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。     

降尘中重金属的形态及其在模拟酸雨下的溶出规律

使用透射、扫描电子显微镜观察大气降尘的形貌,运用BCR分级提取法和火焰原子吸收分光光度法研究大气降尘中重金属元素Cu,Pb,Zn,Cr,Ni,Mn,Fe和Cd的含量及形态分布,探讨模拟酸雨条件下大气降尘中重金属元素的溶出规律.结果表明:小粒径降尘较大粒径比表面积大,吸附能力也较强;大气降尘中重金属元素(除Fe外)均以残渣态为主, Cd含量极小,未检出;粒径相同的降尘中,Fe含量最高,主要以可还原态存在,可提取态达到70%以上;Cu,Pb,Zn,Cr,Ni和Mn均以残渣态为主;Cu,Pb和Cr在小颗粒中相对富集,造成小粒径降尘的生物危害性更大;模拟酸雨条件下,Cu,Pb,Mn,Fe和Zn的溶出量均随pH降低而增大.      

垃圾焚烧飞灰中重金属的分布规律及浸出特性

文章研究了上海某垃圾焚烧厂不同粒径飞灰中重金属的分布特性。结果表明,大部分飞灰聚集在38～280μm,其中在38～53μm飞灰约占总量的50%。飞灰中重金属在不同粒径中的含量分布规律均为:Pb>Zn>Cu>Cr>Cd>Ni;除Ni和Cr外,重金属Zn、Cd、Cu和Pb都普遍表现出向小颗粒富集的趋势。重金属在不同粒径中的浸出量均为:Pb>Zn>Cr>Ni>Cu>Cd;Cr、Ni、Cu和Cd的浸出量随飞灰粒径的减小呈增加趋势,而Zn在106～280μm和Pb在75～106μm处的浸出量都经历了一个陡增过程。不同重金属的主要化学形态各不相同,除Ni和Cr外,其它重金属的主要形态都呈不稳定性。随着飞灰粒径的减小,碳酸盐结合态的Cd、Pb、Zn、Cu和铁锰氧化物结合态的Pb、Zn、Cu的量逐渐增加;残留态的Zn和有机结合态的Cu则不增反减;Ni和Cr的各形态分布规律不明显。     

垃圾焚烧厂排放颗粒物组分粒径分布特征

本研究采用静电低压撞击器(ELPI)采集垃圾焚烧厂排放颗粒物,分析颗粒物中元素和碳组分,对其中OC、EC和重金属元素在14个粒径段的粒径特征进行分析,并建立了垃圾焚烧厂源PM_1、PM_(2.5)和PM_(10)的元素和碳组分成分谱,以期为精细化来源解析提供参考.结果表明,垃圾焚烧厂排放颗粒物的主要组分有Al、Si、S、Ca、Cr、Fe、OC和EC等(质量分数≥1%),其中OC和Ca的含量较高,在PM_(2.5)中的质量分数分别为10. 15%和12. 37%;重金属含量Cr Pb Zn Mn Cu Cd Ni,其中Cr和Pb在PM_(2.5)中的质量分数分别为1. 83%和0. 74%,Cr在PM_1中的质量分数达到3. 53%; OC在2. 39～3. 99μm和6. 68～9. 91μm这2个粒径段的含量达到峰值,分别占OC总含量的15. 02%和20. 45%,但在细颗粒物中的含量高于在粗颗粒物中的含量,EC在细颗粒物中的含量远高于在粗颗粒物中的含量,在0. 382～0. 613μm粒径段占14. 8%; Cr、Mn、Ni、Cu、Zn、Cd和Pb等重金属元素主要富集于细颗粒中.     

水坝建设影响下澜沧江中游沉积物重金属形态分析及污染指数研究

采集了漫湾库区和大朝山库区25个采样断面的沉积物样品.每个库区均从上游到下游分为河流区、过渡区和湖泊区,研究了沉积物中As、Cd、Cr、Cu、Mn、Ni、Pb、Zn元素的含量和赋存形态差异,利用次生相与原生相分布比值法(RSP)分析重金属元素的污染水平.结果表明,各库区从上游到下游沉积物中的重金属元素和碳氮元素均呈现出增加的趋势,而沉积物的中值粒径呈现出减小的趋势.漫湾库区的As、Cd、Zn元素平均含量均高于大朝山库区;大朝山库区的Cr、Mn、Ni、Pb元素平均含量均高于漫湾库区.在重金属赋存形态中,Cd和Mn元素以可交换态和残渣态为主;Cu、Pb以有机质态和残渣态为主;其余重金属元素均以残渣态为主.沉积物中的可交换态在有机碳的络合作用下转化成有机质态.在水坝建设的影响下沉积物中细颗粒和有机质含量明显上升,重金属在细颗粒物和有机质的共同作用下蓄积于坝前的沉积物中.PSR分析结果表明,在水坝运行影响下,各库区湖泊区和过渡区的污染水平均高于河流区.其中,Cd元素所有地区处于重度污染水平;Mn和Pb大部分区域处于中度污染水平;Cu元素大部分区域处于轻度污染水平;其余元素基本无污染.     

