蒽醌染料中间体催化强化偶氮染料生物脱色

考察了醌还原菌群利用6种蒽醌染料中间体对偶氮染料生物脱色的催化强化作用.结果表明,溴氨酸(1-氨基-4-溴蒽醌-2-磺酸, BAA)的催化强化效果最好;游离态菌群以BAA作为氧化还原介体可催化强化多种偶氮染料的生物脱色,其中对酸性大红3R脱色的适宜条件为pH 6～9之间;外加葡萄糖浓度400～600 mg/L;BAA浓度19～34.2 mg/L,染料起始浓度≤900 mg/L.在此条件下,最大脱色率约为95%、达到最大脱色率的时间<7 h.同时发现,投加氧化还原介体BAA浓度为38～57mg/L时,固定化菌群降解酸性大红3R(180 mg/L)的最大脱色率在14 h内达到93%;在不补加BAA的情况下,固定化菌群经7次循环使用后,脱色率仍保持在85%以上.     

酸性偶氮染料还原产物强化偶氮染料生物脱色

考察醌还原菌群利用酸性偶氮染料的生物还原产物对偶氮染料生物脱色的强化作用.结果表明,酸性红B 等酸性偶氮染料的还原产物作为氧化还原介体可以强化多种偶氮染料的生物脱色.当酸性红B 还原产物浓度为0.2mol/L 时,其对活性艳红KE-3B 最佳脱色pH 值为7~11,在4~40℃范围内脱色率随温度上升而提高.根据高效液相色谱-质谱对酸性红B 还原产物的分析结果,推测起氧化还原介体作用的物质是2-氨基-4-磺酸基-1-萘酚     

酵母Candida krusei对合成染料的脱色

通过筛选实验,从土壤中新分离到1株对活性艳红K-2BP具有明显脱色效果的酵母菌株Y-G-1,经鉴定为克鲁斯假丝酵母Candida krusei.该菌株对含活性艳红K-2BP起始浓度为200mg/L的培养基,最大脱色率为99%,达到最大脱色率的时间是12h.克鲁斯假丝酵母的最佳接种量应不低于5%(体积分数),培养基最适pH在4～9之间,氮源(NH₄)₂SO₄浓度不低于0.1%,相对应的碳源葡萄糖浓度不低于0.5%.对脱色机理的研究表明,该菌株对活性艳红K-2BP的去除属于降解脱色.此外,该菌株对另外9种染料(50mg/L)的脱色率在62%～96%之间.其中,对偶氮染料弱酸艳红B、活性黑KN-B和活性红M-3BE的脱色率都达到了90%以上,对三苯甲烷染料(酸性媒介漂蓝B)的脱色率达到了93%.表明克鲁斯假丝酵母在染料废水的处理上可能具有较好地应用潜能.     

高盐条件下染料酸性橙7的生物降解特性

对偶氮染料废水厌氧-好氧生物处理中的高盐度抑制生物活性和芳香胺自氧化问题,通过多种强化策略,考察了NaCl为100g/L时酸性橙7(AO7)的生物降解特性.结果表明,加入葡萄糖(0.5g/L)、蛋白胨(1g/L)和酵母粉(0.5g/L)有利于高盐条件下AO7的生物降解.进水中加入酸性红B对AO7的脱色有加速作用.耐盐污泥中加入蒽醌形成的蒽醌-污泥自固定化体系可以促进AO7脱色,当蒽醌浓度为100mg/L时,AO7最大脱色率约为92%.以活性炭毡作为生物载体,厌氧和好氧体系均可实现稳定运行,且体系污泥沉降性良好,脱色速率达26.67mg/(L×h),且可有效抑制脱色中间产物1-氨基-2-萘酚的好氧自氧化,使COD去除率始终保持在90%以上.     

介体厌氧催化活性艳红K-2BP脱色及构效特性研究

研究了筛选出的4种结构相似的醌类氧化还原介体对活性艳红K-2BP厌氧脱色的促进作用,并分析了介体促进效果与其化学结构活性相关性. 在35℃中温厌氧条件下,采用间歇批量实验法,测定不同体系中介体催化活性艳红K-2BP脱色效果.结果表明,①结构相似的醌类氧化还原介体蒽醌(AQ)、1,5-二氯蒽醌(1,5-AQ)、1,8-二氯蒽醌(1,8-AQ)和1,4,5,8-四氯蒽醌(1,4,5,8-AQ),均促进活性艳红K-2BP脱色,反应速率提高了1.4～3倍;②当醌类介体投加浓度为4 mmol·L^-1,活性艳红K-2BP染料浓度为300 mg·L^-1时,促进作用由大到小的顺序为:1,8-AQ>1,5-AQ>AQ>1,4,5,8-AQ;③ 当活性艳红K-2BP染料浓度为300 mg·L^-1时,1,8-AQ促进效果最佳且脱色速率常数随1,8-AQ浓度的增加而增加呈线性关系;④介体促进效果与介体取代基团数量、位置和电子共轭效应相关.本研究初步建立了氧化还原介体定性/定量构-效关系数学模型,探究和完善非水溶性氧化还原介体催化强化理论体系.     

