超高效液相色谱-三重四极杆串联质谱法分析茶叶中联苯肼酯残留与风险评估
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摘要
建立了QuEChERS分散固相萃取技术净化茶叶,超高效液相色谱-三重四极杆串联质谱(UPLC-MS/MS)法测定茶叶鲜叶和成茶中联苯肼酯残留的分析方法。利用该方法研究了43%联苯肼酯悬浮剂在茶叶鲜叶生长中的残留降解规律,并对其在茶叶饮用中的安全性进行了风险评估。结果表明,联苯肼酯在0.002 5～1.00mg/L浓度范围内的线性关系良好,相关系数r为0.994 2。在0.020、0.20、2.0mg/kg添加浓度下,绿茶中联苯肼酯的平均回收率分别为79.3%、88.6%、103.4%,相对标准偏差(RSD)分别为6.1%、5.9%、3.7%;红茶中联苯肼酯的平均回收率分别为79.3%、82.6%、103.3%,RSD分别为6.7%、4.5%、4.7%;鲜叶中联苯肼酯的平均回收率分别为91.1%、94.4%、91.0%,RSD分别为4.3%、3.8%、7.6%。方法检出限(LOD,S/N=3)为1.5μg/kg,定量限(LOQ,S/N=10)为5μg/kg。由于不同地区和时间的茶叶生长稀释作用、气候温度的不同,43%联苯肼酯悬浮剂在茶鲜叶生长中半衰期为1.4～2.9天;按照推荐剂量和1.5倍推荐剂量施药1～2次,结果表明,10天后成茶中的联苯肼酯残留量均小于5mg/kg。根据风险评估结果,建议我国茶叶中联苯肼酯最大残留限量(MRL)值可设为5mg/kg。
A convenient and sensitive residue analysis method for bifenazate in fresh tea leaves and made tea was developed and validated by ultra high performance liquid chromatography coupled with triple quadrupole tandem mass spectrometry(UPLC-MS/MS)followed by dispersive solid phase extraction cleanup.The calibration curve is linear over the concentration of 0.002 5-1.00 mg/L for bifenazate with the correlation coefficient(r)of 0.994 2.The average recoveries of bifenazate at three spiked concentration levels(0.020,0.20,2.0 mg/kg)in green tea sample matrixes are 79.3%,88.6% and103.4% with the relative standard deviations(RSDs)of 6.1%,5.9% and 3.7%,in black tea sample matrixes are 79.3%,82.6%and 103.3% with RSDs of 6.7%,4.5%and 4.7%,in fresh tea leaves are 91.1%,94.4% and 91.0% with RSDs of 4.3%,3.8%and 7.6%,respectively.The limit of detection(LOD,S/N=3)of befenazate is1.5μg/kg,and the limit of quantitation(LOQ,S/N=10)of bifenazate in different matrixes is 5μg/kg.This proposed method was successfully applied in the degradation and final residue study of 43% bifenazate suspension concentrate(SC)in the field treatment experiment.The degradation half-life time of bifenazate in fresh tea leaves is in the range of 1.4-2.9 days.According to the recommended dose and the 1.5 times of recommended dose after 1-2 times,the results show that the final residual amount of bifenazate in made tea after 10 days is less than 5 mg/kg.According to the results of risk assessment,it is suggested that the maximum residue limit(MRL)of bifenazate in tea can be set to 5 mg/kg for tea drinking with the pre-harvest intervals(PHI)of 10 days,this is a safety threshold for the human body.
