唑胺菌酯在黄瓜体内的代谢、传导及其环境行为研究

发布时间：2018-06-06 09:11

本文选题：唑胺菌酯 + 代谢　；参考：《沈阳农业大学》2017年博士论文

【摘要】：唑胺菌酯是沈阳化工研究院创制的一种新型甲氧丙烯酸酯类杀菌剂,杀菌谱广、杀菌活性高,2011年,95%唑胺菌酯原药与20%唑胺菌酯悬浮剂获得国内临时登记,登记的防治对象为黄瓜白粉病。我们以唑胺菌酯为研究对象,建立了该药剂和两个代谢产物的在黄瓜、土壤中的痕量检测方法,研究了唑胺菌酯在黄瓜植株内的代谢、传导过程,以及在土壤中的淋溶、吸附、土壤降解、水-沉积物系统降解、鱼类急性毒性和生物富集试验,并在田间进行了20%唑胺菌酯悬浮剂的土壤和黄瓜的消解试验。基于HPLC-MS/MS建立了唑胺菌酯及其代谢产物唑胺菌酯-Ml、唑胺菌酯-M2在黄瓜、土壤中的简单、快速、准确的QuEChERS测定方法。黄瓜样品经乙腈提取,PSA和GCB填料净化后,HPLC-MS/MS分析;土壤样品经乙腈提取,PSA填料净化后,HPLC-MS/MS分析。采用MRMESI正离子模式,唑胺菌酯及其代谢产物的定量离子对分别为382.1/164.2、368.1/164.1和352.2/189.1,三个组份在3.2 min-3.9 min之内被分离开。唑胺菌酯在0.05?10.0μg/L(唑胺菌酯代谢产物在0.5?100.0μg/L)范围内有良好的线性相关性,相关系数均大于0.9988,在试验土壤和黄瓜中的平均添加回收率为78.8%?93.8%,相对标准偏差均小于6.9%,符合农药残留检测要求。采用HPLC-MS/MS技术,对唑胺菌酯在黄瓜苗中的代谢、降解及传导性进行了研究。研究结果表明唑胺菌酯在黄瓜中消解较快,半衰期为2.0?2.2d。同时唑胺菌酯在黄瓜苗中具有较好的内吸性和传导性,可以通过根茎和叶片吸收,并可实现根茎→叶片、叶片→叶片及叶片→根茎传导,因而表现出较好的保护和治疗活性。通过对经唑胺菌酯处理的黄瓜苗和未经处理的黄瓜苗样品进行分析比较,发现了唑胺菌酯的2个代谢产物,分子量分别为367.2(唑胺菌酯-Ml)和351.2(唑胺菌酯-M2)。通过对唑胺菌酯及其代谢产物的质谱进行解析,鉴定了2个代谢产物的可能结构式,并通过合成确证了这两个代谢产物。采用土壤薄板层析法和土柱淋溶法研究了唑胺菌酯在三种土壤中的淋溶特性,结果表明:唑胺菌酯在三种土壤中的移动性属于“不移动”和“难淋溶”,不易随降水或土壤毛细作用进入地下水中,不易造成地下水的污染。研究了唑胺菌酯在黑土、红土和水稻土中的吸附特性,在黑土中的吸附率最大,其次是水稻土,红土中的吸附率最小,并符合Freundlich吸附等温模型。唑胺菌酯在黑土、红土和水稻土中的Kf值分别为127.8、49.8和85.2,Koc值分别为7473.7、4742.9和14947.4,唑胺菌酯在黑土和水稻土中的吸附等级为“Ⅱ”级,属于“较易土壤吸附”,在红土中的吸附等级为“Ⅲ”级,属于“中等土壤吸附”。唑胺菌酯在三种土壤中的吉布斯自由能变化均小于40 KJ/mol,属于物理吸附。有机质含量和阳离子交换量是影响土壤吸附的重要因素。唑胺菌酯好氧条件下在黑土中的降解半衰期为67.3 d,降解特性为“Ⅱ级(中等降解)”;红土、水稻土中的降解半衰期分别为96.3d和110.0d,降解特性均为“Ⅲ级(较难降解)”;积水厌气条件明显缩短了唑胺菌酯的降解半衰期,三种土壤降解特性均为“易降解”。唑胺菌酯土壤降解半衰期与土壤有机质含量呈现出一定的负相关性。在田间条件下开展了 20%唑胺菌酯悬浮剂在辽宁沈阳、山东寿光和浙江杭州一年三地的土壤消解试验,半衰期为12.9～14.9d,相比实验室条件下的降解明显加快,这可能受试验期间光照以及降雨的影响。唑胺菌酯在高碳好氧、高碳厌氧、低碳好氧及低碳厌氧四种条件下的降解半衰期为5.0～6.5d,属于“易降解”。四种条件下水-沉积物系统水相中唑胺菌酯含量变化与系统降解的总趋势接近,呈现明显的消解下降趋势,唑胺菌酯在水-沉积物系统中的降解主要受水体中浓度变化的影响,而沉积物相对整个水-沉积物系统中的农药降解的影响并不显著。以斑马鱼为试验用鱼,进行了唑胺菌酯的急性毒性和生物富集试验。鱼类急性毒性试验LC50(96h)为0.20mg/L,95%置信限为0.17～0.23mg/L,对斑马鱼“高毒”。以流水式法进行了鱼类生物富集试验,4.8 h换水一次,以LC50 (96h)的1/10、1/100浓度设置药液的浓度处理,即0.02 mg/L和0.002 mg/L,吸收阶段进行12天,清除阶段进行4天。配制浓度为0.002 mg/L时,吸收速率常数为69.3 d-1;清除速率常数为0.9945 d-1;动态生物富集系数为69.7。配制浓度为0.02 mg/L时,吸收速率常数为45.0 d-1;清除速率常数为0.8036 d-1;动态生物富集系数为56.0,属于“中等富集性”。
[Abstract]:Azolomide is a new methoxy acrylate fungicide created by Shenyang Chemical Research Institute, which has a wide spectrum of bactericidal spectrum and high bactericidal activity. In 2011, 95% zazolamides and 20% azolomide esters were temporarily registered in China. The control object of the registration was cucumber powdery mildew. The metabolism of the metabolites in cucumber and soil, the metabolism and the conduction process of azolomate in cucumber plants, and the leaching, adsorption, soil degradation, water sediment system degradation in the soil, the acute toxicity and bioaccumulation of fish in the soil, and the soil and cucumber of 20% azolomide ester suspending agent in the field were carried out in the field. Based on HPLC-MS/MS, a simple, fast and