螺虫乙酯及其代谢物在梨和土壤中的残留及消解动态
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摘要
为建立梨和土壤中螺虫乙酯及其代谢物螺虫乙酯-烯醇-糖苷(S-glu)、螺虫乙酯-酮-羟基(S-keto)、螺虫乙酯-烯醇(S-enol)和螺虫乙酯-单羟基(S-mono)的残留分析方法,以及明确螺虫乙酯在梨中的残留规律,采用体积分数为1%的乙酸乙腈为提取剂,以N-丙基乙二胺(PSA)和无水硫酸镁为分散净化剂的QuEChERS方法,利用超高效液相色谱-串联质谱(UPLC-MS/MS)在选择反应监测模式(SRM)下检测,外标法定量。结果显示:螺虫乙酯在0.0005～0.1 mg/L范围内,S-glu在0.005～0.5 mg/L范围内,S-keto、S-enol和S-mono在0.0005～0.5 mg/L范围内各化合物的质量浓度与质谱峰面积间均具有良好的线性关系(R~2≥0.999);在0.005～0.7 mg/kg添加水平下,螺虫乙酯及其代谢物在梨果中的平均回收率为84%～109%,相对标准偏差(RSD)为1.2%～3.3%;在土壤中平均回收率为86%～102%,RSD为1.1%～3.6%。最低检测浓度(LOQ)为5μg/kg。该方法检测速度快、灵敏度高、重现性好,适用于梨和土壤中螺虫乙酯及其代谢物残留的快速检测和确证。按推荐剂量进行田间施药,当梨果成熟采收时,螺虫乙酯及其代谢物在梨中的残留量之和在0.023～0.056 mg/kg之间,低于中国规定的最大残留限量标准(0.7 mg/kg);在土壤中的残留量在0～0.015 mg/kg之间。螺虫乙酯及其代谢物在梨果和土壤中的消解动态均符合一级反应动力学方程,半衰期分别为为12.4 d和7.1 d。田间残留试验结果表明,螺虫乙酯用于梨树害虫防治是安全的。
A method for the simultaneous determination of spirotetramat and its metabolites such as spirotetramat-enol-glucoside(S-glu), spirotetramat-keto-hydroxy(S-keto), spirotetramat-enol(S-enol)and spirotetramat-mono-hydroxy(S-mono) in pear and soil was developed. The residual dissipation dynamics of spirotetramat in pears was determined. The residues in samples were extracted with acetonitrile(containing 1% acetic acid) and cleaned up by dispersivemethod with Npropylethylenediamine(PSA) and anhydrous magnesium sulfate as cleaning agents. Then the samples were detected by ultra performance liquid chromatography-tandem massspectrometry under selective reaction monitoring mode, and quantified by external standard method. The results showed good linearity(R2 ≥ 0.999) between mass concentration and peak area of mass spectra of each compound when the concentrations of spirotetramat ranged from 0.005 to 0.10 mg/L; S-glu from 0.005 to0.5 mg/L; S-keto, S-enol and S-mono from 0.000 5 to 0.5 mg/L, respectively. When the fortified levels ranged from 0.005 to 0.7 mg/kg, the average fortified recoveries in pear were in the range of 84% to109% and the reletive standard deviations(RSD) were 1.2%-3.3%. The average fortified recoveries in soil were in the range of 86% to 102% and the RSD were 1.1%-3.6%. The limits of quantification(LOQ)were 5 μg/kg. The method is rapid, sensitive and reproducible. Therefore, It is suitable for the rapid detection and identification of spirotetramat and its metabolite residues in pear and soil. According to the recommended dosage, the total residues of spirotetramat and its metabolites were 0.023-0.056 mg/kg in the fruit and 0-0.015 mg/kg in the soil when the pear was ripe and harvested. The half-life of spirotetramat in pear fruit was 12.4 d, and the half-life in soil was 7.1 d. Therefore, it is safe to use spirotetramat for the pest control of pear tree.
