新农药氯虫酰胺在醇液中的光解

分别以氙灯和紫外灯为光源,对氯虫酰胺在甲醇和乙醇中的光解动力学及降解机理进行了研究。结果表明,在氙灯和紫外照射下,氯虫酰胺在甲醇和乙醇中的光解符合一级反应动力学规律。在模拟太阳光氙灯辐射下,氯虫酰胺在甲醇和乙醇中的光解半衰期分别为1．58h和2．57h,而紫外光辐射下分别为1．49min和1．60min。采用LC-MS对氯虫酰胺光解产物进行分离和鉴定,推断氯虫酰胺在醇中的光解途径主要涉及到分子环合和重排生成光解产物A[2-（2-溴-4H-吡唑并[1,5．d]吡啶并[3,2-b]B,4]恶嗪-4-基亚氨基）-5-氯-N,3-二甲基苯甲酰胺]和B[2-（3-溴-1-（3-羟基吡啶-2-基）-1H-吡唑-5-基）-6-氯-3,8-二甲基喹啉-4（3H）-酮1。     

吡虫啉的光解水解和土壤降解

在实验室测定了吡虫啉的光解，不同ＰＨ条件下的水解与在东北黑土等３种不同土壤的降解。试验结果表明，在３００Ｗ低压汞灯下，吡虫啉水相溶液的光解呈一级反应动力学反应，光解半衰期为６．８１ｈ；在ＰＨ５、ＰＨ７、ＰＨ９的缓冲溶液中的水解半衰期分别为３０．６、１３．６与８．０ｄ；     

吡虫啉的光解水解和土壤降

在实验室测定了吡虫啉的光解、不同ｐＨ条件下的水解与在东北黑土等３种不同土壤中的降解。试验结果表明，在３００Ｗ低压汞灯下，吡虫啉水相溶液的光解呈一级反应动力学反应，光解半衰期为６．８１ｈ；在ｐＨ５、ｐＨ７、ｐＨ９的缓冲溶液中的水解半衰期分别为３０．６、１３．６与８．０ｄ；在东北黑土、太湖水稻土和江西红壤中的降解半衰期分别为１０．７、１１．１和４．１ｄ。     

冰晶中双氧水的UV光解

本文采用253.7 nm的紫外灯光解冰晶中的双氧水,研究其光解率随光照时间和温度的变化.以及Cl~-,SO_4~(2-)和CO_3~(2-)对其降解的影响,结果表明,相同条件下三种离子对其影响大小依次为:Cl~->SO_4~(2-)>CO_3~(2-).对比冰晶和水溶液中双氧水的光解,冰晶中双氧水的光解速率低于水溶液中双氧水的光解速率.紫外-可见光谱(UV-vis)分析其光解产物,没有发现新的物质生成.由此可以认为,冰晶中双氧水主要在冰晶笼子中进行反应,少部分在类似液体层(QLL)中降解.     

水中硝基氯苯光解动力学

本文研究了硝基氯苯(邻、间、对位)在纯水及江水中的光化学分解。结果表明光化学反应均属表观动力学一级反应。从它们在纯水(氙灯下)、纯水(300—400nm光照下)、纯水(阳光下)、天然水(阳光下)中分解的速度常数来看,pH、腐殖质、硝酸根对光解影响较大,无机盐对光解无显著影响,硝基氯苯在pH>6的纯水中光解有中间产物生成。     

TiO2与Cu2O光催化降解对硝基苯酚比较研究

分别采用自制的纳米TiO2和Cu2O研究对硝基苯酚的光催化降解.结果表明,模拟阳光条件下,100mg·l-1对硝基苯酚水溶液的氧化亚铜催化反应半衰期为20.0min,而二氧化钛不具备可见光催化能力;在SGY-1多功能光化学反应器中,TiO2催化降解对硝基苯酚的半衰期是48.1min.产物分析表明,n-型半导体二氧化钛的光催化反应存在两种降解历程,生成二羟基硝基苯或脱除硝基.而p-型半导体氧化亚铜催化的光降解反应未检出脱硝基产物,仅检出1,2-二羟基-4-硝基苯.     

