磁性竹基炭对Pb2+、Cd2+与Cu2+的吸附机理研究

采用微波辐照技术,以枯竹子为碳源制备了磁性竹基炭(BBMC),并将其用于对重金属离子Pb2+、Cd2+与Cu2+的吸附去除.同时,分析了吸附时间、pH值、离子强度及初始金属离子浓度等条件对吸附的影响,讨论了BBMC对3种金属离子的吸附特性与吸附机理.结果表明,金属离子在BBMC上的吸附符合Langmuir等温模式和准二级动力学吸附方程;吸附的机理可归结为金属阳离子与BBMC上的H+之间的离子交换作用,且吸附能力可能与金属离子半径有关,呈现出Pb2+Cd2+Cu2+的趋势,重金属离子Pb2+、Cd2+与Cu2+的最大平衡吸附量分别为16.2、14.0和9.5 mg·g-1.     

球形棕囊藻对Pb2+的吸附动力学

研究了球形棕囊藻对金属离子Pb2+在球形棕囊藻上的生物吸附特性.结果显示,Pb2+在球形棕囊藻上的生物吸附可以分为2个阶段,第1阶段为物理吸附,在10min内快速达到平衡;第2阶段为金属离子向藻内部的迁移,过程缓慢.通过拟合得到了吸附过程的准二级动力学方程,参数k为0.0025 g·mg-1·min-1,qe为19.8 mg·g-1.吸附等温线结果表明.Pb2+在球形棕囊藻上的生物吸附可以用Langmuir来描述,最大吸附量qmax为20.2 mg·g-1.     

酿酒酵母对Ag^＋的吸附特性研究

为了深入探讨酿酒酵母吸附贵金属离子Ag+的特性,研究了吸附时间、离子浓度、初始pH值、温度对废弃酿酒酵母吸附Ag+的影响,并分析了动力学、热力学以及等温吸附特性.结果表明,酵母吸附Ag+的过程进行得很快,当Ag+初始浓度为1mmol·L-1、细胞浓度2 g·L-1条件下,反应10 min,Ag+可以达到平衡吸附量的86%以上.随后在24 h内吸附量缓慢增加,去除率基本维持在51%～55%左右.酵母吸附Ag+的过程可以用准一级和准二级动力学方程描述,后者模拟效果更好.酵母吸附Ag+的等温吸附过程可以用Langmuir方程描述,但Freundlich方程拟合效果较差.当Ag+初始浓度为0～8 mtool·L-1、酵母浓度2·L-1条件下,酵母吸附Ag+的Langmuir理论饱和生物吸附容量为0.385 mmol·g～.在pH 2.0-7.2范围内,吸附量随着溶液初始pH值升高而升高.10～40℃范围内,温度对酵母吸附Ag+的影响不如pH值的影响显著,特别是在低离子浓度下尤其如此.酵母吸附Ag+的较适宜温度为20～30℃.热力学分析表明,酵母吸附Ag+具有自发性、熵增特征.     

酿酒酵母吸附Zn(Ⅱ)过程中阳离子(K+,Mg2+,Na+,Ca2+)的变化分析

研究了酿酒酵母无缓冲溶液体系吸附Zn(Ⅱ)的过程中各种阳离子的变化情况.研究结果表明,当Zn(Ⅱ)的初始浓度是0.08～0.8 mmol·L-1,酵母浓度约1 g·L-1,初始pH为5.65,反应38h内,酵母的Zn(Ⅱ)吸附量为74.8～654.8μmol·g-1,去除率达到76.4%～92.8%,pH值升高0.55～1.28.吸附过程中酵母首先快速释放大量K ,其次是Mg2 和Na ,Ca2 的释放量较少,数量级一般可分别达到几百、几十和几个μmol·g-1.以离子交换为基础计算的各阳离子释放量总和一般超过Zn(Ⅱ)的吸附量,证明酵母吸附Zn(Ⅱ)的机理之一是离子交换,但不唯一.无缓冲溶液体系酵母吸附Zn(Ⅱ)的过程中溶液pH值升高,H 被吸收,K 等阳离子释放,是生物体细胞的本质属性,与Zn(Ⅱ)是否存在无关,但是Zn(Ⅱ)可以促进阳离子的释放以及降低酵母对H 的吸收,也反映出Zn(Ⅱ)与H 之间可以竞争细胞表面吸附位.死酵母的吸附量低于未处理酵母,与阳离子交换能力关系不大,可能与细胞表面变形导致Zn(Ⅱ)吸附困难有关.     

