高分子重金属絮凝剂MAPEI的制备及性能研究

通过酰胺化反应将重金属络合剂巯基乙酸(TGA)接入高分子絮凝剂聚乙烯亚胺(PEI)的分子链中,合成了新型高分子重金属絮凝剂巯基乙酰聚乙烯亚胺(MAPEI),以达到用同一种絮凝剂既能除重金属又能除浊的目的.实验结果表明:①该絮凝剂对Cu2 有很好的捕集功能,Cu2 的最高去除率可达95%以上;②pH值对MAPEI除Cu2 、去浊的效果有一定的影响但影响不大,pH值低时除浊效果较好,pH值较高时除Cu2 效果较好;③当Cu2 和致浊物质共存时,会互相促进彼此的去除;④废水中Ca2 的存在会促进Cu2 的去除,Fe3 的存在会抑制Cu2 的去除.     

高分子重金属絮凝剂MAPEI处理含镉废水的研究

以聚乙烯亚胺、巯基乙酸为原料,通过酰胺化反应合成了一种新型高分子重金属絮凝剂巯基乙酰聚乙烯亚胺(MAPEI),研究其处理含镉废水的性能,并对几个影响因素进行了考察。实验结果表明:①该絮凝剂对Cd2+有很好的捕集性能,最高去除率可达99.9%以上;②水中常见阳离子Na+、K+、Mg2+对Cd2+的去除起促进作用;③水中常见阴离子C l-、SO42-、NO3-对Cd2+的去除也起促进作用;④pH值在6.0至8.0范围内变化时,pH值越高去除Cd2+的效果越好;⑤Cd2+和致浊物质共存时,会相互促进彼此的去除。     

高分子重金属絮凝剂PEX捕集Ni2+及除浊性能研究

以聚乙烯亚胺、NaOH、CS2为原料,在一定条件下合成了一种新型两性高分子重金属絮凝剂--聚乙烯亚胺基黄原酸钠(PEX),研究了其捕集Ni2 及除浊性能,并对几个影响因素作了考察.实验结果表明:(1)该絮凝剂对Ni2 有很好的捕集功能,Ni2 的最高去除率可达99%以上;(2)pH值对PEX投加量有一定的影响,但对Ni2 的最高去除率影响不大;(3)水中存在碱金属或碱土金属离子时在一定程度上会促进Ni2 的去除;(4)当有Fe3 存在时,在较低pH值下会明显降低Ni2 的去除,但当pH值升高时对Ni2 的去除有促进作用;(5)Cl-与NO3-的存在可促进PEX对Ni2 的去除,而SO42-的存在对Ni2 的去除有抑制作用,需增加投药量才能得到较好的去除;(6)Ni2 和致浊物质共存时,会互相影响彼此的去除.     

新型高分子絮凝剂对水中有机配位汞的捕集性能

将二硫代羧基引入到聚乙烯亚胺中,制备出一种新型高分子絮凝剂聚乙烯亚胺基黄原酸钠(PEX).以含汞水样为处理对象,考察了水样pH值对PEX去除Hg2+效果的影响,并研究了水样中存在有机配位剂EDTA、柠檬酸铵以及氨基乙酸等时,PEX捕集Hg2+的性能.实验结果表明,在不同pH值下,该絮凝剂对Hg2+均具有很好的捕集效果,Hg2+的最高去除率均可达到100%.pH值对PEX投加量有一定的影响,同样去除率下, pH值较低时,PEX投加量相对较多.水样中EDTA的存在,在一定程度上会抑制Hg2+的去除,但增加PEX投加量会减弱或消除此影响.柠檬酸铵的存在会促进Hg2+的去除;而氨基乙酸的存在,在较低pH值下会促进Hg2+的去除,pH值升高时其对Hg2+的去除表现为抑制作用.絮体浸出实验表明汞的浸出率较低,PEX—Hg絮体具有很好的稳定性,不易引起二次污染.     

重金属絮凝剂PEX对水中铅的去除性能研究

在合成高分子重金属絮凝剂聚乙烯亚胺基黄原酸钠(PEX)的基础上,研究了该絮凝剂处理含铅离子废水的效能,并对一些影响因素进行了考查。研究结果表明:高分子重金属絮凝剂PEX对铅离子的捕集效率较高,去除率可达90%以上;pH值对PEX去除铅离子有一定的影响,pH=5.0时去除效果最好;Mg2+﹑Ca2+、EDTA、柠檬酸、焦磷酸钠以及致浊物质的存在均能促进铅离子的去除;絮体残渣稳定性好,金属离子易回收,回收率可达到70.0%。     

一种改性高分子絮凝剂的制备

对传统高分子絮凝剂聚乙烯亚胺进行接枝改性,使其在去除水中浊度的同时捕集去除水中的重金属离子。将巯基乙酸通过酰胺化反应接入聚乙烯亚胺的分子链中,生成改性高分子絮凝剂巯基乙酰聚乙烯亚胺(MAPEI)。主要研究MAPEI的制备条件,如反应物比例(n(PEI)∶n(TGA))、反应物浓度、催化剂用量、反应时间、反应初始pH值、反应温度等,最终得出MAPEI的最佳反应条件,反应物n(PEI)∶n(TGA)=1∶2,4%浓度的PEI溶液;反应时间为12 h;反应体系的pH值无需调节,pH为2.5;反应温度为室温。同时通过红外光谱和元素分析对MAPEI进行性能表征。     

