氟唑磺隆、甲基二磺隆、炔草酯和炔草酸在小麦中的残留分析
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摘要
以QuEChERS前处理方法为基础,采用高效液相色谱-串联质谱(HPLC-MS/MS)检测技术,建立了除草剂氟唑磺隆、甲基二磺隆、炔草酯及其代谢物炔草酸4种化合物在小麦中残留的分析方法。麦粒样品中加入5 mL体积分数为0.1%的甲酸水溶液后,以10 mL乙腈提取,用50 mg C_(18)与100 mg无水硫酸镁净化;麦秆样品中加入10 mL体积分数为2%的甲酸水溶液后,以10 mL乙腈提取,用100 mg C_(18)与200 mg无水硫酸镁净化。结果表明:氟唑磺隆在0.005、0.01和0.1 mg/kg,甲基二磺隆在0.01、0.02和0.1 mg/kg,炔草酯和炔草酸在0.05、0.1和0.5 mg/kg添加水平下,4种化合物在麦粒中的回收率在76%～97%之间,在麦秆中的回收率在83%～102%之间,相对标准偏差均小于10%,r> 0.99。4种化合物在麦粒和麦秆中的定量限分别为:氟唑磺隆0.005 mg/kg,甲基二磺隆0.01 mg/kg,炔草酯和炔草酸均为0.05 mg/kg。该方法可满足小麦样品中4种化合物的残留分析要求。
A modified QuEChERS method was developed and validated for the determination of flucarbazone-sodium, mesosulfuron-methyl, clodinafop-propargyl and clodinafop in wheat kernel and straw by high-performance liquid chromatography coupled with tandem mass spectrometry(HPLCMS/MS). The wheat kernel was extracted with 10 mL acetonitrile, after 5 mL 0.1% formic acid solution was added to improve the extraction efficiency. Samples were cleaned up by 50 mg C_(18) and 100 mg anhydrous MgSO_4. After adding 10 mL 2% formic acid solution, the wheat straw was extracted with 10 mL acetonitrile. 100 mg C18 and 200 mg anhydrous MgSO_4 were used to clean up the samples. The average recoveries of four compounds in wheat kernel and wheat straw were 76%-97% and 83%-102%,respectively, with the relative standard deviations(RSDs) for those four compounds less than 10%.Good linearity was achieved with determination coefficients higher than 0.99. The limit of quantity(LOQ) is 0.005 mg/kg for flucarbazone-sodium, 0.01 mg/kg for mesosulfuron-methyl, 0.05 mg/kg for clodinafop-propargyl and clodinafop. This method meets the requirements of pesticide residue analysis.
A modified QuEChERS method was developed and validated for the determination of flucarbazone-sodium, mesosulfuron-methyl, clodinafop-propargyl and clodinafop in wheat kernel and straw by high-performance liquid chromatography coupled with tandem mass spectrometry(HPLCMS/MS). The wheat kernel was extracted with 10 mL acetonitrile, after 5 mL 0.1% formic acid solution was added to improve the extraction efficiency. Samples were cleaned up by 50 mg C_(18) and 100 mg anhydrous MgSO_4. After adding 10 mL 2% formic acid solution, the wheat straw was extracted with 10 mL acetonitrile. 100 mg C18 and 200 mg anhydrous MgSO_4 were used to clean up the samples. The average recoveries of four compounds in wheat kernel and wheat straw were 76%-97% and 83%-102%,respectively, with the relative standard deviations(RSDs) for those four compounds less than 10%.Good linearity was achieved with determination coefficients higher than 0.99. The limit of quantity(LOQ) is 0.005 mg/kg for flucarbazone-sodium, 0.01 mg/kg for mesosulfuron-methyl, 0.05 mg/kg for clodinafop-propargyl and clodinafop. This method meets the requirements of pesticide residue analysis.
引文
[1]范添乐,魏芩杰,陈小军,等.氟唑磺隆在野燕麦中的内吸传导特性[J].农药学学报,2018,20(6):1-5.FAN T L,WEI Q J,CHEN X J,et al.Uptake and translocation of flucarbazone-sodium in Avena fatua[J].Chin J Pestic Sci,2018,20(6):1-5.
[2]ELIASON R,SCHOENAU J J,SZMIGIELSKI A M,et al.Phytotoxicity and persistence of flucarbazone-sodium in soil[J].Weed Sci,2004,52(5):857-862.
[3]VAZAN S,OVEISI M,BAZIAR S.Efficiency of mesosulfuronmethyl and clodinafop-propargyl dose for the control of Lolium perenne in wheat[J].Crop Prot,2011,30(6):592-597.
[4]GUI W J,DONG Q X,ZHOU S L,et al.Waterborne exposure to clodinafop-propargyl disrupts the posterior and ventral development of zebrafish embryos[J].Environ Toxicol Chem,2011,30(7):1576-1581.
[5]食品中农药最大残留限量:GB 2763-2016[S].北京:中国标准出版社,2017.Maximum residue limits for pesticides in food:GB 2763-2016[S].Beijing:Standards Press of China,2017.
[6]侯红敏,乔琳,刘惠敏,等.高效液相色谱法测定小麦中氟唑磺隆残留量[J].现代农药,2015,14(1):35-36,43.HOU H M,QIAO L,LIU H M,et al.Determination offlucarbazonesodium residue in wheat by HPLC[J].Mod Agrochem,2015,14(1):35-36,43.
