采用离石黄土原位修复煤矸石渗滤液污染地下水

为以较好的技术手段和较低的经济成本治理煤矸石淋滤液、矿坑废水对地下水的污染,通过土柱淋滤试验、PRB (permeable reactive barrier)模拟试验以及场地修复试验,对煤矸石淋滤液中重金属(Zn、Mn、Pb、Cr、Cu、Cd、Hg)及As的吸附性进行了研究. 土柱淋滤试验结果表明:离石黄土(粒径0.05~0.10mm)、亚砂土(粒径0.05~0.10mm)和细沙(粒径>0.10~0.25mm)对煤矸石淋滤液中的重金属(Zn、Mn、Pb、Cr、Cu、Cd、Hg)及As的吸附能力为离石黄土>亚砂土>细沙,其中离石黄土对As的分配系数为2.26L/kg.模拟槽试验表明,在地下水流速为0.20m/d、m(煤矸石):m(离石黄土)分别为5和7的情况下,淋滤液中的As能够全部被黄土墙吸附;m(煤矸石):m(离石黄土)为10时,部分As透过黄土墙向下游迁移. 5个月的场地修复试验表明,利用离石黄土作为PRB的吸附材料能够较好地去除地下水中的重金属(Zn、Mn、Pb、Cr、Cu、Cd、Hg)和As,厚约0.5m的离石黄土墙对被煤矸石淋滤液污染的地下水中Cr的去除率最高,达到70.97%,对Pb的去除率最低,为43.14%.      

煤及其燃烧产物中有害痕量元素的淋滤特性研究

通过对我国西北部上湾与石嘴山电厂原煤、底灰和飞灰中As、Pb、Cd、Mop、Mo、Co和U等有害痕量元素在不同条件下的淋滤实验,采用原子荧光光谱（AFS）和电感耦合等离子体质谱法（ICP-MS）测定了痕量元素在2套（6个）样品、3种淋滤介质、4个不同时间段获取的淋滤液中的浓度,对比不同元素间淋出率、60h的最大淋出率和淋滤强度的差异性,分析痕量元素在不同条件下的淋滤特性;通过对比元素在原煤和燃煤产物中的含量、60h的最大淋出率以及淋滤液中元素的浓度,参考相关地下水的环境质量标准对痕量元素的环境效应进行了综合评价：As与Se的淋滤性较差,淋滤液中的最大浓度较低,对环境造成危害的可能性很小;Pb与Cd在淋滤液中的最大浓度较高,可能对环境造成危害.Mo与Co的淋出性好,淋出率高,同时淋滤液中的最大浓度是三类地下水环境质量标准的5～10倍,对环境造成危害的可能性最大.     

合山市东矿矿区煤矸石淋滤液特征及其环境影响分析

以广西合山市东矿矿区的一座大型煤矸石堆为研究对象,通过采集煤矸石堆上的煤矸石样品进行浸溶试验,对煤矸石矿物化学成分以及煤矸石浸溶液、淋滤液中水化学成分进行了测试并对环境的影响进行了对比分析。结果表明:在煤矸石浸溶试验过程中,浸溶液水样pH值一直处于6.3~6.6之间,略显酸性,浸溶初期10h内,只有Cd、As和Pb浓度相对较高;背景样的pH值为7.89,略显碱性,其中SO2-4、Cd、Ni、Pb浓度分别为9.097 9mg/L、0.000 1mg/L、0.001 5mg/L、0.000 5mg/L,As浓度小于仪器检测限,故没有检测出来,并且背景样中的各项指标均符合《地表水质量标准》中的一类标准;而3个煤矸石淋滤液水样pH值处于5.5~6.5之间,都显酸性,并且淋滤液水样中SO2-4、Cd、Ni、Pb、As的浓度均远远超出了背景样,其中超出最多的为D-1样品中的SO2-4浓度为背景样的207倍,超出最少的为D-3样品中的Cd浓度为背景样的7倍;煤矸石淋滤液中重金属Cd、Ni、Pb、As的浓度都超过了背景样及雨水样,对环境的危害较大,若煤矸石继续堆积在矿区还将进一步危及水体、恶化水质。     

