丙烷脒在土壤中吸附、迁移及水解动力学研究
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摘要
丙烷脒(Propamidine)属于芳香二脒类化合物,是西北农林科技大学无公害农药研究服务中心在前期工作的基础之上近几年研究开发的新型杀菌剂,并且已经获得国家农药登记(原药登记证号为LS20040092,2%丙烷脒水剂登记证号为LS20040130)。丙烷脒属于内吸性杀菌剂,可在植物体内吸收、分布和代谢,具有保护和治疗双重功效。该药主要用于防治田间和大棚内蔬菜、果树和经济作物上由灰霉病菌“Botrytis”引起的多种植物病害。
该药是一种结构新颖的化合物,水溶性强,为水制剂。农药在土壤中的吸附迁移及水解是农药在土壤-水环境中归宿的主要支配因素,目前国内外尚未有对丙烷脒的吸附、迁移、降解等环境行为的研究,同时研究新型农药丙烷脒在环境中吸附、迁移、水解是新农药登记时必备的资料,也是评价一种新农药在环境中安全性的重要指标。本论文以丙烷脒为研究对象,对其在土壤中的吸附、迁移及其水解等环境行为进行研究,主要得到了如下研究结果:
1.建立了新型杀菌剂丙烷脒的反相离子对高效液相色谱定量分析方法,色谱柱为BDS C18柱,流动相为含3.0mmol/L十二烷基磺酸钠的甲醇/水(V/V=80:20)溶液,流速1.0mL/min,二极管阵列检测器,检测波长为258.7nm,该方法中丙烷脒的标准偏差为0.209,变异系数为0.109%,线性相关系数为0.9983。
2.对丙烷脒在土壤中的吸附和移动性分别采用平衡振荡法和土壤层析法进行了研究,对振荡时间、温度、pH值以及土壤有机质等影响因素作了初步探讨,结果表明丙烷脒在土壤中的吸附性很强。水相浓度初始为1000-3000μg/mL时丙烷脒在土壤中吸附符合线性吸附等温方程,丙烷脒在江西红土、河南二合土和陕西黄土上的吸附常数Kd分别为25.42、33.93和40.34mL/g,丙烷脒在三种土壤中的吸附能力依次增强。丙烷脒有机质吸附常数KOM值在陕西黄土、河南二合土和江西红土中分别为4287.68、4294.81和12665.92,表明丙烷脒在陕西黄土和河南二合土上属于移动性很弱,在江西红土上属于不移动。丙烷脒在土壤同时存在物理吸附和化学吸附。丙烷脒在土壤的吸附能力主要受其土壤有机质和pH值影响显著。丙烷脒在土壤中的相对移动值Rf为0.047,属于很弱移动性。
3.通过实验室模拟试验,研究了丙烷脒在不同pH值、温度及不同水体条件下的水解动态。结果表明:不同pH值、温度及不同的水体对丙烷脒水解速率影响并不显著,丙烷脒水解半衰期长,在正常环境条件下,为181.929d。
The propamidine, which is one of few proprietary property rights in our country, has been obtained country registration (The propamidine registration code is LS20040092, The registration number of 2% Propamidine SL is LS20040130). It was patented in China (The application number is 02114480.X and 200410073073.X).
Adsorption, transferability and hydrolysis are important environmental behaviors of pesticides. Assessing the adsorption, transferability and hydrolysis of new pesticides has become an integrated part of studies concerning the environmental safety of pesticide. Because this compound is new and unique, there is no its studies on aspect of environmental behavior in the world. In this paper, adsorption, transferability and hydrolysis were studied. The main results were summarized as follows:
1. A method was established for determining Propamidine by ion-pair revered-phase high performance liquid chromatography. A C18 column was used with a mobile phase of V(methanol):V(water) =80:20, 3.0mmol/L SDS .The sample was detected with an ultraviolet detector at 258.7nm. The results showed that the standard deviation was 0.209; the coefficient of variation was 0.109%; the linear correlation was 0.9983.
2. Adsorption isotherms of Propamidine in three selected soils were studied by using batch equilibrium method, including optimum ratio of water/soil, the time of reaching adsorption equilibrium, temperature, soil pH and soil organic matter; the transferability of Propamidine in the soils also was studied by soil thin layer chromatography. The result shows that there is strong adsorption ability of Propamidine in three soils. The adsorption isotherms of in three soils all were linear, distribution coefficients(Kd) ranged from25.42mL/g and 33.93mL/g to 40.34mL/g, and the order of soils adsorption of Propamidine followed: Shanxi Yellow soil>He’nan Fluvo-aquic soil >Jiangxi Red soil. According to the analysis of the correlation between Kd and physical and chemical properties of the soils, organic matter content of soils and soil pH were the dependent factor in the adsorption. Free energy of adsorption in soil indicated that the adsorption belonged to physical and chemical reaction. Rf(relative flow) of Propamidine was 0.047. The transferability gradation of Propamidine in the soils wasⅠgrade.
