应用化学提取法评价大气颗粒物中重金属的生物有效性

以广州市楼顶降尘为研究对象,在分析其粒度分布和重金属总量的基础上,采用单一化学提取法（DWLP、TCLP）和多级化学提取法（SEP）研究了大气颗粒物中4种重金属元素的生物有效性。结果表明：样品中96％以上颗粒小于100μm,其中10μm和2．5μm以下颗粒分别占33％和11％。大气颗粒物中重金属含量很高,Cu、Pb、Zn和Cd的平均含量分别为362．43、1033．81、830．32和5．80mg／kg,是广东省环境土壤背景值的17～64倍。单一提取法中,TCLP的提取效率明显高于DWLP,表明pH值是影响大气颗粒物中重金属释放的主要因素。SEP法结果显示,Zn和Cd的生物可利用态比例远高于Cu和Pb。经DWLP和TCLP法提取后,颗粒物中重金属的总含量有不同程度的降低,生物可利用态所占比例明显增加。通过综合分析,发现SEP此其他两种方法更适用于评价大气颗粒物中重金属的生物有效性。     

浙江西沪港重金属Pb的配位容量及其形态

根据2000年6月l0(14日在浙江西沪港采集的海水样品，用AA-800石墨炉原子吸收分光光度技术和阳极溶出伏安法测定样品中重金属Pb的含量，获得Pb在海水中受特定的有机配体控制结果如下：(1)溶解态Pb的表观配位容量和条件稳定常数分别为50．0nmol／dm^3和9．73，表层海水中Pb溶解态总量为1．92nmol／dm^3。(2)不同胶体粒级(小于或等于0．2、0．4、1．0μm粒级)中Pb的含量分别为1．25、1．67、2．11nmol／dm^3；其中于0．2～0．4μm粒级间的颗粒物含Pb的量为0．42nmol/dm^3；于1．0～0．4μm粒级间的颗粒物含Pb的量为0．44nmol／dm^3。     

不同粒径大气颗粒物几种重金属成分分析及其致空变性研究

采集冬季太原市一采样点不同粒径大气颗粒物，经分析，总悬浮颗粒物日均浓度为１．０４ｍｇ／ｍ＾３，严重超标。其中粒径小于７．０μｍ的占４９．６％，小于３．３μｍ的占３３．５％。颗粒物无机提取液中５种金属元素的浓度由高到低依次为Ｐｂ，Ｍｎ，Ｃｒ，Ｎｉ和Ｃｄ。每种元素均呈随颗粒物粒径减小浓度增高的趋势。以ＳＯＳ显色法和小鼠体内骨髓细胞染色体畸变试验检测颗粒物的无机提取淮和模拟肺泡液溶出液的遗传毒性，表明小     

长江水系河流沉积物重金属元素含量的计算方法研究

采用长江水系约２６０个背景样点沉积物原样和小于６３μｍ细粒沉积物中１１种重金属元素（铜、铅、锌、镉、汞、钴、镍、砷、铬、锰和铁）含量的数据，研究了数据的频率分布特征和变异系数，比较了算术均值、几何均值和中位数与由Ｂｏｘ－Ｃｏｘ变换而得到的对称均值间的大小关系，结果表明，大多数重金属元素含量服从对数正态分布；采用算术均值表示均值会有较大的偏差，且这种偏差随变异系数的增大而增大；采用中位数偏差较小，但     

空气颗粒物中有机污染物粒径分布规律的研究

采用色谱一质谱联用技术（ＧＣ—ＭＳ），系统分析了１０００多个不同粒径颗粒物样品中的有机污染物，结果表明：环境空气颗粒物中有机污染物集中分布于细颗粒物上，几乎所有的多环芳烃（ＰＡＨ）和一半以上的苯并［ａ］芘［Ｂ（ａ）ｐ］吸附在粒径小于０．３８μｍ的极细尘中。     

无机型城市景观水体表观污染的悬浮颗粒物粒度分布特征:以中国运河苏州段为例

基于悬浮颗粒物粒度分布特性能为水环境表观质量研究提供重要信息,以流经苏州市市内运河水为研究对象,探讨无机型城市景观水体中不同表观污染程度下水中悬浮颗粒物的粒度分布特性及其影响因素,从悬浮颗粒物的粒径角度来解释无机型景观水体表观污染机制.结果表明,无机型水中悬浮颗粒物以单峰分布为主,中值粒径范围13~25.2μm,组分Ⅱ(粒级3.8~16μm)是优势组分,体积分数范围29.4%~59.6%;水体表观污染的敏感组分为组分Ⅱ(粒级3.8~16μm)和组分Ⅳ(粒级32~64μm),表观污染指数(SPI)与组分Ⅱ和组分Ⅳ体积分数关系具有分段性,分段节点是浊度为45NTU处,浊度小于45NTU时,SPI值与组分Ⅱ体积分数呈显著正相关,与组分Ⅳ体积分数呈显著负相关;当浊度大于或等于45NTU时关系相反.影响苏州运河水粒径分布的因素主要是生物因子和水动力条件,生物因子的作用主要表现为藻类的增加,水动力条件的作用是使水体发生再悬浮,导致水中大颗粒物质的增加.     

