拟除虫菊酯类农药的降解与代谢研究进展

拟除虫菊酯类农药残留引发各种环境污染和食品安全问题,文章主要综述了该农药的生物降解、光降解和生物代谢三个方面的国内外研究现状。生物降解是其分解代谢的重要环境过程之一,微生物、哺乳动物、水生生物、昆虫及植物等对拟除虫菊酯的代谢都具有不可替代的作用,其中微生物降解菌的分离、微生物的酶促降解及其衍生的基因工程菌技术迅速发展,为通过基因克隆高效表达拟除虫菊酯降解酶提供依据。合理利用光能可有效去除拟除虫菊酯,光敏化降解与光猝灭降解研究可有助于农药混配的效果分析。通过拟除虫菊酯在生物体内的代谢分析可为治疗人体农药中毒提供有效方法。文章还讨论了吸附作用、氧化作用对拟除虫菊酯的降解效果。     

紫外活化过硫酸盐降解水中三氯蔗糖动力学和机制

以新兴污染物人工甜味剂三氯蔗糖（SUC）为对象,研究紫外活化过硫酸盐（UV/PS）对其的降解效果.考察UV光强、PS投加量、溶液初始pH值和阴离子浓度等因素的影响,解析UV/PS降解SUC过程中的降解产物并评估其生态毒性.结果表明,对比单一UV和单一PS,UV/PS降解SUC效果更为明显,SUC降解反应速率常数随光强、PS投加量增加而增大,中性条件更有利于SUC降解,背景离子NO₃^-和HCO₃^-对UV/PS降解SUC有一定的抑制作用,而Cl^-和SO₄^2-促进降解过程.基于高分辨质谱HRMS和GC-MS解析出16种中间产物,降解过程主要涉及羟基化、氧化和醚裂解等反应.发光细菌毒性实验和ECOSAR预测结果表明,UV/PS降解SUC过程中会产生毒性高于母物质的中间产物,对生态环境存在潜在威胁.     

Effect of copper on the degradation of pesticides cypermethrin and cyhalothrin

The influence of coexisting copper (Cu) ion on the degradation of pesticides pyrethroid cypermethrin and cyhalothrin in soil and photodegradation in water system were studied.Serial concentrations of the pesticides with the addition of copper ion were spiked in the soil and incubated for a regular period of time,the analysis of the extracts from the soil was carried out using gas chromatography (GC).The photodegradation of pyrethroids in water system was conducted under UV irradiation.The effect of Cu~(2 ) on the pesticides degradation was measured with half life (t_(0.5)) of degradation.It was found that a negative correlation between the degradation of the pyrethroid pesticides in soil and Cu addition was observed.But Cu~(2 ) could accelerate photodegradation of the pyrethroids in water.The t_(0.5) for cyhalothrin extended from 6.7 to 6.8 d while for cypermethrin extended from 8.1 to 10.9 d with the presence of copper ion in soil.As for photodegradation,t_(0.5) for cyhalothrin reduced from 173.3 to 115.5 rain and for cypermethrin from 115.5 to 99.0 min.The results suggested that copper influenced the degradation of the pesticides in soil by affecting the activity of microorganisms.However, it had catalyst tendency for photodegradation in water system.The difference for the degradation efficiency of pyrethroid isomers in soil was also observed.Copper could obviously accelerate the degradation of some special isomers.     

一株氯氰菊酯降解真菌的筛选鉴定及其降解特性研究

从雅安市售砖茶中分离筛选出一株对氯氰菊酯具有较高降解能力的真菌菌株YAT,根据其形态学及ITS序列分析,将该菌鉴定为黑曲霉(Aspergillus niger).菌株YAT在PD培养基中168 h内对50 mg·L-1氯氰菊酯的降解率为54.83％,对氯氰菊酯的降解率与菌体生物量呈正相关.动力学研究表明,菌株YAT降解氯氰菊酯的过程符合一级动力学方程,在测试的底物(氯氰菊酯)浓度、温度、pH范围内,氯氰菊酯半衰期为85.750～281.958 h,较高温度及偏碱性条件有利于氯氰菊酯的降解,底物浓度越高,其半衰期越长.此外,菌株YAT对50 mg·L-1溴氰菊酯、氰戊菊酯、氟氯氰菊酯和氯菊酯的120 h降解率分别为27.53％、58.00％、53.23％和25.34％.     

