本文選題：氯溴蟲(chóng)腈 + 氣相色譜��； 參考：《湖南大學(xué)》2014年碩士論文

【摘要】：氯溴蟲(chóng)腈，試驗(yàn)代號(hào)：HNPC-A3061，化學(xué)名稱為1-(2-氯乙氧)甲基-4-溴-2-(4-氯苯基)-5-三氟甲基吡咯-3-腈，是我國(guó)研制的具有自主知識(shí)產(chǎn)權(quán)的新型芳基吡咯類殺蟲(chóng)劑。目前，有關(guān)氯溴蟲(chóng)腈的光化學(xué)降解動(dòng)力學(xué)及其殘留等方面的研究，國(guó)內(nèi)外均未見(jiàn)報(bào)道。為了解氯溴蟲(chóng)腈農(nóng)業(yè)應(yīng)用的安全性，，本文進(jìn)行了下列研究：（1）氯溴蟲(chóng)腈在環(huán)境樣品中的殘留分析方法；（2）氯溴蟲(chóng)腈在甘藍(lán)和土壤中的光化學(xué)降解動(dòng)力學(xué)；（3）氯溴蟲(chóng)腈在甘藍(lán)和土壤中殘留量；（4）不同溶劑對(duì)氯溴蟲(chóng)腈的光化學(xué)降解動(dòng)力學(xué)的影響。主要研究結(jié)果如下： 1、建立了氯溴蟲(chóng)腈在甘藍(lán)及土壤中的殘留分析方法。土壤樣品經(jīng)乙腈振蕩提取、二氯甲烷萃取，甘藍(lán)樣品經(jīng)乙腈超聲提取、鹽析作用，過(guò)弗羅里硅土/活性炭混合物（質(zhì)量比為50:1）柱凈化，氣相色譜-電子捕獲檢測(cè)器（GC-ECD）檢測(cè)。結(jié)果表明：在0.01～10mg/L范圍內(nèi)氯溴蟲(chóng)腈峰面積與進(jìn)樣質(zhì)量濃度呈現(xiàn)良好的線性關(guān)系，R2=0.9995，在氯溴蟲(chóng)腈添加水平0.01～1.0mg/kg范圍內(nèi)，甘藍(lán)和土壤的平均回收率為96.0%～102.4%，相對(duì)標(biāo)準(zhǔn)偏差為3.4%～8.1%。方法的最小檢出（LOC）為2×10-11g，最小檢測(cè)濃度（LOQ）為0.01mg/kg。該方法的靈敏度、準(zhǔn)確度、精密度及專一性均符合農(nóng)藥殘留分析的要求，適用于甘藍(lán)和土壤中氯溴蟲(chóng)腈的殘留分析檢測(cè)。 2、通過(guò)兩年三地田間試驗(yàn)，研究了氯溴蟲(chóng)腈在甘藍(lán)和土壤中的光化學(xué)消解動(dòng)力學(xué)。結(jié)果表明，2012年氯溴蟲(chóng)腈在湖南、河北和江蘇等三個(gè)試驗(yàn)點(diǎn)甘藍(lán)上的消解半衰期分別為5.28、5.14、6.16d，土壤中的消解半衰期分別為13.05、7.87、11.12d；2013年甘藍(lán)上的消解半衰期分別為7.17、6.42、10.73d，土壤中的消解半衰期分別為2.75、2.32、5.94d。根據(jù)我國(guó)農(nóng)藥殘留等級(jí)標(biāo)準(zhǔn)，氯溴蟲(chóng)腈屬于易降解農(nóng)藥。 3、氯溴蟲(chóng)腈在甘藍(lán)和土壤中的殘留量的研究結(jié)果表明：以10%氯溴蟲(chóng)腈懸浮劑的有效成分施藥劑量18g a.i./ha和27g a.i./ha，噴施3～4次，距最后一次施藥14d，氯溴蟲(chóng)腈在甘藍(lán)和土壤中的最大殘留量分別為0.290mg/kg和0.141mg/kg，建議氯溴蟲(chóng)腈在甘藍(lán)上的最大允許殘留限量為1.0mg/kg，安全間隔期為14d。 4、氯溴蟲(chóng)腈在不同溶劑中的光化學(xué)降解動(dòng)力學(xué)研究表明：以氙燈、紫外燈為光源，氯溴蟲(chóng)腈在甲醇、正己烷、乙腈、水等四種溶劑介質(zhì)中的光解規(guī)律符合一級(jí)動(dòng)力學(xué)方程，光降解速率順序是：正己烷＞甲醇＞水＞乙腈，而丙酮對(duì)氯溴蟲(chóng)腈的光解表現(xiàn)出極強(qiáng)的光猝作用。同一溶劑中氯溴蟲(chóng)腈的初始濃度與其光解速率成負(fù)相關(guān)，這與其單位量所能接受的光能子有光。而在不同光源間的比較，氯溴蟲(chóng)腈在紫外光照條件下的降解速率明顯快于氙燈條件下的光照，可以推測(cè)氯溴蟲(chóng)腈的光解有效光源段主要集中在紫外區(qū)。綜上所述，氯溴蟲(chóng)腈的的光降解受光源、溶劑、溫度、初始濃度等因素所影響。
[Abstract]:Chlorobromochloronitrile, codenamed as: HNPC-A3061, is a new type of aryl pyrrole insecticides with intellectual property rights developed in China. The chemical name is 1-O2-Chloroethoxy) methyl -4-bromo-2-oxy-4-chlorobenzenyl pyrrolidene -5-trifluoromethylpyrrolidene (5-trifluoromethylpyrrolidene-3-nitrile). At present, studies on the photochemical degradation kinetics and residues of chlorbromochloronitrile have not been reported at home and abroad. In order to understand the safety of chlorbromofenitrile in agriculture, In this paper, the following studies have been carried out on the residue analysis of chlorbromochloronitrile in environmental samples; determination of chlorbromochloronitrile in cabbage and soil by photochemical degradation kinetics / 3) chlorbrominonitrile residues in cabbage and soil Effects of photochemical degradation kinetics of brominonitrile. The main findings are as follows: 1. A method for the residue analysis of chlorbromoteronitrile in cabbage and soil was established. Soil samples were extracted by acetonitrile oscillation, dichloromethane was extracted, and cabbage samples were extracted by acetonitrile ultrasonic extraction, salting out, column purification