α-二羰基化合物的结构-致突活性关系

采用ＡＭ１方法计算了６个α－二羰基化合物与ＤＮＡ碱基岛嘌呤环外Ｎ＾２发生紊电加成反应的速率控制步骤的活化能及分子结构和电子结构。研究其结构－知必凶线性回归结果表明;可用烷化反应活化能、ＬＵＭＯ能量、分子量表面积比和羰基面原子的正电性表示化合物的致突活性指数,获得很好的回归效果（Ｌ顺归系数Ｒ＝０．９９９８）。以本文提出的方程对这些化合物的估性进行计算,秘得到的结果与实验结果吻合得很好。     

1,3-丁二烯与DNA交联机理的研究——代谢产物在DNA大沟股间交联反应的AM1计算

采用ＡＭ１方法计算了环境致癌物１,３－丁二烯（ＢＤ）的代谢产物１,２－环氧－３,４－丁烯（ＥＢ）和１,２,３,４－二环氧丁烷（ＤＥＢ）与ＤＮＡ腺嘌呤和胞嘧啶烷化反应过程速率控制步骤的活化能,以及ＤＥＢ在ＤＮＡ大沟侧与不同序列ＤＮＡ片断生成烷化股间横向交联产物的结构和能量．结论认为：用烷化反应的难易程度难以解释ＤＥＢ的致突性比ＥＢ约大１００倍的实验事实;强致突的ＤＥＢ可与碱基发生２次烷化反应,生成ＤＮＡ交联产物;而ＥＢ则不能交联,这可能为２者基因毒性差异巨大的分子机制;同时ＤＥＢ在ＤＮＡ大沟侧可与多种不同的ＤＮＡ序列发生股间横向交联,对比在小沟侧只与２种序列交联,此发生股间横交联几率的差异合理地解释了ＤＥＢ致突的碱基选择性     

水溶液中α-萘乙酸的光降解研究

为了解α－萘乙酸在环境中滞留、迁移和转化等行为,以降低率紫外灯和荧光灯为光源,对水溶液中的ＮＡＡ进行光降解。研究结果表明,主波长为２５４ｎｍ的紫外光能有效降解ＮＡＡ,降解呈一级动力学反应,而主波长为３６５ｎｍ的长波光对ＮＡＡ几乎不降解;添加ＴｉＯ２能有效催化ＮＡＡ的降解,采用ＧＣ－ＭＳ技术鉴定了几种光解主要产物,ＮＡＡ的光降解包括氧化脱羧和芳环的氧化断裂过程。     

DNA加合物的致癌作用研究进展

综述了遗传毒性化学物质与ＤＮＡ的加合作用，以及ＤＮＡ加合物形成后在致癌作用中的影响，说明ＤＮＡ加合物的形成及剂量关系可以为化学物质致癌能力的指标，比较了ＤＮＡ加合物检测方法的特点及ＤＮＡ加合物研究的前景。     

DNA氧化损伤在太阳光致M13mp2噬菌体突变中的作用

以野生型大肠菌ＣＳＨ５０及ｍｕｔＭ缺陷的大肠菌ＭＦ６７为宿主，观察了太阳光对Ｍ１３ｍｐ~２噬菌体单链ＤＮＡ ｌａｃＺα基因区域的致突变性．结果显示，太阳光照射引起噬菌体ｌａｃＺα基因区域的突变，在ｍｕｔＭ缺陷的宿主中更为明显；０．２５ｍｏｌ／Ｌ的甘露醇可以部分拮抗太阳光的致突变作用．以ＥＳＲ自旋捕捉法检测了太阳光、长波紫外线（ＵＶＡ）及中波紫外线（ＵＶＢ）照射Ｍ１３ｍｐ~２噬菌体样品中的自由基，结果还显示，太阳光和ＵＶＡ照射可引起羟自由基的产生，而ＵＴＢ照射则没有明显的自由基信号产生说明太阳光致突变作用与ＤＮＡ氧化损伤有关，羟自由基在其中发挥一定的作用     