丝瓜瓤固定简青霉吸附废水中Pb2+和Cu2+的机理

采用一种新型固定载体——丝瓜瓤,固定简青霉(Penicillum sp.),研究其在溶液中对金属离子Pb2 和Cu2 的吸附效果,并探讨其生物吸附机理,分析其动力学特性.实验结果表明,用丝瓜瓤固定简青霉能高效去除废水中Pb2 和Cu2 .研究发现,溶液pH值对吸附过程有较大影响,最佳吸附pH值在5.5附近;最佳吸附温度为25～35℃;溶液浓度在10～500 mg·L-1范围内,固定化简青霉菌对重金属的吸附随金属离子浓度的增加而增加;吸附过程符合Langmuir等温吸附模型;生物吸附平衡时间约为60min.用0.1mol·L-1HCl解吸,循环吸附-解吸5次后,固定化简青霉吸附金属离子的能力几乎不受影响     

酸和热处理对海泡石结构及吸附Pb2+、 Cd2+性能的影响

通过X射线衍射、傅里叶变换红外光谱及比表面积分析等研究了酸和热处理对天然海泡石结构的影响,并考察不同处理后的海泡石样品吸附重金属Pb2+、Cd2+性能.结果表明,海泡石比表面积均随盐酸浓度、处理时间的增加而略有增大,而结构无明显变化,0.5 mol·L-1 HCl处理时,天然海泡石中的CaCO3未能被完全去除,6.0 mol·L-1 HCl处理72 h时,海泡石比表面积达到最大301.47 m2·g-1.盐酸热处理并不能提高海泡石的比表面积,也不会使海泡石结构产生明显变化.不同类型酸处理对海泡石比表面积提高顺序依次为:HCl>HNO3>H2SO4;海泡石经焙烧后比表面积迅速下降,由100℃的21.44 m2·g-1下降到900℃的0.17 m2·g-1.重金属吸附实验表明,盐酸处理浓度和时间对海泡石吸附Pb2+、Cd2+离子性能无明显影响;不同酸处理对海泡石吸附Pb2+、Cd2+离子性能存在一定影响,H2SO4处理后海泡石对Pb2+、Cd2+离子吸附量明显高于HCl和HNO3处理.海泡石焙烧处理后对Pb2+离子吸附量无明显影响,但对Cd2+离子吸附量在焙烧700℃以上时增加明显.     

耐受铅真菌的筛选及其对Pb2+吸附的初步研究

从铅锌矿周围土壤样品中分离、筛选出一株耐铅真菌(命名为PY),对菌株进行了形态观察、生理生化实验及18SrRNA序列分析,并对该菌株的生物吸附性能进行了分析试验.结果表明,菌株PY为镰刀菌属(JQ267373),该菌株在Pb2+浓度550mg·L-1、湿菌量10g·L-1、pH=5.5、25℃、160r·min-1的条件下振荡吸附75min时,对Pb2+的吸附率可达到84%,吸附量为46.2mg·g-1.在Pb2+浓度为750mg·L-1时,其吸附率为77.9%.在25℃时,菌株PY对Pb2+的吸附模型符合Langmuir和Freundlich吸附等温方程.     