of the mixture (mass ratio of 50: 1), gas chromatography-electron capture detector (GC-ECD). The results showed that there was a good linear relationship between the peak area of chlorbromofenitrile and the sample concentration in the range of 0.01~10mg/L. In the range of 0.01~1.0mg/kg, the average recovery of cabbage and soil was 96.00.102.4, and the relative standard deviation was 3.4% 8.1. The minimum detectable LOC was 2 脳 10 ~ (-11) g and the minimum detection concentration was 0.01 mg / kg 路kg ~ (-1) 路L ~ (-1) 路L ~ (-1) 路min ~ (-1) 路L ~ (-1). The sensitivity, accuracy, precision and specificity of the method meet the requirements of pesticide residue analysis. It is suitable for the determination of chlorbromochloronitrile in cabbage and soil. 2. The photochemical degradation kinetics of chlorbromochloronitrile in cabbage and soil was studied by two years and three field experiments. The results showed that chlorbromoteronitrile was found in Hunan Province in 2012. In Hebei and Jiangsu provinces, the digestion half-life of cabbage was 5.285.14 ~ 6.16 days, and that of soil was 13.05 ~ 7.87 ~ 11.12 days, respectively, and that of cabbage in 2013 was 7.17 ~ 6.42 ~ 10.73 days, and that in soil was 2.752.32 ~ 5.94 days, respectively. According to the standard of pesticide residue grade in China, chlorbromochloronitrile is a biodegradable pesticide. The residue of chlorbromofenitrile in cabbage and soil was studied. The results showed that the effective component of 10% chlorobromochloronitrile suspension was sprayed 3 times at the dosage of 18g a.i./ha and 27g a.i.r.ha. The maximum residual amounts of chlorbromofenitrile in cabbage and soil were 0.290mg/kg and 0.141 mg / kg, respectively, 14 days after the last application. The maximum allowable residue limit of chlorbromochloronitrile in cabbage was 1.0 mg / kg and the safe interval was 14 days. The kinetic study of photochemical degradation of chlorbromofenitrile in different solvents showed that the photolysis of chlorbromochloronitrile in methanol, n-hexane, acetonitrile and water was in accordance with the first-order kinetic equation with xenon lamp and ultraviolet lamp as light source, and chlorbromofenitrile in methanol, n-hexane, acetonitrile and water. The order of photodegradation rate is n-hexane > methanol > water > acetonitrile, while acetone has a strong photoquenching effect on the photolysis of chlorbrominonitrile. The initial concentration of chlorbromofenitrile in the same solvent is negatively correlated with the photolysis rate, which is related to the photonic energy per unit amount of chlorbromochloronitrile. Compared with different light sources, the degradation rate of chlorbromochloronitrile under UV irradiation was significantly faster than that under xenon lamp, so it can be inferred that the effective light source of chlorbromofenitrile was mainly concentrated in the ultraviolet region. In conclusion, the photodegradation of chlorbromochloronitrile is affected by light source, solvent, temperature, initial concentration and so on.
【學(xué)位授予單位】：湖南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2014
【分類號(hào)】：X592;X53

