混晶纳米TiO_2薄膜光催化降解亚甲基蓝

以钛酸四丁酯为原料采用浸渍提拉法在普通瓷片表面制备TiO2混晶薄膜,用XRD对薄膜进行表征,选用亚甲基蓝催化降解考察TiO2混晶薄膜的催化能力,探讨了紫外光光照强度、亚甲基蓝初始浓度和pH对光催化降解的影响。结果表明:600℃煅烧4h可制备金红石为13.2%的混晶薄膜,平均粒径为22nm;初始浓度在0.313～0.937mg/L,催化反应符合一级动力学方程,半衰期随初始浓度的增加而减小;在光照强度为40W和pH为13时降解率为45.6%,并可多次重复使用。     

纳米TiO2薄膜在不同基质表面的负载及光催化性能

以釉面陶瓷和普通钠钙玻璃为载体,用溶胶凝胶法在其表面进行了纳米TiO2薄膜的负载.采用X射线衍射法(XRD)、扫描电子显微镜(SEM)和X射线光电子能谱仪(XPS)对薄膜进行了表征与分析.结果表明,TiO2为完全的锐钛矿型,平均粒径约为15nm;TiO2薄膜在2种载体上分布均匀,膜厚约为300nm;TiO2薄膜在釉面陶瓷表面呈连续分布,而在玻璃表面上出现了破裂现象;2种载体中的一些基质离子在TiO2薄膜均有渗透.光降解实验表明,2种载体上的TiO2薄膜对亚甲基蓝的降解均符合一级反应动力学.TiO2/釉面陶瓷催化活性大于TiO2/玻璃,该薄膜对实际生产多菌灵废水具有催化降解作用.2种载体上的TiO2薄膜重复使用20次,对亚甲基蓝的去除率降低约2%.     

多孔TiO2薄膜电极/泡沫镍硬模板制备及其光电催化性能

以泡沫镍为载体,活性炭为造孔剂,采用硬模板法制备泡沫镍负载多孔TiO2薄膜(Porous TiO,films/foam nicel,PTFN)电极,并利用XRD和SEM等测试手段对其结构进行表征.同时,通过亚甲基蓝溶液的光电催化降解反应,对其光电催化活性进行评价,并探讨阳极偏压、通气速率、亚甲基蓝初始溶液浓度和活性炭造孔剂量对降解效率的影响规律.结果表明:相对于未加模板造孔剂的TiO2薄膜电极的光电催化性能,泡沫镍负载多孔TiO2薄膜具有更好的光电催化性能,原因是高比表面积电极有利于为光电催化提供高浓度的亚甲基蓝分子,使反应速率加快;另外,存在最佳的光电催化降解条件,即当外加阳极偏压为3 V,通气速率为40 L·h-1,n(活性炭造孔剂最):n(前驱体中钛)(即C/Ti)为10％,亚甲基蓝溶液初始浓度为1mg·L-1时,光电催化降解效率最高.同时,研究发现,亚甲基蓝在光电催化降解过程中,通过自由基的氧化发生了C=N键的断裂去甲基化,最后被降解为H2O、CO2和SO42-、NO3-、Cl-离子.     

氧气热处理的TiO2纳米管阵列光电催化降解亚甲基蓝的研究

采用原位阳极氧化法在Ti基底上制备了高度有序的TiO2纳米管阵列薄膜,SEM图像表明TiO2纳米管定向排列整齐,分布均匀,其管径范围在70～100 nm.XRD结果证明,阳极氧化法制备的TiO2纳米管为无定型晶型,经退火后为具有良好光催化活性的锐钛矿型.以亚甲基蓝（methylene blue）为目标物研究了TiO2纳米管光电催化性能及影响因素,结果表明,以0.1 mol/L NaCl为电解质,在氧气热处理气氛下,外加偏压为0.5 V、pH=3.25、光照强度为1 000μW/cm2、纳米管薄膜表面积为2 cm×2 cm且MB初始浓度为10 mg/L的条件下,TiO2纳米管阵列薄膜光电催化降解MB的降解效率可达99.56%.电化学阻抗谱分析显示,光电催化降解过程的速控步骤均为表面反应步骤,外加偏压减小了界面电荷转移阻抗,提高了光生载流子的分离效率.     

CdS/TiO2复合半导体薄膜的制备及其光催化性能

以微弧氧化法制备出锐钛矿型TiO₂,进而以化学水浴法沉积CdS,通过调控时间,制备CdS/TiO₂复合半导体薄膜. X射线检测表明,微弧氧化所制备的TiO₂为锐钛矿结构, 化学水浴法制备的CdS主要以离子离子的方式沉积在TiO₂薄膜上. SEM及可见光催化降解亚甲基蓝的试验表明,沉积时间为15 min的复合半导体薄膜上的CdS粒子呈圆球形、单层孤立、均匀地分散在TiO₂表面,绝大多数粒子的粒径在nm级别,分布比较均匀,对亚甲基蓝有着较好的光催化性能,与TiO₂薄膜相比,复合半导体薄膜的光催化性能有很大的提高. 结合光催化评价结果,对复合半导体薄膜的光催化剂机制进行了讨论.      