Zn2+和Mn2+处理水钠锰矿后对Pb2+吸附量的影响

分别采用Zn2+和Mn2+处理锰平均氧化度较高的水钠锰矿,对比研究了经不同浓度的Zn2+和Mn2+处理后矿物的锰平均氧化度、d110面网间距、对Pb2+的最大吸附量以及吸附过程中Zn2+和Mn2+的最大释放量等的变化.同时,通过Zn2+和Mn2+与水钠锰矿表面反应行为的不同,进一步明确矿物结构中的八面体空穴数量与重金属吸附量的关系.研究结果表明,水钠锰矿经Zn2+和Mn2+分别处理后,矿物类型未改变,并具有相似的晶体形貌.Zn2+溶液处理水钠锰矿时,随着Zn2+浓度的增大,水钠锰矿的锰平均氧化度和d110面网间距不变,说明结构中空穴数量未改变,Zn2+通过占据部分吸附点位,导致其对Pb2+的最大吸附量从3190 mmol·kg-1减少为2030 mmol·kg-1.而Mn2+溶液处理水钠锰矿时,大多数Mn2+被氧化为Mn3+,这些Mn3+部分位于八面体空穴上下方的吸附位点,部分进入八面体空穴中.随着加入的Mn2+浓度增大,Mn2+被氧化为Mn3+而进入八面体空穴的数量增多,锰平均氧化度减小,d110面网间距从0.14160 nm增大至0.14196 nm,说明结构中空穴数量减少,对Pb2+的最大吸附量从3190 mmol·kg-1减少至1332 mmol·kg-1.对比研究结果表明,水钠锰矿结构中的八面体空穴数量对Pb2+的吸附量的大小起着非常重要的作用.     

酿酒酵母吸附Zn(Ⅱ)过程中阳离子(K+，Mg2+，Na+，Ca2+)的变化分析

研究了酿酒酵母无缓冲溶液体系吸附Zn(Ⅱ)的过程中各种阳离子的变化情况.研究结果表明,当Zn(Ⅱ)的初始浓度是0.08～0.8 mmol·L^-1,酵母浓度约1 g·L^-1,初始pH为5.65,反应38h内,酵母的Zn(Ⅱ)吸附量为74.8～654.8μmol·g^-1,去除率达到76.4%～92.8%,pH值升高0.55～1.28.吸附过程中酵母首先快速释放大量K⁺,其次是Mg²⁺和Na⁺,Ca²⁺的释放量较少,数量级一般可分别达到几百、几十和几个μmol·g^-1.以离子交换为基础计算的各阳离子释放量总和一般超过Zn(Ⅱ)的吸附量,证明酵母吸附Zn(Ⅱ)的机理之一是离子交换,但不唯一.无缓冲溶液体系酵母吸附Zn(Ⅱ)的过程中溶液pH值升高,H⁺被吸收,K⁺等阳离子释放,是生物体细胞的本质属性,与Zn(Ⅱ)是否存在无关,但是Zn(Ⅱ)可以促进阳离子的释放以及降低酵母对H+的吸收,也反映出Zn(Ⅱ)与H⁺之间可以竞争细胞表面吸附位.死酵母的吸附量低于未处理酵母,与阳离子交换能力关系不大,可能与细胞表面变形导致Zn(Ⅱ)吸附困难有关.     

巯基乙酸改性橘子皮对Cu2+的吸附性能

研究了经巯基乙酸改性的橘子皮吸附剂对Cu2+的吸附性能,并考察了溶液pH值、吸附时间、Cu2+初始浓度及温度对吸附性能的影响.结果表明,吸附过程可以很好地用准二级动力学方程描述,吸附等温线用Langmuir方程的拟合效果优于Freundlich方程;;在pH=5.3、25℃条件下的最大吸附容量为70.671mg·g-1;;吸附过程为化学吸附,且经巯基乙酸改性的橘子皮可重复使用5次以上.     

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.     

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.     

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.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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