活性炭负载纳米TiO2对腐殖酸光催化降解动力学

采用溶胶-凝胶法制备了以颗粒活性炭(GAC)为载体的纳米TiO2/AC复合催化剂,并将其用于腐殖酸的光催化降解.动力学研究表明,TiO2/AC光催化降解腐殖酸过程可用Langmuir-Hinshelwood(L-H)动力学模式表示.L-H表观反应速率常数KLH=0.1124mg·L-·1min-1,吸附平衡常数K*=0.3402L·mg-1.活性炭负载TiO2对腐殖酸的光催化降解过程,体现了活性炭与TiO2的协同作用,活性炭的吸附作用提高了光催化反应速率.     

天然麦饭石负载TiO2的光催化性能研究

采用溶胶-凝胶法制备了二氧化钛负载于天然麦饭石表面热处理后得到复合光催化剂TiO2/麦饭石,并通过N2吸附-脱附、XRD及IR对其进行表征。探讨了以天然麦饭石为载体制备具有较高光催化活性的负载型TiO2/天然麦饭石复合物的各种影响因素:焙烧温度,加投量,pH值等。研究结果表明:200℃焙烧条件下TiO2/麦饭石复合物具有最大的光催化活性,达到了纯TiO2的光催化效果:对罗丹明B脱色率随着光催化剂增多而增大;对罗丹明B在pH值7～9时具有最大的降解率,开拓和优化TiO2光催化效能的新途径。     

Fe~(3+)-TiO_2/AC光催化剂的制备及其光催化性能

以活性炭(AC)为载体,通过溶胶-凝胶法制备了Fe3+离子掺杂的TiO2/活性炭(Fe3+-TiO2/AC)负载型光催化剂,通过SEM、XRD、UV-Vis等手段对光催化剂进行了表征。以125W高压汞灯作为光源,通过对罗丹明B的光降解反应,主要考察了温度对Fe3+-TiO2/AC复合体的光催化活性的影响。结果表明,温度在600℃条件下焙烧的Fe3(+0.15%)-TiO2/AC具有最好的光催化活性。     

负载型活性炭/TiO2光催化降解苯酚的研究

在温和条件下(75℃和常压),通过在酸性水溶液中水解钛酸四丁酯并回流提高其结晶度,制备了锐钛矿型的TiO2.将此TiO2负载于粉末活性炭上,并用之来降解模拟废水苯酚.实验结果表明,该负载型催化剂的光催化效果要优于纯TiO2以及P25 TiO2加活性炭的混合体系.0.58g负载型催化剂降解0.4L浓度为100mg·L-1的苯酚溶液,经18W紫外灯光照6h后溶液中的苯酚去除率达到98%.同时,载体活性炭上吸附的苯酚量也随着光照时间逐渐减少,6h后残留的量仅为初始值的3.5%.     

TiO_2/ACFs催化剂光催化降解染料废水活性研究

以活性炭纤维为载体,采用溶胶-凝胶法制备得到了活性炭纤维负载二氧化钛光催化剂(TiO2/ACFs),并且以亚甲基蓝为模型化合物模拟研究了活性炭纤维负载二氧化钛光催化剂(TiO2/ACFs)对染料废水的光催化活性。通过扫描电镜(SEM)、XRD等表征方法对活性炭纤维负载二氧化钛光催化剂(TiO2/ACFs)的结构进行了研究。SEM表征显示,大部分二氧化钛以膜的形式均匀地包裹在活性炭纤维丝上,二氧化钛膜层的厚度大约为330 nm,还有一部分TiO2是以颗粒的形式负载在活性炭纤维上。FT-IR分析可知,ACF与TiO2之间有Ti—O—C键生成,说明TiO2与ACF结合牢固,TiO2不易脱落。通过对亚甲基蓝降解可知当煅烧温度为500℃时,TiO2/ACF的光催化性能最好,通过对比发现500℃煅烧制备的催化剂也具有最好的循环使用性能,经过4次循环后该催化剂对亚甲基蓝的去除率仍达到90.2%。     

