沸石的载铁改性及饮用水除氟试验研究

为避免使用含铝材料,采用新方法制得载铁改性斜发沸石,并通过一系列静态及动态试验对其除氟性能及影响因素进行了研究.结果表明:经过改性活化的斜发沸石滤料的除氟容量(DC)得到显著提高,静态达0.665 mg/g,动态达0.2 mg/g,分别约为原沸石除氟容量(0.03 mg/g)的20和7倍.载铁改性斜发沸石对F的吸附符合Langmuir吸附等温模式,其最适pH为6～7,氟吸附速率快,再生稳定;同时其也能高效去除饮用水中的锰离子,除锰容量(MRC)达2.442 mg/g.对高氟地下水的处理效果证明,该滤料不仅降氟达到国家饮用水标准,而且具有再生简易、使用寿命长等特点.     

天然活化沸石负载壳聚糖对高氟水的处理

为提高天然沸石对氟的吸附能力,采用活化天然沸石负载壳聚糖改性处理,研究了除氟剂的性能,确定了除氟剂的最佳改性条件:2.0%冰醋酸溶液,壳聚糖浓度为0.05 g/mL,壳聚糖:沸石(质量比)=0.07,室温下改性5 min。最适除氟条件:pH=6.0,粒径1~2 mm,100 r/min的速度搅拌反应50 min,静置0 min。吸附剂对F-的吸附过程符合Langmuir吸附等温线,对氟离子的饱和吸附容量为10.63 mg/g。     

新型除氟剂竹炭的优选和改性方法实验研究

采用不同产地的竹炭进行除氟研究,分别进行了直接除氟和改性后除氟的效果比较。在水浴恒温振荡箱,振荡速度100 r/min,温度30件下,保持固液比0.03,反应1.5 h,处理初始氟浓度10 mg/L的溶液,浙江丽水的机械竹炭的直接除氟效果比其它地方的竹炭都好,其对氟去除率为47.8%。通过该竹炭的直接除氟工艺参数优化结果可知,pH是影响竹炭除氟的关键因素,最佳值为4;随着竹炭量的增大,氟离子的去除率明显上升;氟离子的初始浓度增大,竹炭的单位吸附量也逐渐上升;反应时间为90 min时,反应逐渐趋于平衡。选用Al2（SO4）3对竹炭进行改性后,浙江丽水的机械竹炭的除氟率有很大的上升;采用MgSO4改性后各类竹炭除氟效果均有所下降。采用Fe2（SO4）3改性后,氟离子的去除率达到91.8%,剩余浓度为0.82 mg/L,达到国家饮用水的标准。     

载镁活化天然沸石处理高氟地下水实验研究

为了研究地下水中阴离子对载镁活化天然沸石除氟效果的影响,考察了4种主要阴离子——Cl-,HCO3-,SO42-,PO43-的影响,并分析了吸附剂的除氟机理及表面结构和成分。结果表明:对于初始氟浓度不同的水样,随着阴离子浓度的增加,吸附剂对氟的去除效率逐渐降低。Cl-对吸附剂除氟效果影响较小,氟去除率降低较慢;随着HCO3-浓度的增大(由100 mg/L到1 000 mg/L),水样pH缓慢由7.48增大到9.44,而氟去除率则由63.78%缓慢下降到52.70%(2 mg/L);SO42-及PO43-对改性沸石除氟效果影响较大,氟去除率降低较快,且SO42-的影响大于PO43-。所以,镁改性天然沸石对该4种阴离子的吸附顺序是:SO42->PO43->HCO3->Cl-。     

La-腐殖酸/Al_2O_3凝胶复合物的制备及其氟吸附性能

以腐殖酸钠为原料,采用凝胶聚合法制备La-腐殖酸/Al2O3凝胶复合物(标记为LHAGC).用N2吸附-脱附试验,XRD,SEM,IR表征吸附剂的结构和形貌,并通过静态吸附试验探讨了LHAGC对水中F-的吸附性能以及吸附饱和LHAGC的再生方法.试验结果表明,LHAGC对F-等温吸附数据与Langmuir吸附等温方程拟合较好,最大吸附容量为219.30 mg·g-1,吸附过程符合准2级动力学方程,液膜扩散和颗粒内扩散过程控制着吸附速率;在p H值为5~11时,F-吸附率较高;当水中Cl-、NO-3、SO2-4、HCO-3或PO3-4以F-质量浓度的15倍存在时,F-吸附率仍能达到94%以上,LHAGC表现出较强的抗干扰能力.将F-吸附饱和的LHAGC用浓度为10-1mol·L-1的Na OH溶液进行脱氟,再用Al Cl3溶液将脱氟后LHAGC表面中和至p H值为5时所获得的再生吸附剂,再生率可达96.08%,由此表明LHAGC的潜在应用前景.     