accurate QuEChERS method for determination of azzolium ester and its metabolite zazomate ester -Ml and zazolamide ester -M2 in cucumber and soil was established based on a simple, rapid and accurate method for determination of QuEChERS. After purification of PSA and GCB fillers, the cucumber samples were purified by HPLC-MS/MS; the soil samples were extracted by acetonitrile and purified by PSA fillers. By using MRMESI positive ion mode, the quantitative ion pairs of azolomate and its metabolites were 382.1/164.2368.1/164.1 and 352.2/189.1, respectively, and three components were separated within 3.2 min-3.9 min, and zzolamines had good linear correlation in the range of 0.05? 10 micron (azolide metabolites in 0.5? 100 g/ L). The average recovery rate in the experimental soil and cucumber was 78.8%? 93.8%, and the relative standard deviation was less than 6.9%, which was in line with the requirements of pesticide residue detection. The metabolism, degradation and conductivity of azolomate in cucumber seedlings were studied by HPLC-MS/MS technology. The results showed that azolomate was quickly eliminated in Cucumber. The half-life is 2? 2.2d., and zolomide ester has good absorbability and conductivity in cucumber seedlings. It can be absorbed through rhizomes and leaves, and can carry out rhizome, leaf, leaf, leaf and rhizome, thus showing good protection and therapeutic activity. The samples of cucumber seedlings were analyzed and compared. 2 metabolites of azolomide ester were found. The molecular weight was 367.2 (zazomate -Ml) and 351.2 (zolomamine ester -M2). By analyzing the mass spectra of azolomide ester and its metabolites, the possible structure of 2 metabolites was identified, and the two metabolites were confirmed by synthesis. The leaching characteristics of azolomate in three soils were studied by soil sheet chromatography and soil column leaching. The results showed that the mobility of azolomate in three soils was "not moving" and "hard to leaching". It was not easy to enter underground water with precipitation or soil capillary action, and it was not easy to cause groundwater pollution. The adsorption characteristics in black soil, laterite and paddy soil are the largest in black soil, followed by paddy soil, the adsorption rate of red soil is the smallest, and the Freundlich adsorption isotherm model is in line with the Kf values of azolomide in black soil, red soil and paddy soil, respectively, 127.8,49.8 and 85.2, Koc values of 7473.74742.9 and 14947.4 respectively, azolomide ester in black soil. The adsorption grade in the paddy soil is "II" grade, which belongs to "easier soil adsorption". The adsorption grade in the red soil is "III" grade and belongs to "medium soil adsorption". The Gibbs free energy of azolomate in three soils is less than 40 KJ/mol, and it belongs to physical