4种纳米氧化铁对大型蚤的急性毒性

为了评价纳米氧化铁材料的水生态安全性,参照国家化学品生态毒性测试标准方法(GB/T13266-91),以大型蚤(Daphniamagna)为受试生物,研究了4种纳米氧化铁水悬浮液(nα-FeOOH:针状,15 nm;nFe3O4:球形,9 nm;nα-Fe2O3:近球形和纺锤形,40 nm;nγ-Fe2O3:针形和近球形,22 nm)对水生甲壳类动物大型蚤的毒性效应。结果显示,4种纳米氧化铁水悬浮液对大型蚤活动抑制的48 h EC50值分别为:0.267、0.097、3.717 mg/L,>100.0 mg/L。据此可得到4种氧化铁纳米材料的毒性大小顺序为:nFe3O4>nα-FeOOH>nα-Fe2O3>nγ-Fe2O3。通过对4种纳米氧化铁水生态安全性的初步评价,表明人工纳米材料的生态毒性和环境效应不容忽视,应重视并深入研究其制毒作用机制。     

纳米γ-Al2O3去除氟离子的机理及行为研究

研究了纳米γ-Al2O3吸附剂对氟离子的吸附行为,考查了吸附平衡时间、温度、溶液的pH等对吸附过程的影响.结果表明,在室温下,纳米γ-Al2O3对氟离子的吸附在3min基本达到平衡;在pH3～9范围内,吸附率达95%以上;吸附过程符合准二级反应动力学模型,其反应的表观活化能(Ea)为10.99kJ.mol-1;颗粒内扩散过程是吸附的主要控制步骤,而颗粒外扩散过程对吸附也有影响;吸附过程符合Langmuir、D-R等温模型,常温下,纳米γ-Al2O3对氟离子的平均吸附能为11.15kJ.mol-1.吸附反应的ΔGθ<0,ΔHθ>0,说明该吸附过程是自发的吸热反应.共存阴离子HCO3-和PO43-、阳离子Cu2+对氟离子的吸附影响较大.纳米γ-Al2O3在动态和静态吸附实验中的除氟效果相近.     

Investigation in the sorption mechanism and behavior of nano γ-Al2O3 for the removal of fluorine ions

研究了纳米γ-Al2O3吸附剂对氟离子的吸附行为,考查了吸附平衡时间、温度、溶液的pH等对吸附过程的影响.结果表明,在室温下,纳米γ-Al2O3对氟离子的吸附在3min基本达到平衡;在pH3～9范围内,吸附率达95%以上;吸附过程符合准二级反应动力学模型,其反应的表观活化能（Ea）为10.99kJ.mol-1;颗粒内扩散过程是吸附的主要控制步骤,而颗粒外扩散过程对吸附也有影响;吸附过程符合Langmuir、D-R等温模型,常温下,纳米γ-Al2O3对氟离子的平均吸附能为11.15kJ.mol-1.吸附反应的ΔGθ〈0,ΔHθ〉0,说明该吸附过程是自发的吸热反应.共存阴离子HCO3-和PO43-、阳离子Cu2＋对氟离子的吸附影响较大.纳米γ-Al2O3在动态和静态吸附实验中的除氟效果相近.     

纳米复合水凝胶的制备及其对重金属离子的吸附

以N-羟甲基丙烯酰胺(HMAm)和2-丙烯酸羟乙酯(HEA)为共聚单体,采用60Co-γ射线低温辐照法,制备了具酰胺基和羟基的新型聚合物水凝胶p(HMAm/HEA),运用原位沉淀法制备了纳米复合水凝胶HMO-p(HMAm/HEA),用于对重金属离子Pb~(2+)和Cu~(2+)的去除.应用SEM、TEM、FTIR等方法对水凝胶进行表征,表征结果证明p(HMAm/HEA)是HMAm和HEA的共聚产物,且纳米水合氧化锰(HMO)成功负载.探讨了溶液初始p H值、反应温度、重金属初始浓度、反应时间、竞争性Ca~(2+)和Na+浓度等因素对纳米复合水凝胶吸附过程的影响,研究表明HMO-p(HMAm/HEA)对Pb~(2+)和Cu~(2+)的吸附过程不受温度的影响;吸附量随着溶液初始p H的升高而增加;吸附过程属于Langmuir单分子层吸附;吸附动力学过程符合准二级动力学吸附;高浓度的Ca~(2+)和Na~+对吸附过程影响不大.XPS图谱进一步证明吸附机制是重金属离子与羟基间的离子交换作用.采用0.05 mol·L~(-1)的HCl溶液为脱附剂,经过4次吸附-脱附循环再生后,纳米复合水凝胶重复利用性好.     