农药阿维菌素在水中的光解动态及机理

为了科学评价农药阿维菌素的环境安全性,采用室内模拟方法研究了其在水环境中的光解动态,考察了波长、光强和添加物质等对阿维菌素光降解的影响,进而利用LC/MS鉴定了其主要降解产物,并对降解机理进行了初步探讨.结果表明:紫外灯辐射波长对阿维菌素的光解速率影响较大,波长越短,越有利于阿维菌素的光降解;模拟太阳光强度越大,阿维菌素的光解速率越快;1%H_2O_2、0.1%TiO_2和10%丙酮作为添加物质都能加快阿维菌素的光解进程;通过分析阿维菌素光解产物的TIC图和质谱图,可能主要有两种代谢产物,分析了其降解途径及机理.     

农药杀虫双的光解和挥发研究

本文研究了农药杀虫双及其降解产物沙蚕毒的光解和挥发,结果表明:杀虫双在水溶液中、沙蚕毒在甲醇溶液中的光解为一级动力学过程。在450W中压汞灯下的光解速率常数分别为0.33min~(-1)和0.15min~(-1),半衰期分别为2.10min和4.70min。在阳光下的光解速率常数分别为0.00308min~(-1)和0.033min~(-1),半衰期分别为3.75h和21.0min。它们在365nm波长下的光解量子产率分别为255.9相36.6。经初步测定,杀虫双、沙蚕毒在25℃时的饱和蒸气压分别为2.6×10~(-6)mm Hg和4.6×10~(-5)mm Hg。     

三种丙烯菊酯系列产品的光解和水解稳定性

研究了富右旋反式丙烯菊酯、Es-生物丙烯菊酯、右旋丙烯菊酯 3种丙烯菊酯系列农药在水体中的光解以及不同温度、pH条件水体中的水解作用。结果表明 ,在 5 0 0W氙灯下 ,3种菊酯类农药在水溶液中的光解均呈一级动力学反应 ,3种农药的光解半衰期分别为 1.84 ,1.37和 1.5 1h ;在 2 5℃的酸性水溶液中 ,3种农药的水解速率很慢 ,半衰期均大于 16 2d ;水温的升高与碱性的增强均能加速水解过程。在 5 0℃的碱性水溶液中 ,3种农药的光解半衰期分别为 0 .2 1,0 .2 2和 0 .18d。虽然 3种丙烯菊酯异构体含量不同 ,但其光解、水解特性没有显著差别。本文对有关水解机理也作了初步分析。     

17种多环芳烃在水溶液中的光解

本文以国产高压汞灯及太阳光为光源,系统地研究了常见的17种多环芳烃(下简称PAH)在甲醇-水、乙腈-水溶液中的光化学降解。结果表明,大多数PAH的光解速率常数(k)与它们的极谱氧化半波电位(E_(1/2)~(ox)有关:E_(1/2)~(ox)值低(易氧化),则k值大(反应快)。黑暗条件下的对照试验未发现PAH降解。还测得了萘的光解产物为邻苯二甲酸,并发现溶液中的溶解氧除去后萘不能光解。这些都表明大部分PAH光解为光氧化反应。另外,用电荷转移复合物(CTC)的形成、解离和单重态氧(~1O_2)的氧化机理,讨论了温度高、助溶剂极性强会加快光解速率的效应。     

The role of thymoquinone as antioxidant protection on oxidative stress induced by imidacloprid in male and female Swiss albino mice

The aim of the present study was to evaluate the possible protective effects of thymoquinone (TQ), an antioxidant agent, against imidacloprid (IMI)-induced oxidative stress in male and female mice. In total, 48 Swiss Albino male and female mice were fed a standard rodent diet and divided into 3 equal groups: the animals in the control group (vehicle treated) were given corn oil, the second group were orally administered 15 mg/kg/day IMI alone, and the third group were orally administered 15 mg/kg/day IMI and with TQ at 10 mg/kg/day for 21 days. During the experimental period, there were no significant changes between initial body weights and final body weights of IMI treated male and female mice. IMI produced significant increase in blood, liver, kidney, and heart malondialdehyde (MDA) levels and decrease in blood and liver glutathione (GSH) levels. In addition, IMI treatment decreased erythrocyte, liver, and kidney superoxide dismutase (SOD) activity in male mice and decreased erythrocyte and liver SOD activity in female mice. Erythrocyte catalase (CAT) activities were found to be low in male and female mice. However, treatment with TQ reversed IMI-induced oxidative stress, lipid peroxidation, and activities of antioxidant enzymes. Moreover, TQ exhibited protective action against the IMI-induced histopathological changes in tissues of male and female mice. In conclusion, TQ was found to be effective in protecting mice against IMI-induced oxidative stress by enhancing antioxidant defense mechanisms.     

