贫燃条件下汽车尾气净化催化剂Ag—SAPO—34湿热稳定性的研究

为解决贫燃条件下汽车尾气净化催化剂湿热稳定性差的问题，采用离子交换法把Ag离子交换到耐湿热性好的磷酸硅铝分子筛SAPO－34上，制备了有良好湿热稳定性的Ag-SAPO-34分子筛催化剂。研究结果表明：该催化剂经600℃、800℃高温水热处理8h后，活性分别平均降低2．3％和5．5％。水热处理初始4h时，催化剂活性下降2－5个百分点。随着水热处理时间增加到8－12h，催化剂活性的下降幅度逐渐减少至1－3个百分点，并趋向于稳定。同时，SEN、XRD表征测试结果表明，催化剂的表面形貌和骨架晶格结构在热处理和水热处理前后没有发生大的变化，这是催化剂耐湿热稳定性的根本原因。     

13X分子筛去除水中重金属离子Cr~(3+)的研究

以13X分子筛作为吸附剂,研究废水中Cr3+的去除。考察了水的pH、Cr3+浓度和吸附时间的影响,通过对不同价态金属离子的吸附探讨了除Cr3+机理,比较了13X分子筛和732型阳离子交换树脂对Cr3+的去除效果。结果表明:水的pH等条件对Cr3+的去除有较大影响;13X分子筛对Cr3+的吸附机理以离子交换吸附为主,符合Langmuir等温吸附模型和Lagergren二级动力学方程,吸附速率控制步骤为颗粒内扩散;达到吸附平衡后,分子筛对Cr3+的去除率为92.2%;分子筛吸附Cr3+的二级反应速率常数为0.004 5 g/(mg.min),比阳离子交换树脂的相应值大。     

Ce3+(La3+))改性Cu-ZSM-5催化剂分解NO活性的研究

 采用一步离子交换法用稀土Ce³⁺(La³⁺对Cu-ZSM-5分子筛改性,并在固定床反应器中进行了催化剂分解NO活性和耐氧性的实验研究.结果表明,离子交换主要发生在分子筛铝羟基和桥联羟基上,其中交换后的铝羟基为活性中心.Ce³⁺更易于交换到桥联羟基上,使铜离子占据活性中心,较低的交换温度和浓度有利于制备高催化活性催化剂.改性Cu-ZSM-5分子筛催化剂可以显著降低活性反应温度和提高空速,在310～390℃的温度范围内,La-Cu-ZSM-5催化剂上NO转化率均在80%以上,表现出良好的活性和较宽的反应温度范围.在O₂体积含量低于9%时,Ce³⁺掺杂Cu-ZSM-5表现出良好的氧稳定性,NO转化率基本保持在84%.     

4A分子筛对水中铅离子的吸附及其机理分析

以4A分子筛、阳离子交换树脂和活性炭作为吸附材料对Pb2+吸附性能进行对比,并通过吸附等温线和动力学方程拟合得到,4A分子筛对Pb2+的吸附速率常数为0.014 9 g/(mg·s),吸附容量为595.2 mg/g,高于阳离子交换树脂的0.000 5 g/(mg·s)和203.3 mg/g,以及活性炭的0.001 9 g/(mg·s)和177.3 mg/g,且吸附过程主要受液膜扩散控制。对比分析4A分子筛对不同价态金属离子Ag+、Pb2+和Cr3+的吸附,结果表明:分子筛对金属离子的吸附与价态数成反比,价态越高,吸附反应速率越低;且吸附过程主要为同电性、等电量的离子交换吸附。分子筛吸附Pb2+前后元素组分、晶体结构和表观形貌的变化表明:分子筛对Pb2+的吸附是分子筛中的Na+与溶液中游离的Pb2+发生离子交换的过程,经吸附后的4A分子筛的晶体结构和表面形貌保持不变。Zeta电位分析表明,4A分子筛与铅离子的作用方式中存在着静电吸引的物理吸附。     

钴铜改性的ZSM-5对低浓度NO吸附性能的研究

利用固定吸附床研究了不同金属离子改性的ZSM-5分子筛对一氧化氮的吸附性能。实验发现:在过渡金属同钴离子一起改性的ZSM-5中,钴铜金属离子共同改性的ZSM-5分子筛对一氧化氮的吸附性能最好;当铜钴离子共同浸渍、铜钴离子浸渍量比(n(Cu) n(Co))为0 8和Al2O3(粘合剂)用量w(Al2O3)为23%时,改性的ZSM-5分子筛既具有良好的吸附性能又有良好的机械强度。另外,实验还发现改性分子筛吸附一氧化氮的穿透时间随吸附温度的升高而缩短,并利用热重技术,分析了吸附剂的热再生问题。      