A convenient and sensitive residue analysis method for bifenazate in fresh tea leaves and made tea was developed and validated by ultra high performance liquid chromatography coupled with triple quadrupole tandem mass spectrometry(UPLC-MS/MS)followed by dispersive solid phase extraction cleanup.The calibration curve is linear over the concentration of 0.002 5-1.00 mg/L for bifenazate with the correlation coefficient(r)of 0.994 2.The average recoveries of bifenazate at three spiked concentration levels(0.020,0.20,2.0 mg/kg)in green tea sample matrixes are 79.3%,88.6% and103.4% with the relative standard deviations(RSDs)of 6.1%,5.9% and 3.7%,in black tea sample matrixes are 79.3%,82.6%and 103.3% with RSDs of 6.7%,4.5%and 4.7%,in fresh tea leaves are 91.1%,94.4% and 91.0% with RSDs of 4.3%,3.8%and 7.6%,respectively.The limit of detection(LOD,S/N=3)of befenazate is1.5μg/kg,and the limit of quantitation(LOQ,S/N=10)of bifenazate in different matrixes is 5μg/kg.This proposed method was successfully applied in the degradation and final residue study of 43% bifenazate suspension concentrate(SC)in the field treatment experiment.The degradation half-life time of bifenazate in fresh tea leaves is in the range of 1.4-2.9 days.According to the recommended dose and the 1.5 times of recommended dose after 1-2 times,the results show that the final residual amount of bifenazate in made tea after 10 days is less than 5 mg/kg.According to the results of risk assessment,it is suggested that the maximum residue limit(MRL)of bifenazate in tea can be set to 5 mg/kg for tea drinking with the pre-harvest intervals(PHI)of 10 days,this is a safety threshold for the human body.
引文
[1]王元元,高宁,李辉辉,冯根锋,肖亚平.杀螨剂联苯肼酯的合成研究[J].精细化工中间体,2011,41(6):13-15.WANG Yuanyuan,GAO Ning,LI Huihui,FENG Genfeng,XIAO Yaping.Study on synthesis of miticide bifenazat[J].Fine Chemical Intermediates,2011,41(6):13-15(in Chinese).
[2]张娇娇.33%联苯肼酯·阿维菌素悬浮剂在柑桔和土壤中的残留及其对品质的影响[D].重庆:西南大学,2017.
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[4]戴魏,李晓刚,陈力华,聂思桥,任竞,梁骥,付启明,张贵群,刘义珂,刘金胜,刘力.联苯肼酯在柑橘及其土壤中的残留分析方法[J].农药学学报,2012,14(6):677-680.DAI Wei,LI Xiaogang,CHEN Lihua,NIESiqiao,REN Jing,LIANG Ji,FU Qiming,ZHANG Guiqun,LIU Yike,LIU Jinsheng,LIULi.Residue analysis of bifenazate in citrus and soil[J].Chinese Journal of Pesticide Science,2012,14(6):677-680(in Chinese).
[5]谢道燕,沈雪凤,杨振国,柴建萍,倪婧,罗雁婕.联苯肼酯悬浮剂的杀螨活性测试及对家蚕的安全性评价[J].蚕业科学,2017,43(4):631-637.XIE Daoyan,SHEN Xuefeng,YANG Zhenguo,CHAI Jianping,NI Jing,LUO Yanjie.Acaricidal activity of bifenazate suspension concentrate and safety evaluation to bombyx mori[J].Science of Sericulture,2017,43(4):631-637(in Chinese).
[6]刘学卿,王洪涛,王英姿.48%联苯肼酯对3种苹果害螨的田间防治效果[J].中国果树,2014,(6):53-55,75.LIU Xueqing,WANG Hongtao,WANG Yingzi.The field contral effect of 43%bifenazate to there kinds of apple mite[J].China Fruits,2014,(6):53-55,75(in Chinese).
[7]KUMARI A,KUMAR A,TEWARY D K,NEDDA G.Field evaluation of bifenazate(acramite 50WP)for control of tea mites[J].Munis Entomology&Zoology,2012,7(2):780-786.
[8]GOTOH T,KITASHIMA Y,GOKA K,NA-GATA T.Susceptibility of the red spider mite,Oligonychus coffeae(Acari:Tetranychidae),to acaricides on tea plants in Japan[J].International Journal of Acarology,2001,27(4):303-307.
[9]中华人民共和国农业农村部农药检定所.农药最大残留限量数据库[EB/OL].http:∥202.127.42.84/tbt-sps/mrlsdb/mrlsdb.do.
[10]PARK E H,GO M J,CHO M S,JIN G M,SANG Y M.Development of analytical method and monitoring for bifenazate in commercial agricultural products[J].The Korean Journal of Pesticide Science,2010,14(1):21-29.
