有机膨润土在Pb2+和p-硝基苯酚复合污染中的吸附及机理

以Pb²⁺、p-硝基苯酚为代表污染物,用实验室模拟法研究了有机膨润土在重金属-有机物混合污染体系中的吸附行为.结果表明,在有机膨润土/Pb²⁺/p-硝基苯酚体系中,溶液中共存Pb²⁺会延缓p-硝基苯酚在有机膨润土上的吸附速率;Pb²⁺与p-硝基苯酚产生竞争吸附,竞争作用的大小与溶液中p-硝基苯酚和Pb²⁺的浓度比c(酚/Pb)以及有机膨润土对污染物的吸附机制有关,相对于吸附机制以分配作用为主的100CTMAB-膨润土,Pb²⁺与p-硝基苯酚在以表面吸附为主的100TMAB-膨润土上的竞争吸附更强.     

CPC在膨润土处理含p-硝基苯酚废水中的增强效应

选用氯代十六烷基吡啶(CPC)和p-硝基苯酚为目标化合物,试验比较了CPC 膨润土直接混合体系和CPC改性有机膨润土对含p-硝基苯酚废水的吸附效果.结果表明,与CPC改性土相比,用相应浓度的CPC 膨润土混合直接处理含p-硝基苯酚废水更为有效,可使p-硝基苯酚的去除率提高2倍以上(45%~98%),并可以节约处理成本且基本不增加表面活性剂二次污染.最经济适宜的CPC投加量与膨润土阳离子交换容量(CEC)相当.     

双阳离子有机膨润土吸附处理水中有机物的性能

分别用长碳链季铵盐（ 如溴化十二烷基三甲铵、溴化十四烷基苄基二甲铵、溴化十六烷基三甲铵、溴化十八烷基三甲铵） 和短碳链季铵盐（ 如溴化四甲基铵） 按一定配比混合改性膨润土,制得一系列双阳离子有机膨润土．研究了双阳离子有机膨润土吸附水中对硝基苯酚、苯酚、苯胺的适宜条件、性能、作用机理．结果表明,双阳离子有机膨润土的层间距、有机碳含量和对有机物的吸附性能与改性时长、短碳链季铵盐的组成及配比有关,水中有机物的去除效果还与其本身的性质有关;所用的双阳离子有机膨润土对有机物的吸附符合 Freundlich或 Langmuir等温式,是表面吸附作用和分配作用共同作用的结果．     

CTMAB-膨润土去除水中有机物的性能及机理

用溴化十六烷基三甲铵（CTMAB）改性膨润土,研究了CTMAB膨润土去除水中苯、甲苯、乙苯、硝基苯、苯胺、苯酚、对硝基苯酚的性能、机理及影响因素。结果表明,CTMAB-膨润土去除水中有机物的能力远大于原土;CTMAB-膨润土对苯、甲苯、乙苯的等温吸附曲线呈线性;对水中苯酚、对硝基苯酚的等温吸附曲线呈非线性;对苯胺、硝基苯的等温吸附曲线基本呈线性。CTMAB-膨润土吸附水中有机物的性能及机理与有机物的水溶性或辛醇－水分配系数有关。     

改性膨润土对Cd(Ⅱ)的吸附性能研究

研究比较了膨润土与改性膨润土作为吸附剂对Cd2 + 的吸附性能。探讨了膨润土的用量、pH值等因素对膨润土吸附Cd2 + 的影响。改性膨润土对Cd2 + 的吸附能力明显增强 ;膨润土的用量、pH值对Cd2 + 的吸附效率影响较大。当pH =8～ 9时 ,改性膨润土用量为 4g L ,对初始浓度为 4 0mg L的Cd2 + 的去除率达 96 %。膨润土原土、改性膨润土对Cd2 + 的吸附等温线均符合Freundlich方程。     

植物多酚改性膨润土吸附重金属镉实验研究

对钙基膨润土、酸活化膨润土、自制单宁酸改性膨润土,通过表征测试研究了膨润土改性后的形态结构变化。结果表明:单宁酸改性膨润土较钙基膨润土结构未发生较大变化;并分别探讨了不同投加量、反应pH及不同初始浓度对单宁酸改性膨润土吸附镉的影响。实验表明:单宁酸改性膨润土对Cd2+的吸附性能优于钙基膨润土及酸活化膨润土,在材料用量越小及反应pH越低时,单宁酸对膨润土吸附Cd2+的促进作用越明显。单宁酸改性膨润土对Cd2+的吸附能用Langmuir吸附方程进行描述,其最大吸附量约为31.25mg/g,比钙基膨润土提高了20.6%。本研究将为非金属矿物在水体及土壤重金属污染修复方面的应用提供理论基础和科学依据。     