A method for the simultaneous determination of spirotetramat and its metabolites such as spirotetramat-enol-glucoside(S-glu), spirotetramat-keto-hydroxy(S-keto), spirotetramat-enol(S-enol)and spirotetramat-mono-hydroxy(S-mono) in pear and soil was developed. The residual dissipation dynamics of spirotetramat in pears was determined. The residues in samples were extracted with acetonitrile(containing 1% acetic acid) and cleaned up by dispersivemethod with Npropylethylenediamine(PSA) and anhydrous magnesium sulfate as cleaning agents. Then the samples were detected by ultra performance liquid chromatography-tandem massspectrometry under selective reaction monitoring mode, and quantified by external standard method. The results showed good linearity(R2 ≥ 0.999) between mass concentration and peak area of mass spectra of each compound when the concentrations of spirotetramat ranged from 0.005 to 0.10 mg/L; S-glu from 0.005 to0.5 mg/L; S-keto, S-enol and S-mono from 0.000 5 to 0.5 mg/L, respectively. When the fortified levels ranged from 0.005 to 0.7 mg/kg, the average fortified recoveries in pear were in the range of 84% to109% and the reletive standard deviations(RSD) were 1.2%-3.3%. The average fortified recoveries in soil were in the range of 86% to 102% and the RSD were 1.1%-3.6%. The limits of quantification(LOQ)were 5 μg/kg. The method is rapid, sensitive and reproducible. Therefore, It is suitable for the rapid detection and identification of spirotetramat and its metabolite residues in pear and soil. According to the recommended dosage, the total residues of spirotetramat and its metabolites were 0.023-0.056 mg/kg in the fruit and 0-0.015 mg/kg in the soil when the pear was ripe and harvested. The half-life of spirotetramat in pear fruit was 12.4 d, and the half-life in soil was 7.1 d. Therefore, it is safe to use spirotetramat for the pest control of pear tree.
引文
[1]Statista:Export volume of pears worldwide in 2017/2018, by leading countries(in 1,000 metric tons)[DB/OL].(2018-09-29). https://www.statista.com/statistics/756511/global-top-pear-exporter-worldwide/
[2]中华人民共和国农业农村部农药检定所.农药登记数据[EB/OL].(2016-03-16)[3019-04-29]. http://www.icama.org.cn/hysj/index.jhtml Pesticide testing institute of the ministry of agriculture and village of the People's Republic of China. Pesticide registration data.(2016-03-16)[3019-04-29]. http://www.icama.org.cn/hysj/index.jhtml
[3]宫亚军,王泽华,康总江,等.新型双向传导杀虫剂-螺虫乙酯对Q型烟粉虱的防治效果[J].植物保护, 2012, 38(6):157-160.GONG Y J, WANG Z H, KANG Z J, et al. Control efficacy of a new two-way systemic insecticide spirotetramat on the whitefly Bemisia tabaci[J]. Plant Prot, 2012, 38(6):157-160.
[4]LABANOWSKA, BARBARA H, PIOTROWSKI W, et al.Usefulness of spirotetramat(Movento 100 SC)to control spider mites on apple, blackcurrant and raspberry in Poland[J]. IOBC/WPRS Bulletin, 2017, 123:115-119.
[5]?ABANOWSKA B H, KORZENIOWSKI M, GASPARSKI T.Efficacy of spirotetramat in the control of the currant-sowthistle(Hyperomyzus lactucae L.)on blackcurrant plantations in Poland[J]. J Hortic Res, 2013, 21(2):73-78.
[6]JAWORSKA K, OLSZAK R W,?ABANOWSKA B H, et al.Efficacy of spirotetramat in the control of pear psylla(Cacopsylla pyri L.)on pear trees in Poland[J]. J Fruit Ornam Plant Res, 2012,20(2):91-106.
[7]张传州. 22.4%螺虫乙酯悬浮剂防治梨木虱的田间药效试验[J].落叶果树, 2015, 47(3):30-31.ZHANG C Z. Field efficacy trials of 22.4%spiro ethyl ester suspension against pear-leaf sucker[J]. Deciduous Fruits, 2015, 47(3):30-31.
[8]陈金翠,王泽华,曹利军,等.三种新型杀虫剂对中国梨木虱的田间防效[J].北方园艺, 2017(17):72-76.CHEN J C, WANG Z H, CAO L J, et al. Control efficacy of three new insecticides to pear psylla Psylla chinensis(Hemiptera:Psyllidae)[J]. North Hortic, 2017(17):72-76.
[9]LIU Y Y, SU X S, JIAN Q, et al. Behaviour of spirotetramat residues and its four metabolites in Citrus marmaladeduring home processing[J]. Food Addit Contam Part, 2016, 33(3):452-459.
[10]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 pestcides in food:GB 2763—2016[S].Beijing:China Standards Press, 2017.
