有机磷农药对海洋扁藻毒性构效关系的密度泛涵理论研究

采用密度泛函理论方法,在B3LYP/6-311G**水平上,计算了11个有机磷农药化合物的结构参数,将结构参数作为理论描述符,导出了有机磷类化合物的分子结构参数与2种盐度(S=20,S=30)下扁藻毒性(-lgEC50)的定量关系式(式(3)和(6)),并用交叉验证法验证,相关系数R分别为0.923 2和0.893 3,交叉验证相关系数q2分别为0.527 0和0.540 5.在此基础上,预测了11种有机磷农药的毒性.研究表明,所得预测方程有较好的稳定性和较强的预测能力.可用于有机磷化合物的-lgEC50预测.     

用于有机磷农药固相萃取的吸附材料的研究进展

有机磷农药由于在环境中相对于有机氯农药容易降解,而成为全球范围内使用最广泛的杀虫剂。尽管有机磷农药已经被证实了低环境持久性,但由于具有生物毒性、高毒性、再生毒性、免疫毒性和基因毒性,造成的残留仍能对人类健康产生危害。样品前处理是有机磷农药残留分析过程的重要步骤,该过程耗费时间,其好坏直接影响整个分析结果的准确性。固相萃取相对液-液萃取由于具有诸如快速、简单和绿色环保的特点及较强的选择吸附性,是目前应用最广泛的农药残留分析样品前处理技术。吸附材料是决定固相萃取过程效能的关键因素。文章介绍了常见的硅吸附材料、碳吸附材料、分子印迹吸附材料及磁性吸附材料在有机磷农药固相萃取领域的研究应用现状,同时对未来研究方向进行了展望。     

A screen-printed, amperometric biosensor for the determination of organophosphorus pesticides in water samples

An amperometric biosensor based on screen-printed electrodes (SPEs) was developed for the determination of organophosphorus pesticides in water samples. The extent of acetylcholinesterase (AChE) deactivation was determined and quantified for pesticide concentrations in water samples. An enzyme immobilization adsorption procedure and polyacrylamide gel matrix polymerization were used for fabrication of the biosensor, with minimal losses in enzyme activity. The optimal conditions for enzyme catalytic reaction on the SPEs surfaces were acetylthiocholine chloride (ATChCl) concentration of 5 mmol/L, pH 7 and reaction time of 4 min. The detection limits for three organophosphorus pesticides (dichlorvos, monocrotophs and parathion) were in the range of 4 to 7 g/L when an AChE amount of 0.1 U was used for immobilization.     

复合垂直流人工湿地对有机磷阻燃剂的净化

为探索有效处理有机磷阻燃剂（OPFRs）废水的方法,本文构建了复合垂直流人工湿地（IVCWs）,探究不同进水C/N比与是否曝气等运行工况下系统对磷酸三（1-氯-2-丙基）酯（TCPP）的去除效率影响,并观察目标物在湿地系统各介质中的迁移行为及相关机理.结果表明,不同工况下IVCWs对TCPP去除效果存在显著差异.与进水C/N=3时系统对TCPP去除率（52.28%±11.64%）相比,增加进水C/N、曝气和两者联用可使去除率分别提高至（68.77%±2.49%）,（57.21%±1.76%）和（89.64%±1.94%）.通过分析系统中各相累积量发现,植物（0.09%）和基质（3.30%）中TCPP的累积有限.火山岩（162.39~435.01ng/g dw）和沸石（131.67~407.74ng/g dw）中TCPP含量显著高于土壤（32.63~149.94ng/g dw）.植物体内,与菖蒲（432.95ng/g dw）、香蒲（665.21ng/g dw）相比,风车草（1288.82ng/g dw）更易TCPP累积.不同植物中TCPP主要富集在根部,有向叶片转移的趋势.探究IVCWs对TCPP的去除潜能及迁移行为,对系统缓解OPFRs污染具有积极意义.     

