粉煤灰源NaY沸石的制备及其对乙酸乙酯的吸附性能研究

采用粉煤灰合成沸石的方法既经济又环保,在乙酸乙酯吸附领域中具有巨大应用前景.遵循节能减排、废物再利用的环保原则,探索了3种不同Si/Al比的粉煤灰、结晶温度、结晶时间和碱浓度4个因素对合成NaY沸石的影响.XRD、氮气吸脱附实验及ICP结果表明,Si/Al比和水热结晶温度对高比表面积NaY沸石的合成影响最大.Si/Al比在1左右的粉煤灰合成的沸石比表面积较低,且晶形中存在大量的NaA沸石,而Si/Al比在2左右的粉煤灰合成了高比表面积且纯度较高的NaY沸石;3种粉煤灰均在65 ℃下合成NaY沸石,但在105 ℃下完全转化为方钠石.实验优化结果表明,最优合成条件为采用Si/Al为2左右的粉煤灰,在2 mol·L^-1碱浓度、65 ℃水热温度下结晶12 h.该条件下合成的NaY沸石比表面积高达654.86 m²·g^-1(比表面积最高的粉煤灰源沸石之一),是原粉煤灰比表面积的22倍左右,对乙酸乙酯的吸附量也由15.4 mg·g^-1增至108.2 mg·g^-1.     

利用粉煤灰合成沸石处理重金属污水研究

本研究中利用粉煤灰合成沸石对含有Cu^2 、Pb^2 、Cd^2 的制备水样进行批处理振荡实验，其吸附容量分别为9．56、0．89和0．25mg／l。实验证明，用合成沸石处理含重金属离子污水达到平衡所需的时间约为3h。对污水中重金属离子的去除率随pH值降低而降低，随沸石用量增加而增加。同等条件下，利用粉煤灰处理含Cu^2 的污水，其吸附容量仅为6．49mg／l，低于合成沸石。     

粉煤灰水热法合成沸石及其对氨氮吸附性能的研究

以粉煤灰为原料,采用NaOH碱熔融制得粉煤灰熟料,由水热法合成沸石产品。通过单因素试验和正交试验考察搅拌陈化时间、水热晶化时间、液固比对合成沸石的氨氮吸附容量的影响。试验结果表明:搅拌陈化时间为12 h、水热晶化时间为6 h、液固比为10时,合成的产品主要为P型沸石,其氨氮吸附容量达最大为6.15 mg/g,并以此为理论基础讨论其运用于水处理工艺中的可能。     

X型粉煤灰沸石吸附丙酮及其动力学研究

文章采用碱熔融水热法合成了X型粉煤灰沸石,通过XRD、XRF、SEM、氮气吸附等手段研究了该沸石的结构组成特点,考察了初始浓度、吸附温度和空速对X型粉煤灰沸石吸附丙酮的影响机制,在此基础上,进一步研究了X型粉煤灰沸石对丙酮的吸附动力学及吸附机理。结果表明：合成的X型粉煤灰沸石品质较高,平均粒径为0.83μm,平均孔径为3.2 nm,比表面积为165.8 m²/g,总孔容积为0.133 8 cm2/g,总孔容积为0.133 8 cm³/g;X型粉煤灰沸石吸附丙酮的过程中,初始浓度、空速和温度越高,穿透时间和饱和时间越短;在实验范围内,升高温度会导致吸附量显著降低,增加空速会使吸附量略有下降,而增加初始浓度会使吸附量明显增加,当温度为40℃,初始浓度为777.9 mg/m3/g;X型粉煤灰沸石吸附丙酮的过程中,初始浓度、空速和温度越高,穿透时间和饱和时间越短;在实验范围内,升高温度会导致吸附量显著降低,增加空速会使吸附量略有下降,而增加初始浓度会使吸附量明显增加,当温度为40℃,初始浓度为777.9 mg/m³,空速为75 h3,空速为75 h^(-1)时,X型粉煤灰沸石对丙酮具有最高的吸附量;Bangham模型和准一阶模型能更好地拟合丙酮在X型粉煤灰沸石上的吸附过程,说明丙酮在X型粉煤灰沸石表面的吸附更符合以物理吸附为主的孔道吸附。     

HDTMA改性粉煤灰沸石对水中铬酸盐的吸附

以自制HDTMA-粉煤灰沸石为吸附剂,对铬酸盐的吸附进行了实验研究。讨论了吸附剂的投入量、废水pH值、吸附温度和吸附时间等各因素对Cr（VI）去除率的影响。研究表明：pH值对Cr（VI）的吸附效率无显著影响,且在HDTMA-粉煤灰沸石的投加量为20 g/L、吸附温度为30℃、吸附时间为60 min的条件下,Cr（VI）的去除率可达90%左右。     

粉煤灰合成沸石处理含氟水的研究

以粉煤灰为主要原料,通过碱融法可以制备对氟离子具有一定吸附性能的沸石,通过正交试验与单因素试验共同考察了陈化时间、晶化时间和固液比对沸石吸附性能的影响,最佳的合成条件是陈化时间为12 h、晶化时间为6h、固液比为1/10,在制作工艺方面为粉煤灰合成沸石提供了重要参考.     

