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+.      

聚乙烯亚胺基黄原酸钠与铁盐共同处理低浊水

以聚乙烯亚胺（PEI）为母体,通过化学反应将二硫代羧基引入到其分子链中,制备出新型高分子絮凝剂聚乙烯亚胺基黄原酸钠（PEX）,采用低浊水样作为考察对象,通过絮凝实验研究PEX分别与Fe （Ⅱ）盐、Fe （Ⅲ）盐对水样中浊度的去除性能.结果表明,PEX单独处理低浊水时,水样的初始浊度和pH值对PEX除浊效果均有一定的影响,除浊效率随着初始浊度的降低而降低,随着pH值的升高而先升高后降低;当初始pH值位于PEX等电点附近时,浊度的去除率可达到最高,初始浊度为10.0,15.0,30.0NTU,浊度的去除率分别为88.46%,91.17%,92.73%.PEX与Fe盐共同除浊时浊度的去除率随着体系pH值的升高先升高后降低,投加Fe （Ⅲ）盐后浊度的去除效果总体上优于投加Fe （Ⅱ）盐后的效果.PEX与Fe盐共同除浊和PEX单独除浊时的絮凝作用机理不尽一致,Fe盐的加入可起到一定的电中和作用.     

两性高分子絮凝剂聚乙烯亚胺基黄原酸钠除浊性能

以不同分子量的聚乙烯亚胺（PEI）为母体,通过化学反应将二硫代羧基引入到其分子链中,制备出3种新型高分子絮凝剂聚乙烯亚胺基黄原酸钠（PEX）,采用2种性质不同的高岭土配制的含浊水样作为考察对象,通过絮凝实验法研究PEX对水样中浊度的去除性能.结果表明,3种PEX对不同性质含浊水样中浊度的去除性能具有一定的差异,浊度的最高去除率随着PEX分子量的增加而升高,随着原浊的增加而略有升高.PEX为两性聚电解质,PEX-1、PEX-6、PEX-60溶液的等电点pH_iep分别为3.8、5.0、8.7;当体系初始pH值位于3种PEX各自等电点处,浊度的去除率最高,可分别达到98.6%、96.6%、91.3%.含浊水样中共存Cu（Ⅱ）或Ni（Ⅱ）时,可明显提高浊度的去除效果.体系中余浊随着静置后Zeta电位绝对值的降低（升高）而减小（增大）.     

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.     

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.     

重金属絮凝剂对水中Cu2+和腐殖酸的去除性能

采用聚丙烯酰胺、甲醛、氢氧化钠、巯基乙酸为原料,制备出重金属絮凝剂巯基乙酰化羟甲基聚丙烯酰胺（MAMPAM）,以含Cu²⁺、含腐殖酸（HA）水样为考察对象,研究MAMPAM对单一和混合体系中Cu²⁺、HA的去除性能.结果表明,MAMPAM对单一体系中Cu²⁺和HA均具有一定的去除效果,且Cu²⁺的去除率随着水样初始pH值的增大而升高;pH值为6.0时,Cu²⁺的最高去除率为95.92%,HA的最高去除率为66.98%.MAMPAM处理混合水样时,Cu²⁺和HA的共存会相互促进彼此的去除,具有协同作用;共存的HA对MAMPAM除Cu²⁺性能的促进作用随着水样中HA浓度或pH值的升高而增强,共存的Cu²⁺对MAMPAM除HA性能的促进作用随着水样中HA浓度的升高而增强.     

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.     

新型重金属絮凝剂巯基乙酰化磺甲基聚丙烯酰胺除铜除浊性能研究

以聚丙烯酰胺、甲醛、亚硫酸氢钠、氢氧化钠、巯基乙酸为原料,通过化学方法制备出一种新型高分子重金属絮凝剂—巯基乙酰化磺甲基聚丙烯酰胺(MASPAM).采用含Cu(Ⅱ)、含浊水样及其混合水样为处理对象,研究了不同Cu(Ⅱ)初始浓度、原浊、pH值等条件下MASPAM对Cu(Ⅱ)和浊度的去除性能.结果表明,MASPAM对水样中的Cu(Ⅱ)和浊度均具有一定的去除效果.对于单一体系,Cu(Ⅱ)初始浓度为25mg·L-1、pH值为6.0时,Cu(Ⅱ)的最高去除率为94.7%;原浊为230 NTU、pH值为6.0时,浊度的最高去除率为88.9%.对于含Cu(Ⅱ)、含浊混合体系,Cu(Ⅱ)、浊度的去除效果相比单一体系均明显提高,最高去除率分别为98.7%、99.8%,表现出显著的协同效应.     

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.     

新型高分子絮凝剂对废水中Cr(Ⅵ)的捕集性能

研究了新型高分子絮凝剂聚乙烯亚胺基黄原酸钠(PEX)对废水中Cr(Ⅵ)的捕集性能,考察了Cr(Ⅵ)初始浓度、p H值、共存无机物以及共存浊度对PEX处理含Cr(Ⅵ)废水的影响.结果表明,PEX在强酸条件下对废水中不同浓度的铬均具有很好的去除效果,体系p H值为2.0时,Cr(Ⅵ)和总Cr的最高去除率可分别达到99.1%和96.6%.废水中共存的影响物质Na Cl、Na F、Na2SO4、Ca Cl2和浊度均会抑制Cr(Ⅵ)的去除,促进总Cr的去除.红外光谱显示,PEX高分子链上的二硫代羧基可将Cr(Ⅵ)还原为Cr(Ⅲ),还原产物Cr(Ⅲ)进一步与PEX分子链上的二硫代羧基、胺基发生螯合反应.     

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.     

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.