4A分子筛去除水中Pb2+、Cd2+、Zn2+、Cu2+性能和机理

文章通过采用SEM、XRD、FTIR分析4A分子筛吸附重金属离子Pb~(2+)、Cd~(2+)、Zn~(2+)、Cu~(2+)前后形貌和结构的变化,探讨了这4种重金属离子在4A分子筛上的吸附性能和机制。研究结果表明:4A分子筛吸附Pb~(2+)和Cd~(2+)后,分子筛的形貌和结构未发生改变,吸附Zn~(2+)和Cu~(2+)后,4A分子筛表面有氢氧化物沉淀附着;吸附Cu~(2+)后,4A分子筛的XRD特征衍射峰消失,表明其晶相结构发生了改变,转化为无定形,此外,属于4A分子筛骨架的部分红外特征吸收峰减弱至几乎消失;Pb~(2+)、Cd~(2+)、Zn~(2+)、Cu~(2+)在4A分子筛上的吸附符合Langmuir等温吸附模型,最大吸附量分别为2.818、2.514、2.317、1.877 mmol/g,而拟二级动力学吸附速率常数Pb~(2+)Cd~(2+)Cu~(2+)Zn~(2+)。4A分子筛对Pb~(2+)和Cd~(2+)的去除机理主要为离子交换吸附和表面沉淀,对Cu~(2+)和Zn~(2+)的去除则既有离子交换吸附和表面沉淀作用,又有化学沉淀作用。     

纳米二氧化锆吸附Pb~(2+)的研究

采用沉淀法合成了纳米级二氧化锆,利用SEM、XRD技术,对纳米ZrO_2进行微观形貌和粒径分析,探讨了吸附时间、吸附温度、pH值以及Pb~(2+)初始浓度对吸附的影响,分析了吸附热力学性质和动力学特性,初步探讨了吸附机理。研究结果表明:在吸附温度为40℃,Pb~(2+)初始浓度为10 mg/L,pH为4.5时,吸附反应40 min后,最大吸附量为17.8 mg/g;纳米ZrO_2对Pb~(2+)吸附等温线符合Langmuir模型,其吸附动力学过程以准二级动力学方程拟合效果最好;温度在303~323 K时,纳米ZrO_2吸附Pb~(2+)的吉布斯自由能ΔG~o<0、焓变ΔH~o<0、熵变ΔS~o<0,表明纳米ZrO_2对Pb~(2+)的吸附是一个自发放热过程。     

碱法提取的混合海洋硅藻粗多糖对铅离子的吸附特性研究

采用浓碱法(40 mg·mL~(-1)NaOH)辅助冻融、加热方法提取混合海洋硅藻粗多糖,通过比较粗多糖得率、总糖、蛋白质及硫酸基含量筛选提取方法,并利用最佳方法提取的粗多糖作为生物吸附剂对Pb~(2+)进行吸附.提取实验结果表明,最优的提取方法为浓碱(40 mg·mL~(-1)NaOH)-冻融法,其粗多糖得率为33.14%,总糖含量为31.65%(480 nm)和27.27%(490 nm),蛋白质含量为6.44%、硫酸基含量为3.23%.吸附结果表明,该粗多糖对Pb~(2+)的吸附在2 h左右达到平衡,在180 r·min-1、25℃、pH=4~6时吸附效果最佳;在初始浓度为600 mg·L-1混合重金属溶液条件下,粗多糖对Cd~(2+)、Pb~(2+)、Cu~(2+)和Ni~(2+)的吸附容量大小顺序为:Ni~(2+)Cu~(2+)Cd~(2+)Pb~(2+)(以物质的量浓度为单位进行评价);粗多糖中含有的小分子糖类杂质对Pb~(2+)吸附的贡献远远大于蛋白质杂质.吸附动力学拟合结果表明,此硅藻粗多糖对Pb~(2+)的吸附过程更符合伪二级动力学模型,且Langmuir方程拟合的可决系数R2大于0.9,说明粗多糖对Pb~(2+)的吸附为单层吸附.     

