O3/H2O2降解阿特拉津影响因素研究

摘要采用O3/H2O2,氧化去除水中内分泌干扰物阿特拉津,考察了反应条件及水质对去除的影响,并对反应机制进行了初步探讨。阿特拉津初始浓度2mg/L,投量为7．5mg/L的O3,单独氧化去除率为27．2％;相同O3投量下,控制H2O2/O,摩尔比为0．75,5min阿特拉津的去除率最高可达96．5％;pH值为7．5～8．5,温度在25～40℃的范围内,都维持了较高的去除率,表明H2O2/O3,体系对阿特拉津的去除效果良好,降解速度快,反应条件温和。0．5mg/L的腐殖酸,对阿特拉津的去除影响不大,腐殖酸浓度为1、2和5mg/L时,平均去除率分别为63．4％、50．7％和30．2％;碳酸氢钠的浓度为50和200mg/L时,去除率分别为88．1％和73．8％,说明水质对阿特拉津的去除影响较大。叔丁醇的浓度为5和20mg/L时,阿特拉津的去除率分别降低到44．7％和27．5％,去除率随自由基抑制剂叔丁醇增加而降低,说明H2O2/O3降解阿特拉津主要为该体系产生的羟基自由基的贡献。     

倒置A/A/O工艺在城市污水处理中的应用研究

通过对常州市城北、清潭两座城市污水处理厂的倒置A／A／O工艺，采用不同的控制参数运行和相应的试验表明：(1)倒置A／A／O工艺对城市污水中有机物、氮和磷都具有较好的处理效果，出水水质达到《城镇污水处理厂污染物排放标准))(GBl8918—2002)一级标准中的A级标准；(2)推荐的相应控制运行参数为：污泥回流比控制在75～150％，气／水比值控制在3．0～5．0；生化反应池MLSS保持在2．50～3．50g／L，水力停留时间为10h，SRT控制为7～10d左右，生化反应池好氧段DO保持在3mg／L；(3)在进水TP浓度较低(≤2．0mg／L)的条件下，可以省略厌氧段，采用缺氧／好氧(A／O)方式运行。     

O3／UV处理苯胺废水的研究

比较了O3/UV和03刖V等3种方法对苯胺废水的处理效果,并探讨了O3/UV方法的作用机理。单独采用UV方法时,苯胺的去除率仅为4-2％,而采用O3/UV方法时,在O3通入量为21．4mg／min,初始pH值为6．74和苯胺质量浓度为100mg／L的条件下,反应10min时苯胺的去除率可达99％。随着苯胺初始浓度增大,反应速率变慢,苯胺降解基本符合伪一级动力学反应规律。     

Fe3++草酸盐络合物/H2O2/日光体系对垃圾渗滤液的处理

以Fe^3 草酸盐络合物／H2O2作光氧化剂，利用太阳光对垃圾渗滤液进行了光氧化降解实验。结果表明：在溶液的初始pH为3．0，H2O2投加量为460mg/L，ρ(Fe^3 )为20mg／L条件下，反应60min后，CODC4去除率可达80％左右；溶液的pH，P(H2O2)和ρ(Fe^3 )对光解过程有显著影响，而且在太阳光的照射下，CODCr去除率比在紫外光下高。在一定实验条件下，用日光／H2O2／草酸铁体系对城市垃圾渗滤液处理效果较好，可作为垃圾渗滤液的深度处理。     

FENTON氧化法处理三苯基膦生产废水的试验研究

采用Fenton试剂氧化处理三苯基膦生产废水,通过正交试验和单因素试验考察了影响因素和反应最佳条件。试验结果表明：对COD去除影响因素的大小顺序为：H2O2〉FeSO4·7H2O〉pH〉反应时间;运行最佳条件为：C（H2O2）：8mL/L,p（FeSO4·7H2O）：1．5g／L,t=120min,pH值=3和分3次投加方式,COD去除率达到为75．3％。     

Fenton试剂降解水中酚类物质的研究

采用Fenton试剂对苯酚、对氯酚、2，4-二氯酚、2，6-二氯酚、间甲酚、对硝基酚和邻硝基酚模拟水样进行处理，并考察了H2O2及FeSO4浓度、pH、反应温度和反应时间对Fenton试剂降解酚类物质的影响，得出Fenton试剂降解酚类物质非常有效，当H2O2浓度为4mmol／L、FeSO4浓度为0．5mmol／L，在pH为3，室温条件下反应40min则Fenton试剂对试验所做7种浓度为50mmol／L的酚类物质的去除率均在98％以上。为该工艺处理实际含酚废水提供了科学依据。     

US／Fenton协同降解苯酚模拟废水

研究了US／Fenton协同作用对水中苯酚的降解效果，探讨了Fenton试剂浓度、H2O2，Fe^2＋配比、溶液pH值等对苯酚降解效果的影响。结果表明：Fenton试剂投加量的增加对降解反应先促进后抑制；当H2O2/Fe^2＋配比为40：1，H2O2投加量为40mmol／L，溶液pH值3．0～7．0时,US／Fenton对苯酚的降解速率最快．反应30min后的降解效率远大于单独US、Fenton试剂氧化处理下的降解效率总和．其表现一级动力学速率常数增强因子可达到2．45，表明US／Fenton联用存在明显的协同效应。     

几种草酸铁络合物体系光降解酞酸酯比较研究

文章在比较研究了几种草酸铁络合物体系对两种酞酸酯DBP和DEHP的光催化降解情况.结果表明:草酸铁络合物和草酸铁络合物/H2O2体系在遮光条件下对DBP和DEHP没有降解作用.在中性pH值条件下,DBP和DEHP在几种反应体系中的降解速率依次为:UV/草酸铁络合物/H2O2＞UV/H2O2＞UV/草酸铁络合物＞UV＞太阳光/草酸铁络合物.UV与草酸铁络合物对DBP和DEHP光降解的协同作用不强,增强因子f分别为1.20和1.07.UV、草酸铁络合物与H2O2的对DBP光降解协同作用也不明显,增强因子f=1.18. UV与H2O2对DBP光降解存在明显的协同作用,增强因子f=8.78.     

A303工艺在处理垃圾渗滤液高浓度氨氮废水工程中的应用

将A3O3工艺用于徐州某垃圾焚烧发电厂渗滤液好氧段处理工程,讨论了工艺流程、构筑物设计参数和运行状况。结果表明,在A3O3反应池有机负荷OLR为0.6 kg(COD)/(m~3·d)、进水COD为1 900~3 000 mg/L、氨氮为1 000 1 650 mg/L的情况下,出水COD800 mg/L和氨氮5 mg/L时,A3O3反应池对COD和氨氮的去除率分别在60%和98%以上。同时分析了pH、DO和温度对氨氮去除率的影响。     

Fenton试剂催化氧化法处理离子交换树脂再生废水

针对离子交换树脂再生废水中的难降解有机物利用Fenton试剂进行催化氧化处理。实验结果表明：当反应条件是H2O2与FeSO4·7H2O摩尔比为5：1、H：O2（30％）投加量为0．35mol／L（4次投加）、pH值为3．5、反应时间为2h时,废水的处理效果最佳;并采用正交实验确定了各反应因素对废水的CODcr去除效果的影响水平。     

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.     

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.     

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.