[11]张月,韩丙军,赵方方.超高效液相色谱-三重四极杆串联质谱法测定木瓜中联苯肼酯及其代谢产物[J].食品科学,2015,36(24):270-273.ZHANG Yue,HAN Bingjun,ZHAO Fangfang.Determining of bifenazate and its metabolite residues in papaya by ultra performance liquid chromatography-tandem mass spectrometry[J].Food Science,2015,36(24):270-273(in Chinese).
[12]欧阳文森,杨仁斌,王洁,聂红英,杨友才.联苯肼酯在柑橘上的残留动态及其标准溶液的贮存稳定性[J].果树学报,2016,33(11):1 431-1 438.OUYANG Wensen,YANG Renbin,WANG Jie,NIE Hongying,YANG Youcai.A study on the residual dynamics of bifenazate in citrus and the storage stability of its standard solutions[J].Journal of Fruit Science,2016,33(11):1 431-1 438(in Chinese).
[13]SATHESHKUMAR A,SENTHURPANDIANV K,SHANMUGASELVAN V A.Dissipation kinetics of bifenazate in tea under tropical conditions[J].Food Chemistry,2014,145(7):1 092-1 096.
[14]肖峥,李海燕,施慧娟,李碧澄.联苯肼酯43%悬浮剂的高效液相色谱分析[J].农药科学与管理,2010,31(8):40-42.XIAO Zheng,LI Haiyan,SHI Huijuan,LIBicheng.Analytical method for the determination of bifenazate 43%SC by HPLC[J].Pesticide Science and Administration,2010,31(8):40-42(in Chinese).
[15]叶艳明,孙克,张敏恒.联苯肼酯分析方法述评[J].农药,2013,52(5):386-388.YE Yanming,SUN Ke,ZHANG Minheng.Areview of analysis methods of bifenazate[J].Agrochemicals,2013,52(5):386-388(in Chinese).
[16]韩凤,杨仁斌,傅强,韩增,杨玉梅.联苯肼酯在柑橘和土壤中的残留分析方法[J].农药,2013,52(2):122-124.HAN Feng,YANG Renbin,FU Qiang,HANZeng,YANG Yumei.Residue analysis of bifenazate in citrus and soil[J].Agrochemicals,2013,52(2):122-124(in Chinese).
[17]ANASTASSIADES M,LEHOTAY S J,STA-JNBAHER D,SCHENCK F J.Fast and easy multiresidue method employing acetonitrile extraction/partitioning and“dispersive solid-phase extraction”for the determination of pesticide residues in produce[J].Journal of AOAC International,2003,86(2):412-431.
[18]LEHOTAY S J,SON K A,KWON H,KOE-SUKWIWAT U,FU W S,MASTOVSKA K,HOH E,LEEPIPATPIBOON N.Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in fruits and vegetables[J].Journal of Chromatography A,2010,1 217(16):2 548-2 560.
[19]PAYAP,ANASTASSIADES M,MACK D,SIGALOVA I,TASDELEN B,OLIVA J,BAR-BA A.Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe(QuEChERS)pesticide multiresidue method in combination with gas and liquid chromatography and tandem mass spectrometric detection[J].Analytical and Bioanlytical Chemistry,2007,389(6):1 697-1 714.
[20]CUNHA S C,LEHOTAY S J,MASTOVSKAK,FERNANDES J O,BEATRIZ M,OLIVEIRAP P.Evaluation of the QuEChERS sample preparation approach for the analysis of pesticide residues in olives[J].Journal of Separation Science,2007,30(4):620-632.
[21]张新忠,罗逢健,刘光明,楼正云,陈宗懋.超高效液相色谱-串联质谱法测定茶叶和土壤中丁醚脲及其代谢物的残留[J].分析化学,2011,39(9):1 329-1 335.ZHANG Xinzhong,LUO Fengjian,LIU Guangming,LOU Zhengyun,CHEN Zongmao.Determination of diafenthiuron and its metabolites in tea and soil by ultra performance liquid chromatography-electrospray ionization tandem mass spectrometry[J].Chinese Journal of Analytical Chemistry,2011,39(9):1 329-1 335(in Chinese).
