气相色谱-串联质谱法检测乙氧氟草醚、唑草酮和乙螨唑在4种香辛料中的残留
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摘要
建立了气相色谱-三重四极杆串联质谱(GC-MS/MS)检测留兰香、桂皮、薄荷和月桂叶中乙氧氟草醚、唑草酮、乙螨唑残留的分析方法。4种香辛料用超纯水饱和,乙腈提取,无水硫酸镁及氯化钠盐析,氨基/石墨化碳黑(NH_2-Carb)固相萃取柱净化,多反应监测模式,气相色谱-串联质谱测定。结果表明:乙氧氟草醚在0.002 5～2 mg/L范围内,唑草酮和乙螨唑在0.01～2 mg/L范围内,3种农药的进样质量浓度与对应的峰面积间呈良好的线性关系,r> 0.99;乙氧氟草醚在0.025、0.5和2 mg/kg 3个添加水平下,在4种香辛料中的平均回收率在86%～112%之间,相对标准偏差(RSD)在2.4%～9.6%之间;唑草酮在0.2、0.5和2 mg/kg 3个添加水平下的平均回收率在87%～114%之间,RSD在2.4%～11%之间;乙螨唑在0.5、2和5 mg/kg 3个添加水平下的平均回收率在86%～116%之间,RSD在3.2%～11%之间。乙氧氟草醚、唑草酮和乙螨唑在4种香辛料中的定量限(LOQ)分别为0.025、0.2和0.5 mg/kg。
An analytical method was developed for the determination of oxyfluorfen, carfentrazoneethyl and etoxazole in Mentha spicata L, Cinnamomum cassia Presl, Mentha piperita L, and Laurus nobilis L using gas chromatography-tandem mass spectrometry(GC-MS/MS). The spice matrices were hydrated by ultrapure water, extracted by acetonitrile followed by the salting out process with anhydrous magnesium sulfate and sodium chloride then purified using the NH_2-Carb column and determined by the GC-MS/MS under MRM mode. The calibration curve showed a good linearity in the range of 0.0025-2 mg/L(oxyfluorfen) and 0.01-2 mg/L(carfentrazone-ethyl and etoxazole), with the correlation efficient above 0.99. The average recoveries of oxyfluorfen in the four kinds of matrices at three spiked levels of 0.025, 0.5 and 2 mg/kg ranged from 86% to 112%, with the relative standard deviation(RSD) between 2.4%-9.6%. The average recoveries of carfentrazone-ethyl at three spiked levels of 0.2, 0.5 and 2 mg/kg ranged from 87% to 114%, with the RSD between 2.4%-11%. The average recoveries of etoxazole at three spiked levels of 0.5, 2 and 5 mg/kg ranged from 86% to 116%,with the RSD between 3.2%-11%. The limit of quantitation(LOQ) of oxyfluorfen, carfentrazone-ethyl and etoxazole in the four spices were 0.025, 0.2 and 0.5 mg/kg, respectively.
An analytical method was developed for the determination of oxyfluorfen, carfentrazoneethyl and etoxazole in Mentha spicata L, Cinnamomum cassia Presl, Mentha piperita L, and Laurus nobilis L using gas chromatography-tandem mass spectrometry(GC-MS/MS). The spice matrices were hydrated by ultrapure water, extracted by acetonitrile followed by the salting out process with anhydrous magnesium sulfate and sodium chloride then purified using the NH_2-Carb column and determined by the GC-MS/MS under MRM mode. The calibration curve showed a good linearity in the range of 0.0025-2 mg/L(oxyfluorfen) and 0.01-2 mg/L(carfentrazone-ethyl and etoxazole), with the correlation efficient above 0.99. The average recoveries of oxyfluorfen in the four kinds of matrices at three spiked levels of 0.025, 0.5 and 2 mg/kg ranged from 86% to 112%, with the relative standard deviation(RSD) between 2.4%-9.6%. The average recoveries of carfentrazone-ethyl at three spiked levels of 0.2, 0.5 and 2 mg/kg ranged from 87% to 114%, with the RSD between 2.4%-11%. The average recoveries of etoxazole at three spiked levels of 0.5, 2 and 5 mg/kg ranged from 86% to 116%,with the RSD between 3.2%-11%. The limit of quantitation(LOQ) of oxyfluorfen, carfentrazone-ethyl and etoxazole in the four spices were 0.025, 0.2 and 0.5 mg/kg, respectively.
