富里酸-高岭土复合体对溶液中铀的吸附效果探究

为提高高岭土对溶液中铀的吸附效果,将富含官能团的富里酸与高岭土结合形成富里酸-高岭土复合体,通过静态对比试验,研究了pH值、反应时间和吸附剂投加量等因素对富里酸-高岭土复合体的铀吸附效率的影响。试验结果表明:富里酸-高岭土复合体对铀的吸附效率与高岭土相比有显著的增加,富里酸-高岭土复合体和高岭土对铀的吸附率在pH值为5时分别可达99%和80%;富里酸-高岭土复合体和高岭土对铀的吸附反应均在反应时间为20 h达到吸附平衡,富里酸-高岭土复合体和高岭土两种吸附剂的吸附反应皆遵循准二级动力学吸附规律;当吸附剂投加量在0.1～0.5 g之间时,随着富里酸-高岭土复合体和高岭土两种吸附剂投加量的增加,铀的吸附率也随之增加,铀的最大吸附率分别可达87%和78%;铀的解吸效率随着富里酸溶液浓度的增加而增加,相较于用超纯水作洗脱剂的空白试验,铀的解吸率可达60%;富里酸-高岭土复合体对溶液中铀的最佳吸附条件为:溶液pH=5、反应时间20 h、吸附剂投加量0.5 g。该研究结果可为提高溶液中铀的提取与去除效率提供理论依据。     

镉铅在粘土上的吸附及受腐殖酸的影响

试验研究了镉和铅2种重金属在蒙脱土和高岭土上的吸附,以及外加腐殖酸的3种组分（富里酸、棕色胡敏酸和灰色胡敏酸）的影响。镉铅在粘土上的吸附随着介质pH的升高而增加。在pH4-8范围内的任意pH点,镉在高岭土上的吸附量因富里酸而降低,因2种胡敏酸而升高;当pH值高于6时,吸附量急剧增加。外加富里酸使得铅在粘土上的吸附在pH＞6时意外出现随着介质pH而降低的趋势。     

烟曲霉菌丝球吸附富里酸的性能及相互作用

采用投加烟曲霉菌丝球方法去除水中的富里酸,研究了pH值、吸附时间、不同富里酸初始浓度、温度、以及菌丝球的投加量对烟曲霉菌丝球吸附富里酸的影响,并利用傅里叶红外光谱技术(FTIR)分析了烟曲霉菌丝球与富里酸的吸附官能团的相互作用。结果表明:烟曲霉菌丝球对富里酸有较好的吸附效果,在最佳pH 4时对富里酸的吸附量为9.49 mg/g;吸附时间10 min时,存在吸附量突降现象,45 min时对富里酸的吸附量最大,随后稍降低至不变。随着富里酸初始浓度的增大,烟曲霉菌丝球对富里酸的吸附量也随着增大。但随着烟曲霉菌丝球的投加量的增大,对富里酸的吸附量逐渐减少。吸附过程中,烟曲霉中的氨基与富里酸分子中的羧基发生了一定的化学作用,同时与羟基等基团形成氢键,为吸热过程。     

富里酸和胡敏酸在蒙脱石上的吸附特性

为进一步揭示有机污染物在黏土矿物上的迁移转化规律,运用1H核磁共振光谱、高效体积排阻色谱、扫描电镜、比表面分析以及傅里叶变换红外光谱等多种分析技术综合分析了富里酸和胡敏酸在蒙脱石上的吸附行为. 结果表明,由于不同官能团与蒙脱石的亲和性不同,富里酸和胡敏酸在吸附过程中均产生组分分级,大分子被优先吸附在蒙脱石表面. 由于疏水性作用,蒙脱石对疏水性更强的胡敏酸的吸附量更大. 蒙脱石吸附富里酸后比表面积和孔容分别下降3.67m2/g和0.005cm3/g,而吸附胡敏酸后则均略微增大,说明具有较大颗粒尺寸的胡敏酸更多地堆积在蒙脱石外表面,而富里酸则更易进入蒙脱石孔隙. 蒙脱石吸附富里酸和胡敏酸后溶液pH分别升高了0.44和0.41,说明发生了配体交换反应. 蒙脱石对富里酸和胡敏酸的吸附量随pH增大和离子强度的降低而减少,表明羟基能够抑制富里酸/胡敏酸负电基团与蒙脱石表面羟基的配体交换反应,而盐离子则能降低蒙脱石和腐殖质间的静电斥力.      

富里酸对重金属在沉积物上吸附及形态分布的影响

以连续碱提取法获得的乌梁素海沉积物中的富里酸为基础,以原状沉积物和去除有机质沉积物为吸附剂,开展了富里酸对重金属在沉积物上吸附行为和形态分布的影响实验研究.结果表明,有机质的去除和富里酸的添加对沉积物吸附重金属均有一定影响;未添加富里酸条件下,有机质的去除对Cu~(2+)影响最大,可导致沉积物对Cu~(2+)的吸附率下降17.85%;随富里酸添加量的增加,2种沉积物对重金属离子的吸附率均逐渐降低,下降速率表现为Cu~(2+)?Cd~(2+)Zn~(2+)Pb~(2+);当富里酸添加量超过5%时,富里酸逐渐成为影响重金属离子吸附率下降的主导因素;随富里酸添加量的增加,原状沉积物和去除有机质沉积物中重金属的形态分布均有明显变化,添加富里酸增加了体系中H~+的浓度,H~+能够置换碳酸盐结合态金属,使碳酸盐结合态金属从沉积物中释放出来,从而导致重金属的碳酸盐结合态与富里酸添加量呈显著负相关,重金属的有机硫化物结合态含量与富里酸添加量呈显著正相关,Cd因亲有机性较弱,其有机硫化物结合态的含量最低且变化幅度最小.     

