苯醚甲环唑和丙环唑在稻田中的残留消解与吸附
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摘要
苯醚甲环唑和丙环唑是三唑类水稻杀菌剂,它能防治水稻纹枯病,具有很好的防治效果。本论文较为系统地研究了苯醚甲环唑和丙环唑在水稻田中的行为与效应,为生态环境效应和环境安全性提供基础数据,指导苯醚甲环唑和丙环唑的科学使用,也是研究苯醚甲环唑和丙环唑在水稻环境中的残留和消解行为以及制定其在水稻环境中合理使用准则的一项基础工作。论文主要内容如下：
第一章为文献综述,分别介绍了苯醚甲环唑和丙环唑的的理化性质和研究进展,目前国内外对苯醚甲环唑和丙环唑的研究主要集中于毒性及特点、药效试验等方面,而在水稻田中的行为与效应研究却鲜见报道,本章对其毒理、药效和分析方法等方面的研究进展进行了简要的介绍和总结。
第二章研究并建立了一种能同时检测苯醚甲环唑和丙环唑的气相色谱分析方法并用于稻田中的残留试验研究中,用来测定稻田水、土壤、稻杆、谷壳和糙米中的苯醚甲环唑和丙环唑的残留量。样品经丙酮振荡提取,后采用液-液分配,经弗罗里硅土净化,气相色谱(ECD)测定。当添加浓度为0.01-0.50 mg/kg之间时,测出苯醚甲环唑和丙环唑在不同稻田样品中的平均回收率为80.81%-112.85%和83.71%-112.11%,相对标准偏差为0.74%-6.11%和2.52%-7.29%。苯醚甲环唑在稻田水、土壤、稻杆、谷壳和糙米中的最低检出浓度分别为5×10-3mg/L,1.25×10-3、2.5×10-3、2.5×10-3、2.5×10-3mg/kg,丙环唑的最低检出浓度分别为1×10-4mg/L,2.5×10-4、5×10-4、5×10-4、5×10-4 mg/kg。该分析方法的准确性、精确性以及灵敏度均达到了农药残留分析的技术要求。
第三章研究了30%苯醚甲环唑·丙环唑乳油在湖南长沙、云南昆明和浙江杭州两年三地的稻田中使用后,苯醚甲环唑和丙环唑在稻田水、土壤、水稻植株中的消解动态。试验结果表明：苯醚甲环唑和丙环唑的消解动态均符合一级反应动力学方程式,其结果具有较高的相关性。苯醚甲环唑在稻田水、稻田土壤和水稻植株中的平均消解半衰期分别为6.67 d,7.81d,6.01 d；丙环唑在在稻田水、稻田土壤和水稻植株中的平均消解半衰期分别为6.57d,7.87d,6.04d。由此可见,苯醚甲环唑和丙环唑在稻田水、土壤和水稻植株中的属易消解农药。
苯醚甲环唑和丙环唑在土壤、稻杆、谷壳和糙米中的最终残留试验结果表明：最后一次施药后的21 d时,苯醚甲环唑和丙环唑在糙米中的残留量均未超过它们的MRL值(0.05 mg/kg),即在试验条件下施用30%苯醚甲环唑·丙环唑乳油,收获水稻的安全间隔期至少为21 d。
第四章研究了苯醚甲环唑和丙环唑在六种供试土壤中的吸附性能和吸附机理。结果表明：苯醚甲环唑和丙环唑的吸附平衡时间分别为24 h和6 h。苯醚甲环唑和丙环唑在六种供试土壤上的吸附情况可以用Freundlich等温吸附方程来拟合,且均表现为物理吸附过程。苯醚甲环唑和丙环唑在杭州水稻土壤中的吸附性最强,移动性最弱,而在太原褐土中的吸附性最弱,移动性最强。土壤理化性质影响苯醚甲环唑和丙环唑的主要因素是土壤有机质的含量,其次是土壤pH值和阳离子交换量。
第五章研究了苯醚甲环唑和丙环唑在六种供试土壤中的消解情况。结果表明：在六种供试土壤中,苯醚甲环唑和丙环唑的消解存在差异,这两种供试农药在杭州黄红壤中消解最快,苯醚甲环唑和丙环唑的消解半衰期分别为13.75 d、6.85 d,在杭州水稻土中消解最慢,苯醚甲环唑和丙环唑的消解半衰期分别为16.27 d、8.25 d。苯醚甲环唑和丙环唑在的消解半衰期受土壤有机质含量影响较大,在酸性条件下,苯醚甲环唑和丙环唑在土壤中较难消解,碱性条件下,两种供试农药较易消解,另外,苯醚甲环唑和丙环唑的消解受阳离子交换量CEC的影响较小。
Difenoconazole and propicondzole were triazole fungicide applied in paddy,they showed good inhibitory effect on the rice sheath blight. The behavior and effect of difenoconazole and propicondzole in paddy were studied in the thesis in order to provide some fundamental datas for the enviormnent saefty and ecological enviroment effect assessment, and also conduce to scientific application of difenoconazole and propicondzole. It was necessary to develop an effective residue analysis method for monitoring the residue and degradation process of difenoeonazole and propicondzole in paddy.At the same time, it is also necessary to establish their reasonable application criterion, which was also basic for evaluating their safety to rice and environment. The main contents were as follows:
Chapter 1:It was a survey article that it introduced physical and chemical properies and advancement on research and development of difenoconazole and propicondzole, respectively. Previous studies focused mainly on toxicity, characterist and efficacy, little information was available about their behvaior and effect in paddy. The thesis summarized briefly that current research informations of difenoconazole and propicondzole about toxicity, potency, analysis method.