[22]张新忠,罗逢健,陈宗懋,刘光明,楼正云.分散固相萃取净化超高效液相色谱串联质谱法研究茶叶和茶汤中茚虫威残留降解规律[J].分析测试学报,2013,32(1):1-8.ZHANG Xinzhong,LUO Fengjian,CHEN Zongmao,LIU Guangming,LOU Zhengyun.Study of indoxacarb residue degradation in tea and tea infusion by ultra high performance liquid chromatography coupled with tandem mass spectrometry after dispersive solid phase extraction cleanup[J].Journal of Instrumental Analysis,2013,32(1):1-8(in Chinese).
[2]张娇娇.33%联苯肼酯·阿维菌素悬浮剂在柑桔和土壤中的残留及其对品质的影响[D].重庆:西南大学,2017.
[3]何建红,胡选祥,赵帅锋,柯汉云,吴燕君,赵丽.联苯肼脂在草莓上的残留降解及其安全使用[J].浙江农业学报,2014,26(5):1 268-1 272.HE Jianhong,HU Xuanxiang,ZHAO Shuaifeng,KE Hanyun,WU Yanjun,ZHAO Li.Degradation of bifenazate residue in strawberry and its safe application[J].Acta Agriculturae Zhejiangensis,2014,26(5):1 268-1 272(in Chinese).
[4]戴魏,李晓刚,陈力华,聂思桥,任竞,梁骥,付启明,张贵群,刘义珂,刘金胜,刘力.联苯肼酯在柑橘及其土壤中的残留分析方法[J].农药学学报,2012,14(6):677-680.DAI Wei,LI Xiaogang,CHEN Lihua,NIESiqiao,REN Jing,LIANG Ji,FU Qiming,ZHANG Guiqun,LIU Yike,LIU Jinsheng,LIULi.Residue analysis of bifenazate in citrus and soil[J].Chinese Journal of Pesticide Science,2012,14(6):677-680(in Chinese).
[5]谢道燕,沈雪凤,杨振国,柴建萍,倪婧,罗雁婕.联苯肼酯悬浮剂的杀螨活性测试及对家蚕的安全性评价[J].蚕业科学,2017,43(4):631-637.XIE Daoyan,SHEN Xuefeng,YANG Zhenguo,CHAI Jianping,NI Jing,LUO Yanjie.Acaricidal activity of bifenazate suspension concentrate and safety evaluation to bombyx mori[J].Science of Sericulture,2017,43(4):631-637(in Chinese).
[6]刘学卿,王洪涛,王英姿.48%联苯肼酯对3种苹果害螨的田间防治效果[J].中国果树,2014,(6):53-55,75.LIU Xueqing,WANG Hongtao,WANG Yingzi.The field contral effect of 43%bifenazate to there kinds of apple mite[J].China Fruits,2014,(6):53-55,75(in Chinese).
[7]KUMARI A,KUMAR A,TEWARY D K,NEDDA G.Field evaluation of bifenazate(acramite 50WP)for control of tea mites[J].Munis Entomology&Zoology,2012,7(2):780-786.
[8]GOTOH T,KITASHIMA Y,GOKA K,NA-GATA T.Susceptibility of the red spider mite,Oligonychus coffeae(Acari:Tetranychidae),to acaricides on tea plants in Japan[J].International Journal of Acarology,2001,27(4):303-307.
[9]中华人民共和国农业农村部农药检定所.农药最大残留限量数据库[EB/OL].http:∥202.127.42.84/tbt-sps/mrlsdb/mrlsdb.do.
[10]PARK E H,GO M J,CHO M S,JIN G M,SANG Y M.Development of analytical method and monitoring for bifenazate in commercial agricultural products[J].The Korean Journal of Pesticide Science,2010,14(1):21-29.
[11]张月,韩丙军,赵方方.超高效液相色谱-三重四极杆串联质谱法测定木瓜中联苯肼酯及其代谢产物[J].食品科学,2015,36(24):270-273.ZHANG Yue,HAN Bingjun,ZHAO Fangfang.Determining of bifenazate and its metabolite residues in papaya by ultra performance liquid chromatography-tandem mass spectrometry[J].Food Science,2015,36(24):270-273(in Chinese).