引文
[1]Chemical Book.Oxyfluorfen[DB/OL].[2018-06-02].https://www.chemicalbook.com/.
[2]Chemical Book.Carfentrazone-ethyl[DB/OL].[2011-06-02].https://www.chemicalbook.com/.
[3]Chemical Book.Etoxazole[DB/OL].[2011-06-02].https://www.chemicalbook.com/.
[4]彭林,李明泽,任文瑾,等.香辛料生理功能的研究进展[J].食品与发酵工业,2012,38(2):157-162.PENG L,LI M Z,REN W J,et al.The advance of physiology functions of spices[J].Food Ferment Ind,2012,38(2):157-162.
[5]史奎春,林苏荣.香辛料在肉制品中的应用探讨[J].中国调味品,2010,35(4):39-42.SHI K C,LIN S R.The discussion on the application of spices in meat products[J].China Cond,2010,35(4):39-42.
[6]眭红卫,许睦农.天然香辛料中的植物化学物及其生理活性研究进展[J].中国调味品,2017,42(5):176-180.SUI H W,XU M N.Research progress on phytochemicals in natural spices and their physiological activities[J].China Cond,2017,42(5):176-180.
[7]PEPPIN J F,PAPPAGALLO M.Capsaicinoids in the treatment of neuropathic pain:a review[J].Ther Adv Neurol Disord,2014,7(1):22-32.
[8]SANTOS L,MARíN S,MATEO E M,et al.Mycobiota and cooccurrence of mycotoxins in Capsicum powder[J].Int J Food Microbiol,2011,151(3):270-276.
[9]ABOU-ARAB A A K,ABOU DONIA M A.Pesticide residues in some Egyptian spices and medicinal plants as affected by processing[J].Food Chem,2001,72(4):439-445.
[10]季颖,张宏军,刘丰茂.国际食品法典和中国农产品分类实用手册:水果、香草和香料[M].中国大百科全书出版社,2015.JI Y,ZHANG H J,LIU F M.Manual of crop classifications between codex and China:Fruits,herbs and spices[M].Encyclopedia of China Publishing House,2015.
[11]HUGGETT D B,BLOCK D S,KHAN I A,et al.Environmental contaminants in the botanical dietary supplement ginseng and potential human risk[J].Human Ecolog Risk Assess:An Int J,2000,6(5):767-776.
[12]HUGGETT D B,KHAN I A,ALLGOOD J C,et al.Organochlorine pesticides and metals in select botanical dietary supplements[J].Bull Environ Contam Toxicol,2001,66(2):150-155.
[13]DURGNAT J M,HEUSER J,ANDREY D,et al.Quality and safety assessment of ginseng extracts by determination of the contents of pesticides and metals[J].Food Addit Contam,2005,22(12):1224-1230.
[14]王峰恩,李瑞菊,方丽萍,等.乙氧氟草醚在大蒜和土壤中的残留动态[J].山东农业科学,2014,46(2):119-124.WANG F E,LI R J,FANG L P,et al.Residue dynamics of oxyfluorfen in garlic and soil[J].Shandong Agric Sci,2014,46(2):119-124.
[15]黄斌,曹坳程,李君,等.二甲戊灵和乙氧氟草醚在生姜上的残留分析及土壤中的消解动态[J].农药学学报,2017,19(1):125-130.HUANG B,CAO A C,LI J,et al.Analysis of pendimethalin and oxyfluorfen residues in Zingiber officinale Roscoe and their dissipation dynamics in soil[J].Chin J Pestic Sci,2017,19(1):125-130.
[16]方旭元,夏高峰,石巧巧,等.QuEChERS-GC-MS法检测当归中9种除草剂残留[J].华南农业大学学报,2017,38(6):79-83.FANG X Y,XIA G F,SHI Q Q,et al.Detection of nine herbicide residues in Angelica sinensis by QuEChERS-GC-MS[J].J South China Agric Univ,2017,38(6):79-83.
[17]张志勇,王冬兰,吴长付,等.唑草酮在水稻和稻田中的气相色谱检测[J].江苏农业学报,2011,27(1):195-198.ZHANG Z Y,WANG D L,WU C F,et al.Determination of herbicide carfentrazone-ethyl residues in rice and paddy with a gas chromatograph-election capture detector[J].Jiangsu J Agric Sci,2011,27(1):195-198.
