复三维电极-生物膜反应器脱除饮用水中硝酸盐的试验研究

研究了连续流复三维电极-生物膜反应器在不同电流、温度和pH条件下的反硝化性能.结果表明,在电流从0mA增加至100mA的过程中,NO3--N去除率随电流增大而升高;电流为100mA时NO3--N去除率最高,达到了73.8%,出水NO3--N浓度为8.27mg.L-1;电流高于100mA时,NO3--N去除率略有下降.电流从0mA增加至150mA的过程中,NO2--N积累量先增加后减少;电流为60mA时NO2--N的积累最为严重.温度为31～35℃时,反硝化效果较好,出水NO3--N浓度低于10mg.L-1;温度为35℃时,NO3--N去除率最高,达到了85.5%.pH值为7.2～8.2时,反硝化效果较为理想,出水NO3--N浓度在10mg.L-1以下,NO2--N浓度低于1mg.L-1.该反应器具有较好的pH缓冲性能,进水pH从5.5上升至9.0的过程中,其出水pH可维持在7.6～8.2,NO3--N去除率在59.6%～80.2%.此外,电流、温度和进水pH还对氨氮的生成量和总磷的去除产生明显影响.通过复三维电极-生物膜反应器与纯电化学反应器的对比试验,对氨氮产生和总磷去除的可能原因进行了分析和探讨.     

DSA类电极催化降解硝基苯及其动力学研究

用新兴的电化学催化系统，采用特殊工艺自制的DSA类电有作为阳极，对模拟硝基苯废水进行降解处理。结果表明，最佳试验条件为：电流密度15mA/cm^21、Na2So4浓度5g/L、pH以中性和碱性较好。在适合的条件下。硝基苯废水CODcr去除率可达到90％以上，DSA类电极能有效地催化降解硝基苯。对试验结果进行的非线性最小二乘法分析表明，硝基苯在电化学催化系统中的降解过程符合一级反应模型，在硝基苯质量浓度200mg／L、pH11．0、Na2SO4浓度10g／L、电流密度15mA/cm62的试验条件下，CODcr去除速度常数为0．0395min^-1。     

好氧颗粒污泥法降解苯胺的特性

在控温摇床上采用好氧振荡的方法,在含有苯胺和硝基苯混合废水处理厂的好氧污泥中,驯化降解苯胺的混合微生物.在驯化过程中发现混合微生物逐渐形成了颗粒污泥,采用此颗粒污泥(混合微生物)进行苯胺降解的实验.结果表明,该混合微生物在以苯胺为唯一碳源和氮源的情况下,具有较强的降解苯胺的能力,且最适宜的温度为28℃,最佳的pH值为7.0,当苯胺的起始浓度为600mg/L时,此条件下在18h内被完全降解,混合微生物降解苯胺的速度达到33.6mg/(L·h).     

交流电场对生物膜胞外聚合物提取过程的影响

利用电场特性,研究了交流电场的电流、频率大小对生物膜胞外聚合物(EPS)提取过程的影响,当电流密度小于10mA/cm²时,外电场对生物膜内微生物细胞影响较小;提取剂不同则对应的最佳提取频率不同,NaOH提取剂较适合的频率范围是10～100Hz;在电场条件一定的情况下,分别探讨了溶液pH值、提取剂浓度等各因素对提取效果的影响.以EDTA钠盐为提取剂,其浓度为2%时,提取效果较好;以2% EDTA钠盐为提取剂时,pH=10提取效果最佳.     

铜锌阴极与BDD阳极电化学脱氮

将铜锌合金电极(Cu∶Zn =2∶1)作为阴极,钛基掺硼金刚石电极(BDD)作为阳极,用活性炭颗粒作为填料,利用间歇式三维电化学反应器脱除水中的硝酸盐氮.研究pH,电流密度,反应器运行方式,初始硝酸盐浓度对硝酸盐氮去除效果的影响.结果显示在pH值为6.8,初始硝酸盐浓度为100 mg·L-1,电流密度为2.0mA·cm-2的条件下,反应5h后,硝酸盐氮的去除率可以达到45.5％,副产物亚硝酸盐和氨氮接近零.     