不同城市功能区地表灰尘Pb水平及粒级行为——以贵阳市为例

本文以我国西南贵州省会城市贵阳为例,对地表按城市功能分区采集灰尘样品,从不同功能区灰尘Pb总量和不同粒级灰尘Pb含量及贡献两个角度探析城市功能对地表灰尘Pb的影响。研究表明,贵阳市地表灰尘Pb平均含量为93.2mg/kg。商贸区和交通区地表灰尘Pb离散度较小,工业区和垃圾站地表灰尘Pb分异较大,住宅区、广场和学校灰尘Pb数据离散度处于中间水平。不同功能区地表灰尘Pb水平存在较大差异,工业区地表灰尘Pb含量显著高于商贸区和垃圾站;广场和学校地表灰尘Pb含量显著高于商贸区和交通区;住宅区Pb含量显著高于交通区。城市功能区从功能和地理位置两个方面影响城区地表灰尘Pb水平。各功能区地表灰尘不同粒级颗粒物中Pb含量存在较大差异,但所有区域地表灰尘中<250μm粒级颗粒物对地表灰尘Pb的贡献基本达到80%。     

空气颗粒物中有机污染物粒分布规律的研究

采用色谱一质谱联用技术（ＧＣ－ＭＳ），系统分析了１０００多个不同粒径颗粒物样品的有机污染物，结果表明，环境空气颗粒物中有机污染物集中分布于细颗粒物上，几乎所有的多环芳煤（ＰＡＨ）和一半以上的苯芘（ａ）芘Ｂ（ａ）ｐ）吸附在粒径小于０．３８μｍ的极细尘中。     

富营养化城市景观水体表观污染下的悬浮颗粒物粒度分布特征

悬浮颗粒物粒度分布特征反映城市景观水体表观污染状况,为研究富营养化城市景观水体表观污染与悬浮颗粒物粒度分布的内在联系及其影响因素,在苏州市市内的典型富营养化河道:枫津河,选取5个代表性取样点,测定水中悬浮颗粒物粒度分布、表观污染指数(SPI)及水质指标,并分析其相关性.结果表明,富营养型水体中悬浮颗粒物具有相似的粒度分布特征,粒度分布存在多峰,且出峰位置大致相同,悬浮颗粒物的粒度分布由多个组分叠加构成.悬浮颗粒物粒度分布最多可分为6个组分,各组分粒径范围分别为1.5μm、1.5~8μm、8~35μm、35~186μm、186~516μm、516μm.组分Ⅲ是优势组分(体积分数均值38.3%~43.2%).组分Ⅲ体积分数与SPI值、Chl-a浓度呈显著正相关,组分Ⅲ体积分数的增大是该类水体表观污染程度加深的粒度结果表征,该组分体积分数的增大主要来自于藻含量增加;组分Ⅳ+组分Ⅴ+组分Ⅵ体积分数在有外源时明显高于无外源时,无外源时组分Ⅳ+组分Ⅴ+组分Ⅵ体积分数与SPI值显著负相关,有外源时组分Ⅳ+组分Ⅴ+组分Ⅵ体积分数与SPI值存在较弱的正相关但未达到显著水平.环境因子(F_v/F_m和DO)和外源因子作用水体主要表观污染物质藻类的含量,进而影响悬浮颗粒物各组分的体积分数和水体表观质量;水动力条件作用悬浮颗粒物粒径,较大水动力使中值粒径增大,对水体表观质量未产生显著影响.     

密云水库上游铁尾矿各粒级组分重金属研究

以北京市密云水库上游铁矿区为研究对象,研究了尾矿砂中重金属的含量及形态与粒级分布之间的关系。采集铁尾矿样品5件,使用尼龙筛将其划分为4个粒级组分(75、75~180、180~250、250μm),使用ICP-OES测定各粒级组分中重金属元素Mn、Cu、Pb、Zn、Ni和Cd元素的含量,并测定Fe元素含量。并用BCR连续提取法和ICP-OES测定各粒级组分中Mn、Cu、Pb、Zn、Ni和Cd元素不同化学形态的含量。重金属总量随粒度分布特征研究表明,同一样品不同粒级组分中重金属总量有很大差异。Mn和Cu元素主要集中在细粒径(75μm)和粗粒径(250μm)组分中,Pb、Zn和Ni元素在粗粒径组分中含量比较高。各个样品相同的粒级组分中,重金属元素含量从高到低依次为MnZnCuNiPbCd。重金属形态随粒度分布特征研究表明,Mn、Cu、Pb元素可交换态和Mn、Cu、Zn、Ni元素易还原态主要集中在细粒径和粗粒径组分中,环境危害性大。不同矿区尾矿样品相同粒级组分中,重金属形态分布有很大差别。重金属元素总量与p H值之间进行相关性分析表明,Mn、Cu元素两两之间表现出非常显著的相关性(r0.9,P0.01),说明这2种元素有相同或相似的来源。Pb、Zn、Cd元素与其它元素相关性很小,说明Pb、Zn、Cd元素与其它元素来源于不同的矿物成分。     

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.     

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.     

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.     

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

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Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.