[12]欧阳文森,杨仁斌,王洁,聂红英,杨友才.联苯肼酯在柑橘上的残留动态及其标准溶液的贮存稳定性[J].果树学报,2016,33(11):1 431-1 438.OUYANG Wensen,YANG Renbin,WANG Jie,NIE Hongying,YANG Youcai.A study on the residual dynamics of bifenazate in citrus and the storage stability of its standard solutions[J].Journal of Fruit Science,2016,33(11):1 431-1 438(in Chinese).
[13]SATHESHKUMAR A,SENTHURPANDIANV K,SHANMUGASELVAN V A.Dissipation kinetics of bifenazate in tea under tropical conditions[J].Food Chemistry,2014,145(7):1 092-1 096.
[14]肖峥,李海燕,施慧娟,李碧澄.联苯肼酯43%悬浮剂的高效液相色谱分析[J].农药科学与管理,2010,31(8):40-42.XIAO Zheng,LI Haiyan,SHI Huijuan,LIBicheng.Analytical method for the determination of bifenazate 43%SC by HPLC[J].Pesticide Science and Administration,2010,31(8):40-42(in Chinese).
[15]叶艳明,孙克,张敏恒.联苯肼酯分析方法述评[J].农药,2013,52(5):386-388.YE Yanming,SUN Ke,ZHANG Minheng.Areview of analysis methods of bifenazate[J].Agrochemicals,2013,52(5):386-388(in Chinese).
[16]韩凤,杨仁斌,傅强,韩增,杨玉梅.联苯肼酯在柑橘和土壤中的残留分析方法[J].农药,2013,52(2):122-124.HAN Feng,YANG Renbin,FU Qiang,HANZeng,YANG Yumei.Residue analysis of bifenazate in citrus and soil[J].Agrochemicals,2013,52(2):122-124(in Chinese).
[17]ANASTASSIADES M,LEHOTAY S J,STA-JNBAHER D,SCHENCK F J.Fast and easy multiresidue method employing acetonitrile extraction/partitioning and“dispersive solid-phase extraction”for the determination of pesticide residues in produce[J].Journal of AOAC International,2003,86(2):412-431.
[18]LEHOTAY S J,SON K A,KWON H,KOE-SUKWIWAT U,FU W S,MASTOVSKA K,HOH E,LEEPIPATPIBOON N.Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in fruits and vegetables[J].Journal of Chromatography A,2010,1 217(16):2 548-2 560.
[19]PAYAP,ANASTASSIADES M,MACK D,SIGALOVA I,TASDELEN B,OLIVA J,BAR-BA A.Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe(QuEChERS)pesticide multiresidue method in combination with gas and liquid chromatography and tandem mass spectrometric detection[J].Analytical and Bioanlytical Chemistry,2007,389(6):1 697-1 714.
[20]CUNHA S C,LEHOTAY S J,MASTOVSKAK,FERNANDES J O,BEATRIZ M,OLIVEIRAP P.Evaluation of the QuEChERS sample preparation approach for the analysis of pesticide residues in olives[J].Journal of Separation Science,2007,30(4):620-632.
[21]张新忠,罗逢健,刘光明,楼正云,陈宗懋.超高效液相色谱-串联质谱法测定茶叶和土壤中丁醚脲及其代谢物的残留[J].分析化学,2011,39(9):1 329-1 335.ZHANG Xinzhong,LUO Fengjian,LIU Guangming,LOU Zhengyun,CHEN Zongmao.Determination of diafenthiuron and its metabolites in tea and soil by ultra performance liquid chromatography-electrospray ionization tandem mass spectrometry[J].Chinese Journal of Analytical Chemistry,2011,39(9):1 329-1 335(in Chinese).
[22]张新忠,罗逢健,陈宗懋,刘光明,楼正云.分散固相萃取净化超高效液相色谱串联质谱法研究茶叶和茶汤中茚虫威残留降解规律[J].分析测试学报,2013,32(1):1-8.ZHANG Xinzhong,LUO Fengjian,CHEN Zongmao,LIU Guangming,LOU Zhengyun.Study of indoxacarb residue degradation in tea and tea infusion by ultra high performance liquid chromatography coupled with tandem mass spectrometry after dispersive solid phase extraction cleanup[J].Journal of Instrumental Analysis,2013,32(1):1-8(in Chinese).