噁唑菌酮和代森锰锌可分散粒剂在番茄和土壤中的消解动态
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摘要
为研究复配试剂噁唑菌酮和代森锰锌可分散粒剂在番茄和土壤中施用后的食品安全性和环境归宿行为,将杀菌剂施用于番茄植株农药残留消解动态试验小区(15 m~2)和土壤动态试验小区(20 m~2),结合HPLC和GC检测技术,通过添加回收建立噁唑菌酮、代森锰锌在番茄和土壤基质中的残留检测方法。结果表明:噁唑菌酮在番茄和土壤中的最小检出量分别为1×10~(-9) g和8×10~(-9) g,最低检出浓度均为0.05 mg/kg,代森锰锌的最小检出量为3.5×10~(-11)g,最低检出浓度为0.035 mg/kg,平均回收率(n=5)为78.01%～106.03%,相对标准偏差平均值均小于5.22%。该方法重复性好,准确度高,试验结果表明番茄中噁唑菌酮、代森锰锌的半衰期为1.61～14.43 d,土壤中其半衰期为2.64～22.35 d,其消解规律遵循一级化学反应动力学方程:C_t=C_0e~(-kt)。
To study the environmental fate and behavior of the compounding agents famoxadone and mancozeb dispersible granules and their impacts on food safety after application in tomato and soil ecosystems, the fungicides were applied to the plot of pesticide residue digestion dynamic test on tomato plant(15 m~2) and the plot of soil dynamic test(20 m~2). With HPLC and GC detection techniques integrated, a method for detecting residues of famoxadone and mancozeb in tomato and soil matrix was established by adding recovery experiments. The results show that: The minimum detectable amounts of famoxadone in tomato and soil are 1×10~(-9) g and 8×10~(-9) g, respectively; for mancozeb, they are 3.5×10~(-11) g. The minimum detectable amount of mancozeb is 3.5×10~(-11) g; and the minimum detectable concentrations in tomato and soil are 0.05 mg/kg and 0.035 mg/kg, respectively. The average recovery rate(n=5) is 78.01%-106.03%, and the average relative standard deviation is less than 5.22%. The method has high accuracy and good repetition. It shows that the half-life of famoxadone and mancozeb are between 1.61-14.43 d in tomato, and between 2.64-22.35 d in soil. The residual digestion follows the kinetic equation of first-order chemical reaction: C_t=C_0e~(-kt).
To study the environmental fate and behavior of the compounding agents famoxadone and mancozeb dispersible granules and their impacts on food safety after application in tomato and soil ecosystems, the fungicides were applied to the plot of pesticide residue digestion dynamic test on tomato plant(15 m~2) and the plot of soil dynamic test(20 m~2). With HPLC and GC detection techniques integrated, a method for detecting residues of famoxadone and mancozeb in tomato and soil matrix was established by adding recovery experiments. The results show that: The minimum detectable amounts of famoxadone in tomato and soil are 1×10~(-9) g and 8×10~(-9) g, respectively; for mancozeb, they are 3.5×10~(-11) g. The minimum detectable amount of mancozeb is 3.5×10~(-11) g; and the minimum detectable concentrations in tomato and soil are 0.05 mg/kg and 0.035 mg/kg, respectively. The average recovery rate(n=5) is 78.01%-106.03%, and the average relative standard deviation is less than 5.22%. The method has high accuracy and good repetition. It shows that the half-life of famoxadone and mancozeb are between 1.61-14.43 d in tomato, and between 2.64-22.35 d in soil. The residual digestion follows the kinetic equation of first-order chemical reaction: C_t=C_0e~(-kt).
引文
[1]Sternberg J A,Geffken D,Jr A J,et al.Famoxadone:the discovery and optimisation of a new agricultural fungicide[J].Pest Management Science,2001,57(2):143.
[2]Zheng Y,Shapiro R W,Jordan D.Synthesis and structural analysis of the active enantiomer of famoxadone,a potent inhibitor of cytochrome bc1[J].Bioorganic&Medicinal Chemistry Letters,2000,10(10):1059-1062.
[3]梁林,李文平,刘伟.噁唑菌酮在马铃薯和土壤中的残留分析方法及消解动态研究[J].农药科学与管理,2017,38(3):34-37.
[4]李彦文,杨仁斌.噁唑菌酮的环境行为及残留毒理研究现状[J].环境保护科学,2006(5):47-48,55.
[5]Liu C Y,Qin D M,Zhao Y Z,et al.Famoxadone residue and dissipation in watermelon and soil[J].Ecotoxicology&Environmental Safety,2010,73(2):183-188.
[6]Likas D T,Tsiropoulos N G,Miliadis G E.Rapid gas chromatographic method for the determination of famoxadone,trifloxystrobin and fenhexamid residues in tomato,grape and wine samples[J].Journal of Chromatography A,2007,1150(1-2):208.
[7]De M A S,Caboni P,Cabras P,et al.A comparison of a gas chromatographic with electron-capture detection and a gas chromatographic with mass spectrometric detection screening methods for the analysis of famoxadone in grapes and wines[J].Journal of Chromatography A,2006,1103(2):362-367.
[8]王寒,龚道新,陈恒辉,等.气相色谱法测定黄瓜和土壤中代森锰锌的残留及其消解动态分析[J].环境监测管理与技术,2018(3)56-59.
[9]卢植新,黄辉晔,林明珍,等.代森锰锌及其代谢物在香蕉和土壤中的消解动态及残留安全性评价[J].农业环境科学学报,2008,27(3):1194-1198.
