纳米活性氧化铝负载磁性纳米零价铁对不同重金属的吸附机理

采用液相还原法将纳米零价铁（nZVI）均匀负载在纳米活性氧化铝（γ-Al₂O₃）表面和孔道内壁上,制备出磁性纳米零价铁/活性氧化铝复合材料（nZVI/γ-Al₂O₃）并对其进行了表征,模拟了5种典型重金属离子Zn（Ⅱ）、Cu（Ⅱ）、Cd（Ⅱ）、Cr（Ⅲ）、Mn（Ⅱ）在nZVI/γ-Al₂O₃上的吸附等温线和动力学,并研究了多元重金属离子体系中竞争吸附和协同吸附行为.结果表明,磁性纳米零价铁负载在纳米活性氧化铝上,不仅克服了因体积效应和表面界面效应所导致的nZVI颗粒团聚,而且使nZVI仍处于稳定的高表面能状态.nZVI/γ-Al₂O₃复合材料兼具高表面积、高还原性和高表面活性,其对Zn（Ⅱ）、Cu（Ⅱ）、Cd（Ⅱ）、Cr（Ⅲ）、Mn（Ⅱ）离子表现出了良好的吸附性能,单一重金属离子的饱和吸附容量分别为53.0、74.9、114.7、99.1、42.9 mg·g^-1.在多元重金属离子体系中5种重金属离子存在竞争吸附和协同吸附作用.当pH为6.67,吸附剂投加量为0.5 g·L^-1,各重金属离子初始浓度为10 mg·L^-1时,300 min内Cr（Ⅲ）、Cu（Ⅱ）、Zn（Ⅱ）、Mn（Ⅱ）的去除率分别高达99.9%、99.9%、99.9%、81.7%,处理后Cr（Ⅲ）、Cu（Ⅱ）、Zn（Ⅱ）平衡浓度均低于检出限,Mn（Ⅱ）和Cd（Ⅱ）平衡浓度分别为1.9 mg·L^-1和6.4 mg·L^-1;在多元体系下Zn（Ⅱ）与其他金属离子存在协同吸附,但Cd（Ⅱ）与其他重金属离子存在竞争吸附,其去除率仅为37.7%.因此,nZVI/γ-Al₂O₃复合吸附材料用于去除废水中典型重金属具有良好的应用前景.     

γ-Al2O3催化臭氧氧化水中嗅味物质机理探讨

以γ-Al₂O₃粉末为催化剂,研究催化臭氧氧化去除水体中典型嗅味物质2-甲基异茨醇（MIB）的效能与机理.结果表明,γ-Al₂O₃能够明显促进臭氧氧化去除MIB,表现出很好的催化活性,叔丁醇对γ-Al₂O₃催化氧化去除MIB过程具有明显的抑制作用.在催化臭氧氧化去除MIB过程中,γ-Al₂O₃表面电荷状态及表面羟基的带电性质与溶液的pH值有关.当溶液pH值与γ-Al₂O₃ 的pH_zpc接近时,γ-Al₂O₃的催化作用最为明显.γ-Al₂O₃催化臭氧氧化过程中自由基的相对量值R_ct比单独臭氧氧化过程高出近1个数量级,这进一步表明γ-Al₂O₃能明显促进臭氧分解产生更多的羟基自由基.最后还考察了不同摩尔比例的臭氧分解促进剂与抑制剂对γ-Al₂O₃催化臭氧分解的影响.     

高压放电等离子体协同锰锆镧铈催化剂降解乙酸乙酯的特性与机制

实验制备了新型Mn-Zr-La-Ce/Al₂O₃、Mn-Zr-Cu和Mn-Co-Ce 3种催化剂,利用SEM-EDS、XRD、BET、FT-IR、O₂-TPD进行表征分析,研究了高压放电协同催化剂对乙酸乙酯的降解因素影响规律（催化剂种类、初始浓度、含氧量和进气气量）,通过对出口气体GC-MS等分析,探讨了高压放电协同催化降解乙酸乙酯的机理.结果表明,高压放电低温等离子体协同Mn-Zr-La-Ce催化剂对于乙酸乙酯的降解效果最好,当电压为40 kV时,降解效率为94.6%,能量效率为1.52 g·kW^-1·h^-1,降解副产物O₃及NO_x浓度较低.降解效率随着初始浓度、气量的增加而较低,但随着含氧量的增加则是先升高后下降.GC-MS等分析结果表明,在降解乙酸乙酯过程中会产生丙酸乙酯和乙酸正已酯等中间产物,最终生成CO₂、H₂O.     