日光辐照草酸铁盐体系降解水中低浓度混合药物及产物的生物毒性评价

在太阳光辐照下以三草酸合铁酸钾为催化剂,分解H2O2产生·OH,对水中的甲硝唑、双氯芬酸钠、磺胺甲基异唑和布洛芬4种常见的痕量药物污染物间歇降解与矿化,并且对降解前后水溶液的毒性进行了评价.以体系的总有机碳为指标,探讨了H2O2的初始浓度、三草酸合铁酸钾的投加量、体系的pH值等因素对水溶液中TOC去除率的影响,确定了最佳操作条件,根据4种药物的化学结构解释了它们在水中的降解速度.以药物水溶液对小球藻的EC50值为指标,对4种药物的联合毒性,以及降解中间产物的生物毒性做出了评价.结果表明,当4种药物的初始浓度都为20mg·L-1时,降解过程适宜条件是pH值为3,H2O2的初始浓度为300mg·L-1,三草酸合铁酸钾的投加量为75mg·L-1.4种药物的降解速度为:甲硝唑布洛芬磺胺甲基异唑双氯芬酸钠.随着中间产物的生成与降解,药物水溶液的生物毒性有先增大后迅速减小的趋势.最后给出了Solar/FeOx/H2O2体系降解水中低浓度药物的表达式.     

阿特拉津和溴氰菊酯降解规律及其分析方法

研究了阿特拉津（ａｔｒａｚｉｎｅ）和溴氰菊酯（ｄｅｌｔａｍｅｔｈｒｉｎ０两类农药在环境介质中的降解行为，详细比较了两者降解性能之间存在的差异，并明确指出它们的降解产物都具有一定的毒性和更强的极性，通过对阿特拉津及其降解产物的研究实例，说明了在研究环境介质中残余微量农药的检测方法时，建立以农药家族及其降解产物为整体的系统分析方法是必要的。     

环境科学基础理论 环境化学

X131200603213不同介质中多环芳烃光降解及与生物耦合降解研究现状/张利红(中科院沈阳应用生态研究所)…∥生态学杂志/中科院沈阳应用生态研究所.-2006,25(4).-461~466环图Q-28多环芳烃(PAHs)是环境中广泛存在的一类有机污染物。它的降解一直是人们关注的课题。光降解就是多环芳烃降解的一种重要形式。对在气相、液相和固相不同介质中的PAHs光降解研究进行了综合论述,重点对PAHs在液相介质的降解速率及影响因素、中间产物及降解机制和反应动力学进行了深入探讨,并介绍了光-生物耦合降解多环芳烃的研究进展。进一步完善PAHs光降解研究…     

TiO_2-Cu~(2 )体系降解偏二甲肼的研究

研究了在TiO2 催化氧化降解偏二甲肼的反应体系中添加Cu2 的效果以及Cu2 浓度、添加H2 O2 、反应体系A/V值以及紫外光与太阳光作光源对偏二甲肼降解率的影响 ,结果表明 ,在TiO2 光催化降解偏二甲肼的反应体系中Cu2 的最佳投加量为 4 0mg/L ,添加适量H2 O2 以及在紫外光照射下 ,适当增大反应液的A/V值都会大大提高偏二甲肼的降解率。同时也研究了偏二甲肼降解中间产物随着反应进程的降解规律。     

1,3—丁二烯与DNA交联机理的研究：代谢产物在DNA大沟股间交联反应的A …

采用ＡＭ１方法计算了环境致癌１，３－丁二烯的代谢物产１，２－环境氧－３，４－丁烯和１，２，３，４－二环氧化烷与ＤＮＡ腺嘌呤和胞嘧啶烷化反应过程速率控制步骤的活化能，以及ＤＥＢ和ＤＮＡ大沟侧与不同序列ＤＮＡ片断生成烷化股间横向联 产物的结构和能量。     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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