草酸对蒙脱石的作用及机理研究

近年来,微生物对粘土矿物的分解作用逐渐成为地球科学研究的重点领域,草酸是微生物重要的代谢产物,研究了小分子有机酸对粘土矿物结构变化的影响,为改善根际土壤环境质量提供科学依据.研究发现,草酸能够破坏蒙脱石的形貌结构,使蒙脱石层状结构变得卷曲;通过破坏蒙脱石结构中的化学键,溶蚀出蒙脱石中的金属元素;C2O42-进入到蒙脱石层间与层间阳离子Ca2+结合生成CaC2O4·H2O,与蒙脱石发生插层作用,使蒙脱石的层间距增大.研究结果可为土壤修复机制提供理论依据.     

蒙脱石伊利石化过程中伊-蒙混层形成的Gibbs自由能

采用Vieillard(2000)提出的计算含水粘土矿物形成的Gibbs自由能的方法,对热液蚀变作用下蒙脱石向伊利石转变过程中伊利石 蒙脱石混层形成的Gibbs自由能进行了计算。根据伊利石 蒙脱石混层的化学成分,详细计算了一个端元伊利石样品形成的Gibbs自由能,其值为 5401.36kJ/mol。该值与已给出的天然伊利石和理想伊利石形成的Gibbs自由能非常相近,表明Vieillard(2000)的方法对计算伊利石 蒙脱石混层形成的Gibbs自由能是可行的。伊利石 蒙脱石形成的Gibbs自由能可进一步用于计算因地下水过量开采而产生的地面沉降的量。     

苏北闵桥含油玄武岩中粘土矿物的组合特征及其应用

苏北闵桥地区含油玄武岩的主要次生蚀变粘土矿物为：皂石，绿泥石，蒙脱石，伊利石，伊利石／蒙脱石混层，高岭石，方沸石等，不同类型的玄武岩中粘土矿物组合不同，最具特征的组合为：致密玄武岩－皂石（为主）＋其它矿物；淬碎玄武岩－蒙脱石（为主）＋伊利石＋伊利石／蒙脱石混层＋高岭石，碎裂玄武岩－皂石（为主）＋绿泥石＋方沸石，蚀变玄武岩中，随着蚀变作用由弱到强，这些粘土矿物可以分成四个带，皂石带－绿泥石带－蒙脱石带－高岭石带，这种分带性与夏威夷玄武岩中热液成因的粘土矿物的分布性具有可比性，在一个玄武岩岩流单元不同部位，特征粘土矿物为：底部－蒙脱石；中倍位－皂石，顶部位－伊利石＋伊利石／蒙脱石混层，风化带特征粘土矿物为蒙脱石，少量高岭石，本文还对利用粘土矿物组合特征在玄武岩含油性，古地理及古环境等方面的应用进行了探讨。     

新农药环境化学行为研究(Ⅶ)除草剂哌草丹(Dimepiperate)在土壤、水环境中的滞留、转化

研究了除草剂哌草丹在土壤、水环境中的吸附、脱附、水解及光解过程．结果指出：哌草丹在土壤上的吸附主要受土壤有机质的影响，粘土矿也有一定作用．吸附和脱附均可用Ｆｒｅｕｎｄｌｉｃｈ方程描述；根据降解产物推测了哌草丹的水解和光降解的机理，哌草丹的水解产物为２苯基丙烯和六氢吡啶等，六氢吡啶可与土壤粘土矿（蒙脱石）作用，并与蒙脱石层间阳离子形成配合物；哌草丹光降解的产物为六氢吡啶、苯乙酮和甲醛     

新农药环境化学行为研究(Ⅶ)除草剂哌草丹(Dimepiperate)在土壤、水环境中的滞留、转化

研究了除草剂哌草丹在土壤、水环境中的吸附、脱附、水解及光解过程.结果指出:哌草丹在土壤上的吸附主要受土壤有机质的影响,粘土矿也有一定作用.吸附和脱附均可用Freundlich方程描述;根据降解产物推测了哌草丹的水解和光降解的机理,哌草丹的水解产物为2-苯基丙烯和六氢吡啶等,六氢吡啶可与土壤粘土矿(蒙脱石)作用,并与蒙脱石层间阳离子形成配合物;哌草丹光降解的产物为六氢吡啶、苯乙酮和甲醛.     