[18]罗佳,沈睿至,杨长志.液相色谱-串质谱法测定大米中异唑草酮及代谢物残留量[J].食品安全质量检测学报,2015,6(7):2863-2868.LUO J,SHEN R Z,YANG C Z.Determination of isoxaflutole and its metabolites residues in rice by liquid chromatography-mass spectrometry/mass spectrometry[J].J Food Saf Qual,2015,6(7):2863-2868.
[19]张夏力,刘新刚,路彩红,等.气相色谱-串联质谱方法测定小麦中唑草酮的残留及消解动态[J].植物保护,2012,38(1):115-119.ZHANG X L,LIU X G,LU C H,et al.Degradation of carfentrazoneethyl in wheat plants using GC-MS/MS[J].Plant Prot,2012,38(1):115-119.
[20]刘晴,彭秧锡,欧晓明,等.乙螨唑在柑橘和土壤中的残留检测方法研究[J].精细化工中间体,2016,46(2):68-72.LIU Q,PENG Y X,OU X M,et al.Determination of etoxazole residue in citrus and soil by GC-NPD[J].Fine Chem Intermed,2016,46(2):68-72.
[21]官帅,张树秋,李慧冬,等.气相色谱-质谱法测定乙螨唑在苹果和土壤中的残留及消解动态[J].农药学学报,2015,17(4):480-485.GUAN S,ZHANG S Q,LI H D,et al.Residues and decline study of etoxazole in apple and soil by gas chromatography-mass spectrometry method[J].Chin J Pestic Sci,2015,17(4):480-485.
[22]李达,户庆云,张琦.多壁碳纳米管分散固相萃取净化-气相色谱三重四级杆质谱联用同时测定桂皮中10种有机磷农药[J].食品安全导刊,2017(31):69-71.LI D,HU Q Y,ZHANG Q.Simultaneous determination of 10organophosphorus pesticides in Cinnamomum cassia by GC-MS/MSwith multi-walled carbon nanotubes dispersed solid phase extraction purification[J].China Food Saf Mag,2017(31):69-71.
[23]CHEN Y,LOPEZ S,HAYWARD D G,et al.Determination of multiresidue pesticides in botanical dietary supplements using gas chromatography-triple-quadrupole mass spectrometry(GC-MS/MS)[J].J Agric Food Chem,2016,64(31):6125-6132.
[24]LI M M,LIU X G,DONG F S,et al.Simultaneous determination of cyflumetofen and its main metabolite residues in samples of plant and animal origin using multi-walled carbon nanotubes in dispersive solid-phase extraction and ultrahigh performance liquid chromatography-tandem mass spectrometry[J].J Chromatogr A,2013,1300:95-103.
[25]陈红平,刘新,王川丕,等.超高压液相色谱-串联质谱测定茶叶中10种极性农药残留[J].分析试验室,2011,30(08):48-53.CHEN H P,LIU X,WANG C P,et al.Determination of 10 polar pesticide residues in tea by ultra high pressure liquid chromatography tandem mass spectrometry[J].Chin J Anal Lab,2011,30(08):48-53.
[26]KWON H,LEHOTAY S J,GEIS-ASTEGGIANTE L.Variability of matrix effects in liquid and gas chromatography-mass spectrometry analysis of pesticide residues after QuEChERS sample preparation of different food crops[J].J Chromatogr A,2012,1270:235-245.
[27]RIMAYI C,ODUSANYA D,MTUNZI F,et al.Alternative calibration techniques for counteracting the matrix effects in GC-MS-SPE pesticide residue analysis-a statistical approach[J].Chemosphere,2015,118:35-43.
[28]SáNCHEZ-BRUNETE C,ALBERO B,MARTíN G,et al.Determination of pesticide residues by GC-MS using analyte protectants to counteract the matrix effect[J].Anal Sci,2005,21(11):1291-1296.
[29]RAHMAN M M,CHOI J H,ABD EL-ATY A M,et al.Pepper leaf matrix as a promising analyte protectant prior to the analysis of thermolabile terbufos and its metabolites in pepper using GC-FPD[J].Food Chem,2012,133(2):604-610.