[11]吴育佳,杨仁斌,聂红英.螺虫乙酯在黄瓜及其土壤中残留量检测方法及残留规律研究[J].中国农学通报, 2015, 31(35):110-115.WU Y J, YANG R B, NIE H Y. Study on residual detection method and residue rule of spirotetramat in cucumber and soil[J]. Chin Agric Sci Bull, 2015, 31(35):110-115.
[12]吴文铸,李菊颖,何健,等.螺虫乙酯在柑橘中的残留消减动态[J].生态与农村环境学报, 2016, 32(6):1003-1007.WU W Z, LI J Y, HE J, et al. Degradation dynamics of spirotetramat residue in citrus[J]. J Ecol Rural Environ, 2016, 32(6):1003-1007.
[13]李菊颖,吴文铸,孔德洋,等.超高效液相色谱-质谱法测定柑橘和土壤中螺虫乙酯及4种代谢产物[J].农药, 2016, 55(1):45-47.LI J Y, WU W Z, KONG D Y, et al. Determination of spirotetramat and its 4 metabolites in citrus and soil by ultra performance liquid chromatography-tandem mass spectrometry[J]. Agrochemicals, 2016,55(1):45-47.
[14]袁文悦,庄惠生.高效液相色谱-串联质谱法测定土壤中螺虫乙酯及其4种代谢产物[J].世界农药, 2017, 39(4):59-63.YUAN W Y, ZHUANG H S. Determination of spirotetramat and its four metabolites residues in soil by UPLC-MS/MS[J]. World Pestic,2017, 39(4):59-63.
[15]孟志远,任莉,宋玥颐,等.液相色谱-串联质谱法同时测定菠菜、土壤及水体中螺虫乙酯及4种代谢物残留[J].农药学学报, 2017,19(4):482-490.MENG Z Y, REN L, SONG Y Y, et al. Simultaneous determination of spirotetramat and its four metabolites in Spinacia oleracea L., soil and water using liquid chromatographytandem mass spectrometry[J].Chin J Pestic Sci, 2017, 19(4):482-490.
[16]陈慧妍,季祥.液相色谱:串联质谱法测定梨果中螺虫乙酯残留量[J].现代园艺, 2018(10):11.CHEN H Y, JI X. Determination of spiro ethyl acetate residues in pears by liquid chromatography tandem mass spectrometry[J].Xiandai Hortic, 2018(10):11.
[17]兰丰,姚杰,周先学,等. QuEChERS-超高效液相色谱-串联质谱法测定果蔬中螺虫乙酯、丁醚脲及代谢物残留[J].农药学学报,2019, 21(2):219-226.LAN F, YAO J, ZHOU X X, et al. Residue of spirotetramat,diafenthiuron and their metabolites in fruits and vegetables by QuEChERS-ultra performance liquid chromatography-tandem mass spectrometry[J]. Chin Pestic Sci, 2019, 21(2):219-226.
[18]PAYáP, ANASTASSIADES M, MACK D, et al. 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]. Anal Bioanal Chem, 2007, 389(6):1697-1714.
[19]LEHOTAY S J, DE KOK A, HIEMSTRA M, et al. Validation of a fast and easy method for the determination of residues from 229pesticides in fruits and vegetables using gas and liquid chromatography and mass spectrometric detection[J]. J AOAC Int,2005, 88(2):595-614.
[20]LEHOTAY S J, MASTOVSKáK, LIGHTFIELD A R. Use of buffering and other means to improve results of problematic pesticides in a fast and easy method for residue analysis of fruits and vegetables[J]. J AOAC Int, 2005, 88(2):615-629.
[21]刘满满,康澍,姚成. QuEChERS方法在农药多残留检测中的应用研究进展[J].农药学学报, 2013, 15(1):8-22.LIU M M, KANG S, YAO C. Research progress of QuEChERS method in pesticide mult-residue analysis[J]. Chin J Pestic Sci, 2013,15(1):8-22.
[22]AOAC. Official Method 2007.01. Pesticide residues in foods by acetonitrile extraction and partitioning with magnesium sulfate[S/OL]. http://www.eoma.aoac.org/methods/info.asp?ID=48938
[23]European Committee for Standardization(CEN):Standard method EN 15662:foods of plant origin-multimethod for the determination of pesticide residues using GC-and LC-based analysis following acetonitrile extraction/partitioning and clean-up by dispersive SPEModular QuEChERS-method[S/OL].(2018-05-23)[2018-09-30].https://standards.cen.eu/dyn/www/f?p=204:110:0::::FSP_PROJECT,FSP_ORG_ID:61387, 6256&cs10DBAB7C706FAC8588AB8D2285F35AF89
[24]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:Chinese Agricultural Press, 2018.