PEI-TGA复配絮凝除浊、去铜的研究

本实验将阳离子絮凝剂聚乙烯亚胺(PEI)和重金属络合剂巯基乙酸(TGA)进行复配,以达到既能除重金属又能除浊的目的.确定了PEI和TGA的最佳投药范围,研究了其对Cu(II)和浊度去除的机理及影响因素.结果表明,对含Cu(II)50mg·L-1的废水,TGA和PEI最佳投药范围分别为80mg·L-1-120mg·L-1和5mg·L-1-20mg·L-1,Cu(II)去除率可达80%以上;在pH2.0-4.0的范围内,Cu(II)去除率随pH升高而升高,在pH＞4.0后达最大值并基本稳定;当Cu(II)和致浊物质同时存在时,二者会促进彼此的去除率,并使最佳投药范围变宽.     

高分子重金属絮凝剂SSXA对Cu2+的捕集性能研究

以淀粉-丙烯酰胺接枝共聚物、NaOH、CS2为原料,在一定条件下合成了一种新型高分子重金属絮凝剂--淀粉基黄原酸酯-丙烯酰胺接枝共聚物.研究了该絮凝剂的除Cu2 、去浊机理,并对硫酸铝浓度、初始Cu2 浓度、pH值、浊度等影响其除铜及去浊效能的因素作了考察.实验结果表明:(1)该絮凝剂对Cu2 有很好的捕集功能,但需要与硫酸铝复配以提高其沉降性能,适合复配使用.Al3 与初始Cu2 的体积摩尔浓度比值为0.3较为适宜,此时Cu2 去除率大于98%;(2)pH值对复配体系的除Cu2 、去浊效果影响不大;(3)Cu2 和致浊物质共存时,会互相促进彼此的去除.对初始Cu2 浓度为25 mg·L-1、浊度为5～300NTU的水样,处理后出水Cu2 浓度小于0.5mg·L-1、浊度小于3NTU.     

改性聚乙烯亚胺捕集和回收水中的Cu2+

为提高含铜废水的处理效果及简化处理流程,采用CS₂、NaOH对聚乙烯亚胺进行改性,制备出一种新型高分子絮凝剂--PEX（聚乙烯亚胺基黄原酸钠）.以含Cu2+水样为处理对象,探讨了初始ρ（Cu2+）、pH、共存无机物质、有机物质以及浊度对PEX捕集Cu2+性能的影响,并考察了螯合絮体中Cu2+的回收情况.结果表明:PEX对含Cu2+水样具有很好的捕集性能,Cu2+去除率最高可达到100%;PEX对Cu2+的去除效果随着水样初始pH的升高而增强,但pH位于PEX等电点处时,Cu2+去除率有所降低.在较低的PEX投加量下,水样中共存的NaCl、CaCl₂、NaNO₃、Na₂SO₄、柠檬酸、焦磷酸钠对PEX去除Cu2+均可起到促进作用,而共存的EDTA、氨基乙酸、浊度对PEX去除Cu2+具有一定的抑制作用;增加PEX投加量后,可减弱或消除上述影响.螯合絮体采用HNO₃溶液进行静态浸泡30 d后,Cu的回收率可达100%.研究显示,PEX能有效去除和回收水样中的Cu2+.      

高分子重金属絮凝剂MAC除Cu2+、去浊性能

以壳聚糖、巯基乙酸等为原料合成了一种新型高分子重金属絮凝剂巯基乙酰壳聚糖(MAC),研究了其除Cu2 与去浊的机理,并对几个因素做了考察.实验结果表明:①MAC具有除铜与去浊的性能,当MAC与HPAM复配时,效果优于单独使用MAC,Cu2 去除率可达98%以上;②用MAC处理Cu2 和浊度共存的体系时,废水中的重金属离子和致浊物质可以起到相互促进去除的作用,出水中[Cu2 ]＜0.5mg·L-1,浊度＜3NTU;原水浊度越大,越有利于Cu2 的去除;③Cu2 的去除率随原水pH值的增大而提高,浊度的去除率则反之.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Effect of sorbed and desorbed Zn(Ⅱ) on the growth of a green alga (Chlorella pyrenoidosa)

Toxic effect of Zn(Ⅱ) on a green alga (Chlorella pyrenoidasa) in the presence of sepiolite and kaolinite was investigated.The Zn-free clays were found to have a negative impact on the growth of C.pyrenoidosa in comparison with control samples (without adding any clay or Zn(Ⅱ)).When Zn(Ⅱ) was added,the algae in the presence of clays could be better survived than the control samples,which was actually caused by a decrease in Zn(Ⅱ) concentration in the solution owing to the adsorption of Zn(Ⅱ) on the clays.When the solution system was diluted,the growth of algae could be further inhibited as compared to that in a system which had the same initial Zn(Ⅱ) concentration as in the diluted system.This in fact resulted from desorption of Zn(Ⅱ) from the zinc-contaminated clays,although the effect varied according to the different desorption capabilities of sepiolite and kaolinite.Therefore the adsorption and desorption processes of Zn(Ⅱ) played an important part in its toxicity,and adsorption and desorption of pollutants on soils/sediments should be well considered in natural eco-environmental systems before their risk of toxicity to aquatic organisms was assessed objectively.