新农药环境化学行为研究(Ⅶ)除草剂哌草丹(Dimepiperate)在土壤、水环境中的滞留、转化

研究了除草剂哌草丹在土壤、水环境中的吸附、脱附、水解及光解过程.结果指出:哌草丹在土壤上的吸附主要受土壤有机质的影响,粘土矿也有一定作用.吸附和脱附均可用Freundlich方程描述;根据降解产物推测了哌草丹的水解和光降解的机理,哌草丹的水解产物为2-苯基丙烯和六氢吡啶等,六氢吡啶可与土壤粘土矿(蒙脱石)作用,并与蒙脱石层间阳离子形成配合物;哌草丹光降解的产物为六氢吡啶、苯乙酮和甲醛.     

几种粘土矿物对Pb~(2+)的吸附作用及其主要影响因素的探讨

对土壤中常见的三种粘土矿物对Pb2+的吸附作用及其主要影响因素进行了探讨。结果表明，三种粘土矿物对Pb2+的吸附能力顺序为：蒙脱石＞伊利石＞高岭石。蒙脱石对Pb2+的吸附受pH的强烈影响，pH高有利于对Pb2+的吸附。与蒙脱石形成复合体形式的有机化合物的存在不利于蒙脱石对Pb2+的吸附。     

放射性废弃物地层处理中粘土的作用

本文简短地途述了地层处理放射性废弃物的概要及粘土矿物在其中的重要作用，若干种类的Ｈ＾＋型粘土和阳离子（Ｌｉ，Ｎａ，Ｍｇ，Ｃａ，Ｓｒ，Ｂａ，ＣＯ）之间的交换性质通过分批实验进行了研究，Ｍｇ，Ｃａ和ＣＯ离子能被粘土强烈地吸附，粘土矿物的ＫＤ值有以下顺序，蒙脱石≥累脱石＞绢云母≥高蛉石＞绿泥石＝多水高岭石，蒙脱石和累脱石的阳离子吸附系数水平约是结果岩及其矿物的１０～１００倍。在一定的水热条件下，蒙脱石可     

含水层中透镜体对地面沉降过程的影响机制

第四系松散沉积物是发生地面沉降的主要地层，由于复杂的沉积环境导致砂与黏土互层出现，并在沉积过程中形成透镜体。由于透镜体的尺度较小，在研究过程中常被忽略，含有透镜体的非均质地层常被概化为均质的弱透水层或含水层。以宁波地面沉降为例，根据实测剖面含水层中透镜体的分布，运用COMSOL Multiphysics数值模拟软件对含水层中透镜体的大小及位置进行刻画并进行数值求解，揭示了含水层中透镜体对地面沉降的影响机制。结果表明：考虑含水层中透镜体存在的地面沉降数值模拟过程的拟合精度高于不考虑透镜体存在的数值模型；含水层中透镜体的存在会改变所在位置处的渗透系数，进而改变区域含水层中地下水渗流场的演化；含水层中不同性质透镜体对地面沉降的影响不同，黏性土透镜体分布广泛的地区地面沉降更大；在地面沉降过程中，渗透系数高于周边区域的透镜体处水头变化值减小，使得该区域地面沉降量减小，且地面沉降量随着透镜体渗透系数的增大而减小。本研究结果可为含透镜体地层的地面沉降研究提供理论依据。     

土壤添加不同粘土矿物对微囊藻毒素在生菜中生物富集的影响

土壤-作物系统中微囊藻毒素的生物富集会对人类健康造成潜在威胁.本研究通过生菜（Lactuca sativa L.var.ramosa Hort.）种植实验比较了土壤添加不同比例的3种粘土矿物（凹凸棒石、蒙脱石和沸石）对微囊藻毒素-LR（microcystin-LR,MC-LR）生物富集的影响,分析含10 μg·L^-1 MC-LR溶液灌溉土壤50 d后,不同处理的MC-LR在生菜中累积量及土壤中的有效态含量和总含量.结果表明,3种粘土矿物能够不同程度有效减少MC-LR在生菜根系和叶片中的富集.5%的凹凸棒石和蒙脱石处理的生菜叶片中MC-LR含量分别较空白处理降低53.0%和52.3%,使得摄入量降低到WHO组织要求的日允许摄入限量范围.添加粘土矿物显著降低了土壤中MC-LR有效态含量.相关分析发现,生菜根系和叶片中MC-LR的含量与土壤MC-LR有效态含量均呈显著正相关.实验结果为蓝藻污染地区削减微囊藻毒素的作物富集提供了科学依据.     

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.     

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.     

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.     

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.