3. Effects of temperature, pH and different water types (distilled water, groundwater, Wei river water) on the hydrolysis of Propamidine was studied. The experimental results showed that temperature, pH, natural water had little influence on the hydrolysis rate of Propamidine. The half-lives of Propamidine in distilled water at 25℃was 181.929d.
该药是一种结构新颖的化合物,水溶性强,为水制剂。农药在土壤中的吸附迁移及水解是农药在土壤-水环境中归宿的主要支配因素,目前国内外尚未有对丙烷脒的吸附、迁移、降解等环境行为的研究,同时研究新型农药丙烷脒在环境中吸附、迁移、水解是新农药登记时必备的资料,也是评价一种新农药在环境中安全性的重要指标。本论文以丙烷脒为研究对象,对其在土壤中的吸附、迁移及其水解等环境行为进行研究,主要得到了如下研究结果:
1.建立了新型杀菌剂丙烷脒的反相离子对高效液相色谱定量分析方法,色谱柱为BDS C18柱,流动相为含3.0mmol/L十二烷基磺酸钠的甲醇/水(V/V=80:20)溶液,流速1.0mL/min,二极管阵列检测器,检测波长为258.7nm,该方法中丙烷脒的标准偏差为0.209,变异系数为0.109%,线性相关系数为0.9983。
2.对丙烷脒在土壤中的吸附和移动性分别采用平衡振荡法和土壤层析法进行了研究,对振荡时间、温度、pH值以及土壤有机质等影响因素作了初步探讨,结果表明丙烷脒在土壤中的吸附性很强。水相浓度初始为1000-3000μg/mL时丙烷脒在土壤中吸附符合线性吸附等温方程,丙烷脒在江西红土、河南二合土和陕西黄土上的吸附常数Kd分别为25.42、33.93和40.34mL/g,丙烷脒在三种土壤中的吸附能力依次增强。丙烷脒有机质吸附常数KOM值在陕西黄土、河南二合土和江西红土中分别为4287.68、4294.81和12665.92,表明丙烷脒在陕西黄土和河南二合土上属于移动性很弱,在江西红土上属于不移动。丙烷脒在土壤同时存在物理吸附和化学吸附。丙烷脒在土壤的吸附能力主要受其土壤有机质和pH值影响显著。丙烷脒在土壤中的相对移动值Rf为0.047,属于很弱移动性。
3.通过实验室模拟试验,研究了丙烷脒在不同pH值、温度及不同水体条件下的水解动态。结果表明:不同pH值、温度及不同的水体对丙烷脒水解速率影响并不显著,丙烷脒水解半衰期长,在正常环境条件下,为181.929d。
The propamidine, which is one of few proprietary property rights in our country, has been obtained country registration (The propamidine registration code is LS20040092, The registration number of 2% Propamidine SL is LS20040130). It was patented in China (The application number is 02114480.X and 200410073073.X).
Adsorption, transferability and hydrolysis are important environmental behaviors of pesticides. Assessing the adsorption, transferability and hydrolysis of new pesticides has become an integrated part of studies concerning the environmental safety of pesticide. Because this compound is new and unique, there is no its studies on aspect of environmental behavior in the world. In this paper, adsorption, transferability and hydrolysis were studied. The main results were summarized as follows:
1. A method was established for determining Propamidine by ion-pair revered-phase high performance liquid chromatography. A C18 column was used with a mobile phase of V(methanol):V(water) =80:20, 3.0mmol/L SDS .The sample was detected with an ultraviolet detector at 258.7nm. The results showed that the standard deviation was 0.209; the coefficient of variation was 0.109%; the linear correlation was 0.9983.
2. Adsorption isotherms of Propamidine in three selected soils were studied by using batch equilibrium method, including optimum ratio of water/soil, the time of reaching adsorption equilibrium, temperature, soil pH and soil organic matter; the transferability of Propamidine in the soils also was studied by soil thin layer chromatography. The result shows that there is strong adsorption ability of Propamidine in three soils. The adsorption isotherms of in three soils all were linear, distribution coefficients(Kd) ranged from25.42mL/g and 33.93mL/g to 40.34mL/g, and the order of soils adsorption of Propamidine followed: Shanxi Yellow soil>He’nan Fluvo-aquic soil >Jiangxi Red soil. According to the analysis of the correlation between Kd and physical and chemical properties of the soils, organic matter content of soils and soil pH were the dependent factor in the adsorption. Free energy of adsorption in soil indicated that the adsorption belonged to physical and chemical reaction. Rf(relative flow) of Propamidine was 0.047. The transferability gradation of Propamidine in the soils wasⅠgrade.
3. Effects of temperature, pH and different water types (distilled water, groundwater, Wei river water) on the hydrolysis of Propamidine was studied. The experimental results showed that temperature, pH, natural water had little influence on the hydrolysis rate of Propamidine. The half-lives of Propamidine in distilled water at 25℃was 181.929d.
引文
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