大气臭氧损耗中双自由基反应机理的量子化学研究

用量子化学ＲＨＦ理论方法研究了单重态双自由基ＮＨ,ＣＨ２、ＣＣＬ２与大气臭氧Ｏ３的反应机理。在３－２１Ｇ水平上用梯度解析技术优化了上述瓜在的反应物、中间体和产物构型,６－３１Ｇ或６－２１Ｇ计算能量,得到了各构型的有关结构数据。计算表明：上述反应分２步进行,双自由基先与Ｏ３反应生成稳定的中间体,然后在光照条件下中间体分解为ＮＨＯ、Ｈ２Ｃ烽ＣＬ２ＣＯ等稳定分子。从动力学看,２步反应分别为「π４ｓ＋Ｗ２     

热处理对含氮活性碳纤维脱除SO2能力的影响

考察中高温热处理对含氮沥青活性碳纤维「ＰＡＣＦ（ＮＨ３）」脱除ＳＯ２的能力的影响结果表明,在９００－１１００℃尤其是在１０００℃下热处理可显著提高ＰＡＣＦ（ＮＨ３）脱除ＳＯ２的能力,当在３０℃下模拟烟气中ＳＯ２、Ｏ２和Ｈ２Ｏ的浓度分别为０．００２ｍｌ／ｍｌ,０．１ｍｌ／ｍｌ和０．１ｍｌ／ｍｌ,气休流动速率为１００ｍｌ／ｍｉｎ时,０．２５ｇ的３种不同比表面物ＰＡＣＦ（ＮＨ３）完全除去ＯＳ２的时间分别     

味精废水处理工艺中的氨氮,硫酸根问题

由于味精废水中ＣＯＤ，ＳＯ＾２－４和ＮＨ３－Ｎ浓度高，ｐＨ值低，使味精废水处理难度较大。本文介绍了味精废水排放标准，提出了利用的味精废不提取酵母蛋白及ＳＯ＾２－４和ＮＨ３－Ｎ对生物处理工艺的影响。     

化学沉淀法去除垃圾渗滤液中的氨氮

为了有效地去除垃圾渗滤液中高浓度的ＮＨ＾＋４－Ｎ而避免传统吹脱法造成吹脱塔内碳酸盐结垢问题,探讨了采用化学药剂诸加ＭｇＣｌ２·６Ｈ２Ｏ和Ｎａ２ＨＰＯ４·１２Ｈ２Ｏ或ＭｇＯ和Ｈ３ＰＯ４使ＮＨ＾＋４－Ｎ生成磷酸铵镁的化学沉淀去除法。小试研究结果表明,当垃圾渗滤液中投加ＭｇＣｌ２·６Ｈ２Ｏ和Ｎａ２ＨＰＯ４·１２Ｈ２Ｏ而使Ｍｇ＾２＋：ＮＨ＾＋４：ＰＯ＾３－４的比例为１：１：１时,在最佳ｐＨ为８．５～９．０     

高含硫味精废水处理的研究

采用吹脱－混凝－厌氧消化－两段ＳＢＲ－絮凝沉淀工艺处理味精废水，试验结果表明，当进水ＣＯＤ为２２３５１ｍｇ／Ｌ，ＳＯ＾２－４５１００００ｍｇ／Ｌ，ＮＨ３－Ｎ７５７１ｍｇ／Ｌ、色度（倍）３９０６和ＰＨ１．３时，出水ＣＯＤ９９ｍｇ／Ｌ、ＳＯ＾２－４９５ｍｇ／Ｌ、ＮＨ３－Ｎｌｍｇ／Ｌ色度１６和ＰＨ６．５，其水质均达到ＧＢ８９７８－１９９６规定的一级排放标准。     