Zr/TiO2纳米颗粒的制备及其光催化活性

以钛酸丁酯,乙醇为原料,用固相合成法制备了Zr/TiO2纳米颗粒,用XRD、TEM对其组成、颗粒大小、形貌进行了表征.通过对罗丹明B的降解反应,考察了Zr/TiO2的光催化活性.结果表明,Zr/TiO2为纳米颗粒,平均粒径为12.7 nm左右,且颗粒均匀;掺杂金属离子Zr提高了TiO2光催化效率,掺杂2.0%Zr的催化剂活性最高.Zr/TiO2的光催化反应,首先是反应物在Zr/TiO2表面发生吸附作用,然后进一步发生光催化降解.     

纳米TiO_2/SiO_2复合颗粒催化性能研究

为了提高纳米TiO2粒子的光催化性能和可回收性,采用溶胶-凝胶法制备了纳米TiO2/SiO2复合颗粒。利用XRD与比表面积测试仪,考察了热处理温度对复合颗粒的比表面积和其中纳米TiO2的粒度与晶型的影响情况,发现纳米TiO2的锐钛矿型转变温度由常规的350℃升高到600～700℃。研究了不同热处理温度的复合颗粒、不同Ti/Si比及其添加量对其光催化性能的影响,发现700℃下热处理2h,Ti/Si比为1.5的复合颗粒对100mg/mL的甲基橙溶液的光催化性能最好,其最佳使用量仅约为1.5g/L。     

负载型纳米TiO2/AC对偶氮染料的光催化降解研究

以钛酸四丁酯和粒状活性炭(AC)为主要原料,采用溶胶-凝胶-浸渍法制备出负载型纳米TiO2/AC催化剂.在流化床反应器中分别对2种典型的偶氮类染料橙黄G、活性艳红X-3B模拟废水进行了光催化降解研究,探讨了pH值、外加氧化剂对光催化降解率的影响,并对催化剂进行了回收再生利用试验.结果表明,TiO2/AC催化剂具有良好的光催化活性、吸附特性及可再生性,60 min后对2种染料反应的光催化降解率分别可达到99.71%和97 12%,反应180 min后的TOC去除率分别达到81.54%和81.99%;反应后TiO2/AC催化剂回收率大于95%,经焙烧再生后对橙黄G反应60 min的光催化降解率仍高达95.93%.     

纳米二氧化钛光催化降解造纸废水的试验研究

以廉价的无机盐四氯化钛为原料,采用溶胶-凝胶法制备出纳米TiO2粉末作为光催化剂,在高压汞灯的光源照射下对河北省某造纸厂废水进行了光催化降解.考察了TiO2光催化剂的热处理温度、用量、pH值、反应时间等因素对废水COD降解率的影响.研究表明:经460℃热处理1 h的Ti02光催化效果较好,在COD浓度300 mg/L,...     

TiO2/活性炭负载光催化剂的制备与光催化性能

以粒状活性炭为载体,钛酸丁酯和乙醇为原料,用溶胶-凝胶法及浸渍法制备负载型TiO2光催化剂.通过加入不同分子量和质量的聚乙二醇降低催化剂表面TiO2的粒径,增大比表面积,提高TiO2/C光催化剂的吸附性和光催化活性.以XDA、SEM、TG-DTA、比表面积、亚甲蓝吸附值、钛的负载量及对亚甲蓝的光催化降解性能对催化剂样品进行了表征.结果表明加入1.0 g PEG2000所制备的TiO2/C前驱体经过450℃焙烧后,TiO2的平均晶粒尺寸为12.9 nm,其晶型为锐钛矿型,其比表面积为997.0m2·g-1,对亚甲蓝的吸附值比活性炭基体增加22.5%,100mg·L-1的亚甲蓝溶液用该催化剂在pH为1.0～9.25范围内,2.5 h的降解率达82.5%～96%.     

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.     

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.     

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.     

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.     

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.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.