Parameters e ect on heterogeneous photocatalysed degradation of phenol in aqueous dispersion of TiO2

Photocatalytic degradation of phenol selected as model compound of organic pollutant had been investigated in aqueous titanium dioxide (TiO2) dispersion under UV irradiation. The e ects of various parameters such as pH, catalyst concentration, phenol concentration, anions, metal ions, electron acceptors, and surfactants on the photocatalytic degradation of phenol were investigated. The degradation kinetics was determined by the change in phenol concentration employing UV-Vis spectrometry as a function of irradiation time. The degradation kinetics of phenol follows pseudo first-order kinetics. The results showed a significant dependence of the photocatalytic degradation of phenol on the functional parameters. The probable promising roles of the additives on the degradation process were discussed     

拟除虫菊酯农药在茶叶中应用的安全性评价

采用田间模拟施药与气相色谱法研究了7种拟除虫菊酯农药在茶园生态环境中的降解动态,茶叶加工过程中的降解和泡茶过程的浸出率及其主要影响因子。根据实验结果推算出通过饮茶进入人体的农药量,结合农药的毒理特性,对拟除虫菊酯农药在茶园生态环境中应用的安全性进行了综合评价。结果表明,拟除虫菊酯农药在茶园中应用的安全性显著高于有机磷农药,在拟除虫菊酯农药之间,其安全性也有较大差异。本研究不仅为茶园使用农药的选择提供了依据,而且首次提出了一种农药对人体安全性的定量评价体系。     

Photocatalytic degradation of dye effluent by titanium dioxide pillar pellets in aqueous solution

Photocatalytic oxidation (PCO) process is an effective way to deal with organic pollutants in wastewater which could be difficult to be degraded by conventional biological treatment methods. Normally the TiO2 powder in nanometre size range was directly used as photocatalyst for dye degradation in wastewater. However the titanium dioxide powder was arduous to be recovered from the solution after treatment. In this application, a new form of TiO2(i. e. pillar pellets ranging from 2.5 to 5.3 mm long and with a diameter of 3.7 mm) was used and investigated for photocatalytic degradation of textile dye effluent. A test system was built with a flat plate reactor(FPR) and UV light source(blacklight and solar simulator as light source respectively) for investigating the effectiveness of the new form of TiO2. It was found that the photocatalytic process under this configuration could efficiently remove colours from textile dyeing effluent. Comparing with the TiO2 powder, the pellet was very easy to recovered from the treated solution and can be reused in multiple times without the significant change on the photocatalytic property. The results also showed that to achieve the same photocatalytic performance, the FPR area by pellets was about 91% smaller than required by TiO2 powder. At least TiO2 pellet could be used as an alternative form of photocatalyst in applications for textile effluent treatment process, also other wastewater treatment processes.     

SO42-改性TiO2催化降解茜素红水溶液

基于SO42-对TiO2超强酸化改性制备了SO42-/TiO2催化剂,以茜素红为目标物试验研究了该催化剂的催化降解性能,并考察了降解条件等因素对脱色率的影响.结果表明,SO42-/TiO2具有较强催化降解性能及一定的光催化活性,降解过程中SO42-流失是催化剂失活的主要原因.在pH=7,催化剂加入量为2.5g/L,起始浓度为140mg/L,太阳光等优化工艺条件下降解效果最好,脱色率达到92%.     

吸附树脂/铁酞菁对甲基橙的光催化降解

针对铁酞菁在水溶液中易于聚合而降低催化活性,同时在均相光催化体系中分离困难、难以重复利用的问题,将铁酞菁负载在吸附树脂上,制得多相催化剂。该催化剂在可见光的照射下能有效地催化H2O2降解偶氮染料甲基橙。考察了催化剂用量、H2O2投加量、pH值、温度等因素对甲基橙去除效果的影响。结果表明,甲基橙初始浓度为50 mg/L,卤灯功率为100 W,催化剂投加量为1.0 g/L,H2O2用量为0.2 mol/L,pH为3,温度为35℃时,反应10 h,甲基橙去除率达到91%,且催化剂所含铁离子无流失,具有很好的稳定性,可重复使用。     

太湖藻源性颗粒物降解过程中营养盐转化及其生态效应

以太湖水体中藻源性颗粒有机物作为切入点,研究了不同环境条件下(有光,无光)藻源性颗粒有机物降解过程中C,N,P等营养元素的形态变化过程,分析了藻源性颗粒有机物对水体营养盐循环和浮游植物生长中的作用.实验结果显示,蓝藻水华过程中,藻源性颗粒有机物最高可占水体总C,N,P比例的81.51%,94.60%,97.47%,是水体营养元素的重要组成部分;有光组颗粒物APA显著高于无光组,说明有光组中颗粒态P降解和转化速率显著高于无光组,但有光组水体中SRP浓度低于无光组,Chl-a浓度高于无光组,说明有光组中藻源性颗粒物降解的同时伴随着藻类的生长,颗粒物释放的SRP被浮游植物吸收并转化为生物量;光照对C,N,P的降解过程有明显影响,无光组颗粒物中C,N,P降解速率是有光组的2倍,可降解比例是有光组的(2.5±0.1)倍;实验中还发现前7d各元素的降解速率要高于之后的降解速率.综上,藻源性颗粒物营养盐总量大,生物可利用性高,降解迅速,且降解产物可被浮游植物吸收,是藻类生长和水华发生重要的营养盐来源.     