污泥-稻壳混烧灰对Pb(Ⅱ)吸附性能的研究

稻壳与污泥协同焚烧是一种富有前景的污泥能源化措施,污泥稻壳混烧灰是一种被忽视的资源。该文旨在探究污泥稻壳混烧灰在高浓度含铅废水处理中的应用潜力,分析了不同污泥和稻壳配比混烧灰的基本理化性质,研究了不同p H和不同Pb~(2+)初始浓度下混烧灰对Pb~(2+)的吸附特性,并初步探究该吸附过程的动力学和吸附机理。结果表明混烧灰对Pb~(2+)的吸附容量可媲美其它经过复杂改性处理的灰渣;在燃烧温度900℃时,污泥掺量60%、稻壳掺量40%制备的混烧灰吸附性能最好,在p H为5,初始Pb~(2+)浓度低于400 mg/L时混烧灰对Pb~(2+)的去除率高于90%;相较于Freundlich等温吸附模型,Langmuir等温吸附模型的拟合结果更好,拟合最大吸附量为108.7mg/g;动力学研究发现混烧灰对Pb~(2+)的吸附行为主要发生在5 h以内。混烧灰对Pb~(2+)去除的主要原因是混烧灰中无定形二氧化硅微水解形成硅醇对Pb~(2+)的作用,无定形二氧化硅表面存在孤立羟基和成对羟基导致了2种吸附产物Pb_2SiO_4和PbSiO_3·xH_2O存在。     

胡敏素对Pb~(2+)吸附的响应面优化及机理

采用Box-Behnken响应面优化实验设计对胡敏素吸附去除水中Pb~(2+)的过程进行了优化,设定吸附时间、吸附剂用量、pH值、温度和Pb~(2+)初始浓度5个影响因素,建立了吸附率与上述因素之间的二次多项式模型,确定了最优吸附条件,对吸附过程的等温模型、热力学特性及吸附机理进行了研究.研究表明吸附剂用量、pH值、温度和Pb~(2+)初始浓度为显著因素.胡敏素对Pb~(2+)吸附的最优条件为:吸附时间85min、投加量1.2g/L、pH=4.7、温度44.5℃、Pb~(2+)初始浓度202mg/L.最优条件下,实测Pb~(2+)吸附率可达92.59%.胡敏素对Pb~(2+)的吸附符合Langmuir等温线方程,最大吸附量为170.28mg/g;计算得知胡敏素吸附Pb~(2+)的热力学状态函数ΔG~0、ΔS~0和ΔH~0分别为-29.30~-24.21k J/mol、126.70J/(mol·K)和13.59k J/mol,吸附过程为吸热过程.胡敏素表面的羰基、羟基、氨基和羧基等活性基团可以和Pb~(2+)发生配位络合作用,Ca、Na和Mg等离子与Pb~(2+)发生离子交换作用.研究结果表明,胡敏素作为一种极具潜力的绿色廉价吸附剂,可用于处理含Pb~(2+)废水.     

土壤芽孢杆菌产胞外聚合物对Pb~(2+)吸附特性研究

根据与细菌菌体结合的紧密程度,胞外聚合物(EPS)可以分为粘液层EPS(S-EPS)、松散附着EPS(LB-EPS)、紧密附着EPS(TB-EPS),以土壤芽孢杆菌作为实验菌株,研究了各层EPS在不同温度、pH值条件下对Pb~(2+)的吸附特性,建立了EPS的吸附动力学模型和吸附等温线模型,并采用扫描电子显微镜(SEM)观察各层EPS吸附Pb~(2+)前后的表观形态的变化.当吸附温度为35℃、pH值为5.5时,S-EPS、LB-EPS、TB-EPS对Pb~(2+)的吸附量分别为91.35、100.61和90.28mg/g,表明LB-EPS对Pb~(2+)的吸附能力更强.各层EPS吸附Pb~(2+)的吸附动力学模型和吸附等温线模型均符合准二级动力学模型和Langmuir等温吸附模型,表明吸附过程分别受化学吸附机理控制和单分子层吸附控制,并通过Langmuir模型计算得到,S-EPS、LB-EPS、TB-EPS对Pb~(2+)的最大吸附量分别为124.224、127.389和119.760mg/g.同时,扫描电镜结果表明吸附前后各层EPS表观形态均差异明显,其中LB-EPS呈肺泡状,具有更大的比表面积,因此更多的Pb~(2+)吸附在其表面.     

