表面活性剂和金属离子对新农药硫肟醚光解的影响

硫肟醚[O-(3-苯氧苄基)-2-甲硫基-1-(4-氯苯基)丙基酮肟醚]是我国研制成功的具有自主知识产权的一种新型杀虫剂.在室内紫外光(λ254 nm)照射下研究了几种表面活性剂和金属离子对硫肟醚在水溶液中光解的影响.试验结果表明,当土温80(Tween80)、十二烷基苯磺酸钙(ABS-Ca)、蓖麻油聚氧乙烯醚(BY)、三氯化铁(FeCl_3)、硫酸铜(CuSO_4)和无水硫酸镁(MgSO_4)分别与硫肟醚以1:1的比例混合后,硫肟醚的光解速率发生了不同程度的改变.ABS-Ca对硫肟醚在水溶液中的光解速率表现出显著的光猝灭降解效应,蓖麻油聚氧乙烯醚类表面活性剂BY对硫肟醚在水溶液中的降解表现出一定程度的光敏化作用.而吐温80对硫肟醚在水体中光解速率的影响则随照光时间而改变,当照光时间小于40 min时,表现为光敏化降解作用,大于40 min时可延缓硫肟醚的光解进程,表现出光猝灭作用.Fe~(3+)使硫肟醚在水溶液中的光解速率增快,表现出明显的光敏化降解效应,而Cu~(2+)和Mg~(2+)使硫肟醚在水体中的光解速率减慢,表现为较强的光猝灭降解作用.硫肟醚在含Tween80、ABS-Ca、BY、FeCl_3、CuSO_4和MgSO_4水溶液中的光解半衰期分别为21.63、34.42、15.29、9.85、43.95和32.20 min,而在不含任何农药化肥的纯净水中的光解半衰期为22.30 min.     

拟除虫菊酯与有机磷农药混合溶液的光敏降解

研究了胺菊酯、甲醚菊酯、丙烯菊酯和氯菊酯以及甲基１６５０、毒死蜱、乐果在高压汞灯照射下的光解速率及其混合物在光解过程中的相互影响。结果表明光解速率顺序与农药的种类有关；两种不同类型杀虫共存时将改变彼此的光解速率，发生光敏作用，有机磷农药对拟除虫菊酯光敏作用的顺序是甲基１６０５〉毒死蜱〉乐果；有机磷农药的摩尔吸光系数与光解速率及敏化作用能力存在一定的相关性。光解产物的检测表明有机磷农药主要通过＾３Ｏ     

外置式联合等离子体光解技术去除苯乙烯气体

开发了用一个高压电源同时产生等离子体和KrI* 准分子紫外辐射的外置式联合等离子体光解(Outer Combined Plasma Photolysis, OCPP)技术,并用于降解模拟流动态苯乙烯气体. 结果表明:在Kr和I₂充入量分别为26.60 kPa和6 mg, 气体流速为3.26 m3/h, 初始ρ(苯乙烯)为1 265 mg/m3,外施电压为9.0 kV的条件下,苯乙烯的去除率达84.4%;与介质阻挡放电技术相比,苯乙烯的去除率提高了20.6%,能率提高了5.7 g/(kW·h). 同时,研究了OCPP技术降解苯乙烯的影响因素,包括Kr和I₂的充入量、石英材质、气体流速、初始ρ(苯乙烯)及反应器结构. 采用红外光谱仪和气质联用仪分析了结焦产物,探讨了OCPP技术降解苯乙烯的机理.      

可见光分解-氯碱氧化法去除废水中的铁氰化物

采用可见光分解（光解）-氯碱氧化法去除模拟废水中的Fe（CN）63-。考察了光解过程中反应时间、初始Fe（CN）63-质量浓度和初始废水pH对Fe（CN）63-去除效果及表观反应速率常数（k（Fe（CN）63-））的影响,以及光解-氯碱氧化法对Fe（CN）63-模拟废水中总氰化物（TCN）的去除效果。实验结果表明：在初始Fe（CN）63-质量浓度6.7 mg/L、初始废水pH 12、反应时间8.0 h的条件下,Fe（CN）63-的去除率为83%,光解过程符合表观一级动力学模型;在初始Fe（CN）63-质量浓度6.7 mg/L、初始TCN质量浓度4.90 mg/L、初始废水pH 12、反应时间12.0 h的条件下,采用光解-氯碱氧化法可使Fe（CN）63-模拟废水的TCN质量浓度降至0.14 mg/L,低于GB 16171—2012的要求（0.2 mg/L）,该过程的限速步骤为Fe（CN）63-的光解破络过程。     

Effect of humic acids on photodegradation of chloroacetanilide herbicides under UV irradiation

The effects of two humic acids (HAs) of different origins on the photodegradation of the chloroacetanilide herbicides acetochlor, propisochlor and butachlor were investigated in this study. One of the tested HAs was a standard sample that was purchased from a commercial source, and the other was isolated from the black soil of Northeast China. The photolysis of all three herbicides followed pseudo-first-order kinetics under ultraviolet (UV) irradiation conditions, regardless of whether HAs were present or not. Both HAs improved the photolysis rates of acetochlor in a dose-reversed way, whereas they inhibited butachlor degradation under all experimental concentrations. The two HAs differed in their effects on propisochlor photolysis, changing from enhancement to inhibition, depending on the origin and concentration of HAs. Element and Fourier Transform Infrared spectroscopy analyses showed that the isolated HAs had more polysaccharides and less aliphatic groups than the commercial HAs, and it was indicated that some characteristic radicals (C═O, O─H and phenolic hydroxyls) in HAs were involved in the photolysis of the herbicides. Gas chromatography/mass spectrometry (GC/MS) analyses indicated that the presence of HAs had no effects on the photolysis pathway and photoproduct species of the three herbicides.     