[10]López-Fernández O,Pose-Juan E,Rial-Otero R,et al.Effects of hydrochemistry variables on the half-life of mancozeb and on the hazard index associated to the sum of mancozeb and ethylenethiourea[J].Environmental Research,2017(154):253-260.
[11]陈武瑛.代森锰锌及其代谢物乙撑硫脲在苹果和土壤中的动态研究[D].湖南农业大学,2010.
[12]方楠,侯志广,张中北,等.代森锰锌在芦笋和豇豆中的残留消解动态[J].农药,2018(2):127-129.
[13]叶倩,黄聪灵,高毓文,等.QuEChERS-超高效液相色谱-串联质谱法测定蔬菜中乙撑硫脲残留[J].中国食品卫生杂志,2018(4)382-386.
[14]Domico L M,Cooper K R,Bernard L P,et al.Reactive oxygen species generation by the ethylene-bis-dithiocarbamate(EBDC)fungicide mancozeb and its contribution to neuronal toxicity in mesencephalic cells.[J].Neurotoxicology,2007,28(6):1079-1091.
[15]Calviello G,Piccioni E,Boninsegna A,et al.DNA damage and apoptosis induction by the pesticide Mancozeb in rat cells:involvement of the oxidative mechanism[J].Toxicology&Applied Pharmacology,2006,211(2):87.
[16]聂春林,付洪涛,欧晓明,等.使用自动顶空进样器测定梨中代森锰锌残留量的电子捕获气相色谱法[J].精细化工中间体,2010,40(6):63-66.
[17]吴俐,陈铭学,牟仁祥.顶空-气相色谱法测定辣椒和苹果中代森锰锌残留[J].分析试验室,2008,27(S2):269-271.
[18]陈士恒,史晓梅,吕岳文,等.QuEChERS-超高效液相色谱-串联四级杆质谱法快速检测番茄酱中19种常见农药残留量[J].食品安全质量检测学报,2015,6(4):1128-1136.
[2]Zheng Y,Shapiro R W,Jordan D.Synthesis and structural analysis of the active enantiomer of famoxadone,a potent inhibitor of cytochrome bc1[J].Bioorganic&Medicinal Chemistry Letters,2000,10(10):1059-1062.
[3]梁林,李文平,刘伟.噁唑菌酮在马铃薯和土壤中的残留分析方法及消解动态研究[J].农药科学与管理,2017,38(3):34-37.
[4]李彦文,杨仁斌.噁唑菌酮的环境行为及残留毒理研究现状[J].环境保护科学,2006(5):47-48,55.
[5]Liu C Y,Qin D M,Zhao Y Z,et al.Famoxadone residue and dissipation in watermelon and soil[J].Ecotoxicology&Environmental Safety,2010,73(2):183-188.
[6]Likas D T,Tsiropoulos N G,Miliadis G E.Rapid gas chromatographic method for the determination of famoxadone,trifloxystrobin and fenhexamid residues in tomato,grape and wine samples[J].Journal of Chromatography A,2007,1150(1-2):208.
[7]De M A S,Caboni P,Cabras P,et al.A comparison of a gas chromatographic with electron-capture detection and a gas chromatographic with mass spectrometric detection screening methods for the analysis of famoxadone in grapes and wines[J].Journal of Chromatography A,2006,1103(2):362-367.
[8]王寒,龚道新,陈恒辉,等.气相色谱法测定黄瓜和土壤中代森锰锌的残留及其消解动态分析[J].环境监测管理与技术,2018(3)56-59.
[9]卢植新,黄辉晔,林明珍,等.代森锰锌及其代谢物在香蕉和土壤中的消解动态及残留安全性评价[J].农业环境科学学报,2008,27(3):1194-1198.
[10]López-Fernández O,Pose-Juan E,Rial-Otero R,et al.Effects of hydrochemistry variables on the half-life of mancozeb and on the hazard index associated to the sum of mancozeb and ethylenethiourea[J].Environmental Research,2017(154):253-260.
[11]陈武瑛.代森锰锌及其代谢物乙撑硫脲在苹果和土壤中的动态研究[D].湖南农业大学,2010.
[12]方楠,侯志广,张中北,等.代森锰锌在芦笋和豇豆中的残留消解动态[J].农药,2018(2):127-129.
[13]叶倩,黄聪灵,高毓文,等.QuEChERS-超高效液相色谱-串联质谱法测定蔬菜中乙撑硫脲残留[J].中国食品卫生杂志,2018(4)382-386.
[14]Domico L M,Cooper K R,Bernard L P,et al.Reactive oxygen species generation by the ethylene-bis-dithiocarbamate(EBDC)fungicide mancozeb and its contribution to neuronal toxicity in mesencephalic cells.[J].Neurotoxicology,2007,28(6):1079-1091.
[15]Calviello G,Piccioni E,Boninsegna A,et al.DNA damage and apoptosis induction by the pesticide Mancozeb in rat cells:involvement of the oxidative mechanism[J].Toxicology&Applied Pharmacology,2006,211(2):87.
[16]聂春林,付洪涛,欧晓明,等.使用自动顶空进样器测定梨中代森锰锌残留量的电子捕获气相色谱法[J].精细化工中间体,2010,40(6):63-66.
[17]吴俐,陈铭学,牟仁祥.顶空-气相色谱法测定辣椒和苹果中代森锰锌残留[J].分析试验室,2008,27(S2):269-271.
[18]陈士恒,史晓梅,吕岳文,等.QuEChERS-超高效液相色谱-串联四级杆质谱法快速检测番茄酱中19种常见农药残留量[J].食品安全质量检测学报,2015,6(4):1128-1136.