~(14)C-丙酯草醚在土壤中的行为与归趋
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摘要
2-嘧啶氧基-N-芳基苄胺类衍生物是我国拥有自主知识产权的自行创制的一类具高效除草活性的农药先导化合物,具有国际原创性。丙酯草醚,化学名为4-[2-(4,6-二甲氧基-2-嘧啶氧基)苄胺基]苯甲酸正丙酯,是该类先导化合物结构中已成功开发的一种新型高效油菜田除草剂,其原药及其10%的乳油制剂(商品名:油力)获得了农业部颁发的农药临时登记证以及国家发展和改革委员会颁发的农药生产批准证书,成为我国为数不多的、具有自主知识产权且先导结构创新的除草剂新品种。但需要指出的是,为了确保环境和农产品的安全,实现大规模商业化应用,有关丙酯草醚环境行为与归趋尤其是结合残留和矿化的研究仍有待深入开展。
     本论文研究以~(14)C标记丙酯草醚(U-~(14)C-苯甲酸正丙酯)为对象,对其在水体和土壤中的降解、吸附解吸、迁移、淋溶、残留(可提态与结合残留)和矿化规律等进行了系统的研究,旨在阐明丙酯草醚的环境行为与归趋,为丙酯草醚科学、安全、合理的使用及其正式登记注册提供理论依据和技术支持,进一步推动丙酯草醚的成果转化和产业化进程。
     主要研究结果如下:
     (1) 丙酯草醚在不同pH水体中的降解满足一级动力学方程,水解半减期为18.2~47.5d,水解反应速率k与半减期T_(1/2)成反比,与水溶液pH呈显著负相关,随着pH的升高,丙酯草醚在水中的降解速率逐渐减慢。
     (2) 丙酯草醚母体化合物在5种土壤中的的降解满足一级动力学反应,半减期为12.3~28.6d,降解速率常数γ与pH呈显著负相关。母体化合物的半减期,灭菌处理均高于对照。
     (3) 在培养60d后,~(14)C-丙酯草醚在5种土壤中的~(14)C-ER占引入量的6.2%~52.1%,其中,碱性土(淡涂泥田)中~(14)C-ER含量最高,酸性土(红砂田)中最低。~(14)C-ER含量与土壤pH呈显著正相关。在整个培养时
ZJ273, Propyl 4-(2-(4, 6-dimethoxypyrimidin-2-yloxy)benzylamino) benzoate is a novel herbicide with the property of high activity, broad spectrum and low toxicity to animals. Its temporary register and production certificate were awarded by Department of Agriculture and National Development and Reform Commission of China, respectively. In order to achieve cosmically commercial application, the mechanism, mode of action, environmental behavior and fate of ZJ273 needed to be studied further.In this study, degradation of ZJ273 parent compound in water and soils, extractable residue (~(14)C-ER), bound residue (~(14)C-BR), mineralization, absorption, desorption, migration and leaching of ~(14)C-labelled ZJ273 in soils were investigated under laboratory condition. The purpose of this study is to evaluate the environmental behavior and fate of ZJ273 in agroecosystem.The results were as follows:The decrease rate of ZJ273 in water with different pH followed the first order rate reaction, the half-life in water were 18.2~47.5 d and positively to water pH.After 60 days of incubation, the content of ~(14)C-ER from ~(14)C-labelled ZJ273 in five kinds of soil ranged from 6.2%~52.1% of applied amount, with the maximum level in alkaline soil (Paddy field on desalting muddy polder) while the minimal in acidic soil (Paddy soil on red sandstone soil). Total ~(14)C-ER content in soils was positively related to soil pH. The half-life values of ZJ273 parent compound in the spiked soils ranged from 12.3 to 28.6d and positively to soil pH. Furthermore, during the whole course of incubation, ~(14)C-ER content and half-life values of the parent compound in sterilized soils were higher than
    that in control. Bound 14C-labelled ZJ273 residue in five kinds of soil accounted for 45.7%~77.6% of applied amount. The pattern of the content of 14C-BR followed the law as acidic soil>neutral soil>alkaline soil. 14C-BR in soils was significantly negative to soil pH. Among the basic properties of soil, pH was found to be the dominant factor affecting BR formation of 14C-labelled ZJ273. 14C-BR content in sterilized soils was lower than that in control. After 60 days of incubation, the rate of 14C-labelled ZJ273 mineralized to 14C-CO2 through opening U-14C-benzoate ring in non-sterilized ranging from 0.2 ~ 19.9% of applied amount and that in sterilized soils was 0.2~0.8%. It was found that microorganism play an important role in course of 14C-labelled ZJ273 mineralized to 14C-CO2 in soils.Adsorptions of 14C-labelled ZJ273 in soils followed Freundlich equation. The adsorption constant Kfwas about 285.6^614.1 and positively related to soil organic matter(OM). 14C-labelled ZJ273 could hardly be desorbed by water. The relation between the adsorption and desorption was negative. The Rf values in the tested soil by means of soil TLC were in range of 0.15 to 0.36 and were negatively related to soil organic matter. The herbicide was middle mobile in acidic soil, but was hardly mobile in the other kinds of soils. The content of 14C-labelled ZJ273 in 2cm-surface of soil-column was positively related to soil organic matter.
引文
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