固相萃取/超高效液相色谱-串联质谱法分析乙烯利在棉籽、棉叶和土壤中的残留
|
摘要
建立固相萃取/超高效液相色谱-串联质谱(SPE/UPLC-MS/MS)检测棉籽、棉叶和土壤中乙烯利残留的分析方法。各基质经甲醇-1%甲酸提取,Oasis MAX色谱柱净化,Cortecs Hilic超高效液相色谱柱进行分离,电喷雾负离子多重反应监测(MRM)模式进行测定。结果表明:在0. 02～1. 94 mg/L范围内,乙烯利在溶剂和各基质提取液中的峰面积与其对应的质量浓度间线性关系均良好,r~2≥0. 996 3;方法的检出限为0. 01mg/kg,定量下限为0. 02 mg/kg;在0. 02、0. 194、3. 88 mg/kg加标水平下,乙烯利在3种基质中的回收率为78. 3%～95. 1%,相对标准偏差(RSD)为1. 9%～5. 2%。该方法具有操作简单、重复性好、灵敏度高等特点,适用于棉籽、棉叶和土壤中乙烯利残留的检测。
A simple and sensitive method was developed for the determination of ethephon residues in cotton seed,cotton leaf and soil by solid phase extraction/ultrahigh performance liquid chromatography-tandem mass spectrometry( SPE/UPLC-MS/MS). The samples were extracted with methanol-0. 1% formic acid,purified with an Oasis MAX column,and separated on a Cortecs Hilic column,finally analyzed in multiple reaction monitoring( MRM) mode via negative electrospray ionization(ESI-). Under the optimum condition,the calibration curves for the analyte were linear in the range of 0. 02-1. 94 mg/L,with correlation coefficients( r~2) not less than 0. 996 3. The limits of detection and quantitation for ethephon were 0. 01 and 0. 02 mg/kg,respectively. At spiked levels of 0. 02,0. 194 and 3. 88 mg/kg,the recoveries for ethephon in three matrices were in the range of 78. 3%-95. 1% with relative standard deviations( RSDs) of 1. 9%-5. 2%. With the advantages of simplicity,high sensitivity,and good repeatability,the method could satisfy the requirements for determination of ethephon in cotton seed,cotton leaf and soil.
A simple and sensitive method was developed for the determination of ethephon residues in cotton seed,cotton leaf and soil by solid phase extraction/ultrahigh performance liquid chromatography-tandem mass spectrometry( SPE/UPLC-MS/MS). The samples were extracted with methanol-0. 1% formic acid,purified with an Oasis MAX column,and separated on a Cortecs Hilic column,finally analyzed in multiple reaction monitoring( MRM) mode via negative electrospray ionization(ESI-). Under the optimum condition,the calibration curves for the analyte were linear in the range of 0. 02-1. 94 mg/L,with correlation coefficients( r~2) not less than 0. 996 3. The limits of detection and quantitation for ethephon were 0. 01 and 0. 02 mg/kg,respectively. At spiked levels of 0. 02,0. 194 and 3. 88 mg/kg,the recoveries for ethephon in three matrices were in the range of 78. 3%-95. 1% with relative standard deviations( RSDs) of 1. 9%-5. 2%. With the advantages of simplicity,high sensitivity,and good repeatability,the method could satisfy the requirements for determination of ethephon in cotton seed,cotton leaf and soil.
引文
[1]Jiang W L,Ma Y,Ma X Y,Ma Y J,Li X Y.China Cotton(姜伟丽,马艳,马小艳,马亚杰,李希风.中国棉花),2013,40(10):11-14.
[2]Zou X,Liu A Y,Li R L.Cotton Sci.(邹茜,刘爱玉,李瑞莲.棉花科学),2015,37(10):25-29.
[3]Yang Z F,Bo C X,Xie L,Zhang Z L.Chin.J.Ind.Med.(杨治峰,薄存香,谢琳,张振玲.中国工业医学杂志),2013,26(1):41-43.