煤矸石中重金属动态淋滤溶出特征研究

以河北邯郸某矿区煤矸石为研究对象,采用动态淋滤实验对煤矸石中重金属的溶出特征进行研究.实验结果表明:①煤矸石中重金属元素背景值影响溶出液中重金属浓度,背景值越高,在动态淋滤过程中析出重金属的浓度越高;②淋滤前期阶段,重金属元素的溶出液浓度较大,随着淋滤时间的增加,浓度在波动中趋于稳定.因此可以得出重金属元素对环境的影响主要发生在淋滤前期;③溶出液中只有Cu元素的浓度超过了国家地表水环境质量标准中的Ⅲ类水质标准,并且溶出液呈弱酸性,符合国家地表水环境Ⅲ类质量标准.     

煤矸石堆放地周围土壤中重金属的污染特性及评价

为了分析煤矸石堆放对周边土壤环境的影响,以某煤矸石山为对象,采集新鲜煤矸石及附近土壤样品,检测其中Cu、Pb、Zn、Cd、Ni、Cr、As和Hg 8种重金属元素的含量,分析了煤矸石和土壤中重金属的相关性,采用多种污染指数评价了重金属污染对该地环境质量的影响。结果表明:该煤矸石堆放地中,重金属污染单因子指数由高到低依次为Ni>Zn>Cu>Cr>Pb>As=Hg=Cd,该堆放地土壤等级总体尚安全,但土壤中Zn、Cr和Cu含量已受到人为污染影响。     

浸泡淋滤作用下煤矸石重金属元素的释放规律及特征研究

为探究天然煤矸石在雨水浸泡淋滤作用下重金属元素的释放规律及特征,通过扫描电镜(SEM)对天然煤矸石进行表征以观察其淋滤前后的微观形貌,借助X射线衍射(XRD)技术测定煤矸石淋滤前后的矿物成分组成及变化情况.结合模拟降水连续静态浸泡与动态淋滤试验,考察在不同固液比、粒径、pH、土壤介质条件下煤矸石中重金属元素的释放规律与特性.结果表明：(1)淋滤后的煤矸石表面凹凸结构较多,淋滤前后煤矸石中各矿物相含量差异较小.(2)As、Mn的浸出浓度均较高,最大释放率大小表现为As>Cd>Cu≈Ni>Mn>Cr>Zn>Pb. As的累积释放对周边土壤环境以及地下水产生不利影响的风险较高.(3)连续动态淋滤试验在pH为3时,Mn、Cu、Zn、Ni的累积释放量明显较高,As、Cr在中性条件下的累积释放量高于在酸性条件下.引入土壤介质这一因素后,Cr、As的累积释放量均明显减少,这两种重金属元素均呈现出在土壤中积累的状态.研究显示：对于相同煤矸石堆存量,降雨量越大,重金属的释放总量越高,固液比为1∶20时,As释放量最高可达2.822μg/L;Cr、As呈现出在土壤中积累...     

煤矸石中重金属动态淋滤溶出特征研究

以河北邯郸某矿区煤矸石为研究对象,采用动态淋滤实验对煤矸石中重金属的溶出特征进行研究。实验结果表明:①煤矸石中重金属元素背景值影响溶出液中重金属浓度,背景值越高,在动态淋滤过程中析出重金属的浓度越高;②淋滤前期阶段,重金属元素的溶出液浓度较大,随着淋滤时间的增加,浓度在波动中趋于稳定。因此可以得出重金属元素对环境的影响主要发生在淋滤前期;③溶出液中只有Cu元素的浓度超过了国家地表水环境质量标准中的Ⅲ类水质标准,并且溶出液呈弱酸性,符合国家地表水环境Ⅲ类质量标准。     

褐煤燃烧过程中重金属元素分布特征及其对环境影响评价

针对云南小龙潭矿区褐煤及燃烧产物中重金属元素As、Cd、Sb、Pb、Hg的含量,通过室内模拟燃烧,研究了5种元素在煤燃烧过程中的分布行为,揭示了它们在燃煤产物中的分配富集特征,分析了这些元素产生的环境影响.结果表明,Hg的挥发性最强,在300℃下就有极高的挥发率,到500℃挥发殆尽,挥发性为Hg ＞As＞ Cd ＞Sb ＞Pb,而重金属的赋存状态对其挥发性有明显的影响.最后通过环境效应评价其燃烧过程的挥发对大气的影响发现在室内模拟燃烧下属重污染,这与室内试验挥发率较大有关,而电厂动态燃烧下为微污染,所以燃烧方式以及燃烧工况等对微量重金属的挥发性有明显的控制作用.     