不同锆负载量锆改性膨润土对水中磷酸盐吸附作用的对比

通过实验对比考察了不同锆负载量的锆改性膨润土对水中磷酸盐的吸附作用.结果表明,锆改性膨润土对水中磷酸盐的吸附动力学过程符合准二级动力学模型,整个过程可以分为快速吸附阶段、缓慢吸附阶段和平衡吸附阶段,其中缓慢吸附阶段的吸附速率受膜扩散和颗粒内扩散所控制.锆改性膨润土对水中磷酸盐的吸附等温实验数据可以采用Langmuir、Freundlich、Sips和Dubinin-Radushkevich等温吸附模型进行拟合.实验条件下,磷酸盐吸附性能随pH增加而降低.溶液共存的Na~+、K~+和Ca~(2+)促进了锆改性膨润土对磷酸盐的吸附,并且Ca~(2+)的促进作用远远大于Na~+和K+,而溶液共存的HCO-3和SO2-4一定程度上抑制了锆改性膨润土对磷酸盐的吸附.锆改性膨润土吸附水中磷酸盐的主要机制为配位体交换并形成内层磷酸盐配合物.锆改性膨润土对水中磷酸盐的吸附能力随着锆负载量的增加而增加,而锆改性膨润土中单位质量ZrO_2对水中磷酸盐的吸附量则随着锆负载量的增加而降低.当ZrO_2负载量由3.61%增加到13.15%时锆改性膨润土的最大单层单位吸附量(以P计)显著地由3.83 mg·g~(-1)增加到9.03 mg·g~(-1),而继续增加ZrO_2负载量至19.63%时锆改性膨润土的最大单层单位吸附量则缓慢地提高到9.66 mg·g~(-1)(以P计).当ZrO_2负载量由3.61%逐渐增加到19.63%时,锆改性膨润土中单位质量ZrO_2的磷酸盐最大吸附量[m(P)/m(ZrO_2)]由106 mg·g~(-1)逐渐下降到49.2 mg·g~(-1).综合考虑吸附剂的经济成本和吸附容量,ZrO_2负载量为13.15%锆改性膨润土更为适合作为吸附剂去除水中磷酸盐.     

对-硝基苯酚在水/有机膨润土界面的吸附行为——热力学特征及机理

研究了水溶液中100TMAB-膨润土,40TMAB/60CTMAB-膨润土,100CTMAB-膨润土吸附对-硝基苯酚过程的热力学及机理.测定了不同温度下的等温吸附曲线,计算了热力学函数(标准吸附自由能变G0、标准吸附焓变H0、标准吸附熵变S0).结果表明,对-硝基苯酚在水相和有机膨润土间的分配系数(K_d)与温度成负相关;其吸附过程为自发的放热反应,无配位基交换、化学键等强的作用力,标准自由能的变小是对-硝基苯酚在有机膨润土上吸附的推动力;100CTMAB-膨润土吸附对-硝基苯酚是一个熵增过程.     

BS+DAS复配修饰膨润土吸附Cr(Ⅵ)和Cd2+的研究

为了研究两性-阴离子复配修饰膨润土对Cr(VI)和Cd2+的吸附性能差异及其机理,并为两性复配修饰黏土矿物治理重金属污染水体提供依据,采用阴离子型有机修饰剂1-癸烷磺酸钠(DAS)复配修饰两性修饰剂十二烷基二甲基甜菜碱(BS-12或BS)修饰膨润土,研究各供试土样对Cr(VI)和Cd2+的等温吸附曲线及不同温度、pH值和离子强度条件对吸附的影响.结果表明,Langmuir模型能较好地拟合各修饰土样对不同类型重金属离子(Cr(VI)和Cd2+)的吸附曲线,其对Cr(VI)和Cd2+的平衡吸附量均呈现BS+150DAS(150%CEC DAS复配修饰膨润土)BS+100DASBS+50DASBS+25DASBSCK(膨润土)的趋势,且对Cr(VI)、Cd2+的最大吸附量(qm)分别为85.92 mmol·kg-1(100BS+150DAS)和321.89 mmol·kg-1(100BS+150DAS).各供试土样对Cr(VI)和Cd2+的吸附均表现为自发、焓增和熵增的特征,升温可增加其对Cr(VI)和Cd2+的最大吸附量.酸性环境有利于各修饰土样对Cr(VI)的吸附,而不利于对Cd2+的吸附.离子强度增加均降低了各修饰土样对Cr(VI)和Cd2+的吸附.     

CTMAB/CPAM复合改性膨润土吸附水中苯酚和硝基苯

用十六烷基三甲基溴化铵(CTMAB)和阳离子型聚丙烯酰胺(CPAM)改性膨润土,制得系列CTMAB-膨润土(C-Bt)、CPAM-膨润土(P-Bt)和复合改性膨润土(C/P-Bt).采用XRD分析了各类有机膨润土的底面间距,并比较了它们吸附水中苯酚和硝基苯的性能.结果显示,C/P-Bt的底面间距大于相应的C-Bt和P-Bt,表明CTMAB与CPAM能同时层插到膨润土层间.C/P-Bt吸附性能优于C-Bt及C-Bt加P-Bt,在相同平衡浓度下(苯酚为7 045 mg/L,硝基苯为409 mg/L),60C/4%P-Bt对苯酚和硝基苯的吸附量分别为150 mg/g和69 mg/g,吸附量比60C-Bt分别提高了26%和28%,比60C-Bt加4%P-Bt分别提高了22%和26%,表现出明显协同吸附效应.这说明CTMAB在C/P-Bt层间的排列模式受CPAM的影响,形成了对有机物亲和能力更强的吸附介质.该新型有机膨润土在有机污染控制中有良好的应用前景.     

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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