Adsorption behavior of imidacloprid pesticide on polar microplastics under environmental conditions: critical role of photo-aging

● Small molecular chains formed on photo-aged polylactic acid microplastics (MPs). ● Oxygen-containing functional groups generated on photo-aged polyamide MPs. ● Photo-aging has the opposite influence on the imidacloprid adsorption on two MPs. ● Electrostatic interactions and hydrogen bonds were the main mechanisms. ● High pH value and low ionic strength increase the adsorption capacity. The photo-aging behavior of microplastics (MPs) in natural environment has become a global concern. The ultraviolet radiation has enough energy to change the polymer structure and physical-chemical properties of MPs. Less attention has focused on the interactions of the photo-aged polar and biodegradable MPs with organic pollutants. This work investigated the structural properties of aged polar polyamide (PA) MPs and biodegradable polylactic acid (PLA) MPs exposed to ultraviolet irradiation and their adsorption behavior and mechanism for neonicotinoid insecticide imidacloprid (IMI). The results showed that the MPs had extensive changes in surface morphology and chemical properties after photo-aging. The C–N bond of PA MPs was disrupted to form more carbonyl groups. The oxygen-containing functional groups on the surface of aged PLA MPs were broken and generated relatively smaller molecules. The adsorption capacity of IMI on PA MPs decreased by 19.2 %, while the adsorption capacity of IMI on PLA MPs increased by 41.2 % after photo-aging. This depended on the natural structure of the MPs and their ability to absorb ultraviolet light. The electrostatic interactions, hydrogen bonds, van der Waals interactions, and polar-polar interactions were the main adsorption mechanisms of IMI on MPs. High initial solution pH and low ionic strength favored the adsorption of IMI by altering charge distribution on the MPs surface. The formation of the humic acid-IMI complexes decreased the concentration of IMI in the water phase and further decreased the adsorption on MPs. These results are enlightening for a scientific comprehension of the environmental behavior of the polar MPs.     

克螨特和霸螨灵及其混剂在水中的光降解

研究了克螨特、霸螨灵在几种水体中的光降解以及 2种农药之间的光敏化或光猝灭效应。结果表明 ,在 3 0 0W高压汞灯光照处理时 (试验试管距光源 8cm) ,克螨特和霸螨灵都极易降解 ,克螨特的光解半衰期为 9.0 6min ,霸螨灵的光解半衰期仅为 1 .4 8min。克螨特在不同水体中的光解率为 :重蒸馏水 >鱼塘水 >河水 >井水 ,霸螨灵的光解率为 :井水 >重蒸馏水 >鱼塘水 >河水 ;2种农药在现采水、过滤水、灭菌水中的光解率依次降低。克螨特和霸螨灵混剂在重蒸馏水中互为光猝灭剂 ,在井水、河水和塘水中霸螨灵对克螨特有极显著的光敏化作用 ,而克螨特对霸螨灵有极显著的光猝灭效应。克螨特、霸螨灵在pH 5和 pH 9缓冲液中光解率比之在 pH 7缓冲液中稍快 ,光猝灭效应也较强烈。在重蒸馏水中太阳光照处理时 ,克螨特和霸螨灵互为光敏剂 ,而高压汞灯下则互为光猝灭剂。     

三唑酮在水中的光化学降解及其影响因素

以太阳光和高压汞灯为光源,研究了水溶液中三唑酮光化学降解的影响因子。结果表明:在不同光源和透光介质下,三唑酮的降解能力从大到小依次为:石英试管 高压汞灯、玻璃试管 高压汞灯、石英试管 太阳光、玻璃试管 太阳光、暗室;水溶液中三唑酮初始浓度越高,其光降解率越低,呈负相关关系;丙酮对三唑酮在水中的光解有极显著的光敏作用,光敏效率与丙酮添加量有显著相关性;三唑酮的光解实质为光氧化作用,溶解氧含量对三唑酮光解有重大影响。     