adsorption. The content of organic matter and the exchange of cation are affected by the soil. The important factor of adsorption is that the half-life of degradation in the black soil under azolide aerobic condition is 67.3 D, and the degradation characteristic is "grade II (medium degradation)". The degradation half life of red soil and paddy soil is 96.3d and 110.0d respectively, and the degradation characteristics are all "grade III (more difficult to degrade)", and the anaerobic condition of water accumulation obviously shortens the degradation of azolomate. During the period, the degradation characteristics of the three kinds of soil were all "easy to degrade". The half-life of azolomate soil degradation was negatively correlated with the content of soil organic matter. In the field, the soil soil digestion test of 20% azolomide ester suspension agent in Shenyang, Shandong Shouguang and Hangzhou of Zhejiang was carried out in the field, and the half-life was 12.9 ~ 14.9d, compared with the half-life of zolomate ester. The degradation in the laboratory conditions is obviously accelerated, which may be affected by light and rainfall during the experiment. The half-life of azolomate in the four conditions of high carbon aerobic, high carbon anaerobic, low carbon aerobic and low carbon anaerobic conditions is 5 ~ 6.5d, which is "easy to degrade". The change of azolide content in the water phase of the water sediment system and the change of the content of azolomide ester in the water sediment system of the four conditions The overall tendency of the system degradation is close, showing a clear decline trend. The degradation of azolomate in water sediment system is mainly influenced by the change of concentration in the water body, while the influence of the sediment on the degradation of pesticides in the whole water sediment system is not significant. The acute toxicity of zzebrafish as a test fish is carried out. The fish acute toxicity test LC50 (96h) was 0.20mg/L, the 95% confidence limit was 0.17 ~ 0.23mg/L, and the zebrafish "high poison" was "high poison". The fish bioaccumulation test was carried out by flow method, 4.8 h was changed to water once, the concentration of LC50 (96h) 1/10,1/100 concentration was set up, that was 0.02 mg/L and 0.002 mg/L, and the absorption stage was 12 days. When the concentration is 0.002 mg/L, the absorption rate constant is 69.3 D-1 and the clearance rate constant is 0.9945 D-1, and the absorption rate constant is 45 D-1 when the dynamic biological enrichment coefficient is 0.02 mg/L, and the clearance rate constant is 0.8036 D-1, and the dynamic bioaccumulation coefficient is 56, which belongs to "medium enrichment".
【学位授予单位】：沈阳农业大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：X592;S481

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