不同类型LDHs负载改性麦饭石对Cr(Ⅵ)吸附性能

在碱性条件下采用水热-共沉淀法,将ZnCl2、MgCl2和AlCl3、FeCl3等不同2价和3价金属化合物两两组合,生成4种层状双金属氢氧化物(LDHs),并负载于天然麦饭石填料表面;分别通过等温吸附试验、解吸附试验、吸附动力学试验、竞争性吸附试验、不同温度及pH值吸附试验,研究LDHs涂层负载改性麦饭石对Cr(Ⅵ)吸附效果的提升作用。结果表明,改性后的各种麦饭石填料对Cr(Ⅵ)的最大理论吸附量均大于天然麦饭石,其中ZnAl-LDHs改性麦饭石对Cr(Ⅵ)的吸附效果最佳,在最适温度15℃时最大理论吸附量接近天然麦饭石的10倍;同时,解吸附试验发现LDHs的负载可以加强填料的重复利用率。所有填料对Cr(Ⅵ)的吸附热力学参数均为ΔGθ0、ΔHθ0、ΔSθ0,表明填料吸附Cr(Ⅵ)过程为可自发进行的放热过程;LDHs负载改性麦饭石对Cr(Ⅵ)的吸附过程均符合准二级反应过程,以化学吸附为主。通过选用合适的金属离子组合方式制备不同的LDHs负载改性麦饭石,可达到有效提高麦饭石吸附水体中Cr(Ⅵ)性能的目的。     

不同类型LDHs负载改性麦饭石对Cr(Ⅵ)吸附性能

在碱性条件下采用水热-共沉淀法,将ZnCl_2、MgCl_2和AlCl_3、FeCl_3等不同2价和3价金属化合物两两组合,生成4种层状双金属氢氧化物(LDHs),并负载于天然麦饭石填料表面;分别通过等温吸附试验、解吸附试验、吸附动力学试验、竞争性吸附试验、不同温度及pH值吸附试验,研究LDHs涂层负载改性麦饭石对Cr(Ⅵ)吸附效果的提升作用.结果表明,改性后的各种麦饭石填料对Cr(Ⅵ)的最大理论吸附量均大于天然麦饭石,其中Zn Al-LDHs改性麦饭石对Cr(Ⅵ)的吸附效果最佳,在最适温度15℃时最大理论吸附量接近天然麦饭石的10倍;同时,解吸附试验发现LDHs的负载可以加强填料的重复利用率.所有填料对Cr(Ⅵ)的吸附热力学参数均为ΔGθ0、ΔHθ0、ΔSθ 0,表明填料吸附Cr(Ⅵ)过程为可自发进行的放热过程;LDHs负载改性麦饭石对Cr(Ⅵ)的吸附过程均符合准二级反应过程,以化学吸附为主.通过选用合适的金属离子组合方式制备不同的LDHs负载改性麦饭石,可达到有效提高麦饭石吸附水体中Cr(Ⅵ)性能的目的.     

Zn系LDHs负载改性石英砂和沸石对Cr(Ⅵ)吸附效果对比及其作用机理研究

为提升人工湿地常用填料对受污染水体中Cr(VI)的吸附性能,采用水热-共沉淀法在碱性条件下制备了Zn系LDHs涂层负载改性沸石和石英砂填料,并运用场发射扫描电子显微镜(SEM)、能谱分析仪(EDS)和BET等手段对改性前后填料的表面形态和化学成分进行了表征.最后,通过等温吸附试验、动力学吸附试验、吸附热力学试验对Zn系LDHs改性填料和天然填料的Cr(VI)吸附效果及其作用机理进行了对比研究.结果表明,通过Zn系LDHs涂层负载,沸石和石英砂对Cr(VI)的吸附类型由以物理吸附为主的多分子层吸附向以化学吸附为主的单分子层吸附转换,有利于吸附水中的Cr(VI);热力学相关参数ΔS~00,ΔG~00,ΔH~00,表明对Cr(VI)的吸附是自发放热过程.相比于天然沸石和石英砂,Zn系LDHs负载改性沸石和石英砂的表面物化性状发生明显变化,最大饱和吸附容量明显提高,尤其是石英砂的最大饱和吸附容量从21 mg·kg~(-1)提升到125 mg·kg~(-1).改性同种天然填料时,ZnAl-LDHs负载改性的效果更佳;而相对于天然沸石的改性,Zn系LDHs负载改性能更有效地提高石英砂对Cr(VI)的吸附能力.因此,本实验中ZnAl-LDHs负载改性石英砂可推荐用于实际人工湿地中Cr(VI)的去除.     