[30]农药残留试验准则:NY/T 788-2004[S].北京:中国农业出版社,2004.Guideline on pesticide residue tials:NY/T 788-2004[S].Beijing:China Agriculture Press,2004.
[2]Chemical Book.Carfentrazone-ethyl[DB/OL].[2011-06-02].https://www.chemicalbook.com/.
[3]Chemical Book.Etoxazole[DB/OL].[2011-06-02].https://www.chemicalbook.com/.
[4]彭林,李明泽,任文瑾,等.香辛料生理功能的研究进展[J].食品与发酵工业,2012,38(2):157-162.PENG L,LI M Z,REN W J,et al.The advance of physiology functions of spices[J].Food Ferment Ind,2012,38(2):157-162.
[5]史奎春,林苏荣.香辛料在肉制品中的应用探讨[J].中国调味品,2010,35(4):39-42.SHI K C,LIN S R.The discussion on the application of spices in meat products[J].China Cond,2010,35(4):39-42.
[6]眭红卫,许睦农.天然香辛料中的植物化学物及其生理活性研究进展[J].中国调味品,2017,42(5):176-180.SUI H W,XU M N.Research progress on phytochemicals in natural spices and their physiological activities[J].China Cond,2017,42(5):176-180.
[7]PEPPIN J F,PAPPAGALLO M.Capsaicinoids in the treatment of neuropathic pain:a review[J].Ther Adv Neurol Disord,2014,7(1):22-32.
[8]SANTOS L,MARíN S,MATEO E M,et al.Mycobiota and cooccurrence of mycotoxins in Capsicum powder[J].Int J Food Microbiol,2011,151(3):270-276.
[9]ABOU-ARAB A A K,ABOU DONIA M A.Pesticide residues in some Egyptian spices and medicinal plants as affected by processing[J].Food Chem,2001,72(4):439-445.
[10]季颖,张宏军,刘丰茂.国际食品法典和中国农产品分类实用手册:水果、香草和香料[M].中国大百科全书出版社,2015.JI Y,ZHANG H J,LIU F M.Manual of crop classifications between codex and China:Fruits,herbs and spices[M].Encyclopedia of China Publishing House,2015.
[11]HUGGETT D B,BLOCK D S,KHAN I A,et al.Environmental contaminants in the botanical dietary supplement ginseng and potential human risk[J].Human Ecolog Risk Assess:An Int J,2000,6(5):767-776.
[12]HUGGETT D B,KHAN I A,ALLGOOD J C,et al.Organochlorine pesticides and metals in select botanical dietary supplements[J].Bull Environ Contam Toxicol,2001,66(2):150-155.
[13]DURGNAT J M,HEUSER J,ANDREY D,et al.Quality and safety assessment of ginseng extracts by determination of the contents of pesticides and metals[J].Food Addit Contam,2005,22(12):1224-1230.
[14]王峰恩,李瑞菊,方丽萍,等.乙氧氟草醚在大蒜和土壤中的残留动态[J].山东农业科学,2014,46(2):119-124.WANG F E,LI R J,FANG L P,et al.Residue dynamics of oxyfluorfen in garlic and soil[J].Shandong Agric Sci,2014,46(2):119-124.
[15]黄斌,曹坳程,李君,等.二甲戊灵和乙氧氟草醚在生姜上的残留分析及土壤中的消解动态[J].农药学学报,2017,19(1):125-130.HUANG B,CAO A C,LI J,et al.Analysis of pendimethalin and oxyfluorfen residues in Zingiber officinale Roscoe and their dissipation dynamics in soil[J].Chin J Pestic Sci,2017,19(1):125-130.
[16]方旭元,夏高峰,石巧巧,等.QuEChERS-GC-MS法检测当归中9种除草剂残留[J].华南农业大学学报,2017,38(6):79-83.FANG X Y,XIA G F,SHI Q Q,et al.Detection of nine herbicide residues in Angelica sinensis by QuEChERS-GC-MS[J].J South China Agric Univ,2017,38(6):79-83.
[17]张志勇,王冬兰,吴长付,等.唑草酮在水稻和稻田中的气相色谱检测[J].江苏农业学报,2011,27(1):195-198.ZHANG Z Y,WANG D L,WU C F,et al.Determination of herbicide carfentrazone-ethyl residues in rice and paddy with a gas chromatograph-election capture detector[J].Jiangsu J Agric Sci,2011,27(1):195-198.
