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.     

超声/镁粉体系协同降解活性艳红

研究了超声/镁粉体系对偶氮染料活性艳红X-3B的降解效果,探讨了溶液pH值、声强、镁粉投加量、辐照时间等因素对染料脱色率的影响。结果表明,当溶液pH=3.5,声强=54.3W/cm2,镁粉投加量为2.122g/L时,20mg/L活性艳红溶液在超声辐照48min后脱色率达99.71%。同时探讨了超声波/镁粉体系的协同降解作用。超声波强化镁粉降解的能力主要表现在机械振荡加速了染料向镁粉表面的传质速度;加入镁粉促进超声产生大量·OH,强化了对染料的声化学脱色和降解。超声波/镁粉联用具有显著协同作用,服从动力学一级反应。     

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.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

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.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

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.