Zn系LDHs覆膜改性人工湿地沸石基质除磷机制

选择Zn系层状双金属氢氧化物(LDHs),采用水热-共沉淀法合成3种不同类型的Zn-LDHs(Fe Zn-LDHs、Co Zn-LDHs和Al Zn-LDHs)并覆膜于常用人工湿地沸石基质表面;利用模拟垂直流人工湿地小试系统,对原始沸石及3种Zn-LDHs覆膜改性沸石基质进行除磷净化实验、等温吸附-解吸实验以及动力学吸附实验,通过上述实验对以Zn-LDHs覆膜改性沸石基质为代表的改性基质除磷机制进行研究.结果表明,Zn-LDHs覆膜改性沸石基质对磷素净化效果具有明显的提升功能,其中以Fe Zn-LDHs覆膜改性基质尤为突出;改性使基质的饱和吸附容量得以提高,增强了基质对磷酸盐的解吸性能,并使沸石基质对磷酸盐的主要吸附类型由物理吸附向化学吸附转换;通过对沸石基质类型及其改性方式的合理选择,可达到利用沸石人工湿地强化除磷以高效净化富营养化水体的目的.     

两种碳酸系Fe-LDHs负载改性沸石对Cd(Ⅱ)吸附特性对比研究

为提升以沸石为代表的天然吸附材料对重金属污染物吸附效果,并将新型功能材料层状双金属氢氧化物（layered double hydroxides,LDHs）有效应用于实际工程,采用水浴-共沉淀法制备两种Fe系碳酸型LDHs即时负载于沸石填料表面,利用场发射扫描电子显微镜（SEM）、能谱分析仪（EDS）和X射线衍射仪（XRD）对改性前后的沸石表面形态、化学成分和晶体结构进行表征;通过等温吸附及解吸附、吸附动力学、吸附热力学、竞争离子吸附和不同pH吸附试验,对比原始及改性沸石对Cd（Ⅱ）的吸附效果及其作用机理.结果表明:①改性沸石对Cd（Ⅱ）的吸附过程更符合Langmuir等温吸附模型和准二级动力学模型.②相较于原始沸石,两种改性沸石对Cd（Ⅱ）的吸附性能明显提升,且MgFe-LDHs负载改性沸石理论最大饱和吸附容量更高.③沸石改性后对Cd（Ⅱ）的吸附由放热过程变为吸热过程.④吸附时间、竞争离子及pH对沸石吸附Cd（Ⅱ）的效果产生不同程度的影响.研究显示,MgFe-LDHs负载改性沸石最大饱和吸附容量显著提升,吸附能力更强,且在不同条件下均表现出优良的吸附特性,具有作为高效除镉填料的潜力.      

氧化锰改性活性炭的优化制备及其对Cd(Ⅱ)的吸附研究

采用浸渍焙烧法制备了活性炭负载氧化锰的除镉(Cd(Ⅱ))吸附剂,通过L_9(3~4)正交试验确定最优制备条件如下:浸渍时间7 h,KMnO_4质量分数2.7%,焙烧温度470℃,焙烧时间2.5 h。通过BET、SEM、FTIR、XRD对改性活性炭(MOAC)进行表征,研究了pH值、吸附时间、初始浓度、吸附温度等对Cd(Ⅱ)吸附效果的影响。结果表明:MOAC表面烃基含氧官能团增多,氧化锰以MnO_2的形式负载到其表面;当MOAC的投加量为0.5 g/L,Cd(Ⅱ)的初始浓度为50 mg/L,溶液pH值为6.0,温度为298 K,吸附时间为12 h时,MOAC对Cd(Ⅱ)的吸附量高达84.15 mg/g,吸附过程符合准二级动力学方程和Langmuir等温吸附方程,热力学参数表明该吸附过程为放热、自发的过程。     

