偏二甲肼水溶液在4A分子筛上吸附平衡与动力学研究

研究了偏二甲肼水溶液在4A分子筛上的吸附平衡和动力学,用Langmuir方程和Freundlich方程拟合了吸附等温线,采用Dünwald-Wagner方法解析浓度随时间的变化关系,求得有效扩散系数Di'。并研究了温度、初始浓度和粒径的变化对Di'的影响。Di'在15℃下C0为2.288%、粒径为250~420μm时为2.45×10-8cm2/s,并随着温度的升高、浓度和粒径的加大而增加。此外还求取了活化能E=3.7×104J/mol和表面扩散指前因子D0=0.12 cm2/s。     

粉煤灰对硝基苯的吸附：动力学和热力学研究

作者在298、308和318 K下,利用动力学、等温线模型和吸附热力学研究了粉煤灰对水溶液中硝基苯的吸附过程。结果表明:此吸附过程更符合拟二级动力学模型,受边界层扩散和粒内扩散共同控制;吸附活化能(Ea)为27.75 kJ/mol;此吸附过程较符合Sips和Langmuir模型,吸附性能良好;吸附热力学参数分别为?G~0(-1.225～-2.760 kJ/mol)<0、00,显示此吸附为自发吸热过程。结合动力学模型、活化能、等温线模型和热力学参数,得出粉煤灰对硝基苯的吸附是物理吸附和化学吸附共同作用。     

粉煤灰碱浸出体系反应过程分析:Ⅱ反应动力学

文章利用Jander方程,对粉煤灰在强碱性条件下的反应动力学进行了研究。研究内容包括:动力学反应阶段的划分;温度对各动力学反应阶段的影响;动力学反应阶段与理论模型的关系以及各阶段反应活化能的计算等。研究结果表明:粉煤灰在碱浸出体系下的反应分为3个阶段,即表明反应阶段,早期扩散阶段以及中后期扩散阶段。各阶段的持续时间与反应温度有密切关系。根据热力学计算,表明反应阶段的活化能为102 kJ/mol,早期扩散阶段的活化能为66 kJ/mol。     

废弃阻燃塑料热失重行为与分解规律的研究

文章主要是研究废弃电子产品阻燃材料的热解回收方法;主要研究废弃阻燃塑料的热失重规律和热分解产物,以印刷线路板为原料利用差热热重分析仪和热裂解色谱和质谱进行了实验室规模热解实验.结果表明:热失重反应的平均活化能为182.294 kJ/mol,指前因子为3.07×1011s-1,反应的温度区间为580K～600K;随着升温...     

钙化物对HCl的脫除动力学研究

采用热重法对氢氧化钙在空气下脱除HCl过程进行了研究，结果表明，钙化物脱氯的最佳温度为600～700℃．钙化物脱氧过程为一级反应．钙化物脱氯的动力学行为可用收缩核模型加以表征．钙化物脱氯的过程存在控制段的转移．反应初期化学反应占主导地位，但随着反应的进行，逐渐受产物层的扩散控制.表面反应活化能及固体扩散活化能分别为58.8kJ/mol及105.73kJ/mol．     

温度对厌氧氨氧化与反硝化耦合脱氮除碳的影响

采用ASBR反应器,研究了温度对厌氧氨氧化与反硝化耦合反应的短期影响.试验结果表明:耦合反应的活化能要小于单纯厌氧氨氧化反应的活化能,厌氧氨氧化与反硝化耦合反应可在一定程度上缓解低温对单纯厌氧氨氧化反应造成的消极影响,温度降低对厌氧氨氧化反应的影响大于对反硝化反应的影响.温度与耦合反应最大比反应速率的关系符合Arrhenius方程,在25~35℃时,耦合反应活化能为49.56kJ/mol,小于厌氧氨氧化反应的活化能66.18kJ/mol,且厌氧氨氧化反应为主导反应,对脱氮的贡献率约为61.29%.9~25℃时耦合反应的活化能为74.91kJ/mol,小于此温度梯度下厌氧氨氧化的活化能106.40kJ/mol,反硝化反应对脱氮的贡献率随温度的降低逐渐升高,9℃时,反硝化反应成为主导反应,对脱氮的贡献率约为75.10%.温度低于25℃时,反应器的容积氮去除速率(NRR)会受温度的影响.     