光照对畜禽粪便中抗生素降解和微生物的影响

为研究光照对粪便发酵降解抗生素的影响,采用固态发酵试验,对比避光和光照培养后不同猪鸡粪中主要残留抗生素浓度和细菌群落组成差异.结果表明,光照促进发酵后粪便的抗生素残留总量下降,在猪粪样品中尤为显著,最高下降23.8%.猪粪中四环素类、氟喹诺酮类和磺胺类抗生素在光培养下的降解总体高于避光培养,且光照降低猪粪中磺胺耐药细菌数量,增加细菌群落多样性和有机质降解相关细菌丰度.光照对鸡粪发酵中抗生素降解的影响在不同样品和光照时间之间差异显著,可抑制部分样品中磺胺类抗生素降解,并伴随磺胺耐药细菌数量的增加以及细菌群落丰度和多样性的下降.有针对性地在养殖粪便尤其是猪粪的堆肥场所提供适度光照将有助于抗生素的削减.     

MOFs衍生CuO/ZnO催化剂的制备及其光催化性能的研究

利用Cu₃(BTC)₂为材料模板制备金属氧化物CuO,通过光沉积引入Zn2+煅烧合成双金属氧化物催化剂CuO/ZnO,研究了该催化剂在可见光条件下对罗丹明B的光催化降解性能,确定了罗丹明B在降解过程中的主要活性物种,并利用液相原位红外技术探究其降解机理。结果表明:MOFs衍生物CuO/ZnO催化剂具有优良的光催化降解能力,可见光响应150 min后,对10 mg/L罗丹明B的降解率最高达到67.56%以上,其中发挥主要作用的活性物种是超氧自由基·O₂-;经过5次循环实验后降解率仍在50%以上,证明该材料具有较好的可重复利用性。通过液相原位红外光谱检测,分析推断罗丹明B分子在降解过程中存在乙基、羧基和苯环芳香环结构的破坏以及氨基副产物的释放过程。该研究结果可为高效光催化体系的开发及污染物降解机理的研究提供参考。     

拟除虫菊酯气相色谱手性拆分方法及其影响因素分析

拟除虫菊酯具有较强的手性特征,包含多种异构体,不同异构体具有不同的生物活性,因此,其异构体的手性拆分具有重要的意义。气相色谱分析法因其分辨率高,峰容量大,灵敏度高、分析时间短,选择性强等特点,已被广泛应用于拟除虫菊酯的手性拆分中。文章通过阐述基于氢键作用、配位作用、包结络合作用的3种手性固定相的拆分机制,综述了气相色谱用于拟除虫菊酯手性分离的研究状况。此外,文章还分析了有机溶剂、水、温度等对拟除虫菊酯在拆分过程中差向异构现象的影响。     

拟除虫菊酯对DPPC脂质体结构的影响

以DPH荧光偏振技术研究了含氰基和不含氰基两类拟菊酯与DPPC单层脂体间的相互作用。拟菊酯作用于膜的疏水区,降低DPPC脂质体的相变温度,加宽相变范围,随其浓度增加对磷脂有序排列的破坏加剧。氯菊酯具有干扰磷脂有序排列的能力,在凝胶态随其浓度的增加,P值降低幅度增大,在液晶态对P值基本无影响。氰基的导入,使北京菊酯、氯氰菊酯和杀灭菊酯既具有干扰磷脂有序排列的能力,又能产生荧光碰撞猝灭,在凝胶态,先降低P值,然后P值增大,当其浓度较大时,P值又略有下降,在液晶态,低浓度对P值影响不大,浓度较高时P值明显上升。     

H2O2对载银TiO2光催化降解Aroclor1260的影响

光催化氧化法降解水中有机污染物是近来发展较为迅速的废水处理技术，以锐钛型载银TiO2为催化剂，在发射光谱波长为254nm，功率的15W紫外灯照射下，考察不同H2O2浓度对Aroclor1260的光催化降解的影响，结果表明：低浓度的H2O2对Aroclor1260的光催化降解有促进作用，而当H2O2的浓度高于30mol/l时，光催化降解受到抑制，而且这种影响对不同PCB单体化合物的效果基本一致。     