Chapter 2:An simultaneously detective and effective gas chromatography analysis methods were established to determine the residue of difenoconazole and propicondzole in paddy water, soil, straw, rice hull and brown rice. Samples were extracted with acetone, purified on liquid-liquid partition and the extract was purified by a chromography column of florisil, subsequently detected by gas chromatography with electron-capture detector. when the added amount changed from 0.01 to 0.50 mg/kg in the samples, the average recoveries of difenoconazole ranged from 80.81% to 112.85% and the coefficient of variations changed from 0.74% to 6.11%. While at the same added amount, the data of propicondzole ranged from 83.71% to 112.11% and changed from 2.52% to 7.29%, respectively. Detectable limits of difenoconazole residue in paddy water, soil, straw, rice hull and brown rice were 5×10-3 mg/L, 1.25×10-3、2.5×10-3、2.5×10-3、2.5×10-3 mg/kg, respectively,and detectable limits of propiconazole residue were 1×10-4 mg/L,2.5×10-4、5×10-4、5×10-4、5×10-4 mg/kg. The accuracy and delicacy of these analysis methods all reached the technique demands of residue analysis of pesticide.
Chapter 3:Difenoeonazole and propiconazole 30% EC was applied in paddy for two years in Changsha,Kunming and Zhejiang, the results of degradation dynamics of difenoconazole and propicondzole revealed that the degradation dynamics of difenoeonazole and propiconazole accoreded with the first class kinetics equation in paddy water, soil and straw, moreover it had high correlation. The average degradation half-lives of difenoconazole were 6.67 days in paddy water,7.81 days in paddy soil and 6.01 days in paddy straw, respectively. At the same time, the average degradation half-lives of propicondzole were 6.57 days in paddy water,7.87 days in paddy soil and 6.04 days in paddy straw.
These results indicated that difenoconazole and propiconazole could be easily degradable in paddy. The final residue experiment of difenoconazole and propicondzole in paddy soil, straw, rice hull and brown rice showed that when the 21th day after the last applied,the residues of difenoconazole and propiconazole were less than the maximum residue limit(0.05 mg/kg). So difenoeonazole and propiconazole 30% EC was applied on the condition of the experiment,the safety interval period was at least 21 days.
Chapter 4:The adsoprtion behavior of difenoconazole and propicondzole was studied by batch experiment with six kinds of soils tested.The results showed:The adsorption equilibrium times of difenoconazole and propicondzole were 24 hours and 6 hours, respectively. It was found that adsorption process of difenoconazole and propicondzole could be described well with Freudlich isotherm equation and there adsorption belonged to physical adsorption.The strongest adsorption occurred on the soil from Hangzhou paddy, and it took place the weakest adsorption on soil from Taiyuan. Among the main physical and chemical characters,organic matter contents played an important role in the adsorption on soils tested,more than pH value and cation exchange capacity.
Chapter 5:The degradation behavior of difenoconazole and propicondzole was studied by batch experiment with six kinds of soils tested.The results showed:the degradation dynamic was different from difenoconazole and propicondzole, The fastest degradation rate occurred on the soil from Hangzhou area, the degradation half-lives of difenoconazole and propicondzole were 13.75 days,6.85 days, and the slowest degradation rate on soil from Hangzhou paddy. the degradation half-lives of difenoconazole and propicondzole were 16.27 days,8.25 days. The organic matter contents played an important role in degradation half-lives of difenoconazole and propicondzole in six kinds of soils tested. Difenoconazole and propicondzole were hardly degrade on acidity condition, but easily degrade on alkalescent condition. The degradation half-lives had a poor correlation with cation exchange capacity, it indicated that they had litter impact on degradation of difenoconazole and propicondzole.