脱水污泥薄层干燥特性及动力学模型分析

采用薄层干燥方式进行脱水污泥热干燥的研究,考察了污泥的干燥特性,并引入薄层干燥模型进行数值分析.结果表明, Logarithmic模型比其他模型更适合薄层污泥干燥分析.应用Fick扩散模型,得到80~150℃条件下薄层污泥干燥的有效扩散系数的变化范围为8.486′10-10~4.386′10-9m2/s,并根据Arrhenius经验公式建立温度与扩散系数的关系,得到污泥干燥时水分扩散的活化能为29.56kJ/mol.     

D113大孔树脂吸附Ni~(2+)的动力学与热力学研究

研究了D113大孔树脂吸附Ni2+的动力学与热力学的特性。动力学研究表明,在298K温度下,D113大孔树脂对Ni2+的吸附符合拟一级动力学方程和拟二级动力学方程,颗粒扩散过程为吸附的控速步骤。热力学研究表明,在实验温度下,D113大孔树脂对Ni2+的吸附符合Langmuir等温方程,吸附焓变ΔHθ=15.1306kJ/mol,熵变ΔSθ=0.1002kJ/mol.K,反应吉布斯自由能ΔGθ随温度升高向负方向增加。热力学参数表明吸附过程为吸热和自发的。     

温度对生物强化除磷工艺反硝化除磷效果的影响

以处理城市污水的中试规模生物强化除磷A2/O活性污泥工艺系统为研究对象,考察了温度对系统COD去除和脱氮除磷效果的影响,特别是温度对活性污泥反硝化除磷性能的影响.结果表明,当温度从(30.9±0.8)℃降低到(9.1±0.6)℃时,A2/O系统的脱氮除磷效果显著下降,系统对TN和TP的污泥去除负荷明显下降.通过污泥反硝化除磷活性实验发现,随着温度的降低,系统中活性污泥的最大厌氧释磷速率、最大好氧吸磷速率和最大缺氧吸磷速率都降低.活性污泥中反硝化除磷菌(DPB)占聚磷菌(PAOs)总量的比例随温度降低稍有下降,但平均值仍维持在47.5％左右.用阿伦尼乌斯公式对实验结果进行拟合,得到系统中活性污泥聚磷菌厌氧释磷反应活化能Ea1为148.0 kJ· mol-1,聚磷菌好氧吸磷反应活化能Ea2为228.8 kJ·mol-1,发生在缺氧条件下反硝化除磷菌的吸磷反应活化能Ea3为315.8 kJ·mol-1.对不同温度下污泥絮体粒径分析结果表明,随温度降低,粒径分布更加集中,系统中活性污泥絮体颗粒平均粒径减小,不利于污泥絮体内部反硝化除磷缺氧微环境的形成.     

萘和菲在黄土上的吸附动力学

研究了萘和菲在天然黄土和阳离子表面活性剂改性黄土上的吸附动力学过程。结果表明,萘和菲在阳离子表面活性剂改性黄土上吸附速率比在天然黄土上的快,同时吸附数据都能很好的符合一级动力学方程;吸附速率与起始浓度、温度及黄土本身的性质有关;萘和菲的吸附速率常数k与温度T成负相关。吸附反应的活化能分别为:-6.196~-1.172kJ/mol和-28.86~-15.70kJ/mol;萘和菲在天然黄土和阳离子改性黄土上的吸附速率由膜扩散和孔扩散过程控制,实验数据可以用扩散动力学方程拟合。本研究为理解多环芳烃在土壤中的迁移规律提供了理论基础,同时有助于理解土壤环境中石油污染物的迁移。     

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.