Electrochemical degradation of p-nitrophenol with different processes

The electrochemical degradation of p-nitrophenol (PNP) under di erent conditions was investigated. The electrochemical behavior of PNP and its reduction product p-aminophenol (PAP) on stainless steel cathode and Ti/Pt anode through cyclic voltammetry were observed. Electrochemical degradation process was performed in an undivided cell and 92% PNP was removed corresponding to a 22% total organic carbon removal. A divided cell was also used and it was found that PNP degradation was mainly attributed to cathodic reduction, while anodic oxidation was responsible for PNP removal due to the reaction with hydroxyl radicals and surface oxide generated on the anode. The sequential electrolytic processes, reduction-oxidation and oxidation-reduction, were compared in the divided cell. In the case of reduction-oxidation process, the total organic carbon removal reached 40%, but PNP removal was the same with the undivided cell. A black deposit was found in the e uent and identified by Fourier transform infrared spectroscopy as a polymer of PAP produced by the 1,4-addition reaction of quinoneimine. Intermediates left in the solution such as hydroquinone, p-benzoquinone and PAP were determined by high performance liquid chromatography. Whereas, the oxidation-reduction process proved unsatisfying.     

Formaldehyde degradation by UV/TiO2/O3process using continuous flow mode

The degradation of formaldehyde gas was studied using UV/TiO2/O3 process under the condition of continuous flow mode. The effects of humidity, initial formaldehyde concentration, residence time and ozone adding amount on degradation of formaldehyde gas were investigated. The experimental results indicated that the combination of ozonation with photocatalytic oxidation on the degradation of formaldehyde showed a synergetic action, e.g,, it could considerably increase decomposing of formaldehyde. The degradation efficiency of formaldehyde was between 73.6% and 79.4% while the initial concentration in the range of 1.84--24 mg/m^3 by O3/TiO2flJV process. The optimal humidity was about 50% in UV/TiO2/O3 processs and degradation of formaldehyde increases from 39.0% to 94.1% when the ozone content increased from 0 to 141 mg/m^3. Furthermore, the kinetics of formaldehyde degradation reaction could be described by Langmuir-Hinshelwood model. The rate constant k of 46.72 mg/（m^3.min） and Langmuir adsorption coefficient K of 0.0268 m^3/mg were obtained.     

TiO2/多孔硅胶对乙烯光催化降解的研究

在可见光或紫外光照的非循环体系中,进行了氧化钛基的催化剂光催化降解乙烯的研究.考察了不同的乙烯初始浓度、不同温度、不同光源和负载贵金属对光降解效率的影响.结果表明,乙烯浓度在38～188 mg/m³范围时,光降解效率随乙烯初始浓度升高而缓慢地线性下降;温度升高有利于光降解;负载的贵金属不仅抑制电子空穴对复合,而且扩大了氧化钛对可见光的吸收,几十倍地提高了氧化钛在可见光的光催化效率.     

4,4’-二溴联苯在水溶液中光降解的动力学研究

多溴联苯作为溴代阻燃剂被广泛应用,从而广泛存在于环境。但少有对于多氯联苯环境行为的研究。文章以4,4’-二溴联苯为研究对象,模拟自然环境,探讨了光源强度、初始浓度、pH值和溶解氧等因素对4,4’-二溴联苯降解的影响,以及在模拟太阳光的照射下,研究了Fe3+和腐殖酸对4,4’-二溴联苯在水溶液中光降解速率的影响。结果表明,在高压汞灯照射下,4,4’-二溴联苯的光降解过程符合准一级动力学规律。提高光源强度可加速4,4’-二溴联苯的降解;初始浓度的增加使4,4’-二溴联苯降解速率减慢;反应液在高pH值和低pH值时,均促进4,4’-二溴联苯的光降解进程;体系中溶解氧增多也同样促进4,4’-二溴联苯的降解;小剂量的添加腐殖酸和Fe3+可以促进4,4’-二溴联苯的降解,但超过一定浓度则抑制其光降解。     

甲苯的光氧化降解试验研究

以气相甲苯为对象,研究其在波长为254 nm紫外光下的光氧化降解反应.同时,考察了甲苯初始浓度、光强和相对湿度对甲苯转化率的影响,分析了甲苯降解中间产物的生成机理.结果表明,随着甲苯初始浓度的增加,甲苯转化率缓慢下降;随着光照强度的增强,甲苯转化率逐渐增加;而提高相对湿度,甲苯转化率则为先升高后降低.在甲苯降解动力学分析中发现其光氧化降解过程符合伪一级反应动力学,且表观速率常数与光照强度成正比.通过对甲苯降解中间产物的分析,发现随着光照强度的增加,含苯环物质的降解更为充分,乙醇、乙酸等的相对含量逐渐增加,苯甲醇、苯甲醛缩二甲醇等的含量逐渐降低,在此基础上提出了甲苯生成含苯环产物及开环生成2-戊酮等的降解机理.