[4]Yang Z F.Study on Reproductive and Immune Toxicity of Male Mice Exposed to Ethephon.Jinan:Jinan University(杨治峰.乙烯利对雄性小鼠生殖毒性和免疫毒性作用的研究.济南:济南大学),2014.
[5]Song X Y,Yang T K.China Oils and Fats(宋晓燕,杨天奎.中国油脂),2000,25(6):45-47.
[6]Tang J Q,Wang Y P,Jiao Y.China Cotton Process.(唐金泉,王毓蓬,焦洋.中国棉花加工),2009,4:32-34.
[7]Zhao X L,Liu D C.China Oils and Fats(赵小龙,刘大川.中国油脂),2014,39(1):23-26.
[8]GB 2763-2016.Maximum Residue Limits for Pesticides in Food.National Food Safety Standard(食品中农药最大残留限量.食品安全国家标准).
[9]Yan J L,Wang L.Chin.J.Health Lab.Technol.(颜金良,王立.中国卫生检验杂志),2008,18(8):1544-1545.
[10]Li G P,Yu R,Shui R.Agrochemicals(李国平,于荣,税融.农药),2011,50(8):580-581.
[11]Qin X,Xu Y M,Sun Y,Zhao L J,Wang Q.Environ.Sci.Technol.(秦旭,徐应明,孙扬,赵立杰,王倩.环境科学与技术),2015,38(8):105-109.
[12]Shang Z,Zhang Y,Wang M Y,Wang M,Zhang C H.Food Ferment Ind.(尚政,张宇,王明月,王萌,章程辉.食品与发酵工业),2014,40(9):152-156.
[13]Cao H E,Xia H,Lu P,Yu P.Agrochemicals(曹洪恩,夏慧,卢平,于平.农药),2011,50(4):286-288.
[14]Chen K Y,Wang Y L,Shen X Z,Ju X,Hu M,Liu Y M,Zhu J H.Chin.J.Pestic.Sci.(陈克云,王艳丽,沈祥震,鞠香,胡梅,刘艳明,祝建华.农药学学报),2018,(4):495-499.
[15]Wu F Q,Jin B L,Chen B,Chen P J,Xiao F.Chin.Agric.Sci.Bull.(吴凤琪,靳保辉,陈波,陈沛金,肖锋.中国农学通报),2010,26(15):115-119.
[16]Xie W,Shi Y Z,Hou J B,Huang C Q,Zhao D,Pan L L,Dong S Z.Chin.J.Chromatogr.(谢文,史颖珠,侯建波,黄超群,赵栋,潘璐璐,董锁拽.色谱),2014,32(2):179-183.
[17]Su Y Z,Li Y M,Shang S,Lei H Q,Hu J M,Luo Q.J.Instrum.Anal.(粟有志,李艳美,尚爽,雷红琴,胡建民,罗琼.分析测试学报),2013,32(10):1237-1241.
[18]Hanot V,Joly L,Bonnechère A,Loco J V.Food Anal.Methods,2015,8(2):524-530.
[19]Li R,Chu D K,Zhang P J,Gao Y Q,Huang S Y.J.Instrum.Anal.(李蓉,储大可,张朋杰,高永清,黄思允.分析测试学报),2015,34(5):502-511.
[20]Li P P,Cheng J,Le Y.J.Instrum.Anal.(李萍萍,程景,乐渊.分析测试学报),2015,34(4):421-427.
[21]Economou A,Botitsi H,Antoniou S,Tsipi D.J.Chromatogr.A,2009,1216(31):5856-5867.
[22]Lehotay S J,Son K A,Kwon H,Koesukwiwat U,Fu W,Mastovska K,Hoh E,Leepipatpiboon N.J.Chromatogr.A,2010,1217(16):2548-2560.
[23]NY/T 788-2004.Guideline on Pesticide Residue Trials.Beijing:Chinese Agricultural Press(农药残留试验准则.北京:中国农业出版社),2004.
[2]Zou X,Liu A Y,Li R L.Cotton Sci.(邹茜,刘爱玉,李瑞莲.棉花科学),2015,37(10):25-29.
