.Shi CF,Liu QY.Synthesis of 2,6-diethy-N-(2-propoxyehthy I)ani Iine as pretilachlor intermediate[J].Liaoning Chem Ind,2016,45(6):690-692.
[13]Ye CM,Wang XJ,Zhang HH.Biodegradation of acetanilide herbicide acetochlor and butachor in soil[J].J.Environ Sci,2002,14(4):524-529.
[14]Xie JQ,Zhao L,Liu K,et al.Enantioseparation of four amide herbicide stereoisomers using high-performance liquid chromatography[J].J Chromatogr A,2016,1471:145-154.
[15]李明月.苯胺类化合物气相及水体中降解机理的理论研究[D].济南:山东大学,2015.Li MY.Degradation mechanism of anilines in the atmosphere and aqueous solution[D].Jinan:Shandong University,2015.
[16]Zhang J,Zheng JW,Bin LB,et al.Biodegradation of chloroacetamide herbicides by paracoccus sp.FLY-8 in vitro[J].J Agric Food Chem,2011,59:4614-4621.
[17]Pinheiro H,Touraud E,Thomas OAromatic amines from azo dye reduction:status review with emphasis on direct UV spectrophotometric detection in textile industry wastewaters[J].Dyes Pigments,2004,61(2):121-139.
[18]Coleman S,Linderman R,Hodgson E,et al.Comparative metabolism of chloroacetamide herbicides and selected metabolites in human and rat liver microsomes[J].Environ Health Perspect,2000,108:1151-1157.
[19]林玲云.过氧化物酶催化酰胺类除草剂废水中特征污染物的聚合去除[D].大连:大连理工大学,2012.Lin LY.Polymerization and removal of characteristic pollutants in chloroacetanilide herbicides wastwaters mediated by horse radish peroxidase[D].Dalian:Dalian University of Technology,2012.
[20]胡贝贞,沈国军,邵铁锋.固相萃取-气质联用法测定啤酒中9种有机磷农药残留[J].化学分析计量,2008,17(1):35-37.Hu BZ,Shen GJ,Shao TF.Determination of nine organo phosphrous pesticides in beer by solid phase extraction and gas chromatography-mass spectrometry[J].Chem Anal Meterag,2008,17(1):35-37.
[21]刘倩真,杨世海,杨美华.酒类中农药残留分析方法研究进展[J].中国公共卫生,2012,28(7):994-988.Liu QZ,Yang Sh,Yang MH.Research Progress on the analysis methods of pesticide residues in liquor[J].Chin J Public Health,2012,28(7):994-988.
[22]Bao X,Zhua Z,Li NQ,et al.Electrochemical studies of rutin interacting with hemoglobin and determination of hemoglobin[J].Talanta,2001,54(4):591-596.
[23]Xie JQ,Zhang LJ,Zhao L,et al.Metolachlor stereoisomers:Enantioseparation,identification andchiral stability[J].J Chromatogr A,2016,1463:42-48.
[24]Mehmet A,Sevket A.Simultaneous determination of aliphatic and aromatic amines in water and sediment samples by ion-pair extraction and gas chromatography-mass spectrometry[J].J Chromatogr A,2006,1129(1):88-94.
[25]Dong XF,Liang SX,Shi ZH,et al.Development of multi-residue analysis of herbicides in cereal grain by ultra-performance liquid chromatography–electrospray ionization-mass spectrometry[J].Food Chem,2016,192:432-440.
[26]Tran A,Hyne R,Doble P.Determination of commonly used polar herbicides in agricultural drainage waters in Australia by HPLC[J].Chemosphere,2007,67(5):944-953.
[27]Rocha CA.Pappas E,Huang CH.Determination of trace triazine and chloroacetamide herbicides in tile-fed drainage ditch water using solid-phase microextraction coupled with GC–MS[J].Environ Pollut,2008,152:239-244.
[28]Zhao RS,Diao CP,Chen QF,et al.Sensitive determination of amide herbicides in environmental water samples by a combination of solid-phase extraction and dispersive liquid-liquid microextraction prior to GC-MS[J].J Sep Sci,2009,32(7):1069-1074.
[29]侯颖.芳氧苯氧丙酸类和氯乙酰胺类除草剂降解菌的分离鉴定、降解基因克隆表达及其代谢途径研究[D].南京:南京农业大学,2011.Hou Y.Isolation,identification of aryloxyphenoxypropionate and chlopoacetamide herbicides-degrading bacteria,cloning and expression of metabolic pathway[D].Nanjing:Nanjing Agricultural University,2011.
[30]Vandana S,Manju G,Archana J,et al.Determination of aromatic primary amines atμg-llevel in environmental waters by gas chromatography–mass spectrometry involving N-allyl-N’-arylthiourea formation and their on-line pyrolysis to aryl isothiocyanates[J].J Chromatogr A,2003,1010:243-253.
[31]Torsten CS,Melanie L,Rainer H,et al.Gas chromatographic determination of aromatic amines in water samples after solid-phase extraction and derivatization with iodine:I.Derivatization[J].J Chromatogr A,1998,810:161-172.
[32]贾劲松,戴京,熊晓妹.气相色谱法测定农药废水中2,6-二乙基苯胺[J].精细化工中间体,2008,38(4):68-70.Jia JS,Dai J,Xiong XM.Determination of 2,6-diethylaniline in the pesticide wastewater by GC[J].Fine Chem Intermed,2008,38(4):68-70.
[33]常青云,周欣,高书涛,等.悬浮固化液相微萃取-气相色谱联用测定水样中酰胺类除草剂残留[J].分析化学,2012,40(4):523-528.Chang QY,Zhou X,Gao ST,et al.Determination of acetanilide herbicides in water samples by liquid phase microextraction based on solidification of floating organic droplet coupled with gas chromatography[J].Chin J Anal Chem,2012,40(4):523-528.
[34]徐晓琴.SPME-GC/MS法测定饮用水中除草剂[J].质量技术监督研究,2009(4):34-38.Xu XQ.SPME-GC/MS method for the determination of herbicides in drinking waters[J].Qual Tech Superv Res,2009(4):34-38.
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