Nafion膜中嵌入Fe~(2+)光催化降解亚甲基蓝的研究

将亚铁离子嵌入Nafion膜中利用Fe3+/Fe2+光催化降解亚甲基蓝,脱色率达90%。研究探讨了降解亚甲基蓝时H 2O2以及pH值的影响。亚甲基蓝光催化降解氧化反应符合一级动力学规律,表观速率常数为0.5689min-1。     

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%。     

Nation膜中嵌入Fe^2＋光催化降解亚甲基蓝的研究

将亚铁离子嵌入Nation膜中利用Fe^3＋／Fe^2＋光催化降解亚甲基蓝，脱色率达90％。研究探讨了降解亚甲基蓝时H2O2以及pH值的影响。亚甲基蓝光催化降解氧化反应符合一级动力学规律，表观速率常数为0．5689min^-1。     

改性粉煤灰降解亚甲基蓝溶液的实验研究

探讨以粉煤灰为戴体制备粉煤灰/TiO2复合物进行光催化降解亚甲基蓝试验.研究各种因素对亚甲基蓝光降解反应的影响,结果表明,当改性粉煤灰投加量为8g/L,亚甲基蓝浓度30 mg/L,高压汞灯250w条件下,在60min左右,亚甲基蓝降解率达到了95%以上.     

高度有序的TiO2纳米管阵列光催化性能研究

采用恒压阳极氧化法在纯钛箔表面制备TiO2纳米管阵列,利用SEM和XRD对其进行了形貌和晶型的分析和表征,并通过TiO2纳米管阵列膜对甲基橙光催化降解,探讨光照时间、甲基橙溶液的初始浓度、溶液的初始pH值和H2O2加入浓度等因素对甲基橙的脱色率影响.结果表明,H2O2加入浓度为50mg·L-1,紫外光照射2h,溶液为中性时,在30 mg·L-1的甲基橙溶液(50mL)中,甲基橙溶液的脱色率达到100%.当H2O2加入浓度进一步增大到100 mg·L-1时,光催化的效率进一步提高,紫外光照射1h,甲基橙溶液的脱色率就已经达到了100%,并未出现抑制光催化的现象.同时还研究了TiO2纳米管阵列电极的稳定性.实验结果表明,随着TiO2纳米管阵列使用次数的增加,其光催化效果略有所下降.     

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.     

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.     

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

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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.     

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.     

Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Sorption of 1-naphthol by plant cuticular fractions

The contribution of aliphatic-rich plant biopolymer to sorption of hydrophobic organic compounds is significantly important because of their preservation and accumulation in the soil environment,but sorption mechanism is still not fully understood.In this study, sorption of 1-naphthol by plant cuticular fractions was examined to better understand the contributions of respective fraction.Toward this end,cuticular materials were isolated from the fruits of tomato by chemical method.The tomato cuticle sheet consisted of waxes (6.5 wt%),cuticular monomer (69.5 wt%),and polysaccharide (24.0 wt%).Isotherms of l-naphthol to the cuticular fractions were nonlinear (N value (0.82-0.90)) at the whole tested concentration ranges.The KodKow ratios for bulk cuticle (TC1),dewaxed cuticle (TC2),cutin (TC4),and desugared cuticle (TC5) were larger than unity,suggested that tomato bulk cuticle and cutin are much powerful solption medium.Sorption capability of cutin (TC4) was 2.4 times higher than the nonsaponifiable fraction (TC3).The 1-naphthol interactions with tomato cuticular materials were governed by both hydrophobic-type interactions and polar (H-bonding) interactions. Removal of the wax and polysaccharide materials from the bulk tomato cuticle caused a significant increase in the sorption ability of the cuticular material.There was a linear negative trend between K_(oc) values and the amount of polysaccharides or fraction's polarities ((N O)/C);while a linear positive relationship between K_(oc) values and the content of cutin monomer (linear R~2=0.993) was observed for present in the cuticular fractions.Predominant sorbent of the hydrophobic organic compounds (HOCs) in the plant cuticular fraction was the cutin monomer,contributing to 91.7% of the total sorption of tomato bulk cuticle.     

Alterations of organ histopathology and metallolhionein mRNA expression in silver barb, Puntius gonionotus during subchronic cadmium exposure

Common silver barb,Puntius gonionotus,exposed to the nominal concentration of 0.06 mg/L Cd for 60 d,were assessed for histopathological alterations(gills,liver and kidney),metal accumulation,and metallothionein(MT)mRNA expression.Fish exhibited pathological symptoms such as hypertrophy and hyperplasia of primary and secondary gill lamellae,vacuolization in hepatocytes,and prominent tubular and glomerular damage in the kidney.In addition,kidney accumulated the highest content of cadmium,more than gills and liver.Expression of MT mRNA was increased in both liver and kidney of treated fish.Hepatic MT levels remained high after fish were removed to Cd-free water.In contrast,MT expression in kidney was peaked after 28 d of treatment and drastically dropped when fish were removed to Cd-free water.The high concentrations of Cd in hepatic tissues indicated an accumulation site or permanent damage on this tissue.     

Seed selections for crystallization of calcium phosphate for phosphorus recovery

Seed induces and promotes the crystallization of calcium phosphate, and acts as carrier of the recovered phosphorus （P）. In order to select suitable seed for P recovery from wastewater, three seeds including Apatite （AP）, Juraperle （JP） and phosphate-modified Juraperle （M-JP） were tested and compared. Batch and fixed-bed column experiments of seeded crystallization of calcium phosphate were undertaken by using synthetic wastewater with 10 mg/L P phosphate. It shows that AP has bad enduring property in the crystallization process, while JP has better performance for multiple uses, and M-JP is a hopeful seed for P recovery by crystallization of calcium phosphate.