上海城市地表灰尘重金属污染粒级效应与生物有效性

以上海中心城区为例,在分析地表灰尘重金属污染粒级效应基础上,研究重金属赋存形态及其生物有效性.结果表明,地表灰尘平均中值粒径为132 μm,低于75 μm粒径级别颗粒物占有最大的体积含量.重金属污染显示出明显的粒级效应,随着粒径降低,重金属含量呈现明显的增加趋势,150 μm和75 μm是主要级别,其中<75 μm颗粒物污染物含量依次为Cr>Pb>Cd>Zn>Ni>Cu.对地表灰尘重金属赋存形态研究表明,Zn以碳酸盐态为主;Ni以残渣态为主;Pb主要为铁锰结合态存在,Cu和Cd则以有机态为主;Cr主要以残渣态存在.重金属活性形态比例依次为Zn>Pb>Ni>Cd>Cu>Cr.与国外城市相比,上海城市地表灰尘Zn、Pb和Ni生物活性比例较大,而Cu和Cd活性比例相对较低,Cr活性水平与其它城市相当,环境危害相对最小.     

连环湖阿木塔泡沉积物中重金属形态及其对环境影响分析

采用了BCR三步提取法,对连环湖阿木塔泡AMT岩芯沉积物中的Mn、Cr、Cu、Fe、Ni、Pb和Zn等7种重金属元素的化学形态进行了分析。结果表明：Cr、Cu、Fe、Ni、Pb、zn元素以残渣态为主,Mn元素以可交换态及碳酸盐结合态为主。Cr、Cu、Ni、Pb的有机物及硫化物结合态、Fe—Mn氧化物结合态含量较高,Zn的有机物及硫化物含量较高。其中,Mn、Cr、Ni和Pb对环境产生危害的可能性最大,对这几元素应该予以足够的关注。     

广西一锰矿区土壤重金属的赋存形态研究

通过对锰矿区土壤重金属全量及其形态分布的分析,结果表明,土壤中Cu、Zn、Pb、Cr 4种金属的含量达到《土壤环境质量标准》的二级标准,Cd含量超过《土壤环境质量标准》的二级标准。从各元素形态分布来看,Cu、Pb主要以铁锰氧化物结合态和残渣态为主;Mn主要以铁锰结合为主;Zn、Cr主要以残渣态为主;Cd不同的样地各形态分布不一;从不同形态的重金属的生物有效性来看,Cu、Cd、Pb、Mn以可利用态和潜在可利用态为主,其中Mn潜在可利用态占为86.1%;Zn、Cr以不可利用态为主。锰矿区Cd与Mn 2种重金属是锰矿区污染土壤修复中主要修复对象。     

模拟酸雨对泉州市交通区表层土壤重金属淋溶的累积释放特征

用模拟酸雨动态淋溶试验方法和改进的BCR四步提取法研究泉州市交通繁忙区表层土壤中重金属的溶出规律及形态变化,用ICP-AES测定浸出液中Ti、Zn、Co、Ni、V、Fe、Mn、Cr、Cu、Pb、Cd和As的含量。结果表明大部分重金属元素(Mn、Fe、Ni、Cu、Zn、Pb)累积释放量随模拟酸雨pH值的降低而增加。对土壤中金属释放过程进行数学方程拟合后发现,应用双常数速率方程能更好地描述V、Co和Ni的释放规律,抛物线方程则能更好地描述Zn的释放过程,修正Elovich方程能更好地描述Ti、Cr、Mn、Fe、Cu和Pb的释放过程,而双常数速率方程和抛物线方程均能很好地描述As、Cd的释放过程。对比淋溶前后重金属形态分布,发现淋溶后土壤中Ti、Cr、Mn、Fe、Co、Ni、Cu、Zn、Pb的生物有效态比例有所增加,而V、Cd和As的生物有效态比例略有降低。     

垃圾焚烧飞灰中重金属的污染特性

以广西和重庆某生活垃圾焚烧厂的焚烧飞灰为研究对象,研究了飞灰中重金属的化学形态、不同粒径下飞灰中重金属含量及浸出毒性。结果表明:广西垃圾焚烧飞灰中含有5种重金属,且都是以残渣态为主要存在形态;重庆垃圾焚烧飞灰中Cr以残渣态为主要存在形态,Zn、Cu和Cd以醋酸可提取态为主要存在形态,具有较大的潜在毒性,毒性较强的Pb只以醋酸可提取态和可还原提取态两种形态存在,危险性非常高,Mn以可还原提取态为主要存在形态。两地飞灰中含量较高的重金属元素都表现出向小颗粒富集趋势。随飞灰颗粒粒径的减小,各重金属浸出量基本呈增加趋势。相比之下,重庆的垃圾焚烧飞灰中Zn、Cu、Pb和Cd的含量和浸出量都高于广西飞灰。广西飞灰中各粒级的飞灰中各元素浸出量均不超标,而重庆飞灰各粒级的飞灰中Zn、Pb和Cd的浸出量严重超标,表明重庆飞灰属于典型危险废物。     

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.