二氧化钛平推流光催化反应器降解染料过程中氮素的变化

研究了在平推流光化学反应器中采用纳米TiO2光催化降解水中染料化合物。结果表明:染料化合物能被光催化有效地降解为NH+4-N、NO-3-N和其他无机离子,不同结构类型染料的降解速率不同,但均符合准一级动力学模型;通过监测降解过程中无机氮产物的含量,发现染料类化合物在光催化过程中有机氮先降解成NH+4-N,再被继续氧化成NO-3-N,由于强氧化环境的作用,NH+4-N向NO-3-N转化过程中,不经过中间价态的NO-2-N。     

硝酸盐抑制油田采出水中硫酸盐还原菌活性研究

硫酸盐还原菌(SRB)的生长代谢可导致油藏酸化,进而引发一系列环境和腐蚀等问题.硝酸盐(NO-3)补加及对硝酸盐还原菌(NRB)的调控是抑制SRB活性进而控制油藏酸化的重要策略.本研究从大庆油田水驱采出液中分离筛选出了1株兼性自养的NRB菌株DNB-8,并分析了在有机碳源充足的条件下不同浓度的NO-3结合使用该菌株抑制SRB富集培养物SO2-4还原活性的作用效果与机制.结果表明,浓度≤1.0 mmol·L-1的NO-3无法抑制SRB的SO2-4还原活性;NO-3浓度>1.0mmol·L-1或NO-2浓度>0.45 mmol·L-1均可有效抑制SRB的SO2-4还原活性.此时,NRB对有机碳源的竞争以及在利用NO-3的同时产生的NO-2是抑制SRB活性的主要机制.另外,大庆油田采出水中SRB富集培养物的细胞内存在异化NO-3还原生成NH+4的代谢途径(NO-2为中间产物).当NO-3浓度较高时,SRB可能通过该代谢途径减轻NO-2引起的抑制效应.     

不同Fe（Ⅲ）对活性污泥异化铁还原耦合脱氮的影响及机理初探

以投放海绵铁-AT-PVF复合填料的SBBR反应器活性污泥作为铁还原菌菌种来源,采用厌氧恒温培养试验,考察了不同Fe(Ⅲ)(氧化铁皮、青矿和红矿)对活性污泥异化铁还原能力及脱氮效果的影响,并对其作用机制进行了初步分析.结果表明:初始基质无NO-2的前提下,各体系Fe(Ⅲ)还原能力与脱氮效果表现出较好的关联性,同时发生NO-2-N和NO-3-N的积累现象.其中,氧化铁皮体系的脱氮效果最好,对NH+4-N、TN的累计去除量分别为75.04和80.99 mg·L-1,容积TN去除率为3.88 mg·L-1·d-1(以N计).更进一步的研究发现,不同培养时间内NH+4氧化量与Fe(Ⅱ)产生量之间符合幂指数关系,R2为0.9521.结合标准吉布斯自由能变化,厌氧环境下IRB参与活性污泥中N素循环的交互作用机制可分为3个子过程,即Fe(Ⅲ)的微生物还原解离耦合NH+4的氧化过程、厌氧氨氧化过程和NO-3-依赖型Fe(Ⅱ)氧化过程,其中,以IRB为主的微生物氧化还原过程对活性污泥中N循环起到了至关重要的作用.     

针铁矿对城市生活垃圾有机组分厌氧发酵的影响

利用PVC管构建厌氧发酵反应器,研究了铁氧化物对有机垃圾厌氧发酵过程中产气及垃圾渗滤液特性的影响.结果表明,添加针铁矿能够促进垃圾的水解酸化效率和产气速率,提高产气量至163.4 L,较空白提高了20%.通过对厌氧消化中间产物Fe2+、NH+4-N、NO-3-N、COD以及有机酸的分析表明,铁氧化物的存在有利于降低系统氧化还原电位,有助于提高厌氧微生物的水解酸化效率;铁氧化物的加入能够促进有机酸的转化,从而降低有机酸对厌氧微生物的抑制作用.     

