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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.