絮凝快速分离水处理技术简介及发展趋势

从排污口废水中筛选到一株能耐受一定浓度Pb~(2+)和Zn~(2+)的低温真菌,将其作为吸附剂,研究了其吸附动力学及吸附方式、温度和pH值对其吸附Pb~(2+)和Zn~(2+)的影响,绘制、拟合吸附等温线,并在模拟废水环境中进行逐级吸附试验。结果表明:Pb~(2+)和Zn~(2+)初始浓度接近100 mg/L时,可在20℃吸附15 min时达到平衡,吸附曲线符合Langmuir等温吸附模型,静态吸附的吸附量偏高。当pH值为4~6,温度在4~15℃时吸附量最大,这正是低温真菌的优势所在。人工配制了含Pb~(2+)和Zn~(2+)的模拟废水,分别经过5级和6级吸附后,出水可达到GB 25466—2010《铅、锌工业污染物排放标准》要求。     

一株低温真菌的筛选及其对重金属离子的吸附研究

从排污口废水中筛选到一株能耐受一定浓度Pb~(2+)和Zn~(2+)的低温真菌,将其作为吸附剂,研究了其吸附动力学及吸附方式、温度和pH值对其吸附Pb~(2+)和Zn~(2+)的影响,绘制、拟合吸附等温线,并在模拟废水环境中进行逐级吸附试验。结果表明:Pb~(2+)和Zn~(2+)初始浓度接近100 mg/L时,可在20℃吸附15 min时达到平衡,吸附曲线符合Langmuir等温吸附模型,静态吸附的吸附量偏高。当pH值为4~6,温度在4~15℃时吸附量最大,这正是低温真菌的优势所在。人工配制了含Pb~(2+)和Zn~(2+)的模拟废水,分别经过5级和6级吸附后,出水可达到GB 25466—2010《铅、锌工业污染物排放标准》要求。     

牛粪源蚓粪及其生物炭对Pb2+、Cd2+的吸附特性

以牛粪源蚓粪(CV)为原料,于350℃下热解制备蚓粪生物炭(标记为CVC350)并表征其物理化学性质,进一步就CV和CVC350对Pb~(2+)和Cd~(2+)的吸附性能进行了研究,结果表明:与CV相比,CVC350的比表面积增大,孔径变小,芳香性和非极性增强.CV和CVC350对Pb~(2+)和Cd~(2+)的等温吸附曲线均符合Langmuir方程,两者对Pb~(2+)的最大吸附量表现为CVC350CV,而两者对Cd~(2+)的最大吸附量间差异不明显.解吸特性研究表明,CV和CVC350对Pb~(2+)的吸附率明显高于其对Cd~(2+)的吸附率,且两者的吸附态Cd~(2+)与其吸附态Pb~(2+)相比均相对更易解吸.CV和CVC350对Pb~(2+)的吸附动力学均为快速吸附过程,而CV和CVC350对Cd~(2+)的吸附动力学则均表现为快速吸附和慢速吸附两个阶段.当溶液初始pH较低时,CV和CVC350对Pb~(2+)和Cd~(2+)吸附量受pH影响明显,且CV和CVC350对Cd~(2+)的吸附受pH变化的影响相对更大.FTIR分析表明,CV对Pb~(2+)和Cd~(2+)的吸附位点主要集中在脂肪醇或脂肪酸、碳酸盐和磷酸盐,而CVC350对Pb~(2+)和Cd~(2+)的吸附位点主要为芳香醇或芳香酸和碳酸盐.     

腐植酸对重金属铅镉的吸附特征

为了揭示腐植酸对单一Pb、单一Cd和Pb、Cd复合污染物的吸附特征,笔者通过吸附模拟实验分析了pH、温度、反应时间和初始浓度等因素变化对风化煤腐植酸吸附重金属离子Pb~(2+)和Cd~(2+)的影响.结果表明,腐植酸对Pb~(2+)的吸附受pH值变化的影响很小,但对Cd~(2+)的吸附随着pH增加而增加;腐植酸对Pb~(2+)和Cd~(2+)吸附饱和的时间均为240 min;对Pb~(2+)和Cd~(2+)的吸附量均随温度的增加而增加;Langmuir吸附模型对腐植酸吸附单一Pb~(2+)、单一Cd~(2+)和铅镉复合态中Pb~(2+)的拟合较好,Freundlich吸附模型则对腐植酸吸附铅镉复合态中Cd~(2+)的拟合较好;准二级动力学模型能较好地拟合腐植酸吸附Pb~(2+)和Cd~(2+)的过程,说明腐植酸对铅镉的吸附为物理吸附和化学吸附的复合吸附过程;铅镉复合态下Pb~(2+)和Cd~(2+)存在竞争吸附,单一Pb~(2+)溶液中加入Cd~(2+)对腐植酸吸附Pb~(2+)基本无影响,但单一Cd~(2+)溶液中加入Pb~(2+)时,Pb~(2+)会与Cd~(2+)产生竞争吸附,从而降低Cd~(2+)的吸附量.本研究结果可为利用腐植酸稳定土壤中Pb~(2+)、Cd~(2+)等重金属离子的技术开发提供参考.     

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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