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 劉政軍;谷淑波;王開(kāi)運(yùn);司樹(shù)鼎;石緒根;;溴蟲(chóng)腈在桑葉中的殘留毒性與降解動(dòng)態(tài)檢測(cè)[J];蠶業(yè)科學(xué);2008年04期

2 陳麗萍;;溴蟲(chóng)腈在菜用大豆上殘留動(dòng)態(tài)及安全使用技術(shù)[J];亞熱帶農(nóng)業(yè)研究;2008年04期

3 王敏欣,李發(fā)生,韓梅,朱書(shū)全,駱緊郁;異丙草胺在水溶液中的光解動(dòng)力學(xué)[J];環(huán)境科學(xué);2003年05期

4 胡繼業(yè),張文吉,李建中,王啟亮;2-烯丙基苯酚在液相中的光化學(xué)降解研究[J];環(huán)境科學(xué)學(xué)報(bào);2004年05期

5 陳九星,曹永松,王躍龍,陳力華,梁驥,李濤,陸貽通;溴蟲(chóng)腈在甘藍(lán)及土壤中的殘留檢測(cè)及降解動(dòng)態(tài)[J];環(huán)境科學(xué)學(xué)報(bào);2005年10期

6 歐曉明,任競(jìng),雷滿香,王曉光,樊德方;新農(nóng)藥硫肟醚在有機(jī)溶劑中的光解[J];環(huán)境科學(xué)學(xué)報(bào);2005年10期

7 張俐;歐曉明;裴暉;;具殺蟲(chóng)殺螨活性的吡咯類化合物研究概述[J];精細(xì)化工中間體;2009年06期

8 陳玲瓏;陳九星;陳力華;付啟明;馬銘;楊輝;張貴群;;高效氯氟氰菊酯在不同有機(jī)溶劑中的光化學(xué)降解研究[J];精細(xì)化工中間體;2010年06期

9 麥燕玲;劉紅梅;劉承蘭;陳文團(tuán);胡美英;;溴蟲(chóng)腈在黃瓜和莧菜中的殘留動(dòng)態(tài)研究[J];華南農(nóng)業(yè)大學(xué)學(xué)報(bào);2007年01期

10 劉斐;郭正元;劉慧琳;石卿;;溴蟲(chóng)腈在稻田環(huán)境中的消解動(dòng)態(tài)研究[J];湖南農(nóng)業(yè)科學(xué);2012年07期

本文編號(hào)：1874013