固相萃取法提取净化生物检材中三类农药的实验研究

本文以常见的六种有机磷类、四种氨基甲酸脂类和五种拟种虫菊酯类农药为对象，研究了用国产ＧＤＸ－４０３或Ｃ１８固相小柱同时提取净化环境样品和生物检材中三种类型的农药，分别采用ＧＣ／ＦＰＤ，ＧＣ／ＮＰＤ和ＧＣ／ＥＣＤ三种特征性气相色谱法进行分析鉴定，为系统分析有机农药提供了一套快速、简便的固相提取方法。     

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     

Organochlorine and organophosphorus pesticide residues in the Atoya river basin, Chinandega, Nicaragua

The hydrographic basin of the Atoya river, located in the Department of Chinandega, one of the main cotton producing regions in Nicaragua, is intensively contaminated by pesticides. Samples of river waters and sediments, as well as strategically selected wells have been analyzed to study variations in the concentrations of organochlorine and organophosphorus pesticide residues between the dry season (November-April) and the rainy season (May-June). Generally, higher concentrations of pesticides have been detected in the river waters and sediments in the dry season. DDT, DDD, DDE compounds and toxaphene are the most frequent organochlorine residues found in the water and sediment samples, while endrin, aldrin, dieldrin and lindane are mainly found in the waters of rivers and wells. Organophosphorus compounds were rarely detected. However, residues of ethion, methyl-parathion and ethyl-parathion were found in high concentrations in some river and well water samples. Generally, organochlorine compounds tend to accumulate in the fine grain-size fractions, rich in organic matter, except DDE, which concentrates basically in the coarse grain-size fractions.     

Persistence and Dissipation of Readymix Formulations of Insecticides In/On Okra Fruits

Dissipation behaviour of ready mix polytrin C 44EC (profenophos 40% + cypermethrin 4%) and spark 36EC (triazophos 35%+.deltamethrin 1%) applied at 1 L/ha in okra crop during Kharif in year 2000 was studied at 0, 1, 3, 5 and 7 days after treatment. Dissipation on 7th day was found to be maximum (98.4%) for profenophos followed by triazophos (86.2%), cypermethrin (73.5%) and deltamethrin (55.7%). Half life (t1/2) values for the above insecticides were 1.35, 2.55, 4.11 and 7.60 days, respectively. All the insecticides followed a first order kinetics. Profenophos and triazophos followed a biphasic dissipation pattern with faster dissipation in phase I (0–1 days) and manifesting slower rate of dissipation in phase II (1–7 days).     

敏化剂特性及其耦合微波强化污泥破解研究

采用污泥活性炭（SAC）、TiO₂/SAC、Fe₃O₄/SAC作为敏化剂,结合微波处理技术对污泥进行了预处理,通过分析滤液中COD、DNA、氮、磷、有机物的含量及组分,探索微波+敏化剂的最佳处理条件.SAC负载TiO₂和Fe₃O₄后强化了其对电磁波的介电损耗和磁滞损耗,tan δ_ε分别增加了1.8和1.3倍,tan δ_μ分别增加到0.26和0.67.TiO₂/SAC投加量为0.25g/gSS时,样品滤液的COD浓度是1900mg/L,是原污泥和单独微波处理的4.52倍和1.86倍;Fe₃O₄/SAC投加量为0.35g/gSS时,样品滤液的COD浓度是2540mg/L,是原污泥和单独微波处理的6.05倍和2.45倍,Fe₃O₄/SAC强化污泥破壁效果更好.此时,样品滤液中TN、TP、蛋白质、多糖浓度分别为原污泥的7.7倍、16倍、7.49倍和71.69倍,微生物胞内和胞外聚合物中的物质大量释放,滤液中的溶解性有机物大大增加.微波+敏化剂的预处理方法有利于对污泥中氮、磷及有机物进行资源化利用与回收.     

Separation of chlorinated hydrocarbons and organophosphorus, pyrethroid pesticides by silicagel fractionation chromatography and their simultaneous determination by GC-MS

A silicagel fractionation procedure for environmental sample extracts, which separates chlorinated hydrocarbons(CHCs) and organophosphorus, pyrethroid pesticides into two groups for subsequent instrumental analysis, was developed in this study. This method was achieved by optimizing the fraction cut-off volume of elution and different solvents. Using fully activated silica gel and cut-off CHCs collection after 10ml 10% dichloromethane (DCM) in n-hexane passing through the column resulted in satisfactory separation of CHCs and organophosphorus, pyrethroid pesticides. This procedure had a higher reliability for CHCs than for organophosphorus, pyrethroid pesticides, because there is a relatively reliable recovery for CHCs. This approach is less expensive due to reducing sample pre-treatment time and solvent consumption.