[25]农药残留分析样本的采样方法:NY/T 789—2004[S].北京:中国农业出版社, 2004.Guideline on sampling residue analysis:NY/T 789—2004[S]. Beijing:Chinese Agricultural Press, 2004.
[26]Food and Agriculture Organization of United Nation(2008).Evaluation of spirotetramat by the joint FAO/WHO meeting on pesticide residues(JMPR)and the joint FAO/WHO meeting on pesticide specifications(JMPS)[R/OL]. Retrieved March 2, 2019from FAO of UN.https://www.fao.org/agriculture/crops/thematicsitemap/theme/pests/lpe/lpe-s/ir/
[2]中华人民共和国农业农村部农药检定所.农药登记数据[EB/OL].(2016-03-16)[3019-04-29]. http://www.icama.org.cn/hysj/index.jhtml Pesticide testing institute of the ministry of agriculture and village of the People's Republic of China. Pesticide registration data.(2016-03-16)[3019-04-29]. http://www.icama.org.cn/hysj/index.jhtml
[3]宫亚军,王泽华,康总江,等.新型双向传导杀虫剂-螺虫乙酯对Q型烟粉虱的防治效果[J].植物保护, 2012, 38(6):157-160.GONG Y J, WANG Z H, KANG Z J, et al. Control efficacy of a new two-way systemic insecticide spirotetramat on the whitefly Bemisia tabaci[J]. Plant Prot, 2012, 38(6):157-160.
[4]LABANOWSKA, BARBARA H, PIOTROWSKI W, et al.Usefulness of spirotetramat(Movento 100 SC)to control spider mites on apple, blackcurrant and raspberry in Poland[J]. IOBC/WPRS Bulletin, 2017, 123:115-119.
[5]?ABANOWSKA B H, KORZENIOWSKI M, GASPARSKI T.Efficacy of spirotetramat in the control of the currant-sowthistle(Hyperomyzus lactucae L.)on blackcurrant plantations in Poland[J]. J Hortic Res, 2013, 21(2):73-78.
[6]JAWORSKA K, OLSZAK R W,?ABANOWSKA B H, et al.Efficacy of spirotetramat in the control of pear psylla(Cacopsylla pyri L.)on pear trees in Poland[J]. J Fruit Ornam Plant Res, 2012,20(2):91-106.
[7]张传州. 22.4%螺虫乙酯悬浮剂防治梨木虱的田间药效试验[J].落叶果树, 2015, 47(3):30-31.ZHANG C Z. Field efficacy trials of 22.4%spiro ethyl ester suspension against pear-leaf sucker[J]. Deciduous Fruits, 2015, 47(3):30-31.
[8]陈金翠,王泽华,曹利军,等.三种新型杀虫剂对中国梨木虱的田间防效[J].北方园艺, 2017(17):72-76.CHEN J C, WANG Z H, CAO L J, et al. Control efficacy of three new insecticides to pear psylla Psylla chinensis(Hemiptera:Psyllidae)[J]. North Hortic, 2017(17):72-76.
[9]LIU Y Y, SU X S, JIAN Q, et al. Behaviour of spirotetramat residues and its four metabolites in Citrus marmaladeduring home processing[J]. Food Addit Contam Part, 2016, 33(3):452-459.
[10]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 pestcides in food:GB 2763—2016[S].Beijing:China Standards Press, 2017.
[11]吴育佳,杨仁斌,聂红英.螺虫乙酯在黄瓜及其土壤中残留量检测方法及残留规律研究[J].中国农学通报, 2015, 31(35):110-115.WU Y J, YANG R B, NIE H Y. Study on residual detection method and residue rule of spirotetramat in cucumber and soil[J]. Chin Agric Sci Bull, 2015, 31(35):110-115.
[12]吴文铸,李菊颖,何健,等.螺虫乙酯在柑橘中的残留消减动态[J].生态与农村环境学报, 2016, 32(6):1003-1007.WU W Z, LI J Y, HE J, et al. Degradation dynamics of spirotetramat residue in citrus[J]. J Ecol Rural Environ, 2016, 32(6):1003-1007.