CuxCe1-xO2/γ-Al2O3催化剂催化燃烧甲苯性能的研究

以γ-Al₂O₃ 为载体,以复合氧化物Cu_xCe_1-xO₂为活性组分,其中,x=0.1,0.2,0.4,0.6,0.8,通过浸渍法制备了一系列Cu_xCe_1-xO₂/γ-Al₂O₃催化剂.在固定床反应器中评价了催化剂对甲苯的催化活性,通过XRD、SEM对催化剂进行表征,并运用ICP-MS分析并计算Cu、Ce的摩尔比以及活性组分的负载量.结果表明,在Cu_xCe_1-xO₂/γ-Al₂O₃催化剂中Cu、Ce摩尔比的实际值与理论值相近,活性组分的负载量在19%以上,而且对甲苯都有较好的低温催化活性,其中当x=0.2时,即Cu_0.2Ce_0.8O₂/γ-Al₂O₃催化剂对甲苯的催化活性最高,其中T₁₀=160 ℃,T₉₀=265 ℃;当甲苯的进口浓度在700~3000 mg·m^-3时,进口浓度对Cu_0.2Ce_0.8O₂/γ-Al₂O₃催化剂的催化活性影响较小,且经过连续80 h的稳定性操作后转化率仍然保持在90%以上.     

多孔不锈钢基氧化铝膜去除水溶液中的Cr(VI)和Cd(II)

通过悬浮粒子浸涂法将合成的γ-Al₂O₃纳米粒子固载于316L多孔不锈钢表面以吸附水溶液中的Cr（VI）和Cd（Ⅱ）.扫描电镜（SEM）和X射线衍射（XRD）测试结果表明,γ相的Al₂O₃纳米粒子均匀地涂在了316L多孔不锈钢基体上,膜体表面沉积厚度约为20 μm.该膜对单一Cr（VI）和Cd（Ⅱ）吸附的最佳pH分别为3.0~4.0和8.0~9.0,吸附均符合动力学准二级模型和Langmuir吸附等温模型,最大吸附量分别为0.603 mg·g^-1和0.399 mg·g^-1.本研究可为水体中的高毒性重金属Cr（VI）和Cd（Ⅱ）去除提供一定的理论和技术参考.     

电场效应与催化湿式氧化协同作用研究

在自行研制开发的一套固定床和复合三维电场一体化连续式催化湿式氧化反应器中,采用浸渍法制备的Mn-Sn-Sb-3/γ-Al₂O₃催化剂,实验研究了苯酚催化湿式氧化、电催化氧化以及电场效应下的催化湿式氧化过程的行为.结果表明,一体化反应器在较低反应温度（t=130℃）和氧分压（PO₂=1.0 MPa）下即可获得相当满意的处理效果,空时仅为27 min时苯酚和TOC的去除率就分别可达到94.0%和88.4%.电场效应下的催化湿式氧化协同降解苯酚的反应速率常数大于单独电催化或催化湿式氧化降解苯酚的反应速率常数,而且还大大超过两者之和,电催化氧化对催化湿式氧化工艺存在明显的协同增效作用.     

氧化锰与氧化铈协同等离子体催化氧化甲醇的活性差异研究

在等离子体催化系统中,不同催化剂常表现出显著的性能差异.本文通过表面氧物种表征及臭氧氧化原位反应,探究了α-MnO₂与CeO₂两种常用催化剂在等离子体催化系统中催化氧化甲醇性能差异的本质原因.等离子体催化氧化甲醇的性能评价结果显示,在相同输入功率下CeO₂对甲醇的转化率和CO₂选择性均高于α-MnO₂.氧气程序升温脱附（O₂-TPD）和X射线光电子能谱（XPS）等表征手段及甲醇常温催化、O₃分解和O₃催化氧化实验结果表明,CeO₂比α-MnO₂拥有更多的表面活性氧,能吸附活化更多的甲醇分子;同时,CeO₂能更有效地利用臭氧分解产生的活性氧物种对甲醇进行深度氧化.进一步通过原位DRIFTS实验研究两种催化剂协同臭氧催化氧化甲醇反应中间产物的变化,结果表明,CeO₂催化剂氧化甲醇的表面副产物较少,而α-MnO₂表面则会累积大量的副产物碳酸盐,从而影响其催化性能.     