NO在Cu—ZSM—5上的催化分解

从铜离子交换液温度，浓度，ＰＨ值，以及铜离子交换的次数，交换的有无中间焙烧这几方面详细地讨论了铜离子交换条件对所制Ｃｕ－ＺＳＭ－５催化剂ＮＯ分解活性的影响；并且考察了Ｃｕ－ＺＳＭ催化分解ＮＯ活性随空速。     

镍、锌、铝对羊角月芽藻(Selenastrum capricornutum)生长及酶活性影响研究

研究了不同浓度镍、锌、铝对常见绿藻羊角月芽藻（Ｓ．ｃａｐｒｉｃｏｒｎｕｔｕｍ）生长速度、蛋白质含量、ＡＴＰ水平、葡萄糖－６－磷酸脱氢酶（Ｇ６ＰＤＨ）、酸性磷酸酶及硝酸还原酶活性的影响．结果表明３种金属离子在所试浓度范围内对羊角月芽藻的生长速度均有抑制作用，但单位藻培养物中蛋白质含量却随着金属离子浓度的增加而增加；高浓度金属离子对酶活性有明显抑制作用；藻细胞中ＡＴＰ水平随着金属离子浓度的增加而下降．提出金属离子对藻类生物产生影响的机理可能是：高浓度金属离子的存在，打破了生物最佳的各种营养元素生物可利用性的平衡．并讨论了藻类生长及生化活性对金属离子反应的相关性．     

黄河水中脯氨酸对Pb(Ⅱ)与表层沉积物相互作用的影响

研究了黄河干流内蒙古清水河段黄河水中表层沉积物与铅（Ⅱ）相互作用以及脯氨酸对其的影响，得出了离子交换率E％－pH关系曲线，该曲线的突跃范围及最大离子交换率E％。结果表明：在我们研究的范围内，脯氨酸深度增加，离子交换率E％增大，并且在pH为0－10的范围内，随着pH值增大，离子交换率E％增大；交换剂为转化沙时的离子交换率E％比未转化沙大。     

不同硅铝比Fe-ZSM-5催化剂对氧化亚氮催化分解性能的研究

以不同硅铝比的H-ZSM-5分子筛为载体,采用离子交换法和化学气相沉积法制备Fe-ZSM-5催化剂,并用XRD、BET、TEM、UV-vis和NH3-TPD等表征手段对催化剂进行分析,研究催化剂中铁的存在状态.结果表明,分子筛的硅铝比影响铁在分子筛中的分布形态,化学气相沉积法和热离子交换法制得硅铝比为25的Fe-ZSM-5-25分子筛催化剂上均匀地分布着粒径为8 nm左右的纳米氧化铁颗粒,并且Fe-ZSM-5-25分子筛催化剂比Fe-ZSM-5-300更容易形成Fe3+x O y团簇.制得的Fe-ZSM-5分子筛催化剂催化分解氧化亚氮(N2O),结果表明,相同的制备方法,硅铝比小的Fe-ZSM-5-25催化剂对N2O分解活性更好;相同硅铝比的Fe-ZSM-5催化剂,采用化学气相沉积法制得的对N2O分解活性最好.另外,O2的存在对Fe-ZSM-5上N2O催化分解活性有抑制作用,而NO对N2O催化分解活性展示了一定的正效应.最后,经过100 h的连续反应,Fe-ZSM-5催化剂依然能够保持催化活性.     

镍、锌、铝对羊角月芽藻(Selenastrum capricornutum)生长及酶活性影响研究

研究了不同浓度镍，锌，铝对常见绿藻羊角月芽藻生长速度，蛋白质含量，ＡＴＰ水平，葡萄糖－６－磷酸脱氢酶，酸性磷酸酶及硝酸还原酶活性的影响。结果表明３种金属离子在所试浓度范围内对羊角月芽藻的生长速度均有抑制作用，但单位藻培养物中蛋白质含量却随着金属离子浓度的增加而增加；高浓度金属离子对酶活性有明显抑制作用；藻细胞中ＡＴＰ水平随着金属离子浓度的增加而下降。     

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.