第一章为文献综述,分别介绍了苯醚甲环唑和丙环唑的的理化性质和研究进展,目前国内外对苯醚甲环唑和丙环唑的研究主要集中于毒性及特点、药效试验等方面,而在水稻田中的行为与效应研究却鲜见报道,本章对其毒理、药效和分析方法等方面的研究进展进行了简要的介绍和总结。
第二章研究并建立了一种能同时检测苯醚甲环唑和丙环唑的气相色谱分析方法并用于稻田中的残留试验研究中,用来测定稻田水、土壤、稻杆、谷壳和糙米中的苯醚甲环唑和丙环唑的残留量。样品经丙酮振荡提取,后采用液-液分配,经弗罗里硅土净化,气相色谱(ECD)测定。当添加浓度为0.01-0.50 mg/kg之间时,测出苯醚甲环唑和丙环唑在不同稻田样品中的平均回收率为80.81%-112.85%和83.71%-112.11%,相对标准偏差为0.74%-6.11%和2.52%-7.29%。苯醚甲环唑在稻田水、土壤、稻杆、谷壳和糙米中的最低检出浓度分别为5×10-3mg/L,1.25×10-3、2.5×10-3、2.5×10-3、2.5×10-3mg/kg,丙环唑的最低检出浓度分别为1×10-4mg/L,2.5×10-4、5×10-4、5×10-4、5×10-4 mg/kg。该分析方法的准确性、精确性以及灵敏度均达到了农药残留分析的技术要求。
第三章研究了30%苯醚甲环唑·丙环唑乳油在湖南长沙、云南昆明和浙江杭州两年三地的稻田中使用后,苯醚甲环唑和丙环唑在稻田水、土壤、水稻植株中的消解动态。试验结果表明：苯醚甲环唑和丙环唑的消解动态均符合一级反应动力学方程式,其结果具有较高的相关性。苯醚甲环唑在稻田水、稻田土壤和水稻植株中的平均消解半衰期分别为6.67 d,7.81d,6.01 d；丙环唑在在稻田水、稻田土壤和水稻植株中的平均消解半衰期分别为6.57d,7.87d,6.04d。由此可见,苯醚甲环唑和丙环唑在稻田水、土壤和水稻植株中的属易消解农药。
苯醚甲环唑和丙环唑在土壤、稻杆、谷壳和糙米中的最终残留试验结果表明：最后一次施药后的21 d时,苯醚甲环唑和丙环唑在糙米中的残留量均未超过它们的MRL值(0.05 mg/kg),即在试验条件下施用30%苯醚甲环唑·丙环唑乳油,收获水稻的安全间隔期至少为21 d。
第四章研究了苯醚甲环唑和丙环唑在六种供试土壤中的吸附性能和吸附机理。结果表明：苯醚甲环唑和丙环唑的吸附平衡时间分别为24 h和6 h。苯醚甲环唑和丙环唑在六种供试土壤上的吸附情况可以用Freundlich等温吸附方程来拟合,且均表现为物理吸附过程。苯醚甲环唑和丙环唑在杭州水稻土壤中的吸附性最强,移动性最弱,而在太原褐土中的吸附性最弱,移动性最强。土壤理化性质影响苯醚甲环唑和丙环唑的主要因素是土壤有机质的含量,其次是土壤pH值和阳离子交换量。
第五章研究了苯醚甲环唑和丙环唑在六种供试土壤中的消解情况。结果表明：在六种供试土壤中,苯醚甲环唑和丙环唑的消解存在差异,这两种供试农药在杭州黄红壤中消解最快,苯醚甲环唑和丙环唑的消解半衰期分别为13.75 d、6.85 d,在杭州水稻土中消解最慢,苯醚甲环唑和丙环唑的消解半衰期分别为16.27 d、8.25 d。苯醚甲环唑和丙环唑在的消解半衰期受土壤有机质含量影响较大,在酸性条件下,苯醚甲环唑和丙环唑在土壤中较难消解,碱性条件下,两种供试农药较易消解,另外,苯醚甲环唑和丙环唑的消解受阳离子交换量CEC的影响较小。
Difenoconazole and propicondzole were triazole fungicide applied in paddy,they showed good inhibitory effect on the rice sheath blight. The behavior and effect of difenoconazole and propicondzole in paddy were studied in the thesis in order to provide some fundamental datas for the enviormnent saefty and ecological enviroment effect assessment, and also conduce to scientific application of difenoconazole and propicondzole. It was necessary to develop an effective residue analysis method for monitoring the residue and degradation process of difenoeonazole and propicondzole in paddy.At the same time, it is also necessary to establish their reasonable application criterion, which was also basic for evaluating their safety to rice and environment. The main contents were as follows:
Chapter 1:It was a survey article that it introduced physical and chemical properies and advancement on research and development of difenoconazole and propicondzole, respectively. Previous studies focused mainly on toxicity, characterist and efficacy, little information was available about their behvaior and effect in paddy. The thesis summarized briefly that current research informations of difenoconazole and propicondzole about toxicity, potency, analysis method.