信号分子强化改性挂膜沸石持续抑制沉积物中氨氮释放

为寻找一种长期有效的底泥修复方式,对沸石进行了改性并挂膜的实验.考察了 4种铝盐[AlCl3、Al(NO3)3、Al2(SO4)3和KAl(SO4)2]改性挂膜沸石对上覆水中氨氮的去除情况.结果表明,AlCl3改性挂膜沸石效果最佳,且最佳改性浓度为0.8 mol·L-1.进一步分析添加信号分子OHHL后,AlCl3改性...     

Ti(Ⅳ)改性颗粒活性炭的除氟性能研究

该研究采用Ti(Ⅳ)改性颗粒活性炭(GAC),并考察改性前后GAC的除氟性能。通过批试验确定Ti(Ⅳ)改性GAC对氟离子的吸附平衡、动力学和机理。实验结果表明该吸附过程符合Langmuir吸附等温线和拟二级动力学模型。初始氟离子浓度的提高和接触时间的延长可以提升吸附性能,而p H和温度的升高会抑制吸附性能。氟离子和羟基基团之间的离子交换作用是主要的吸附机理。批试验结果证明Ti(Ⅳ)改性GAC对氟离子就有优异的去除效果,能将水体水氟离子浓度降至饮用水标准限之下(1.0 mg/L)。Ti(Ⅳ)改性GAC具有良好的再生性能和工艺适应性,能处理同时含有氟离子和有机物污染的混合水体。     

磁性铝基MOF的表征和对水体中氟化物吸附性能研究

我国多地的地表水受到成土母质或背景值的影响,氟离子浓度均超过1.0 mg/L,即高于GB 3838-2002《地表水环境质量标准》Ⅲ类标准限值.为了实现地表水的快速降氟和吸附材料的便捷回收,通过水热法制备了磁性Al-MOF@Fe₃O₄吸附材料,使用扫描电极（SEM）、X射线衍射仪（XRD）、X射线光电子能谱仪（XPS）和孔隙度分析仪（BET）对材料的形貌和化学组成进行了表征.结果表明:①Al-MOF@Fe₃O₄具有不规则的晶体形状和直径更小的介孔结构,能够提供更高的比表面积吸附氟离子.②吸附试验结果表明,Al-MOF/Fe₃O₄的吸附量达到了75.2 mg/g,吸附过程更加符合拟二阶动力学模型,证明了化学吸附是该除氟过程的主要机理.③增加吸附剂投加和降低氟离子初始浓度,有助于提高除氟效率,但却难以得到较高的吸附量,同时碱性条件不利于氟离子的吸附,阴离子对除氟性能的影响程度表现为CO₃2- > HCO₃- > SO₄2- > PO₄3- > Cl-.④对吸附机理的研究表明,氟离子是通过取代Al-OH实现稳定和快速地脱离水体,使用NaOH溶液淋洗可以实现吸附剂的高效再生.⑤5次循环吸附试验后,复合材料依然保留了71.4 mg/g的吸附能力和良好的磁性.在实际地表水中进行除氟试验,该吸附剂可以将氟化物浓度从1.17 mg/L降至0.2 mg/L以下.研究显示,Al-MOF@Fe₃O₄纳米材料可以作为地表水除氟材料,实现对低浓度氟离子的高效去除.      

改性天然介质材料的除氟特性研究

饮水中氟含量超标可引发严重的地方性氟中毒。如何高效、经济地降低饮用水中氟含量对保证供水水质安全意义重大。以石英砂、沸石、煤矸石和壳聚糖4种天然介质材料为载体,制备铁/铝改性吸附剂,通过静态吸附试验、等温吸附试验和动力学吸附试验,对比研究了4种改性天然介质材料的除氟效果。结果表明:载铝煤矸石和载铁沸石两种改性材料均表现出较好的氟吸附性能,在本试验条件下两种改性材料的除氟率分别达85.1%和83%;动力学吸附试验结果显示,两种改性材料对氟的吸附在1～2h内基本完成,在4h内达到吸附平衡。可见,利用天然介质材料改性去除水环境中氟污染效果显著,前景广阔。     

活性炭表面改性及其对磷(V)吸附性能的研究

以硝酸、氢氧化钠、氯化铁、海藻酸钠(SA)为改性剂,采用浸渍法制备了六种改性粉末活性炭,研究其对磷(V)的吸附性能。结果表明,以FeCl3直接改性和NaOH/FeCl3复合改性的粉末炭(分别标记为PAC-3和PAC-6)对磷(V)的吸附能力最强,在室温下,处理质量浓度为30 mg/L的磷(V)溶液25 mL,pH为5.0,PAC-3用量为0.4 g,吸附90 min,吸附率可达99%,吸附后的PAC-3可用0.1 mol/LNaOH溶液洗脱再生。共存物质中,NaNO3没有影响,Na2SO4抑制作用不大,Na2CO3和C(rⅥ)有增强作用,其中C(rⅥ)的增强作用显著。吸附机制是静电吸引、离子交换和络合反应共同起作用,以络合反应为主。     

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.     

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.     

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.     

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.     

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.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

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.