凹凸棒石的表面修饰及对水中Cr（Ⅵ）吸附动力学和热力学的研究

以壳聚糖为生物质碳源,采用一步水热碳化法对凹凸棒石表面进行有机修饰,并采用扫描电镜(SEM)、拉曼(Raman)光谱、元素分析(EA)、X光电子能谱(XPS)、Zeta电势分析、热重分析(TGA)等对改性凹凸棒石进行表征分析.同时,通过静态吸附实验,研究了改性凹凸棒石对Cr(Ⅵ)吸附去除的性能,考察了温度对吸附性能的影响,探讨了吸附动力学和热力学规律.结果表明,改性凹凸棒石表面富含含氧基团和氨基等活性基团;对总铬的吸附行为符合准二级动力学方程;表观吸附活化能为13.4 k J·mol~(-1),表明既有静电吸附,也有配位吸附,且以静电吸附为主;对总铬的吸附等温线符合Langmuir方程.在温度为298、308、318和328 K时,最大吸附量分别为203.3、232.6、267.4和322.6 mg·g~(-1),说明改性凹凸棒石是一种新型环保高性能的除铬材料.在研究的温度范围内,ΔH~0为19.8 k J·mol~(-1),ΔG~0为-19.5~-23.7 k J·mol~(-1),ΔS~0为72.1~131.8 J·mol~(-1)·K~(-1),表明该吸附是一吸热的、自发的、熵增过程.     

磁性石墨烯吸附水中Cr(Ⅵ)研究

以氧化石墨和铁盐为原料,采用化学沉淀法制备出磁性石墨烯复合材料,运用静态吸附实验研究了吸附动力学、热力学、等温吸附模型以及不同因素如p H、温度、时间对Cr(Ⅵ)吸附的影响.结果表明,吸附动力学符合假二级动力学模型;与Freundlich模型相比,Langmuir模型更适合描述吸附过程.热力学参数为:ΔHθ=33.89 k J·mol-1,ΔSθ=120.15 J·(mol·K)-1,ΔGθ=-2.51 k J·mol-1(303 K),这表明吸附过程是吸热并且自发的.实验最佳p H值为2,升高温度和延长时间均有利于吸附的进行.初始Cr(Ⅵ)浓度为5 mg·L-1时,重复利用3次后吸附量由3.9 mg·g-1下降到2.1 mg·g-1.在磁铁存在的条件下吸附剂可轻易从溶液中分离出来,利用Na OH可使其再生,因此可作为去除Cr(Ⅵ)的良好吸附剂.     

臭氧氧化降解水中三氯乙烯的效能研究

卤代烃是地下水污染中常见的有机污染物,三氯乙烯(Trichloroethylene,TCE)作为一种典型的卤代烃,具有高检出率、易挥发、致癌性等特征,而对地下水中TCE的治理一直是研究的热点.因此,本文以TCE为目标污染物,采用臭氧氧化技术对其进行降解效能分析,重点考察了不同臭氧投加量、初始p H、温度、初始TCE浓度对臭氧氧化降解水中TCE的影响,并对反应产物及可能的臭氧氧化机理进行了推测.结果表明,溶液的初始p H、臭氧投加量、初始TCE浓度均会对TCE的降解效率和降解速率产生一定的影响.在优化的实验条件下(p H=9、臭氧投加量5mg·L~(-1)、TCE初始浓度1 mg·L~(-1)、温度30℃),TCE在2 h的降解率可以达到100%,反应结束后TCE脱氯率为71.1%.动力学实验表明,臭氧氧化TCE的反应符合伪一级动力学.热力学研究表明,臭氧氧化TCE的焓变(ΔH)为15.53 k J·mol~(-1),熵变(ΔS)为-226.5 J·mol~(-1)·K~(-1),活化能E_a为18.05 k J·mol~(-1),表明臭氧氧化TCE的反应易于进行.机理研究表明,臭氧氧化降解TCE主要是由臭氧分解所形成的羟基自由基进行的.     