活性与非活性克雷伯氏菌对水中Pb2+的吸附性能

针对从云南某矿山废水中分离出的1株克雷伯氏菌(Klebsiella sp.),研究其活性菌体(AK)和非活性菌体(IK)对水溶液中Pb~(2+)的吸附性能。研究了pH、吸附剂用量、反应时间和初始Pb~(2+)浓度、背景阴离子和共存阳离子对AK和IK吸附Pb~(2+)的影响,采用Zeta电位和FTIR分析进一步阐述2种吸附剂吸附Pb~(2+)的差异。在不同的实验条件下,AK对Pb~(2+)的吸附量均高于IK。AK和IK的吸附动力学均符合伪二级动力学模型,吸附等温线都能更好地使用Langmuir模型拟合。背景阴离子NO32-、Cl-和SO42-对AK和IK去除Pb~(2+)影响不大。Pb~(2+)、Zn~(2+)和Cd~(2+)3种重金属离子共存时,AK和IK对Pb~(2+)的吸附具有选择性。Zeta电位和FTIR分析表明,AK比IK具有更强的结合Pb~(2+)的能力,参与反应的基团主要是羟基、氨基和羧基。     

斜六方晶型纳米α-Fe2O3光催化剂溶液燃烧制备方法研究

开创了溶液燃烧法制备纳米氧化物的技术,用硝酸铁和特定的还原荆燃料合成出了纳米级斜六方晶型纳米α-Fe2O3.首先对氧化剂和可燃物的种类设计,并根据化学计量法计算出合适的配比,然后把相应的硝酸铁和燃料按照得到的比例配制成水溶液,放在微波妒中通过微波加热的方法加热到500℃以上,溶液先蒸发浓缩,到一定程度后生成大量泡沫,然后进行自发的燃烧性氧化还原反应,从而得到超细的氧化物晶体.通过测定产物的XRD可以确定产物为纳米级的斜六方晶系氧化铁.     

pH值和离子对诺氟沙星在胡敏酸上吸附特征的影响

根据OECD Guideline 106批平衡实验,研究了pH值、Ca2+浓度和离子类型对诺氟沙星在胡敏酸上吸附特征的影响.结果表明,吸附系数(Kd)随着pH值的增大有先增加后减小的趋势,在pH 4.0和pH 6.0时吸附系数较大.红外光谱表明,pH 3.0有利于诺氟沙星和胡敏酸形成氢键; pH6.0和7.0时胡敏酸的羧基可能与诺氟沙星的氨基形成了肽键.诺氟沙星在胡敏酸上的吸附量和Kd值随着溶液中Ca2+离子浓度的增加而逐渐减小,表明两者之间存在阳离子吸附和竞争吸附.不同类型的阳离子和阴离子的加入都能导致诺氟沙星在胡敏酸的吸附特性存在差异.阳离子的影响趋势主要为价态的影响,即价态越高,在胡敏酸表面吸附位点的吸附能力就越强,对诺氟沙星吸附阻碍作用越显著,表现在诺氟沙星的最大吸附量(Qm)为:M+ (Na+、K+、NH4+) >M2+ (Mg2+、Ca2+、Zn2+);其次受阳离子的离子半径和水解作用的影响.而只有能水解的阴离子才能对诺氟沙星在胡敏酸上的吸附产生明显的阻碍作用.     

不同腐蚀体系中低合金钢锈层的拉曼光谱研究

利用激光拉曼光谱法研究了舰船用镍铬系低合金钢在天然海水以及分别添加双氧水、高氯酸钾和过硫酸钠的NaCl（3.5％）溶液等4种体系中浸泡后腐蚀锈层的物相组成。结果表明：在含双氧水体系和天然海水体系中,钢样的内外锈层物相主要是α-Fe2O3、γ-FeOOH和Fe3O4。高氯酸钾和过硫酸钠腐蚀体系,其腐蚀锈层的外锈层除了含有α-Fe2O3和γ-FeOOH外还出现了γ-Fe2O3,内锈层只含有α-Fe2O3和γ-FeOOH,未发现Fe3O4。说明镍铬系低合金钢在含双氧水体系和天然海水体系中的腐蚀锈层物相组成差异最小。     