水热条件对粉煤灰沸石离子交换性能的影响

沸石的离子交换性能是决定其应用价值的一个重要指标。为衡量粉煤灰沸石的应用性能,本研究主要考察了反应温度、反应时间以及添加剂等水热反应条件对合成粉煤灰沸石产品离子交换性能(CEC,Cation Exchange Capacity)的影响。结果表明,产品的CEC值随着反应温度和反应时间增加而增大,至120℃、6h达到最大。添加剂十六烷基三甲基溴化铵和95%乙醇有效促进了NaP1沸石的结晶过程,均可使产品CEC值提高10%以上。合成NaP1型粉煤灰沸石的最佳水热反应条件为:反应温度120℃,反应时间6h,液固比(mL/g)为8,氢氧化钠浓度为2mol/L,95%乙醇作为添加剂。所得粉煤灰沸石产品CEC值达到最大值198.31cmol/kg。     

水热合成温度对纳米TiO2特性及其可见光波段光催化性能的影响

以乙醇-丙酮-吡啶为溶剂，采用水热法制备了在可见光波段（≤450nm）具有良好光催化活性的纳米TiO2粉体,通过XRD、TEM、DTA、漫反射谱（DRS）与光电压谱等手段，研究了水热合成温度及250℃热处理对合成纳米TiO2粉体的材料特性，以及在可见光激发下纳米TiO2对甲基橙光催化降解的影响．结果显示，纳米TiO2晶型（锐钛矿）与粒径不随水热合成温度及热处理（250℃）条件的变化发生明显改变；各样品的表面吸附物状态以及可见光响应特性在未经热处理时随水热合成温度变化发生明显变化，而在经250℃热处理后则差异不明显；样品的表面吸附物状态、可见光响应以及可见光催化活性之间有显著关联，水热合成温度显著地影响了纳米TiO2粉体的表面吸附物状态及可见光催化活性。     

粉煤灰吸附去除弱酸性艳蓝印染废水

利用粉煤灰对弱酸性艳蓝印染废水进行了处理。研究表明：粉煤灰的粒径、灰水比、废水pH值以及振荡吸附时间对粉煤灰的吸附能力均有较大影响。在以下工艺条件下：20℃,粉煤灰的粒径200目,灰水比为1：30,pH为2．0,振荡吸附2．5h,弱酸性艳蓝印染废水经粉煤灰处理后,COD值由576mg／L降至71mg／L,COD去除率可达87．7％：废水色度可从10000倍降为50倍,色度的去除率达99．5％,出水pH为6．5。出水水质达到了国家印染废水一级排放标准(GB4287—92)。     

PDAC改性粉煤灰处理印染废水的试验研究

采用高分子絮凝剂聚二甲基二烯丙基氯化铵（PDAC）和粉煤灰为原料,利用水溶液吸附的方法合成改性粉煤灰,并应用于印染废水的处理。通过正交试验和单因素影响试验,考察了改性的最佳工艺参数。结果表明,在吸附反应时间2h,反应温度40℃,改性荆PDAC浓度50g／L,pH值3．4的最佳条件下,改性粉煤灰对废水色度和COD的去除效果最好。     

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.     

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.     

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.     

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.     

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.     

Effect of sorbed and desorbed Zn(Ⅱ) on the growth of a green alga (Chlorella pyrenoidosa)

Toxic effect of Zn(Ⅱ) on a green alga (Chlorella pyrenoidasa) in the presence of sepiolite and kaolinite was investigated.The Zn-free clays were found to have a negative impact on the growth of C.pyrenoidosa in comparison with control samples (without adding any clay or Zn(Ⅱ)).When Zn(Ⅱ) was added,the algae in the presence of clays could be better survived than the control samples,which was actually caused by a decrease in Zn(Ⅱ) concentration in the solution owing to the adsorption of Zn(Ⅱ) on the clays.When the solution system was diluted,the growth of algae could be further inhibited as compared to that in a system which had the same initial Zn(Ⅱ) concentration as in the diluted system.This in fact resulted from desorption of Zn(Ⅱ) from the zinc-contaminated clays,although the effect varied according to the different desorption capabilities of sepiolite and kaolinite.Therefore the adsorption and desorption processes of Zn(Ⅱ) played an important part in its toxicity,and adsorption and desorption of pollutants on soils/sediments should be well considered in natural eco-environmental systems before their risk of toxicity to aquatic organisms was assessed objectively.