[3]Yang Z F,Bo C X,Xie L,Zhang Z L.Chin.J.Ind.Med.(杨治峰,薄存香,谢琳,张振玲.中国工业医学杂志),2013,26(1):41-43.
[4]Yang Z F.Study on Reproductive and Immune Toxicity of Male Mice Exposed to Ethephon.Jinan:Jinan University(杨治峰.乙烯利对雄性小鼠生殖毒性和免疫毒性作用的研究.济南:济南大学),2014.
[5]Song X Y,Yang T K.China Oils and Fats(宋晓燕,杨天奎.中国油脂),2000,25(6):45-47.
[6]Tang J Q,Wang Y P,Jiao Y.China Cotton Process.(唐金泉,王毓蓬,焦洋.中国棉花加工),2009,4:32-34.
[7]Zhao X L,Liu D C.China Oils and Fats(赵小龙,刘大川.中国油脂),2014,39(1):23-26.
[8]GB 2763-2016.Maximum Residue Limits for Pesticides in Food.National Food Safety Standard(食品中农药最大残留限量.食品安全国家标准).
[9]Yan J L,Wang L.Chin.J.Health Lab.Technol.(颜金良,王立.中国卫生检验杂志),2008,18(8):1544-1545.
[10]Li G P,Yu R,Shui R.Agrochemicals(李国平,于荣,税融.农药),2011,50(8):580-581.
[11]Qin X,Xu Y M,Sun Y,Zhao L J,Wang Q.Environ.Sci.Technol.(秦旭,徐应明,孙扬,赵立杰,王倩.环境科学与技术),2015,38(8):105-109.
[12]Shang Z,Zhang Y,Wang M Y,Wang M,Zhang C H.Food Ferment Ind.(尚政,张宇,王明月,王萌,章程辉.食品与发酵工业),2014,40(9):152-156.
[13]Cao H E,Xia H,Lu P,Yu P.Agrochemicals(曹洪恩,夏慧,卢平,于平.农药),2011,50(4):286-288.
[14]Chen K Y,Wang Y L,Shen X Z,Ju X,Hu M,Liu Y M,Zhu J H.Chin.J.Pestic.Sci.(陈克云,王艳丽,沈祥震,鞠香,胡梅,刘艳明,祝建华.农药学学报),2018,(4):495-499.
[15]Wu F Q,Jin B L,Chen B,Chen P J,Xiao F.Chin.Agric.Sci.Bull.(吴凤琪,靳保辉,陈波,陈沛金,肖锋.中国农学通报),2010,26(15):115-119.
[16]Xie W,Shi Y Z,Hou J B,Huang C Q,Zhao D,Pan L L,Dong S Z.Chin.J.Chromatogr.(谢文,史颖珠,侯建波,黄超群,赵栋,潘璐璐,董锁拽.色谱),2014,32(2):179-183.
[17]Su Y Z,Li Y M,Shang S,Lei H Q,Hu J M,Luo Q.J.Instrum.Anal.(粟有志,李艳美,尚爽,雷红琴,胡建民,罗琼.分析测试学报),2013,32(10):1237-1241.
[18]Hanot V,Joly L,Bonnechère A,Loco J V.Food Anal.Methods,2015,8(2):524-530.
[19]Li R,Chu D K,Zhang P J,Gao Y Q,Huang S Y.J.Instrum.Anal.(李蓉,储大可,张朋杰,高永清,黄思允.分析测试学报),2015,34(5):502-511.
[20]Li P P,Cheng J,Le Y.J.Instrum.Anal.(李萍萍,程景,乐渊.分析测试学报),2015,34(4):421-427.
[21]Economou A,Botitsi H,Antoniou S,Tsipi D.J.Chromatogr.A,2009,1216(31):5856-5867.
[22]Lehotay S J,Son K A,Kwon H,Koesukwiwat U,Fu W,Mastovska K,Hoh E,Leepipatpiboon N.J.Chromatogr.A,2010,1217(16):2548-2560.
[23]NY/T 788-2004.Guideline on Pesticide Residue Trials.Beijing:Chinese Agricultural Press(农药残留试验准则.北京:中国农业出版社),2004.