[7]段劲生,王梅,孙明娜,等.高效液相色谱法测定小麦和土壤中炔草酯及其代谢物炔草酸的残留量[J].农药学学报,2013,15(1):121-124.DUAN J S,WANG M,SUN M N,et al.Determination of clodinafoppropargyl and its metabolite clodinafop in wheat and soil by high performance liquid chromatography[J].Chin J Pestic Sci,2013,15(1):121-124.
[8]XUE J,LI H,LIU F,et al.Determination and dissipation of flucarbazone-sodium and its metabolite in wheat and soils by LC-MS/MS[J].Inter J Environ Anal Chem,2014,94(5):479-492.
[9]NI Y X,YANG H,ZHANG H T,et al.Analysis of four sulfonylurea herbicides in cereals using modified Quick,Easy,Cheap,Effective,Rugged,and Safe sample preparation method coupled with liquid chromatography-tandem mass spectrometry[J].J Chromatogr A,2018,1537:27-34.
[10]张少军,杨更亮,郑振山,等.甲基二磺隆在小麦和土壤中的残留动态研究[J].河北农业大学学报,2009,32(3):12-16.ZHANG S J,YANG G L,ZHENG Z S,et al.Study on the residue dynamics of mesosulfuron-methyl in wheat and soil[J].J Agric Univ Hebei,2009,32(3):12-16.
[11]GUAN W B,MA Y Q,ZHANG H Y.Dissipation of clodinafoppropargyl and its metabolite in wheat field ecosystem[J].Bull Environ Contam Toxicol,2013,90(6):750-755.
[12]ANASTASSIADES M,LEHOTAY S J,?TAJNBAHER D,et al.Fast and easy multiresidue method employing acetonitrile extraction/partitioning and“dispersive solid-phase extraction”for the determination of pesticide residues in produce[J].J AOAC Inter,2003,86(2):412-431.
[13]International Union of Pure and Applied Chemistry[DB/OL].[2018-09-13].http://sitem.herts.ac.uk/aeru/iupac/Reports/441.htm.
[14]农作物中农药残留试验准则:NY/T 788-2018[S].北京:中国农业出版社,2018.Guideline for the testing of pesticide residues in crops:NY/T788-2018[S].Beijing:China Agriculture Press,2018.
[2]ELIASON R,SCHOENAU J J,SZMIGIELSKI A M,et al.Phytotoxicity and persistence of flucarbazone-sodium in soil[J].Weed Sci,2004,52(5):857-862.
[3]VAZAN S,OVEISI M,BAZIAR S.Efficiency of mesosulfuronmethyl and clodinafop-propargyl dose for the control of Lolium perenne in wheat[J].Crop Prot,2011,30(6):592-597.
[4]GUI W J,DONG Q X,ZHOU S L,et al.Waterborne exposure to clodinafop-propargyl disrupts the posterior and ventral development of zebrafish embryos[J].Environ Toxicol Chem,2011,30(7):1576-1581.
[5]食品中农药最大残留限量:GB 2763-2016[S].北京:中国标准出版社,2017.Maximum residue limits for pesticides in food:GB 2763-2016[S].Beijing:Standards Press of China,2017.
[6]侯红敏,乔琳,刘惠敏,等.高效液相色谱法测定小麦中氟唑磺隆残留量[J].现代农药,2015,14(1):35-36,43.HOU H M,QIAO L,LIU H M,et al.Determination offlucarbazonesodium residue in wheat by HPLC[J].Mod Agrochem,2015,14(1):35-36,43.
[7]段劲生,王梅,孙明娜,等.高效液相色谱法测定小麦和土壤中炔草酯及其代谢物炔草酸的残留量[J].农药学学报,2013,15(1):121-124.DUAN J S,WANG M,SUN M N,et al.Determination of clodinafoppropargyl and its metabolite clodinafop in wheat and soil by high performance liquid chromatography[J].Chin J Pestic Sci,2013,15(1):121-124.
[8]XUE J,LI H,LIU F,et al.Determination and dissipation of flucarbazone-sodium and its metabolite in wheat and soils by LC-MS/MS[J].Inter J Environ Anal Chem,2014,94(5):479-492.
[9]NI Y X,YANG H,ZHANG H T,et al.Analysis of four sulfonylurea herbicides in cereals using modified Quick,Easy,Cheap,Effective,Rugged,and Safe sample preparation method coupled with liquid chromatography-tandem mass spectrometry[J].J Chromatogr A,2018,1537:27-34.
[10]张少军,杨更亮,郑振山,等.甲基二磺隆在小麦和土壤中的残留动态研究[J].河北农业大学学报,2009,32(3):12-16.ZHANG S J,YANG G L,ZHENG Z S,et al.Study on the residue dynamics of mesosulfuron-methyl in wheat and soil[J].J Agric Univ Hebei,2009,32(3):12-16.
[11]GUAN W B,MA Y Q,ZHANG H Y.Dissipation of clodinafoppropargyl and its metabolite in wheat field ecosystem[J].Bull Environ Contam Toxicol,2013,90(6):750-755.
[12]ANASTASSIADES M,LEHOTAY S J,?TAJNBAHER D,et al.Fast and easy multiresidue method employing acetonitrile extraction/partitioning and“dispersive solid-phase extraction”for the determination of pesticide residues in produce[J].J AOAC Inter,2003,86(2):412-431.
[13]International Union of Pure and Applied Chemistry[DB/OL].[2018-09-13].http://sitem.herts.ac.uk/aeru/iupac/Reports/441.htm.
[14]农作物中农药残留试验准则:NY/T 788-2018[S].北京:中国农业出版社,2018.Guideline for the testing of pesticide residues in crops:NY/T788-2018[S].Beijing:China Agriculture Press,2018.