桉树遗态结构HAP/C复合材料对水中Cu (Ⅱ)的吸附特征

采用自制桉树遗态羟基磷灰石/碳复合材料(PBGC-HAP/C)为吸附剂,溶液体系pH值、Cu(Ⅱ)初始浓度和材料粒径为影响因素,研究了PBGC-HAP/C吸附Cu(Ⅱ)的具体特征与机制.结果表明,当溶液为弱酸性时(pH=5),吸附效果最佳;增大反应体系初始浓度不利于吸附效果的提升;减小吸附剂粒径对吸附有促进作用.准二级动力学可准确描述该吸附过程,计算获取的吸附容量0.99、1.93和4.03 mg·g-1与实验值0.99、1.93和4.05 mg·g~(-1)高度接近;Langmuir模型很好地拟合了吸附过程,表明吸附是单层吸附,温度升高有利于吸附进行;热力学实验结果ΔGθ0、ΔSθ0和ΔHθ0,显示该吸附过程是自发、熵增的吸热过程.SEM、EDS、XRD和FTIR对吸附前后材料表征分析可知PBGC-HAP/C表面的含氧官能团与Cu(Ⅱ)发生的化学络合反应为主要净化机制,同时伴随着物理吸附、静电吸附和离子交换作用.     

固定化改性累托石微球对水中染料橙黄Ⅱ的吸附

旨在为提高累托石对染料的吸附效率,便于其在工业中的应用,采用十六烷基三甲基溴化铵(HDTMA)对天然累托石进行改性,并利用聚乙烯醇(PVA)、海藻酸钠等材料固定改性累托石粉末,制备了微球状吸附剂。考察了固定化改性累托石微球对水中橙黄Ⅱ的吸附性能以及吸附热力学和动力学规律。结果表明,等温吸附规律可用Freundlich和Langmuir模式较好地模拟。吸附活化焓ΔH0呈正值,且吸附体系的ΔH0<-TΔS0,整个吸附过程活化熵的影响大于活化焓,适当升温有利于加速吸附反应的进行。吸附动力学规律符合准一级、二级吸附速率模型、Bangham模式和Elovich模型。膜扩散过程是吸附过程的控制步骤。     

DMF在大孔吸附树脂上的吸附热力学及动力学研究

研究了大孔吸附树脂吸附N,N-二甲基甲酰胺(DMF)的热力学与动力学特性.经过初步筛选,发现NKA-Ⅱ型大孔吸附树脂对DMF具有良好的吸附与再生性能.在温度为298、和318K条件下分别测定了吸附平衡数据并应用Freundlich和Langmiur等温吸附方程进行拟合,结308果表明,DMF在NKA-Ⅱ型大孔吸附树脂上的吸附平衡符合Freundlich等温吸附方程.在此基础上,通过热力学分析发现ΔH>0、ΔG<0、ΔS>0,表明DMF在大孔吸附树脂上的吸附属于可自发进行的物理吸附,吸附过程吸热,但吸附热较小,温度对吸附过程的影响较小.吸附动力学研究中分别采用一级速率方程、准二级速率方程和二级速率方程对吸附过程进行模拟,结果表明,准二级动力学方程的计算值与实验值吻合良好,适合描述NKA-Ⅱ型大孔吸附树脂对DMF的吸附过程.     

复合金属改性生物炭对水体中低浓度磷的吸附性能

通过FeCl_3和KMnO_4溶液对果壳生物炭进行浸渍改性,探索复合改性生物炭(Fe:Mn=1:1)对低浓度磷的吸附性能.结果表明,铁锰复合改性生物炭对低浓度磷的吸附效果远远大于铁改性及锰改性; SEM和FT-IR测定表明,铁锰复合改性后生物炭表面可能存在铁锰氧化物和铁氢氧化物.在磷浓度为0. 5 mg·L~(-1)、温度为298 K、固液比(mg∶L)为500时,吸附量为0. 96 mg·g~(-1).当溶液的pH为4～10,均具有较高的去除率和吸附量.等温吸附实验数据符合Freundlich方程,为多层吸附.吸附热力学研究表明,ΔG~θ0、ΔH~θ 0和ΔS~θ 0,说明该吸附是自发、熵增加的吸热过程.吸附动力学分析发现,改性后生物炭在60 min内基本达到吸附平衡,吸附过程符合准二级动力学方程,以化学吸附为主.可为天然水体和污水处理厂低浓度除磷提供理论数据支撑.     

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.     

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.     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

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

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Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.     

Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.