[13]李菊颖,吴文铸,孔德洋,等.超高效液相色谱-质谱法测定柑橘和土壤中螺虫乙酯及4种代谢产物[J].农药, 2016, 55(1):45-47.LI J Y, WU W Z, KONG D Y, et al. Determination of spirotetramat and its 4 metabolites in citrus and soil by ultra performance liquid chromatography-tandem mass spectrometry[J]. Agrochemicals, 2016,55(1):45-47.
[14]袁文悦,庄惠生.高效液相色谱-串联质谱法测定土壤中螺虫乙酯及其4种代谢产物[J].世界农药, 2017, 39(4):59-63.YUAN W Y, ZHUANG H S. Determination of spirotetramat and its four metabolites residues in soil by UPLC-MS/MS[J]. World Pestic,2017, 39(4):59-63.
[15]孟志远,任莉,宋玥颐,等.液相色谱-串联质谱法同时测定菠菜、土壤及水体中螺虫乙酯及4种代谢物残留[J].农药学学报, 2017,19(4):482-490.MENG Z Y, REN L, SONG Y Y, et al. Simultaneous determination of spirotetramat and its four metabolites in Spinacia oleracea L., soil and water using liquid chromatographytandem mass spectrometry[J].Chin J Pestic Sci, 2017, 19(4):482-490.
[16]陈慧妍,季祥.液相色谱:串联质谱法测定梨果中螺虫乙酯残留量[J].现代园艺, 2018(10):11.CHEN H Y, JI X. Determination of spiro ethyl acetate residues in pears by liquid chromatography tandem mass spectrometry[J].Xiandai Hortic, 2018(10):11.
[17]兰丰,姚杰,周先学,等. QuEChERS-超高效液相色谱-串联质谱法测定果蔬中螺虫乙酯、丁醚脲及代谢物残留[J].农药学学报,2019, 21(2):219-226.LAN F, YAO J, ZHOU X X, et al. Residue of spirotetramat,diafenthiuron and their metabolites in fruits and vegetables by QuEChERS-ultra performance liquid chromatography-tandem mass spectrometry[J]. Chin Pestic Sci, 2019, 21(2):219-226.
[18]PAYáP, ANASTASSIADES M, MACK D, et al. 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]. Anal Bioanal Chem, 2007, 389(6):1697-1714.
[19]LEHOTAY S J, DE KOK A, HIEMSTRA M, et al. Validation of a fast and easy method for the determination of residues from 229pesticides in fruits and vegetables using gas and liquid chromatography and mass spectrometric detection[J]. J AOAC Int,2005, 88(2):595-614.
[20]LEHOTAY S J, MASTOVSKáK, LIGHTFIELD A R. Use of buffering and other means to improve results of problematic pesticides in a fast and easy method for residue analysis of fruits and vegetables[J]. J AOAC Int, 2005, 88(2):615-629.
[21]刘满满,康澍,姚成. QuEChERS方法在农药多残留检测中的应用研究进展[J].农药学学报, 2013, 15(1):8-22.LIU M M, KANG S, YAO C. Research progress of QuEChERS method in pesticide mult-residue analysis[J]. Chin J Pestic Sci, 2013,15(1):8-22.
[22]AOAC. Official Method 2007.01. Pesticide residues in foods by acetonitrile extraction and partitioning with magnesium sulfate[S/OL]. http://www.eoma.aoac.org/methods/info.asp?ID=48938
[23]European Committee for Standardization(CEN):Standard method EN 15662:foods of plant origin-multimethod for the determination of pesticide residues using GC-and LC-based analysis following acetonitrile extraction/partitioning and clean-up by dispersive SPEModular QuEChERS-method[S/OL].(2018-05-23)[2018-09-30].https://standards.cen.eu/dyn/www/f?p=204:110:0::::FSP_PROJECT,FSP_ORG_ID:61387, 6256&cs10DBAB7C706FAC8588AB8D2285F35AF89
[24]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:Chinese Agricultural Press, 2018.
[25]农药残留分析样本的采样方法:NY/T 789—2004[S].北京:中国农业出版社, 2004.Guideline on sampling residue analysis:NY/T 789—2004[S]. Beijing:Chinese Agricultural Press, 2004.
[26]Food and Agriculture Organization of United Nation(2008).Evaluation of spirotetramat by the joint FAO/WHO meeting on pesticide residues(JMPR)and the joint FAO/WHO meeting on pesticide specifications(JMPS)[R/OL]. Retrieved March 2, 2019from FAO of UN.https://www.fao.org/agriculture/crops/thematicsitemap/theme/pests/lpe/lpe-s/ir/