固定化蒽醌对偶氮染料生物降解促进作用研究

采用非水溶性蒽醌固定化技术对偶氮染料生物降解促进作用进行了研究,对比了海藻酸钙,聚乙烯醇-硼酸,聚乙烯醇-海藻酸钙和琼脂4种固定化技术,探讨了溶解氧对脱色过程的影响和固定化蒽醌系统脱色广谱性.研究结果表明,固定化蒽醌可提高多种偶氮染料生物厌氧脱色速度1.5～2倍和降低偶氮染料脱色过程氧化还原电位-10～-15 mV;经4次循环使用后,其加速作用仍保持在90%以上;固定化蒽醌微生物系统具有很强抗氧冲击能力.     

东方伊萨酵母YP-1对染料活性艳红K-2BP的脱色

利用含染料的选择性培养基从土壤中分离出一株对活性艳红K-2BP有明显脱色效果的酵母菌株YP-1,经鉴定为东方伊萨酵母Issatchenkia orientalis.结果表明,该酵母菌对￡400mg/L的活性艳红K-2BP有较好的脱色效果.对于活性艳红K-2BP起始浓度为100mg/L的培养基,该菌株可在12h达到99%以上的最大脱色率,其最佳接种量为10%(体积分数),最适pH值在3~9之间,氮源(NH4)2SO4的浓度30.02%,碳源葡萄糖的浓度30.2%.脱色机理研究结果表明,该酵母对活性艳红K-2BP的去除是先吸附后生物降解.此外,该菌株对初始浓度为200mg/L的偶氮染料活性黑KN-B的脱色率也可达99.5%.     

酵母Candida krusei对合成染料的脱色

通过筛选实验,从土壤中新分离到1株对活性艳红K-2BP具有明显脱色效果的酵母菌株Y-G-I,经鉴定为克鲁斯假丝酵母Candida krusei．该菌株对含活性艳红K-2BP起始浓度为200mg／L的培养基,最大脱色率为99％,达到最大脱色率的时间是12h．克鲁斯假丝酵母的最佳接种量应不低于5％（体积分数）,培养基最适pH在4～9之间,氮源（NH4）2S04浓度不低于0．1％,相对应的碳源葡萄糖浓度不低于0．5％．对脱色机理的研究表明,该菌株对活性艳红K-2BP的去除属于降解脱色．此外,该菌株对另外9种染料（50mg／L）的脱色率在62％～96％之间．其中,对偶氮染料弱酸艳红B、活性黑KN-B和活性红M-3BE的脱色率都达到了90％以上,对三苯甲烷染料（酸性媒介漂蓝B）的脱色率达到了93％．表明克鲁斯假丝酵母在染料废水的处理上可能具有较好地应用潜能．     

Al-Cu双金属体系对活性艳红X-3B的脱色研究

以典型偶氮染料活性艳红X-3B为模型污染物,采用测定染料去除率、TOC去除率、苯胺生成量的方法及添加EDTA的对照试验,考察Al-Cu双金属体系对偶氮染料废水的脱色机理和脱色动力学.结果表明,在近中性条件下处理30min后脱色率就可达到83%左右;处理120min后脱色率高达96.4%,其中约为34%的色度去除是由于活性艳红X-3B被还原为苯胺,约为20%和30%的色度去除是由于铝离子混凝和铝刨花表面吸附.染料废水脱色是一个先大量吸附再进行内电解还原逐步降解的过程,铝离子的絮凝-吸附作用能有效促进色度的去除.脱色反应可视为表观一级反应,提高反应温度可以加快脱色速率.     

染料脱色菌的筛选及对活性艳红X-3B的脱色研究

从广州某印染厂生化处理池的活性污泥中筛选到三株对活性艳红X-3B具有高效脱色作用的真菌,其中菌株HMX-3的脱色能力最强。考察了培养时间、温度、培养方式、pH值以及染料浓度对HMX-3脱色能力的影响。结果表明,菌株HMX-3对150mg/L X-3B的24h脱色率达65.8%,经60h可使其完全脱色;HMX-3对活性艳红X-3B脱色的最适温度为25℃~35℃,最佳pH值为6~8,且振荡培养较静置培养条件下的脱色率高;随染料浓度的增加,脱色率降低,但对于400mg/L的X-3B在72h时的脱色率可达86.7%。     

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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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.