不同状态MnO2对废水中As(III)的吸附研究

利用MnO2对含As(III)废水进行了吸附实验, 结果表明, MnO2对As(III)有着较强的吸附能力, 其饱和吸附量为44.06mg/g(δ-MnO2)和17.9mg/g(ε-MnO2), 阴离子的存在使MnO2吸附量有所下降, 一些阳离子(如Ga3+、In3+)可增加其吸附量, 吸附后的MnO2经解吸后可重复使用.     

凹凸棒石/γ-Fe_2O_3/碳纳米复合材料的制备及其对苯酚的吸附作用

为获得同时具有有机亲和性和磁分离特性的吸附材料,以凹凸棒石黏土和废活性白土为原材料,通过铁盐水解共沉淀和在氢气气氛下程序升温煅烧的方法,制备廉价的凹凸棒石γ-Fe2O3/碳纳米复合材料.运用磁化率分析,红外吸收光谱,透射电镜,X射线衍射分析和碳含量分析对其进行了表征,并研究了复合材料吸附去除水中苯酚的动力学、吸附试验中pH的影响及同等条件下与其他吸附材料吸附性能的对比.结果表明,复合材料的磁化率值为2 769×10-8m3/kg,用磁分离工序即可把该吸附材料从溶液中快速分离出来;铁的磁性氧化物以γ-Fe2O3的形态负载到凹凸棒石表面,颗粒直径为10～60nm;碳以无定形的形态负载在凹凸棒石晶体表面;复合材料中的ω(碳)为7.4%,材料中出现了有机官能团-CH3和-CH2-.对苯酚的吸附试验表明,复合材料对苯酚的去除率是凹凸棒石原矿的3倍.     

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.     

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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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.     

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.     

Sorption of 1-naphthol by plant cuticular fractions

The contribution of aliphatic-rich plant biopolymer to sorption of hydrophobic organic compounds is significantly important because of their preservation and accumulation in the soil environment,but sorption mechanism is still not fully understood.In this study, sorption of 1-naphthol by plant cuticular fractions was examined to better understand the contributions of respective fraction.Toward this end,cuticular materials were isolated from the fruits of tomato by chemical method.The tomato cuticle sheet consisted of waxes (6.5 wt%),cuticular monomer (69.5 wt%),and polysaccharide (24.0 wt%).Isotherms of l-naphthol to the cuticular fractions were nonlinear (N value (0.82-0.90)) at the whole tested concentration ranges.The KodKow ratios for bulk cuticle (TC1),dewaxed cuticle (TC2),cutin (TC4),and desugared cuticle (TC5) were larger than unity,suggested that tomato bulk cuticle and cutin are much powerful solption medium.Sorption capability of cutin (TC4) was 2.4 times higher than the nonsaponifiable fraction (TC3).The 1-naphthol interactions with tomato cuticular materials were governed by both hydrophobic-type interactions and polar (H-bonding) interactions. Removal of the wax and polysaccharide materials from the bulk tomato cuticle caused a significant increase in the sorption ability of the cuticular material.There was a linear negative trend between K_(oc) values and the amount of polysaccharides or fraction's polarities ((N O)/C);while a linear positive relationship between K_(oc) values and the content of cutin monomer (linear R~2=0.993) was observed for present in the cuticular fractions.Predominant sorbent of the hydrophobic organic compounds (HOCs) in the plant cuticular fraction was the cutin monomer,contributing to 91.7% of the total sorption of tomato bulk cuticle.     

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.     

Seed selections for crystallization of calcium phosphate for phosphorus recovery

Seed induces and promotes the crystallization of calcium phosphate, and acts as carrier of the recovered phosphorus （P）. In order to select suitable seed for P recovery from wastewater, three seeds including Apatite （AP）, Juraperle （JP） and phosphate-modified Juraperle （M-JP） were tested and compared. Batch and fixed-bed column experiments of seeded crystallization of calcium phosphate were undertaken by using synthetic wastewater with 10 mg/L P phosphate. It shows that AP has bad enduring property in the crystallization process, while JP has better performance for multiple uses, and M-JP is a hopeful seed for P recovery by crystallization of calcium phosphate.