单宁酸铁吸附去除水中无机氮的性能与机制研究

通过批量吸附实验,研究了一种新型吸附材料——单宁酸铁吸附去除水中无机氮(NH+4-N、NO-2-N和NO-3-N)的效果及其吸附机制.结果表明,单宁酸铁对NH+4-N和NO-2-N具有优先选择性,当单宁酸铁与NH+4-N和NO-2-N的质量比为200时,NH+4-N和NO-2-N去除率均大于95%.运用吸附动力学模型、Weber-Morris方程、Langmuir和Freundlich方程进行实验数据拟合的结果表明,NH+4-N和NO-2-N在单宁酸铁表面分别进行单分子层和多分子层的吸附,其吸附过程符合二级动力学模型,并且颗粒外部扩散和表面吸附起主要的作用.NH+4-N与分布于单宁酸铁外表面的氧负离子通过静电作用结合,NO-2-N则与单宁酸铁中的铁离子通过静电作用和配位作用结合.本研究为单宁酸铁作为吸附剂的发展与应用提供了科学依据.     

改性橘子皮对水中高氯酸盐及共存阴离子的竞争吸附研究

模拟多种阴离子共存的水体环境,采用氨基改性处理后的橘子皮作为吸附剂,研究其在不同离子共存条件下对高氯酸盐的竞争吸附.分析在不同pH条件下,竞争性阴离子对高氯酸盐吸附的影响;探讨单、双组分体系下的热力学、动力学吸附机理;采用红外光谱分析(FTIR)表征不同竞争吸附条件下吸附剂材料的结构特征.结果表明,不同pH范围内,3种阴离子与Cl O-4发生竞争吸附,其影响顺序不同:pH3时,其影响顺序为SO2-4NO-3PO3-4;3pH10时,其影响顺序为SO2-4PO3-4NO-3;pH10时,3种阴离子对Cl O-4吸附的影响趋于相同.单组分吸附下,改性橘子皮对Cl O-4、NO-3、SO2-4、PO3-4的最大吸附量分别为217.72、134.97、89.9、65.79 mg·g-1;竞争条件下,共存阴离子对Cl O-4吸附的影响顺序为PO3-4SO2-4NO-3,并且改性橘子皮对Cl O-4的吸附符合Freundlich等温线模型及准二级动力学模型,表明化学吸附为吸附的主要速率控制步骤.红外光谱分析结果证明了NO-3、SO2-4、PO3-4均在改性橘子皮吸附Cl O-4的过程中发生了竞争吸附.     

巢湖十五里河不同水力特性区沉积物及间隙水营养盐的分布特征

为揭示水力特性对小河流沉积物及间隙水中氮磷营养盐分布特征的影响,在巢湖十五里河河道上,选择支流交汇处、弯道淤积处、弯道冲刷处、河岸坍落处、水生植物生长区、平直河段、河内浅滩等7种水力特性类型,采集深度约40cm的沉积物柱状样,并按2cm厚度现场分层,得到136个样品.在实验室分析测试的基础上,解析沉积物与间隙水氮磷垂直剖面特征及沉积物-上覆水界面氮磷营养盐的源/汇关系,拟合间隙水剖面NH＋4-N、NO-3-N和PO3-4-P浓度,并对采样点位进行聚类分析.研究结果表明：不同水力特性区沉积物氮磷含量差异明显;弯道冲刷处和河岸坍塌处间隙水剖面NH＋4-N、NO-3-N和PO3-4-P浓度相对较低,且垂直变化不大,但在水生植物生长区则变化明显;不同水力特性区的水-土界面NH＋4-N、NO-3-N源/汇关系,具有很好的一致性,而PO3-4-P则差异明显;在沉积深度0～16cm范围内,除水生植物生长区外,其它各水力特性区间隙水NH＋4-N、NO-3-N和PO3-4-P浓度在垂直剖面基本上都可以借助指数函数y=exp（a＋bx＋cx2）拟合,这与湖泊、水库等宽阔水域存在一定差异.     

