【作者】 刘慧群；

【导师】 郑永权；

【作者基本信息】 东北农业大学 ， 农药学， 2009， 硕士

【摘要】 本文主要研究了农药溴菌腈和多菌灵在黄瓜和土壤中的残留分析方法、消解动态规律及其最终残留量,以期对40%多·溴·福可湿性粉剂在黄瓜上的安全性使用进行评价,为制定该药安全使用准则、产品登记及溴菌腈在黄瓜上的最大残留限量提供重要的理论及科学依据。主要研究结果如下:1.分别建立了新型农药溴菌腈在黄瓜和土壤中的气相色谱和气相色谱-串联质谱连用分析方法。样品采用丙酮提取,二氯甲烷对提取液进行萃取。萃取液浓缩用丙酮定容,气相色谱(NPD)和气相色谱-串联质谱联用测定。气相色谱(NPD)的最小检出量为1×10-11 g,溴菌腈在黄瓜和土壤的最低检出浓度为0.1 mg/Kg,在0.1 mg/Kg、0.5 mg/Kg和1 mg/Kg三个添加水平,溴菌腈在黄瓜和土壤中的平均回收率分别为82.57%～87.69%和91.25%～93.09%,相对标准偏差分别为5.37%～6.04%和2.40%～4.32%。气相色谱-串联质谱联用的最小检出量为1×10-11 g,溴菌腈在黄瓜和土壤的最低检出浓度为0.1 mg/Kg,在0.1 mg/Kg、0.5 mg/Kg和1 mg/Kg三个添加水平,溴菌腈在黄瓜和土壤中的平均回收率分别为91.54%～108.93%和99.03%～110.87%,相对标准偏差分别为4.57%～5.85%和4.02%～8.68%。两种分析方法的灵敏度、准确度高,精密度好,均能够满足溴菌腈在黄瓜和土壤中的残留检测需要。2.分别建立了农药多菌灵在黄瓜和土壤中超高效液相色谱-串联质谱联用和高效液相色谱分析方法。样品采用乙酸乙酯提取,超高效液相色谱-串联质谱联用测定,多反应监测技术确定多菌灵的两对离子m/z 191.2/ 132和m/z 191.2/ 160为定性离子,m/z 191.2/ 160为定量离子。仪器的最小检出量为3×10-12 g,多菌灵在黄瓜和土壤的最低检出浓度为0.01 mg/kg,在0.01 mg/kg、0.05 mg/kg和0.1 mg/kg三个添加水平,多菌灵在黄瓜和土壤中的平均回收率分别为96.75%～101.87%和98.15%～109.48%,相对标准偏差分别为2.77%～3.31%和2.99%～5.64%。两种方法的灵敏度、准确度、精密度等均符合农药残留检测的要求,但液相色谱-串联质谱联用测定的灵敏度更高。高效液相色谱测定多菌灵的最小检出量为2×10-10 g,多菌灵在黄瓜和土壤中的最低检出浓度均为0.1 mg/Kg,在0.1 mg/Kg、0.5 mg/Kg和1 mg/Kg三个添加水平,多菌灵在黄瓜和土壤中的平均回收率分别为86.09%～91.79%和95.30%～97.10%,相对标准偏差分别为2.50%～3.58%和2.13%～3.27%。3.采用田间试验方法,研究了40%多·溴·福可湿性粉剂在黄瓜和土壤中残留消解动态规律及其最终残留量。通过在山东、河南、浙江和北京一年四地田间试验,对40%多·溴·福可湿性粉剂按推荐剂量2倍处理黄瓜及其土壤样品,残留消解动态规律表明,40%多·溴·福可湿性粉剂在黄瓜及其土壤中降解过程符合一级动力学数学模型。多菌灵在土壤中消解半衰期为4.9～6.9天,在黄瓜中消解半衰期为2.0～2.8天。溴菌腈在黄瓜中消解半衰期为1.1～1.5天。说明此农药属于易降解农药。4.按照田间试验设计方案,2008年一年四地的试验结果显示,40%多·溴·福可湿性粉剂在黄瓜及其土壤中分别按照推荐剂量(150克制剂/亩),施药3次,在收获期距最后一次施药问隔为5天时,多菌灵和溴菌腈在黄瓜中的最高残留量分别为≤0.366 mg/Kg和<0.2mg/Kg。更多还原