海南三亚近岸海域水化学要素的分布特征和变化规律

本文调查研究了海南三亚近岸海域水化学要素的浓度和分布，结果表明：（１）表层ＤＯ、ＮＯ－２、ＮＯ－３、ＮＨ＋４、ＰＯ３－４和ＣＯＤ的平均浓度分别为４１１．９、０．０５、０．４７、１．７９、０．１６μｍｏｌ／ｄｍ３和１．３１ｍｇ／Ｌ。（２）河流输入对沿岸海域水化学要素的影响主要集中于ＮＨ＋４和ＣＯＤ，对ＰＯ３－４和ＮＯ－３的浓度影响不明显，海域总体为一贫营养盐区域。采用主成分分析表明控制水化学要素的主要因子是河流的输入和由此导致了的生物旺发。     

热处理对含氮活性碳纤维脱除SO_2能力的影响

考察中高温热处理对含氮沥青基活性碳纤维［ＰＡＣＦ（ＮＨ３）］脱除ＳＯ２的能力的影响结果表明，在９００—１１００℃尤其是在１０００℃下热处理可显著提高ＰＡＣＦ（ＮＨ３）脱除ＳＯ２的能力．当在３０℃下模拟烟气中ＳＯ２、Ｏ２和Ｈ２Ｏ的浓度分别为０．００２ｍｌ／ｍｌ、０．１ｍｌ／ｍｌ和０．１ｍｌ／ｍｌ，气体流动速率为１００ｍｌ／ｍｉｎ时，０．２５ｇ的３种不同比表面积的ＰＡＣＦ（ＮＨ３）完全除去ＳＯ２的时间分别从热处理前的０．２５ｈ、１ｈ和１ｈ延长到热处理后的１ｈ、２ｈ和３．５ｈ，ＳＯ２穿透后的稳态浓度从热处理前的７３％、５４％和３８％下降到热处理后的３２％、２４％和１０％．脱硫活性的提高主要是由于热处理增强了ＰＡＣＦ（ＮＨ３）对ＳＯ２和Ｏ２的吸附作用，加速了ＳＯ２的氧化反应．     

取代芳烃对发光菌的毒性及定量结构与活性相关

通过测定取代芳烃对发光菌毒性，用Ｆｒｅｅ－Ｗｉｌｓｏｎ法和分子连接性法研究了取代芳烃结构与活性的相关性，取代基的毒性顺序为：－Ｂｒ＞－ＣＯＯＨ＞－ＮＯ２≈－Ｃｌ＞－ＣＨ３＞ＮＨ２。建立了ＥＣ５０与ＬＣ５０的相关性，并预测一些化合物的ＬＣ５０值，结果和实测值符合较好。     

硝化细菌在氨氮深度处理中的应用研究

通过使用硝化细菌增养液挂膜，用生物接触氧化法对生活污水处理厂出水以及富营养化河水中的氨氮进行了处理。试验结果表明：在很短的水力停留时间条件下（１ｈ），污水厂出水经处理后ＮＨ３－Ｎ全部达标并小于８ｍｇ／Ｌ，其去除率达７０％；ＮＯ＾－２－Ｎ小于４ｍｇ／Ｌ。富营养化河水在ＨＲＴ为１．２ｈ时，出水ＮＨ３－Ｎ与ＮＯ＾－２均小于１ｍｇ／Ｌ。试验出水中的氮主要以ＮＯ＾－３－Ｎ的形式存在。     

异戊二烯与O3的大气化学反应研究

研究室温下石英玻璃反应器中异戊二烯与Ｏ３的暗反应,长光路ＦＴＩＲ法得到的实验结果表明,在本模拟反应条件下异戊二烯－Ｏ３反应体系中,主要产物甲基丙烯醛、甲基乙烯基酮和ＨＣＨＯ的产率分别为３７．４％、２０．２％和５５．１％,通过红外谱图的分析可确定反应中的其它产物为ＨＣＯＯＨ、ＣＯ和ＣＯ２等,对异戊二烯与Ｏ３的反应机理进行了探讨。     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

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.