生物炭负载纳米零价铁制备及修复六价铬污染土壤技术研究进展

近年来,纳米零价铁颗粒（nZVI）应用于Cr（Ⅵ）污染修复治理技术研究备受关注。生物炭负载型纳米零价铁（nZVI@BC）作为纳米零价铁改性技术之一,具有低成本、易制备和修复效果优越等优点,但此技术应用于Cr（Ⅵ）污染土壤修复方面研究尚不多。生物炭（BC）主要通过植物秸秆热解生成,生物炭负载纳米零价铁（nZVI@BC）则通过生物炭与纳米零价铁在热解-液相还原法或一步热解法合成。制备的nZVI@BC能够有效解决纳米零价铁团聚和钝化等缺点,显著提高纳米零价铁（nZVI）利用率。综述了生物炭负载纳米零价铁（nZVI@BC）应用于修复Cr（Ⅵ）污染土壤反应机理和研究进展,总结出提升该材料性能的途径有:通过调整BC热解条件和改性BC以提升BC性能;适当的质量比（BC/nZVI）;使用聚乙二醇（PEG）、羧甲基纤维素（CMC）、污泥衍生的BC和茶多酚（TP）提高nZVI稳定性。nZVI@BC材料能够提高土壤中有机质含量,在Cr（Ⅵ）修复治理方面极具应用前景。     

零价纳米铁吸附去除水中六价铬的研究

利用液相还原法制备的零价纳米铁(nZVI)进行了去除水中Cr(Ⅵ)的实验研究.结果表明,nZVI对Cr的去除效果明显优于还原铁粉和粉末活性碳;pH值越小、初始Cr浓度越低、nZVI放置时间越短及投加量越大均有利于水中Cr(Ⅵ)的去除,最佳去除率近100%;反应动力学拟合结果表明,nZVI去除六价铬符合准二级动力学模型;反应后nZVI颗粒的扫描电镜及电子能谱结果显示Cr占12.02%(wt),结合对反应溶液中Cr(Ⅵ)和Cr(Ⅲ)分析,说明吸附、还原与共沉淀可能是nZVI去除水中六价铬的主要机理.     

应用纳米零价铁处理模拟含Cr(Ⅵ)无氧地下水

研究了实验室自制的纳米零价铁处理模拟含Cr(Ⅵ)无氧地下水的影响因素、吸附动力学,并结合体系中Fe2+浓度、氧化还原电位、Zeta电位和理论计算得到的pe-pH图对纳米零价铁去除Cr(Ⅵ)的机制进行了探讨.实验结果表明,纳米零价铁对Cr(Ⅵ)的去除率随着初始Cr(Ⅵ)/Fe质量比的升高而降低.当溶液的pH为7.0,初始Cr(Ⅵ)/Fe质量比为0.025、0.050、0.075和0.100时,相应地Cr(Ⅵ)的去除率分别为100.0%、85.6%、72.7%和39.6%.酸性条件更有利于纳米零价铁对Cr(Ⅵ)的去除,当初始Cr(Ⅵ)/Fe质量比为0.100,溶液的pH为3.0、5.0、7.0、9.0和11.0时,体系中Cr(Ⅵ)的去除率分别为73.4%、57.6%、39.6%、44.1%和41.2%.纳米零价铁去除Cr(Ⅵ)的过程符合拟二级动力学方程.当溶液的pH为7.0,初始Cr(Ⅵ)/Fe质量比为0.025时,吸附速率常数(k)最大,为9.76×10-3g.(mg.m in)-1.Cr2O27-吸附到纳米零价铁表面后被迅速地还原为Cr3+,生成的Cr3+与纳米零价铁表面的FeOOH结合生成Cr-Fe膜.而Cr-Fe膜将阻断电子在纳米零价铁与Cr2O27-之间的传输,Cr(Ⅵ)得不到还原,从而纳米零价铁对Cr2O27-的去除以吸附为主.     