[18]罗佳,沈睿至,杨长志.液相色谱-串质谱法测定大米中异唑草酮及代谢物残留量[J].食品安全质量检测学报,2015,6(7):2863-2868.LUO J,SHEN R Z,YANG C Z.Determination of isoxaflutole and its metabolites residues in rice by liquid chromatography-mass spectrometry/mass spectrometry[J].J Food Saf Qual,2015,6(7):2863-2868.
[19]张夏力,刘新刚,路彩红,等.气相色谱-串联质谱方法测定小麦中唑草酮的残留及消解动态[J].植物保护,2012,38(1):115-119.ZHANG X L,LIU X G,LU C H,et al.Degradation of carfentrazoneethyl in wheat plants using GC-MS/MS[J].Plant Prot,2012,38(1):115-119.
[20]刘晴,彭秧锡,欧晓明,等.乙螨唑在柑橘和土壤中的残留检测方法研究[J].精细化工中间体,2016,46(2):68-72.LIU Q,PENG Y X,OU X M,et al.Determination of etoxazole residue in citrus and soil by GC-NPD[J].Fine Chem Intermed,2016,46(2):68-72.
[21]官帅,张树秋,李慧冬,等.气相色谱-质谱法测定乙螨唑在苹果和土壤中的残留及消解动态[J].农药学学报,2015,17(4):480-485.GUAN S,ZHANG S Q,LI H D,et al.Residues and decline study of etoxazole in apple and soil by gas chromatography-mass spectrometry method[J].Chin J Pestic Sci,2015,17(4):480-485.
[22]李达,户庆云,张琦.多壁碳纳米管分散固相萃取净化-气相色谱三重四级杆质谱联用同时测定桂皮中10种有机磷农药[J].食品安全导刊,2017(31):69-71.LI D,HU Q Y,ZHANG Q.Simultaneous determination of 10organophosphorus pesticides in Cinnamomum cassia by GC-MS/MSwith multi-walled carbon nanotubes dispersed solid phase extraction purification[J].China Food Saf Mag,2017(31):69-71.
[23]CHEN Y,LOPEZ S,HAYWARD D G,et al.Determination of multiresidue pesticides in botanical dietary supplements using gas chromatography-triple-quadrupole mass spectrometry(GC-MS/MS)[J].J Agric Food Chem,2016,64(31):6125-6132.
[24]LI M M,LIU X G,DONG F S,et al.Simultaneous determination of cyflumetofen and its main metabolite residues in samples of plant and animal origin using multi-walled carbon nanotubes in dispersive solid-phase extraction and ultrahigh performance liquid chromatography-tandem mass spectrometry[J].J Chromatogr A,2013,1300:95-103.
[25]陈红平,刘新,王川丕,等.超高压液相色谱-串联质谱测定茶叶中10种极性农药残留[J].分析试验室,2011,30(08):48-53.CHEN H P,LIU X,WANG C P,et al.Determination of 10 polar pesticide residues in tea by ultra high pressure liquid chromatography tandem mass spectrometry[J].Chin J Anal Lab,2011,30(08):48-53.
[26]KWON H,LEHOTAY S J,GEIS-ASTEGGIANTE L.Variability of matrix effects in liquid and gas chromatography-mass spectrometry analysis of pesticide residues after QuEChERS sample preparation of different food crops[J].J Chromatogr A,2012,1270:235-245.
[27]RIMAYI C,ODUSANYA D,MTUNZI F,et al.Alternative calibration techniques for counteracting the matrix effects in GC-MS-SPE pesticide residue analysis-a statistical approach[J].Chemosphere,2015,118:35-43.
[28]SáNCHEZ-BRUNETE C,ALBERO B,MARTíN G,et al.Determination of pesticide residues by GC-MS using analyte protectants to counteract the matrix effect[J].Anal Sci,2005,21(11):1291-1296.
[29]RAHMAN M M,CHOI J H,ABD EL-ATY A M,et al.Pepper leaf matrix as a promising analyte protectant prior to the analysis of thermolabile terbufos and its metabolites in pepper using GC-FPD[J].Food Chem,2012,133(2):604-610.
[30]农药残留试验准则:NY/T 788-2004[S].北京:中国农业出版社,2004.Guideline on pesticide residue tials:NY/T 788-2004[S].Beijing:China Agriculture Press,2004.