Chapter 2:An simultaneously detective and effective gas chromatography analysis methods were established to determine the residue of difenoconazole and propicondzole in paddy water, soil, straw, rice hull and brown rice. Samples were extracted with acetone, purified on liquid-liquid partition and the extract was purified by a chromography column of florisil, subsequently detected by gas chromatography with electron-capture detector. when the added amount changed from 0.01 to 0.50 mg/kg in the samples, the average recoveries of difenoconazole ranged from 80.81% to 112.85% and the coefficient of variations changed from 0.74% to 6.11%. While at the same added amount, the data of propicondzole ranged from 83.71% to 112.11% and changed from 2.52% to 7.29%, respectively. Detectable limits of difenoconazole residue in paddy water, soil, straw, rice hull and brown rice were 5×10-3 mg/L, 1.25×10-3、2.5×10-3、2.5×10-3、2.5×10-3 mg/kg, respectively,and detectable limits of propiconazole residue were 1×10-4 mg/L,2.5×10-4、5×10-4、5×10-4、5×10-4 mg/kg. The accuracy and delicacy of these analysis methods all reached the technique demands of residue analysis of pesticide.
Chapter 3:Difenoeonazole and propiconazole 30% EC was applied in paddy for two years in Changsha,Kunming and Zhejiang, the results of degradation dynamics of difenoconazole and propicondzole revealed that the degradation dynamics of difenoeonazole and propiconazole accoreded with the first class kinetics equation in paddy water, soil and straw, moreover it had high correlation. The average degradation half-lives of difenoconazole were 6.67 days in paddy water,7.81 days in paddy soil and 6.01 days in paddy straw, respectively. At the same time, the average degradation half-lives of propicondzole were 6.57 days in paddy water,7.87 days in paddy soil and 6.04 days in paddy straw.
These results indicated that difenoconazole and propiconazole could be easily degradable in paddy. The final residue experiment of difenoconazole and propicondzole in paddy soil, straw, rice hull and brown rice showed that when the 21th day after the last applied,the residues of difenoconazole and propiconazole were less than the maximum residue limit(0.05 mg/kg). So difenoeonazole and propiconazole 30% EC was applied on the condition of the experiment,the safety interval period was at least 21 days.
Chapter 4:The adsoprtion behavior of difenoconazole and propicondzole was studied by batch experiment with six kinds of soils tested.The results showed:The adsorption equilibrium times of difenoconazole and propicondzole were 24 hours and 6 hours, respectively. It was found that adsorption process of difenoconazole and propicondzole could be described well with Freudlich isotherm equation and there adsorption belonged to physical adsorption.The strongest adsorption occurred on the soil from Hangzhou paddy, and it took place the weakest adsorption on soil from Taiyuan. Among the main physical and chemical characters,organic matter contents played an important role in the adsorption on soils tested,more than pH value and cation exchange capacity.
Chapter 5:The degradation behavior of difenoconazole and propicondzole was studied by batch experiment with six kinds of soils tested.The results showed:the degradation dynamic was different from difenoconazole and propicondzole, The fastest degradation rate occurred on the soil from Hangzhou area, the degradation half-lives of difenoconazole and propicondzole were 13.75 days,6.85 days, and the slowest degradation rate on soil from Hangzhou paddy. the degradation half-lives of difenoconazole and propicondzole were 16.27 days,8.25 days. The organic matter contents played an important role in degradation half-lives of difenoconazole and propicondzole in six kinds of soils tested. Difenoconazole and propicondzole were hardly degrade on acidity condition, but easily degrade on alkalescent condition. The degradation half-lives had a poor correlation with cation exchange capacity, it indicated that they had litter impact on degradation of difenoconazole and propicondzole.
引文
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