粉煤灰基多孔材料负载纳米铁的制备及其对龙胆紫的去除效果

为制备新型可再生吸附反应材料,以工业废弃物粉煤灰、棕榈壳等为主要原料,烧结制备FAP（粉煤灰基多孔材料）,并以FAP为载体负载纳米零价铁,制备FAP/nZVI（粉煤灰基纳米零价铁多孔材料）,以散失率、龙胆紫去除率、纳米零价铁负载量等为指标,确定FAP及FAP/nZVI的最佳制备条件,并考察二者对染料龙胆紫的去除特性.结果表明:① FAP的最佳制备条件为m（粉煤灰）:m（膨润土）:m（棕榈壳）=190:95:15,升温速率10℃/min,烧结温度800℃,保温时间30 min.② FAP/nZVI最佳制备条件为m（Fe）/m（FAP）1:3,振荡时间1 h,选用抗坏血酸为稳定剂,过程中无需使用惰性气体;SEM结果表明纳米零价铁被成功负载于FAP上.③ FAP/nZVI对200 mg/L龙胆紫的去除率为94.8%,FAP同条件下的去除率仅为26.2%,FAP/nZVI对龙胆紫的去除同时存在物理吸附和化学还原作用,并且纳米零价铁的还原占主导作用.④ FAP/nZVI再生10次后30 min内对100 mg/L龙胆紫去除率高达97.6%.研究显示,FAP可将纳米零价铁氧化产物Fe2+固定在表面,经还原后可再生为纳米零价铁,具有良好的再生性能.      

碳基材料负载纳米零价铁去除六价铬的研究进展

近年来,纳米零价铁(nZVI)因具有比表面积大、还原能力强、成本低的特点被用于去除环境中的六价铬〔Cr(Ⅵ)〕,然而由于高表面能、固有磁力等因素的影响,nZVI具有易团聚、易氧化和不稳定的缺点,限制了其广泛应用. 鉴于此,本文以碳材料作为支持材料改性nZVI,比较了制备碳基nZVI复合材料的方法,分析了不同碳基nZVI复合材料去除Cr(Ⅵ)的反应效能,阐述了影响复合材料去除Cr(Ⅵ)的因素. 结果表明:①湿化学法合成的复合材料有利于提高nZVI的分散性,减少团聚. 热转化法合成的复合材料有利于节约成本,提高碳材料和nZVI的结合性. ②不同碳材料负载nZVI能有效提高nZVI的分散性、稳定性和抗氧化性. ③碳基材料负载nZVI能有效降低环境因素对nZVI的负面影响. ④碳基nZVI复合材料能提高对Cr(Ⅵ)的去除能力,其对Cr(Ⅵ)的最大吸附容量比nZVI高1.2～20倍. 本文旨在深入了解碳基nZVI复合材料的合成方法,提高碳基nZVI复合材料的性能,以期为开发高效稳定的碳基nZVI复合材料修复环境中的Cr(Ⅵ)提供一些启示.      

纳米零价铁/生物炭材料吸附Cr(Ⅵ)的研究

为治理工业废水中重金属铬污染,该文以梧桐叶为原料、绿茶滤液为绿色还原剂制备出纳米零价铁/生物炭复合材料,对材料的微观形貌、所含官能团、元素组成等理化性质进行表征,考察其对水中Cr（Ⅵ）的吸附去除性能。结果表明：纳米零价铁颗粒均匀附着于光滑舒展的生物炭表面,材料含有酚类、烯烃、芳香化合物和醇类等多种有机化合物,负载纳米零价铁后生物炭本身的石墨结构无显著变化,XRD谱图具有零价铁的特征峰。600℃热解制备生物炭,Fe/C负载比为1∶24的负载纳米零价铁生物炭材料,投加量2.0 g,对50 mL初始浓度为10 mg/L Cr（Ⅵ）溶液吸附60 min后,最大去除率为58.72%。     

桉树生物炭负载绿色合成纳米零价铁去除水中Cr (Ⅵ)

