微波镧有机交联改性膨润土吸附磷的研究

用浸泡的方法把制备好的镧改性的膨润土,再用十六烷基三甲基溴化氨表面活性剂进行改性,制备一种新的吸附剂交联有机膨润土应用于除磷研究,其效果比原来的镧改性的无机吸附剂吸附量提高了30%。其最佳制备工艺为:表面活性剂的浸泡浓度为5%,微波功率为166W,微波辐射时间为6m in,溶液的pH为3~4,震荡时间为45m in。磷去除率达到了99%以上,吸附量达到了60mg/g以上,从而为含磷废水的处理提供了一条高效、经济的新途径。     

改性膨润土粉末对克百威的吸附

分别用季铵盐阳离子表面活性剂十六烷基三甲基溴化铵(CTMAB)和阴离子表面活性剂十二烷基苯磺酸钠(SDBS)改性钠基膨润土,研究改性膨润土吸附水中氨基甲酸脂类农药克百威的效果、机理及主要影响因素。结果表明,改性膨润土的有机碳含量和用土量影响其对克百威的吸附去除率。表面活性剂通过插层进入膨润土间,有效扩张了膨润土的层间距,有机插层效果明显。100CTMAB-10SDBS膨润土为最佳的吸附剂类型,最佳用土量20.00 g/L,吸附平衡时间为3 h,平衡去除率为92.60%。改性膨润土对克百威的吸附符合Freundlich模型,变形公式的相关系数在98%以上。     

改性膨润土吸附去除水中氨氮的实验研究

以表面活性剂十六烷基三甲基溴化铵（CTMAB）溶液和聚合铝、聚合铁溶液为改性剂,制备了相应的改性膨润土吸附剂：CTMAB有机膨润土、铝柱撑膨润土和铁柱撑膨润土,用以吸附去除水中的氨氮。结果表明：在最佳吸附实验条件下。几种改性膨润土均能够较好地吸附水中的氨氮,改性膨润土的吸附能力大于原土,吸附量的顺序为：铝柱撑膨润土〉铁柱撑膨润：L〉CTMAB有机膨润土〉原土。改性膨润土对氨氮的吸附是一个快速的过程,可在60min达到吸附平衡,吸附等温线符合Langmuir和Freundlich方程。     

膨润土载锆除磷复合材料的研究

以钠化膨润土为载体,用浸渍法将锆负载到膨润土上,对固液比、改性剂浓度和浸渍时间进行优化,制备出高效除磷复合材料。采用IR、XRD、SEM分析表征了其结构,考察了投加量、反应时间、温度、磷废液初始浓度、pH值对磷吸附的影响,实验结果表明:在改性剂浓度为5g/L,固液比1∶20,室温以150 r/min恒温振荡4 h的条件下,氧氯化锆成功负载到膨润土上,钠化并改性后膨润土的层间距和吸附性能有所改善;在磷浓度为50 mg/L的酸性环境中,投加0.6g复合材料、吸附60min,能去除90%以上的磷,吸附过程符合Langmuir等温模型和Lagergren一级动力学方程。因此,该复合材料是一种潜在吸附剂。     

聚合氯化铝-镧改性膨润土的制备及除磷除藻研究

为快速去除富营养化水体中的磷和藻类,采用PAC(聚合氯化铝)和镧对膨润土进行复合改性,制备PLMB(聚合氯化铝-镧改性膨润土)吸附剂,并采用BET(全自动比表面及孔隙度分析仪)、SEM(扫描电镜)、FTIR(傅里叶红外光谱仪)、XRD(X射线衍射仪)、ICP-OES(电感耦合等离子发射光谱仪)和zeta电位分析仪对材料进行表征,使用吸附动力学和吸附等温线描述PLMB对磷的吸附机理,考察吸附剂用量、pH和腐殖酸对PLMB同步除磷除藻的影响. 结果表明:①PLMB表面具有很多层状结构,能够提供更多吸附位点,聚合氯化铝和镧成功负载于膨润土上,镧含量达到5.02%. ②PLMB能高效吸附水中的磷,吸附量达到57.629 mg/g,吸附等温线符合Langmuir等温吸附模型,吸附动力学符合颗粒内扩散模型和准二级动力学模型. ③当PLMB投加量为300 mg/L时,富营养化水样中浊度、SRP(可溶性活性磷)、TP(总磷)和Chla(叶绿素a)的去除率分别为98.7%、96.2%、94.1%和72.7%. ④水样pH为5~10时,pH增大对PLMB的除磷除藻性能具有促进作用. ⑤腐殖酸对SRP的去除无显著影响,对浊度、TP和Chla的去除有负面作用. 研究显示,PLMB表现出优异的磷吸附性能,能够同步去除水体中的磷和藻类,在富营养化水体的生态修复中具有较大应用价值.      

羟基铁柱撑膨润土处理含磷废水的研究

以羟基铁为柱化剂对天然膨润土进行柱撑改性制备了羟基铁柱撑膨润土,研究了其对废水中磷的吸附性能和影响因素。结果表明:羟基铁能够进入到膨润土的层间,使其层间距增大,表面积增加;羟基铁柱撑膨润土对废水中的磷有很好的去除效果,在常温下,当改性膨润土投加量为4 mg/L,溶液pH值为5,反应时间为60 min,处理质量浓度为20 mg/L的含磷废水时,磷的去除率达到93.9%。平衡吸附量与平衡质量浓度之间的关系更好地符合Langmuir等温吸附方程所描述的规律。     

改性低品质膨润土处理柴油废水

选择阴阳离子十六烷基三甲基溴化铵CTMAB-十二烷基磺酸钠SDBS改性低品质膨润土,在8%的CTMAB:SDBS=5:1有机膨润土用量6.0 g/L,温度30℃,pH4~8之间,搅拌速度150 r/min,搅拌时间30 min的最优条件下,对50.0 mg/L的柴油吸附量可达到8.06 mg/g。改性后膨润土阳离子交换容量增加了1.6倍。红外光谱图和XRD谱图显示,表面活性剂已经进入膨润土层间。有机膨润土可同时吸附废水中的重金属铬和柴油,吸附均符合Freundlich等温式,对柴油的吸附是分配作用和表面吸附共同作用的结果,对重金属铬主要是表面吸附。     

稀土吸附剂对废水深度除磷研究

通过浸渍——干燥——焙烧法制备预载镧氧化物稀土吸附剂，探讨了该吸附剂对水中磷的吸附性能。研究表明在镧离子浓度为0．025mol／1、pH为10-11的溶液中浸渍，于500℃温度下焙烧制得的稀土吸附剂，其除磷效果可达95％。     

同步脱氮除磷吸附剂的制备工艺及性能表征

采用改性溶液浸泡改性的方法,对粉煤灰沸石进行改性,制备同步脱氮除磷吸附剂。实验结果表明,粉煤灰沸石在改性浓度0.5%,改性pH为10,改性时间24 h,改性固液比1:5的条件下,制得的吸附剂对氨氮、磷的去除率均在90%以上,氨氮吸附平衡时间可缩短至30 min,改性后BET比表面积略有减小(由45.804 m2/g降至43.761 m2/g),改性没有改变粉煤灰沸石的晶型结构,属于表面改性。     

钛铁柱撑膨润土吸附法处理亚甲基蓝的性能研究

以乙醇、钛酸丁酯与硝酸的混合液改性天然膨润土,制备出了钛铁柱撑膨润土。并以此土为吸附剂吸附亚甲基蓝溶液,研究了投土量、温度和吸附时间对吸附效果的影响。结果表明,投土量、温度、吸附时间对吸附效果都有较大影响。     

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.