多环芳烃（PAHs）在不同腐殖酸组分中的赋存特征和氧化降解效果研究

选取腐殖酸重要组分胡敏酸、富里酸、胡敏素为研究对象,研究了不同老化时间下多环芳烃(PAHs)在腐殖酸各组分中的赋存特征.同时,探究了过硫酸钠、高锰酸钾、芬顿试剂、过氧化氢4种氧化剂氧化PAHs过程中污染物在腐殖酸和上清液中的分布情况,确定胡敏酸、富里酸、胡敏素中PAHs的降解效率.实验结果表明,PAHs在胡敏素中存在吸附滞后现象,老化前期胡敏素对PAHs的吸附速率慢、吸附量少,但老化后期出现吸附量的反超,因此,胡敏素、胡敏酸和富里酸中PAHs的最终吸附量并没有明显差异.高环PAHs在3种腐殖酸组分中的吸附速率和最终吸附量远小于低、中环PAHs.过硫酸钠和高锰酸钾能够较好地去除胡敏酸、富里酸、胡敏素中的大部分PAHs,去除率均在95%左右,芬顿试剂对胡敏酸、富里酸和胡敏素中总PAHs的去除效果差别不大,去除率均在79.36%~88.05%之间;过氧化氢对胡敏酸和胡敏素中PAHs的去除率分别为82.82%和61.77%,而对富里酸中PAHs的去除效果最差,去除率仅为43.96%.过硫酸钠和高锰酸钾是氧化PAHs类有机污染土壤的最佳氧化剂,能够有效提高不同组分腐殖酸中PAHs的去除率.     

富里酸红外特征差异与其吸附沥青质行为间关系的研究

通过考察连续碱提富里酸级分的红外光谱及其与沥青质间的吸附行为特征,探讨了富里酸官能团红外特征差异与沥青质吸附行为间的关系。结果表明:连续碱提得到的各级富里酸所含官能团整体组成结构相近,但是在含氧基团和芳香族基团的红外特征上存在较大差异,其红外特征峰面积表现为:一级富里酸>三级富里酸>二级富里酸;随着富里酸中OH基团、芳香基团以及C—O基团红外特征的增强,其对沥青质的吸附速率增大,结合力增强,总体呈正相关关系,而其吸附沥青质展现出的非线性特征愈弱,总体呈负相关关系;适当升温会使吸附特征参数随基团红外特征强度发生变化,分析认为,升温引起的分子热运动增强以及吸附结合强度大小改变可能是导致该现象的主要原因。     

腐殖酸对土壤吸持汞的影响研究

采用吸附 解吸热力学和动力学方法研究了腐殖酸各组份对土壤吸持汞的影响 ,发现该试验条件下 ,腐殖酸能提高土壤对汞吸持能力 ,但不同组份其作用效果不同 ,富里酸在提高土壤吸持汞方面作用较短暂且不稳定 ,胡敏酸在增强土壤吸附固定汞的数量和速率上却好于富里酸。     

老化前后微塑料对富里酸的吸附

由于微塑料(MPs)在地表水环境中的广泛存在以及对水中有机污染物的较强吸附能力,其与地表水中天然有机物间的相互作用不容忽视.为深入了解微塑料对天然有机物的影响,开展了老化前后聚酰胺66(PA66)和聚丙烯(PP)两种微塑料吸附富里酸(FA)的研究.结果表明,老化前后的微塑料吸附富里酸的试验数据较好地拟合了准二级动力学模...     

高岭土的改性及其对Cr(Ⅵ)的吸附特性

采用煅烧、酸浸的方法对高岭土进行改性,通过对SEM、XRD、FT-IR、EDS、孔结构表征及高岭土对Cr(Ⅵ)的去除能力研究,确定高岭土的改性条件,考察改性高岭土对Cr(Ⅵ)的吸附特性. 结果表明:①高岭土的改性适宜条件为煅烧温度800℃、煅烧时间3h、c(HCl)为4mol/L;煅烧使高岭土的结构发生变化,活性增强;酸改使高岭土孔隙通畅,吸附性能增强. ②改性高岭土吸附Cr(Ⅵ)的优化条件为粒度0.15mm、用量10g/L、吸附温度30℃、吸附时间15min,该条件下ρ〔Cr(Ⅵ)〕为100mg/L时废水中Cr(Ⅵ)的去除率可达91.4%. ③高岭土对Cr(Ⅵ)的吸附过程符合准二级吸附动力学模型,相比于Freundlich方程,其吸附等温式更符合Langmuir方程.      

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.     

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.     

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.     

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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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.     

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.     

Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Alterations of organ histopathology and metallolhionein mRNA expression in silver barb, Puntius gonionotus during subchronic cadmium exposure

Common silver barb,Puntius gonionotus,exposed to the nominal concentration of 0.06 mg/L Cd for 60 d,were assessed for histopathological alterations(gills,liver and kidney),metal accumulation,and metallothionein(MT)mRNA expression.Fish exhibited pathological symptoms such as hypertrophy and hyperplasia of primary and secondary gill lamellae,vacuolization in hepatocytes,and prominent tubular and glomerular damage in the kidney.In addition,kidney accumulated the highest content of cadmium,more than gills and liver.Expression of MT mRNA was increased in both liver and kidney of treated fish.Hepatic MT levels remained high after fish were removed to Cd-free water.In contrast,MT expression in kidney was peaked after 28 d of treatment and drastically dropped when fish were removed to Cd-free water.The high concentrations of Cd in hepatic tissues indicated an accumulation site or permanent damage on this tissue.