【Abstract】 In order to provide basic data for residual rule of 40%Carbendazim·Bromothalonil·Thiram, analysis methods of 40%Carbendazim·Bromothalonil·Thiram residue and degradation in cucumber and soil, and its final residues were studied. The results were shown as follows:1.Residue analysis method of bromothalonil was established in cucumber and soil. The bromothalonil could be extracted with acetone, and then re-extracted with dichloromethane. After being concentrated by evaporation, the residue was reconstituded with acetone and detected in GC(NPD) and GC-MS. The limit of detection in GC(NPD) was 1×10-11 g, and limits of quantitation of bromothalonil in cucumber and soil were both 0.1 mg/Kg. In the three levels of 0.1 mg/Kg, 0.5 mg/Kg and 1 mg/Kg, the average recoveries in cucumber and soil were 82.57%～87.69% and 91.25%～93.09%, respectively, and the relative standard deviations were 25.37%～6.04% and 2.40%～4.32%, respectively. The minimum detectable limit of the GC-MS was 1×10-11 g, and the minumun detectable concentration of Bromothalonil in cucumber and soil was all 0.1mg/Kg. In the three level of 0.1 mg/Kg, 0.5 mg/Kg and 1 mg/Kg, the average recoveries in cucumber and soil were 91.54%～108.93% and 99.03%～110.87%, with the relative standard deviations were 4.57%～5.85% and 4.02%～8.68%, respectively. The sensitivity, accuracy and precision of the method well satisfied the essential rules of pesticide residue determination.2. Residue analysis method of carbendazim was established in cucumber and soil. The sample was extracted with ethyl acetate and determined by UPLC-MS/MS. The precursor ion/product ion transitions were m/z 191.2/130 and m/z 191.2/160 at the mode of multi-reaction monitor and m/z 191.2/160 was used for quantification. The limit of detection in UPLC-MS was 3×10-12 g, and limits of quantitation of carbendazim in cucumber and soil were both 0.01 mg/Kg. In the three levels of 0.01 mg/Kg, 0.05 mg/Kg and 0.1 mg/Kg, the average recoveries in cucumber and soil were 96.75%～101.87% and 98.15%～109.48%, with the relative standard deviations were 2.77%～3.31% and 2.99%～5.64%, respectively. The sensitivity, accuracy and precision of the two methods well satisfied the essential rules of pesticide residue determination, but the sensitivity of UPLC-MS determination was better. The limit of detection in HPLC was 2×10-10 g, and limits of quantitation of carbendazim in cucumber and soil were both 0.1 mg/Kg. In the three levels of 0.1 mg/Kg, 0.5 mg/Kg and 1 mg/Kg, the average recoveries in cucumber and soil were 86.09%～91.79% and 95.30%～97.10%, with the relative standard deviations were 2.50%～3.58% and 2.13%～3.27%, respectively.3. Degradation dynamic of 40%Carbendazim·Bromothalonil·Thiram in cucumbers and soil was studied by a one-year four fields (2008) experiments in Shandong, Zhejiang, Henan and Beijing. The cucumbers and soil were treated with the pesticides at recommended dosage and two times of the recommendation dosage. Samples of cucumber and soil were analysised at different time, then the degradation procedure was corresponding to the mathematic pattern: C=C0e-kt. The half lifes of carbendazim in soil were 4.9～6.9 d, and that in cucumber were 2.0～2.8 d. The half lifes of bromothalonil in cucumber were 1.1～1.5 d. The result showed that carbendazim and bromothalonil were degraded easily in cucumber and soil.4. With sprayed 40%Carbendazim·Bromothalonil·Thiram on cucumbers and soil at recommended dosage by a one-year four fields (2008) experiment in Shandong, Zhejiang, Henan and Beijing, on the 5th day after the last application, the final residue of Carbendazim and Bromothalonil in cucumber was≤0.366 mg/Kg and <0.2 mg/Kg.更多还原