对羟基联苯在黄河兰州段底泥上的吸附行为

为研究典型有机污染物在黄河兰州段的吸附规律及影响因素,以黄河兰州段的底泥为供试样品,选择对羟基联苯(phydroxy biphenyl,PHB)为代表性有机污染物,采用批量实验法研究了底泥对PHB的吸附动力学和热力学特征及其影响因素.结果表明,黄河兰州段底泥对PHB吸附动力学的最优模型为准二级动力学模型,吸附热力学过程更符合单分子层吸附的Langmuir等温吸附模型(R20.974),在25~45℃温度范围内,PHB在黄河兰州段底泥上的吸附平均自由能(E)在0.913~1.00 k J·mol~(-1)之间,吸附过程中,ΔGθ和ΔHθ均小于0,ΔSθ均大于0,表明黄河兰州段底泥对PHB的吸附过程主要是物理吸附,属于自发放热过程且体系的混乱度是增加的.分析黄河兰州段底泥对PHB吸附影响因素的结果表明,粒径越小,黄河底泥对PHB的吸附量越大;PHB的初始质量浓度越高,黄河底泥对PHB的吸附量越大;当p H在4.23~7.00之间时,吸附量随pH升高而缓慢下降,当pH7.00时,吸附量随pH升高急剧下降,且在pH=10.3附近,吸附量几乎为零;体系中离子强度增大,PHB吸附量增大,但当离子强度到一定值时,由于竞争吸附作用,会抑制底泥对PHB的吸附,造成吸附量的下降.     

对硝基苯酚在高炉水淬渣上的吸附机制及表面分形研究

研究了对硝基苯酚(p-NP)在高炉水淬渣(WBFS)上的吸附情况,用电镜扫描(SEM)、X射线衍射仪(XRD)、红外光谱仪(FTIR)、比表面积测定仪(BET)等对高炉水淬渣的理化性质进行了表征.通过批量平衡实验,从动力学和热力学角度探讨了对硝基苯酚在高炉水淬渣上的吸附作用机制.结果表明,吸附等温线能较好地用Freundlich模型来描述.ΔH和ΔS值分别为3.29 k J·mol~(-1)和4.66 J·(mol·K)~(-1),表明对硝基苯酚在高炉水淬渣上的吸附是属于吸热熵增的过程,无化学键等强作用力.ΔG值随着温度的升高而逐渐降低,说明高炉水淬渣对对硝基苯酚吸附的自发性与温度呈正比.高炉水淬渣对对硝基苯酚的吸附可分为快速的表面覆盖和慢速的内部扩散吸附2个过程,整个吸附过程符合伪二级动力学模型.运用Freundlich吸附分形模型计算了不同温度下高炉水淬渣表面的分形维数D分别为2.78、2.80、2.84以及2.87,表明高炉水淬渣的表面确实存在着分形现象,温度越高,D值越大.     

高炉水淬渣吸附Zn~(2+)的平衡与动力学研究

研究了Zn~(2+)在高炉水淬渣(WBFS)上的吸附情况,并用电镜扫描(SEM)、电感耦合等离子体质谱分析仪(ICP)及X射线衍射仪(XRD)等对高炉水淬渣的理化性质进行了表征.通过批量平衡实验,从动力学和热力学角度探讨了Zn~(2+)在高炉水淬渣上的吸附作用机理.结果表明:吸附等温线能较好地用Langmiur模型来描述,分离因子RL值介于0~1之间,属于优惠吸附.ΔH和ΔS值分别为52.45 k J·mol~(-1)和167.52J·mol~(-1)·K~(-1),表明Zn~(2+)在高炉水淬渣上的吸附是吸热过程,并且吸附过程增加了系统的混乱度,而ΔG值仅仅在温度高于318 K后才为负值,说明高炉水淬渣对Zn~(2+)吸附的自发性与温度成正比.吸附动力学很好地符合伪二级动力学模型,以化学吸附为主.高炉水淬渣重金属浸出浓度低,环境安全性能优良,可以作为一种较为理想的吸附剂.     

流动搅动法研究针铁矿对亚砷酸盐的吸附特征

采用流动搅动法,在溶液p H、浓度和温度影响条件下,研究针铁矿对亚砷酸盐吸附的特征.结果表明,在不同条件下,亚砷酸盐的吸附过程分为快反应和慢反应这2个阶段.随溶液p H的升高,砷的吸附量逐渐降低,表观吸附速率常数(k')逐渐增大,半反应时间(t1/2)也就越小,砷的吸附反应达到平衡时间就越短,且砷的扩散速率常数b值也逐渐降低.溶液p H 3.0和p H7.0时,砷最大吸附量分别为246.9 mg·kg~(-1)和99.8 mg·kg~(-1).随着砷浓度的升高,针铁矿对砷的吸附量增加,表观吸附速率常数(k')逐渐增大;砷浓度为0.10 mg·L~(-1)和1.00 mg·L~(-1)时,砷的最大吸附量分别为96.5 mg·kg~(-1)和249.1 mg·kg~(-1).Freundlich方程中吸附常数Kf值随着时间的延长逐渐降低,其吸附能力是逐渐减弱的.Langmuir方程分配因子RL在0~1之间,表现为针铁矿上砷的吸附为优惠吸附.随着温度的升高,针铁矿对砷的吸附量增加,表观吸附速率常数k'值也逐渐升高.温度为298K和313 K时,砷最大吸附量分别为241.1 mg·kg~(-1)和315.6 mg·kg~(-1).用抛物线扩散方程b值来计算扩散过程的伪热力学常数,砷吸附反应的活化能(E*a)为14.60 k J·mol~(-1).砷扩散活化焓变(ΔHθ)随着温度的升高有所降低,ΔHθ均为正值,扩散过程为吸热反应,升高温度有利于砷的吸附;活化自由能变(ΔGθ)随着温度的上升而升高,升高温度有利于加快扩散过程;ΔSθ值均为负,说明吸附反应使体系有序度增加.     