忻州市环境空气PM10和TSP中水溶性阴离子特征分析

利用中流量采样器收集忻州市采暖季和非采暖季4个监测点位的PM10和TSP样品,通过离子色谱法测定SO2-4、NO-3和Cl-的质量浓度,并以此3种水溶性阴离子的时空分布、相关性参数和特征比值来探讨其在环境空气中的污染特征和来源.结果表明,采暖季PM10和TSP中3种水溶性阴离子的总质量浓度分别为14.24μg·m-3和21.97μg·m-3,明显高于非采暖季(分别为8.56μg·m-3和11.84μg·m-3).采暖季和非采暖季3种水溶性阴离子总质量在PM10中所占比例分别为15.70%和13.19%,在TSP中所占比例分别为12.16%和8.84%,离子主要富集在PM10中.采暖季4个采样点位3种阴离子的质量浓度均高于非采暖季,采样点位DC的阴离子质量浓度高于其它点位,时空差异明显.采暖季NO-3与SO2-4相关性显著,说明二者形成过程的控制因子相同;非采暖季Cl-与SO2-4、NO-3的相关性显著,说明三者具有共同来源.NO-3/SO2-4比值在0.31~1.41之内,相对较高,暗示机动车尾气对空气颗粒物的影响突出,但均值都小于1,表明空气污染来源仍以燃煤等固定源排放为主.总体而言,忻州市水溶性阴离子的污染属于机动车尾气和燃煤的复合型污染.     

离子色谱法测定PM_(2.5)中水溶性无机阴离子

为确定PM2.5中水溶性无机阴离子的含量,本文采用戴安ICS900离子色谱仪对F-、Cl-、NO-2、NO-3、SO2-4进行测量,实验表明,这种测量方法操作简单、测量结果准确度高、测量速度快,能同时测定多种水溶性无机阴离子。     

Fe0还原地下水中2,4-DNT影响因素及产物

为了解零价铁(Fe0)修复污染地下水中微量2,4-二硝基甲苯 (2,4-DNT)还原规律,采用序批试验,考察地下水中常见阴离子(Cl-,NO₃-和PO₄3-)及重金属Cr(Ⅵ)对Fe0还原2,4-DNT能力的影响,并分析了Fe0还原2,4-DNT的中间产物和最终产物.结果表明:Cl-与NO₃-均能显著提高2,4-DNT的还原降解率,当反应进行120 min时,溶液中c(Cl-)由0 mmol/L增加到1 mmol/L,Fe0对2,4-DNT的还原降解率由31.4%增加到97.2%;溶液中c(NO₃-)由0 mmol/L增加到1 mmol/L,还原降解率由31.4%增加到78.9%;PO₄3-则表现为明显的抑制作用,当反应进行120 min时,溶液中c(PO₄3-)由0 mmol/L增加到1 mmol/L,还原降解率由31.4%降至2.1%.Cr(Ⅵ)能与2,4-DNT竞争Fe0提供的活性电子,当ρ〔Cr(Ⅵ)〕为20 mg/L时,Cr(Ⅵ)对Fe0还原2,4-DNT能力的抑制作用显著.Fe0还原2,4-DNT的中间产物为4-氨基-2硝基甲苯(4A2NT)和2-氨基-4硝基甲苯(2A4NT),最终产物为2,4-二氨基甲苯(2,4-DAT).因此,在地下水硝基苯类污染物零价铁修复实践中,应考虑地下水中离子组分对反应过程的影响;2,4-DNT的还原最终产物为2,4-DAT,无法进一步降解,需后续处理.      

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.     

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.     

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.     

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.     

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.     

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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