以桉树叶提取物绿色合成的纳米零价铁（nZVI）为主体,使用桉树生物炭（EBC）负载,成功制备一种高效去除Cr （Ⅵ）的复合材料（EBC-nZVI）,考察单一材料和复合材料去除Cr （Ⅵ）的效果差异和循环利用潜力;并研究投加量和溶液初始pH对去除效果的影响.使用GC-MS分析合成前后提取液中成分变化,通过SEM-EDS、FTIR、XRD和XPS对材料表征,结合吸附动力学和吸附等温线实验讨论去除机制.结果表明,绿色合成过程中桉树叶提取液提供了充当还原剂和封端剂的生物分子,复合材料分散性良好并有效缓解nZVI的钝化.复合材料去除Cr （Ⅵ）的过程中EBC和nZVI表现出协同作用,在pH为3,投加量1g·L^-1条件下对100mg·L^-1的Cr （Ⅵ）溶液去除率达到99.5%以上,且具有良好的循环利用潜力.EBC-nZVI吸附过程符合准二级动力学模型和Langmuir吸附等温模型,活性位点与Cr （Ⅵ）的化学吸附过程是去除速率的主要限制因素.EBC-nZVI与Cr （Ⅵ）的反应机制是nZVI和Fe （Ⅱ）将吸附的Cr （Ⅵ）还原为Cr （Ⅲ）,然后通过表面络合、官能团吸附和共沉淀以FeOOH、Fe₂O₃、Cr （OH）₃和Cr₂O₃的形式实现去除.     

氨基改性生物炭负载纳米零价铁去除水中Cr(VI)

以聚乙烯亚胺（PEI）为功能单体,玉米秸秆生物炭为载体,制备了氨基改性生物炭负载型纳米零价铁（nZVI@PEI-HBC）,并利用扫描电镜（SEM）、红外光谱（FTIR）和X射线光电子能谱（XPS）等手段对材料进行了表征,分析了溶液pH、温度、材料投加量等因素对其去除Cr（VI）的影响及其去除机理.结果表明：在投加量为0.5 g·L^-1,温度为20℃,pH值为5,Cr（VI）初始浓度为20 mg·L^-1条件下,各材料对Cr（VI）的去除率大小为nZVI@PEI-HBC > nZVI > PEI-HBC > HBC.SEM显示nZVI颗粒较均匀地分散在生物炭表面,FTIR分析表明PEI改性后材料表面增加了氨基等重金属配位基团,这可能是nZVI@PEI-HBC去除Cr（VI）效果更好的原因.影响因素研究表明,材料具有较好稳定性,老化28 d后其Cr（VI）去除性能变化不大;酸性环境、升温、增大材料投加量均有利于nZVI@PEI-HBC对Cr（VI）的去除.机理研究发现,水中溶解氧加速了nZVI的腐蚀和Fe（II）的释放,促进Cr（VI）还原为Cr（III）,然后通过共沉淀作用和氨基等基团的吸附作用被去除.     

有机配体对膨润土负载纳米零价铁还原Cr(Ⅵ)的影响

六价铬〔Cr(Ⅵ)〕因具有剧毒性和致癌性而被广泛关注. 以Fe(Ⅲ)与 NaBH₄反应制得负载型的纳米铁(B-NZVI),并对该材料做了TEM和AAS的表征;深入考察B-NZVI去除Cr(Ⅵ)的动力学规律,以及草酸、柠檬酸、草酸钠、柠檬酸钠等有机配体对膨润土负载纳米零价铁还原Cr(Ⅵ)去除速率的影响,并对其影响机理进行初步探讨. 结果表明,膨润土负载纳米零价铁对Cr(Ⅵ)的去除行为符合Langmuir-Hinshelwood模型,其k_obs为0.011 97 min-1;草酸、柠檬酸、草酸钠和EDTA可促进B-NZVI对Cr(Ⅵ)的还原去除作用;柠檬酸钠则起到抑制作用. a      

甘蔗渣负载纳米零价铁吸附剂去除水中Cr(Ⅵ)的研究

以改性甘蔗渣做载体,采用液相还原法制备负载型纳米零价铁吸附剂,研究了原甘蔗渣、改性甘蔗渣、纳米零价铁及纳米零价铁/改性甘蔗渣4种物质对于水中Cr(Ⅵ)的吸附特性,探讨了反应时间、溶液pH值、固液比、Cr(Ⅵ)初始浓度等因素对于Cr(Ⅵ)吸附效果的影响。实验结果表明:4种吸收剂中,纳米零价铁/甘蔗渣的吸附能力最好,在pH=4,固液比=0.5 g/L,Cr(Ⅵ)初始浓度小于25 mg/L时,可全部去除Cr(Ⅵ)。并对甘蔗渣基纳米零价铁和Cr(Ⅵ)的反应机理进行了初探。     

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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