低贵金属含稀土复合型汽车排气净化催化剂研究

研究了３种低钯含稀土复合型汽车排气净化催化剂的制备工艺条件、活性和热稳定性。结果表明：所研制的催化剂对ＣＯ、ＨＣ的起燃温度分别在１８２℃～２１０℃之间；完全氧化温度在２３０℃～２５０℃之间。具有起燃温度低、活性高的特性。高温处理后，Ｔ５０％和Ｔ１００％仅上升了８℃～２４℃，说明热稳定性良好。少量贵金属Ｐｄ分浸法以及在活性氧化铝涂层上使用无机胶粘剂的制备工艺能提高催化剂的热稳定性     

甲醇燃料车尾气净化催化剂的研究(Ⅰ)──单组分催化剂对甲醇的深度氧化

利用色谱－微反联用技术对甲醇深度氧化进行了研究。结果表明：甲醇在所有催化剂上氧化时均产生副产物甲醛及甲酸甲酯;非贵金属氧化物催化剂以Ｃｕ－Ｏ／ｒ－Ａｌ２Ｏ３的活性最优,其最佳负载量为１０％－２０％,不同的制备方法中以均匀沉淀法制备的催化剂最好;贵金属催化剂中Ａｇ／ｒ－Ａｌ２Ｏ３的活性较好,其甲醇氧化的Ｔ５０,Ｔ９５分别只有１３５℃和１９０℃,而且伴生的甲醛及甲酸甲酯浓度也较低。不同催化剂的活性与其     

柴油机排放碳颗粒物的催化燃烧

在热天平装置上考察了柴油机和碳颗粒物燃烧催化剂的活性，讨论了样品制备因素对样品失重的影响，这些因素包括碳颗粒物组成、催化剂栽体、催化剂与碳颗粒物质量比，着重筛选了催化剂的组份，得到了组份催化剂ＣｕＣｌ２－ＫＣｏ－ＮＨ４ＶＯ３其５５０℃焙烧后能使样品的Ｔｍ和Ｔｆ值都降低１８０℃以上，并对催化剂的热稳定性进行了研究。     

Mn-Cu-O负载型催化剂上CO氧化性能的研究

研究了ＺｒＯ２或Ａｌ２Ｏ３负载Ｍｎ－Ｃｕ－Ｏ体系催化剂ＣＯ催化氧化活性，以及物相结构，表面氧性能与活性的关系。结果表明，锆基催化剂的氧化活性明显优于铝基催化剂，起燃温度Ｔ５０低达５０℃，ＺｒＯ２载 利于活性组份形成高活性物相，并促进表面吸附氧的脱附，表现出催化剂表面吸附氧的脱附温度高低次序与其氧化活性有一致的对应关系。     

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。     

催化氧化CS2的催化剂及其性能研究

以ＣＳ２作为含硫废气的处理对象，研究了Ｐｔ－Ｍｏ负载，在改性天然丝光沸石上对ＣＳ２的催化氧化活性，以及添加Ｖ对催化剂活性的影响。研究表明，Ｐｔ－Ｍｏ－Ｖ和改性载体之间存在着共催化作用，在Ｐｔ－Ｍｏ－Ｈ＾＋Ｍ催化剂上由于Ｖ的添加，使催化剂处理ＣＳ２的浓度和ＳＤＹ值明显提高。在反应温度３１０℃，空速５００ｈｒ＾－１和ＣＳ２浓度为３７０ｍｇ／ｍ＾３转化率达到１００％，ＳＯｘ放出率接近９５％－１００％。     

新型复合金属氧化物催化剂用于汽车尾气NOx净化的实验研究

采用固定床反应装置,模拟汽车尾气,研究新型复合金属氧化催化剂ＷＣＸ－Ｉ（Ｒｅ－Ｎｉ－Ｃｏ－Ｃｕ－Ｏｘ／Ｆｅ２Ｏ３）对ＣＯ还原ＮＯ反应和ＣＨ４还原ＮＯ反应的催化活性,催化剂的抗ＳＯ２中毒性能,抗积炭性能．结果表明ＷＣＸ－Ｉ催化剂对ＮＯ／ＣＯ和ＮＯ／ＣＨ４反应均具有较好的高温活性．在本研究实验条件下,４００℃以上时ＣＯ对ＮＯ的稳定还原率在９３％以上,６００℃以上时ＣＨ４对ＮＯ的稳定还原率在９２％以上．在１０００ｍｌ／ｍ３ＳＯ２－Ｎ２的高硫气氛中强制中毒及在１．０％ＣＯ－１０％ＣＯ２－Ｎ２的缺氧气氛中强制积炭若干小时后的催化剂试样对ＮＯ／ＣＯ反应的催化活性几乎未见降低     

TFJF型燃烧催化剂用于烘漆废气治理的研究

研制了一种贵金属－天然沸石／堇青石蜂窝体（ＴＦＪＦ）催化剂。通过实验室研究和部分漆包线石实际使用,考察了ＴＦＪＦ催化剂对漆包线机烘漆废气的治理效果。实验结果表明,对芳烃转化率为９８％的温度为１８０－２２０℃,甲酚为２２０－２４０℃;催化剂可８００℃以上的高温;实用结果表明,对烘漆废气良好的净化率,对二甲苯的去除率为９７％以上,出口浓度＜５０ｍｇ／ｍ＾３,同时不可以回收热能。     

甲醇燃料车尾气净化催化剂的研究(Ⅱ)──多组分催化剂对甲醇的深度氧化

利用色谱－微反联用技术研究多种多元催化剂对甲醇深度氧化的活性,并借助于ＸＲＤＢＥＴ等手段考察焙 烧温度对活性的影响,结果表明,不同的催化剂对甲醇氧化时均有甲醛及甲酸甲酯伴生,其伴生温度区间及最大伴生浓度随不同催化剂而变化;３２－３７号催化剂的活性明显高于双组分催化剂,添加少量稀土金属氧化物ＣｅＯ２和贵金属Ｐｄ对活性均有一定的改善作用,提高焙烧温度,催化剂表面发生烧结,对活性有不良影响。     

[Cu—γ—Al2O3]催化剂处理染料废水工艺条件研究

采用「Ｃｕ－γ－Ａｌ２Ｏ３」催化剂对由活性艳红Ｘ－３Ｂ配制的ＣＯＤｃｒ为５７００ｍｇ／Ｌ色度３１００倍的实际染料废水进行了催化氧化试验，试验表明，在控制ｐＨ＝４－５，Ｈ２Ｏ２用量为５．０ｍｇ／Ｌ，催化剂用量为３．０ｇ／Ｌ，ｔ＝７０℃和反应时间为２ｈ条件下，可获得ＣＯＤｃｒ去除率为７７％－７８％，脱色率为９９％的良好效果，且催化剂可再生使用。     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

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.     

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.     

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.     

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.