Fate of permethrin in model outdoor ponds

Abstract

In 1979 and 1980, outdoor artificial ponds were treated with ¹⁴C‐pennethrin (labelled at either the cyclopropyl or methylene position) at 0.028 kg/ha (15 ug/L). Uptake of permethrin by duckweed and hydrosoil was monitored by direct combustion, TLC‐autoradiography, HPLC, and liquid scintillation counting. Rapid loss of permethrin from the waiter coincided with the detection of five degradation products in the water at concentrations below 2.0 ug/L. The products were cis‐ and trans‐cyclopropyl acid, phenoxybenzoic acid, and phenoxybenzyl alcohol, and an unknown non‐cleaved product of permethrin. Permethrin was readily sorbed by duckweed but was not persistent. Permethrin residues in the hydrosoil, which was the major sink for permethrin added to the ponds, were persistent and were detected at 420 days post‐treatment. Cis‐permethrin was more persistent in the hydrosoil than the trans‐permethrin. The results indicated that permethrin in water was short‐lived at an application rate of 15 ug/L because of the rapid degradation of permethrin in the water and sorption of permethrin by the hydrosoil and vegetation. However, at one year post‐treatment, permethrin residues were still detected in the hydrosoil at 1.0 ug/kg.     

除草剂绿草定-2-丁氧基乙酯的降解特性及降解机制研究

按照《化学农药环境安全评价试验准则》的规定并参考美国EPA导则,采用室内模拟试验方法,研究了绿草定-2-丁氧基乙酯在环境中的降解特性.结果表明,25℃时绿草定-2-丁氧基乙酯在pH =4、7、9缓冲溶液中的水解半衰期分别为533 d、21.8 d、＜1 d;高温、碱性条件下绿草定-2-丁氧基乙酯极易水解,其水解反应速率随反应介质pH值的增大、反应温度的升高而增大;初步确定绿草定-2-丁氧基乙酯分子在水溶液中生成的水解产物主要是绿草定.绿草定-2-丁氧基乙酯在土壤中迅速降解,酸性土壤中其降解趋势遵循一级动力学模型,中性和碱性土壤中其降解动态不能用一级动力学模型进行简单的拟合;绿草定-2-丁氧基乙酯在土壤中的降解形式主要为化学水解作用,降解生成绿草定和丁氧基乙醇;土壤pH和有机质含量是影响其土壤降解速率的主要因素,pH和有机质含量越高,其土壤降解速率越快.在人工光源氙灯条件下,绿草定-2-丁氧基乙酯在水溶液和土壤表面的光化学降解均符合一级动力学反应,不同介质对绿草定-2-丁氧基乙酯光解的影响差异显著.     

Nitrite and nitrate induced photodegradation of monolinuron in aqueous solution

Here we evidenced the photo-induced degradation of monolinuron, a phenylurea herbicide, through the 300–450 nm light excitation of nitrite and nitrate species. The degradation pathways were compared to those obtained under direct photolysis at 254 nm. When using NO₃^– and NO₂^– as photoinducers, hydroxyphenyl-substituted photodegradation products were found to be formed specifically through the involvement of OH° radicals. NO^– and NO₂-phenyl substituted compounds were also observed as a result of the production of NO° and NO₂° radicals. Half-lives of monolinuron in aqueous solutions were measured in various conditions of concentrations of substrate and inducer, oxygen content and pH.     

水体中胺鲜酯残留量的测定及其光解特性

建立了利用固相萃取-气相色谱(SPE-GC)测定水体中胺鲜酯残留量的方法.考查了3种不同固相萃取柱(C18、florisil、OasisR HLB)对水溶性农药胺鲜酯的吸附效果,发现它们对水中胺鲜酯的萃取效率依次为8%、13% 和96%;进一步研究了利用OasisR HLB萃取水中胺鲜酯的最佳条件(洗脱剂二氯甲烷用量4～8 mL),OasisR HLB(60 mg)小柱对胺鲜酯的保留容量高达200 μg·柱-1.运用该方法测定胺鲜酯光解试验样品,结果表明胺鲜酯质量浓度的对数与光照时间呈良好的线性关系.胺鲜酯在氙灯下的光化学降解符合一级动力学反应,光解半衰期为82 min,较易光解.     

挥发性有机物(VOCs)的不同化学去除途径:城市与区域站点的对比

VOCs在大气中主要是与OH自由基、NO₃自由基和O₃等反应氧化去除,部分OVOCs的自身光解也是重要的化学去除途径.本研究基于2018年和2019年秋季在珠三角地区的城市和区域站点的外场观测实验,使用VOCs、常规痕量气体及气象参数的观测数据,对烷烃、烯烃、芳香烃和OVOCs等VOCs组分不同化学去除途径的去除速率进行分析.结果表明,烷烃和芳香烃主要通过与OH自由基反应去除,最高占比超过99%.与NO₃自由基和O₃的反应可贡献烯烃去除速率的80%以上,特别是一些天然源的烯烃(如单萜烯)与NO₃自由基的氧化去除是贡献最大的氧化途径.光解是甲醛最重要的去除途径,在两个站点均达到了50%以上,酮类的光解贡献会高于其他OVOCs类物质.OH自由基的氧化去除途径在城市和区域站点的人为源及天然源VOCs去除中占主导地位.区域站点,烯烃尤其是天然源的烯烃物种,与NO₃自由基和O₃反应的贡献要高于城市站点.本研究对促进不同VOCs物种在大气中的去除...