海南小海沉积物中的重金属分布特征及潜在生态风险评价

对小海沉积物进行采集,测定了沉积物中的Cu、Pb、Cd、Zn、Hg、As重金属的含量,用单因子指数法和Hakanson生态风险指数法评价了沉积物中重金属综合污染效应.研究结果表明:小海湾内沉积物中Cu、Pb、Cd、Zn、Hg、As的平均含量分别为0.20 mg/kg、0.18 mg/kg、0.30 mg/kg、0.22 mg/kg、0.44 mg/kg、0.23 mg/kg.沉积物所监测的重金属中,Hg金属的空间波动程度最高,其他重金属的空间波动程度较低.沉积物质量评价结果表明:小海沉积物中主要的重金属污染因子是As,其重金属影响因子的顺序为As＞Hg＞Pb＞Cr＞Zn＞Cu＞Cd;各种重金属的潜在生态危害系数大小顺序为Hg＞As＞Cd＞Pb＞Cu＞Cr＞Zn;潜在生态风险指数 RI平均值为37.06,属于轻微潜在生态风险.     

承德市滦河流域土壤重金属地球化学基线厘定及其累积特征

选择承德市滦河流域为研究区,系统采集了351个表层土壤样品(0～20cm),测定了Cu、Ni、Cd、Cr、Pb、Zn、Hg、V、Ti、Mn、As和Co共12种重金属的含量,运用基于参比元素的标准化方法和累积频率曲线法确定了12种重金属元素的地球化学基线值,结合主成分分析法与地统计方法统计结果,分析了重金属的空间结构和分布特征,利用地累积指数法对不同土壤类型和土地利用方式表层土壤重金属累积程度进行了分类评价.结果表明,滦河流域表层土壤V、Ti、Cd、Pb、Mn和Co元素地球化学基线值高于河北省背景值,As、Zn、Cr、Cu、Ni和Hg元素地球化学基线值低于河北省背景值.表层土壤重金属总体累积程度由强至弱为:Cd Pb Cu Ti Mn Zn Cr Ni Co V Hg As,80%以上的土壤样品中Pb、Ti、V、As和Co元素属无累积-中度累积水平,70%以上土壤样品中Hg、Mn、Ni、Cu、As、Cd和Cr元素属无累积-中度累积水平.土壤重金属总体累积程度在棕壤、褐土和潮土中依次增大;在工矿用地、灌木林地中较高,林地、草地中相对最低.农用地表层土壤中Pb、Cd元素累积程度相对较高,分别有27. 69%和25. 38%的样品属中等以上累积水平.滦河流域表层土壤Ti、V、Co、Ni和Cr元素同源性较高,与原生高地质背景相关; Cd、Pb、Zn,Mn、Cu和As元素污染累积受成土母岩和人为因素共同作用影响,Hg元素累积则主要来源于人为活动.     

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.     

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.     

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.     

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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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.     

Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Alterations of organ histopathology and metallolhionein mRNA expression in silver barb, Puntius gonionotus during subchronic cadmium exposure

Common silver barb,Puntius gonionotus,exposed to the nominal concentration of 0.06 mg/L Cd for 60 d,were assessed for histopathological alterations(gills,liver and kidney),metal accumulation,and metallothionein(MT)mRNA expression.Fish exhibited pathological symptoms such as hypertrophy and hyperplasia of primary and secondary gill lamellae,vacuolization in hepatocytes,and prominent tubular and glomerular damage in the kidney.In addition,kidney accumulated the highest content of cadmium,more than gills and liver.Expression of MT mRNA was increased in both liver and kidney of treated fish.Hepatic MT levels remained high after fish were removed to Cd-free water.In contrast,MT expression in kidney was peaked after 28 d of treatment and drastically dropped when fish were removed to Cd-free water.The high concentrations of Cd in hepatic tissues indicated an accumulation site or permanent damage on this tissue.