甲基对硫磷对三种拟除虫菊酯杀虫剂的光敏降解研究

本文以高压汞灯和自然阳光为光源，研究了甲基对硫磷对氧氰菊酯、溴氰菊酯和氰茂菊酯在玻片表面光致降解的影响。结果表明：甲基对硫磷与三种拟除虫菊酯农药混合照光处理后，可使拟除虫菊酯农药的光解速度加快。氯氰菊酯、氰戊菊酯和溴氰菊酯的光解半衰期，在高压汞灯下比其单独照光分别缩短１２．１８、８．４６和７．３３倍，在阳光下则分别缩短４．７３，２．６５，和４．４６倍。甲基对硫磷对三种拟除虫菊酯农药表现出显著的光敏     

A polyunsaturated hydrocarbon (3, 6, 9, 12, 15, 18-heneicosahexaene) in the marine food web

An olefinic hydrocarbon (all-cis-3,6,9,12,15,18-heneicosahexaene, HEH)_was islated from marine planktonic plants and animals. Its structure was established by ultraviolet, infrared and mass spectrometry in combination with chemical techniques. The olefin occurs in many species of marine planktonic algae and is probably derived from the corresponding docosahexaenoic acid. Rhincalanus nasutus accumulates HEH nonselectively from its algal food together with the triglyceride lipids. Other, related copepods contain little or no HEH even when grown in cultures of algae that provide R. nasutus with that olefin. The presence of HEH in marine vertebrates suggests that, within the animal lipids, hydrocarbons are remarkably stable. This work has practical implications for studies of the marine food web and of marine pollution with persistent chemicals.Contribution No. 2485 of the Woods Hole Oceanographic Institution, Woods Hole, Massachusetts 02543, USA.     

Photoelectrocatalytic degradation of camphor on TiO2/RuO2 electrodes

The degradation of camphor using titanium/ruthenium dioxide (TiO₂/RuO₂; 70:30) electrodes was investigated in a photoelectrochemical thin-film reactor under near UV light irradiation. Two different electrolytes (Na₂SO₄ and NaCl) were used in this work. Camphor degradation was monitored by solvent extraction methods and gas chromatography (GC) analysis. Comparative studies between photoelectrochemical, electrochemical, photolytic, and heterogeneous photocatalytical process were carried out. When NaCl was used, the degradation efficiency of camphor was improved, probably on account of electrochemical generation of active chlorine species and their photochemical conversion to chlorine radicals. Under these conditions camphor was completely mineralized at reaction times of 30 min.     

Humic acids decrease the photodegradation of the sunscreen UV filter 2-phenylbenzimidazole-5-sulfonic acid in natural waters

The sunscreen UV filter 2-phenylbenzimidazole-5-sulfonic acid (PBSA) is an emerging pollutant recently detected in surface waters. PBSA is photolabile in pure water and sunscreen cream. PBSA photoinduces DNA damages. However, the photochemical behavior and environmental persistence of PBSA are not well known. Here, we studied the photochemical transformation of PBSA in sea and continental waters. Results show that photodegradation is dependent on water constituents. Whereas low concentrations of humic acids accelerate PBSA photodegradation slightly, high concentrations of humic acids inhibit the photodegradation. Colloidal organic matters of high molecular weights are the main water constituents inhibiting photodegradation. The estimated solar photolytic half-life of PBSA at environmental concentration levels ranged from 3?days from June to August to 35?days in December. Findings show that PBSA is not persistent in waters that are low in colloidal organic matters.     

丁虫腈在环境中的降解特性

采用室内模拟试验研究丁虫腈在水体中的光解、水解及其在3种不同类型土壤中的降解特性。结果表明,丁虫腈在酸性和中性条件下比较稳定,不易水解,而在碱性条件下水解较快,在50℃、pH值为9．0的缓冲溶液中降解半衰期为26．7d。通过对水解产物的鉴定,推断丁虫腈的水解机理为碱催化水解。在[光]照度为2500lx、紫外强度为25I．LW·cm-2的人工光源氙灯条件下,丁虫腈的降解半衰期为1．5h,主要降解产物为氟虫腈。丁虫腈在太湖水稻土、江西红壤和陕西潮土中培养180d后均未发生明显降解,表明该农药在土壤中较难降解。