三维电解法处理苯酚废水的粒子电极研究

用浸渍法制备了分别以Cu、Zn、Ni、Ce、Fe、Co、Mn、Sn等为单组分以及Mn和Sn为双组分氧化物、以γ-Al₂O₃为载体的负载型电催化剂, 并填充于阴阳极间以构成三维电极电催化降解苯酚模拟废水.结果表明, 所选用的几种粒子电极都显示了一定的催化活性, 可不同程度地提高苯酚的去除效率, 其中Mn、Sn单组分和双组分氧化物对苯酚降解具有较高的催化活性, 且Mn与Sn物质的量比为2时双组分金属氧化物的催化活性最高. 在0.25 A的电流下处理150 min, 可使目标有机物的去除率达90.8%, TOC去除率也达到80.7%. 加入·OH清除剂叔丁醇的研究表明, 本体系中苯酚的电催化氧化是由直接氧化和间接氧化的协同作用共同去除.     

低温等离子体结合锰基催化剂去除乙酸乙酯的研究

利用固态法和溶胶-凝胶法分别制备了钙钛矿（LaMnO₃）和八面体分子筛（OMS）两种锰基催化剂,在不同工况（输入电压、初始浓度、停留时间和催化剂放置量）条件下考察了等离子体催化对乙酸乙酯的降解特性.结果发现,锰基催化剂的加入显著提高了乙酸乙酯的去除率,减少了副产物的生成,并且OMS的催化活性高于LaMnO₃;此外,乙酸乙酯去除率随着电压的升高而增加,随着污染物初始浓度的增大而减少,并随停留时间的增长而变大;催化剂放置量为0.2 g时催化效果最佳.OMS催化剂在等离子体催化长期运行过程中表现出较好的稳定性.基于X射线衍射（XRD）、X射线光电子能谱（XPS）、H₂程序升温还原（H₂-TPR）、比表面积测试（BET）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）等手段对锰基催化剂物理化学性质的分析表明,OMS具有较高的催化活性主要归功于其拥有更高比例的Mn⁴⁺/（Mn³⁺+Mn⁴⁺）和吸附氧（O_ads）/晶格氧（O_latt）.     

ZnMnxCo2-xO4活化过一硫酸盐降解有机污染物

分别以Zn（CH₃COO）₂·2H₂O、Mn（CH₃COO）₃·2H₂O和Co（CH₃COO）₂·4H₂O为锌源、锰源和钴源,采用溶胶-凝胶自燃烧法成功制备了ZnMn_xCo_2-xO₄（x=0~2）复合物,并用X射线衍射和X射线光电子能谱对其进行表征.同时,还研究了Mn/Co物质的量比、催化剂用量及PMS用量对目标污染物降解的影响.结果表明,该复合物可催化活化过一硫酸钾（PMS）降解有机污染物,当催化剂中x=0.8,催化剂投加量为0.2 g·L^-1,PMS用量为0.4 mmol·L^-1（0.25 g·L^-1）时,20 μmol·L^-1（10 mg·L^-1）罗丹明B（RhB）可在15 min内完全降解.ZnMn_0.8Co_1.2O₄的高催化活性主要归功于Mn³⁺和Co²⁺的协同效应.将ZnMn_xCo_2-xO₄-PMS体系用于亚甲基蓝、结晶紫、金橙、双酚A、4-氯酚等其他污染物的降解,也取得了较好的效果.基于电子自旋共振ESR和自由基猝灭实验的结果,可以推测该反应体系中活性物种为硫酸根自由基和羟基自由基.     

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.     

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.