3种吸附剂对污水磷污染去除性能与机制比较

为探索高效利用膨润土、红壤和炉渣去除农业污水磷污染的可行性,对比分析了3种吸附剂对人工合成含磷污水的吸附去除特性,结合SEM、XDS和BET等测试结果以及等温吸附、吸附动力学及Ca2+释放量探讨了3种材料对磷的吸附机制.结果表明,炉渣对磷的吸附能力高于膨润土和红壤,吸附过程均适合Langmuir等温吸附方程(R2 0. 96),对磷的理论饱和吸附量为:炉渣(16. 87 mg·g~(-1))红壤(1. 21 mg·g~(-1))膨润土(0. 92 mg·g~(-1)).炉渣对磷的吸附动力学特征符合Elovich方程(R2=0. 966),而膨润土和红壤对磷的吸附特征则更适合准二级动力学方程(R2为0. 982和0. 959).炉渣的Ca2+释放量(10. 46 mg·g~(-1))显著大于膨润土(0. 31 mg·g~(-1))和红壤(0. 03 mg·g~(-1))(P 0. 05).红壤对磷的吸附量随着p H的升高而降低;膨润土在初始p H为7. 0时,吸附量最低;但初始p H值对炉渣去除磷的影响不大.相比红壤和炉渣,膨润土解吸较快,易于进行重复利用.综上所述,吸附材料的磷吸附能力主要与其结构、化学组成、Ca2+释放能力及溶液初始p H值等有关,炉渣较膨润土和红壤对磷酸盐有着更强的去除能力,适合处理农村污水磷污染.     

Ca-Al-LDH对富里酸吸附性能的研究

采用乙醇辅助液相共沉淀法制备Ca-Al-LDH(层状双金属氢氧化物),运用X射线衍射仪(XRD)和傅里叶变化红外光谱仪(FA-RT)对吸附前后的Ca-Al-LDH样品进行表征,并研究了Ca-Al-LDH对富里酸的吸附性能及其影响因素。结果表明:Ca-Al-LDH对富里酸吸附容量随p H的变化呈先增加后递减趋势,在p H为4时吸附容量达35.5 mg/g;吸附过程在24 h达到平衡;添加电解质Na NO3可抑制富里酸的吸附作用;吸附过程符合Langmuir模型,且吸附动力学过程符合准二级动力学方程。     

高岭石、针铁矿及其二元体对胡敏酸的吸附特性

研究了高岭石、针铁矿及其混合物(KGM)和复合物(KGC)的表面性质及吸附胡敏酸的特性.结果表明,4种物质的比表面积(SSA)表现为针铁矿KGCKGM高岭石,KGM的SSA接近两种纯物质的平均值,而KGC的SSA明显升高.高岭石、针铁矿、KGM和KGC的等电点(IEP)分别为3.2、7.9、6.1和6.7;初始p H=5.0时,其表面Zeta电位分别为-13.9、38.2、14.3和19.7 m V.4种样品对胡敏酸的动力学吸附过程适合用准二级动力学模型描述,表明化学吸附是主要作用机制.一、二位Langmuir模型可较好地拟合等温吸附数据(R~2为0.962~0.993),其中二位Langmuir模型对KGM和KGC吸附数据的拟合度R~2分别为0.989和0.993;Freundlich模型对等温吸附数据的拟合度较低,但两种二元体的拟合度高于两种纯物质.初始p H=5.0时,高岭石、针铁矿、KGM和KGC对胡敏酸的吸附容量(q_(max))分别为6.02、61.83、35.13和42.10 mg·g~(-1);两种二元体的q_(max)都高于两种纯物质q_(max)的平均值,其中KGC的q_(max)明显升高.热力学参数表明,4种样品对胡敏酸的吸附均属于吸热反应,其中高岭石的吸附为非自发过程,其余样品的吸附为自发过程.     

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.     

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.     

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.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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