黄河兰州段底泥对硝基苯的吸附行为

选择硝基苯为代表性污染物,研究了黄河兰州段底泥对硝基苯的动力学吸附和热力学吸附过程,并对离子強度、pH值和粒径等对吸附的影响进行了分析.结果表明,硝基苯在黄河兰州段底泥上的动力学吸附经历了3个阶段:快速、慢速和吸附平衡阶段,0~2h为快速吸附阶段,2~15h为慢吸附阶段,15h后吸附达到平衡.黄河兰州段底泥对硝基苯的动力学吸附过程较好地符合准二级吸附动力学模型;热力学吸附较好地符合Langmuir等温吸附模型;在吸附过程中,吸附自由能△G~θ小于0,焓变△H~θ及熵变△,S~θ均大于0,表明黄河兰州段底泥对硝基苯的吸附是ー个自发吸热且吸附体系的混乱度増大的等温吸附过程.吸附影响因素分析结果显示:当Ca~(2+)离子浓度在0~0.05mol/L时,黄河兰州段底泥对硝基苯的吸附量随Ca~(2+)离子浓度的増大而增加,当Ca~(2+)离子浓度増大到0.1mol/L时,吸附量減少,说明在此离子强度下,Ca~(2+)抑制了底泥对硝基苯的吸附.当pH3~5和7~10范围内时,底泥对硝基苯的吸附量随pH值增大明显减小,当pH5~7范围内时,吸附量随pH值增大基本保持不变.底泥粒径对黄河兰州段底泥吸附硝基苯有显著影响,其饱和吸附量随底泥粒径的减小而增大.     

高铁酸钾处理废水中硝基苯的研究

本实验以高铁酸钾为水处理剂,对其在废水中的硝基苯的去除进行了研究,考察了高铁酸钾的用量、pH值、反应时间及硝基苯的初始浓度四个影响因素对硝基苯去除率的影响,最终确定了高铁酸钾去除硝基苯的最佳反应条件为：初始pH值为9,高铁酸钾与硝基苯的摩尔比为10：1,反应时间30min,初始浓度小于254．5mg/L时,硝基苯的去除率最佳,达到到6．2％。     

气体扩散电极制备及其对苯酚降解效果的研究

以质量比9∶1的活性炭和乙炔黑制备气体扩散电极,着重研究电流密度、pH值、曝气量等因素对H2O2产生量的影响.结果表明:pH值在较大范围内均适用;电流密度控制在50～75 mA/cm2,曝气量确定为5 L/min时,反应产生H2O2较多.另外,利用该气体扩散电极做阴极,石墨电极做阳极,以Na2SO4为电解质,研究了电解时间、电流密度、pH值、初始苯酚浓度、曝气量等因素对苯酚降解效果的影响.结果表明:在电流密度为75 mA/cm2、曝气量为5 L/min、初始pH=3的条件下,当苯酚的初始浓度为80 mg/L时,1 h后其去除率达77%.     

电极-生物膜法处理铜酸洗废水

采用自行设计的反应器,用电极-生物膜法对铜酸洗废水进行了直接处理.结果表明,经过铜离子梯度驯化的反硝化微生物可以适应铜离子的存在并有效完成反硝化过程,在最佳工艺条件(电流密度为0.1mA/cm²,C/N为1.07)时,出水中总无机氮(TN)去除率达到98%以上,铜离子浓度<1mg/L,pH值在7左右,且不存在二次污染.电极-生物膜法可同步高效地实现中和、反硝化及铜离子的去除.验证了通过交换电极回收铜的可行性.     

膜电解氢自养MBBR反应器深度转化水中高氯酸盐

建立膜电解电化学氢自养MBBR反应器（移动床生物膜反应器）用于去除水中高氯酸盐,微生物利用阴极电解产生的氢气将高氯酸根还原为氯离子,而后氯离子在阳极发生氧化析氯反应生成活性氯进一步提升出水水质,从而实现高氯酸根的深度转化.利用该反应器研究了高氯酸根的转化过程及相关影响因素,结果表明：进水ClO₄^-浓度为（4.98±0.091）mg/L,维持HRT（水力停留时间）为4h,施加电流由6mA增加至15mA,反应器对高氯酸根的去除率由（39.75±2.09）%增加至（98.99±0.05）%,总出水活性氯浓度由（0.057±0.003）mg/L增加至（0.070±0.002）mg/L,pH值稳定在7.96~8.11,浊度较低为（0.89±0.27）NTU.进一步增大施加电流（20mA）,导致阴极室溶液pH值超过9.5,进而影响微生物活性,去除率急剧下降至（30.75±1.19）%.利用扫描电子显微镜（SEM）观察反应器内微生物形貌,发现反应器内微生物均附着于填料表面,以短杆菌为主,增殖缓慢.运用高通量测序技术对接种及运行第24d的微生物群落结构展开分析.结果显示,反应器运行过程中,菌群多样性下降,Thauera菌属为主要的氢自养还原优势菌属,其丰度达到8.25%.     

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.     

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.     

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.     

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.