煤矸石复垦后溶出液中污染因子的土壤吸附性能研究

采用静态试验法对煤矸石复垦后溶出液中污染因子的土壤吸附性能进行了研究;研究结果表明,煤矸石静态溶出主要污染因子为F-、SO42-和重金属Mn;改性基底土壤在不影响对其它污染因子吸附的前提下,能够对SO42-起到较好的吸附效果;改性基底土壤对SO42-、F-、Mn、As的饱和吸附量分别为14.80 mg/g、0.085 mg/g、0.0087 mg/g、0.073μg/g;SO42-、F-、Mn、As解吸率和解吸因数都很低,分别为4.32%和4.52×10-2,3.31%和3.43×10-2,1.44%和1.46×10-2和0.78%和7.9×10-2。     

改性土壤对矸石溶出液中主要污染因子的吸附特征

主要通过静态试验研究了平煤集团十二矿矸石的静态溶出特征和改性土壤对矸石浸溶液中主要污染因子吸附特征;结果表明,煤矸石浸泡液中主要污染因子为SO4^2-F-、F^-重金属Mn;改性土壤对SO4^2-、F^-及重金属Mn等污染因子的吸附等温式分别符合Temkin等温式、Freundlich等温式和Freundlich等温式,饱和吸附量分别为14．80mg／g、0、085mg／g和0.0087mg／g;主要发生了配位吸附等专性吸附,吸附稳定性高,不易解吸。     

响应曲面分析优化改性粉煤灰漂珠对水中氟的吸附性能及机理研究

为提升粉煤灰漂珠对水溶液中氟的吸附性能,以氧化钙为原料,采用煅烧法制备钙改性粉煤灰漂珠吸附材料.通过响应曲面分析中的Box-Behnken设计吸附氟试验,探讨各吸附因数及其交互作用对吸附效果的影响,确定最佳吸附条件.利用SEM（扫描电镜）、EDS（能量散射光谱）、XRD（X射线衍射）以及BET比表面积等手段对吸附材料进行表征,并结合吸附动力学、吸附等温试验探讨钙改性粉煤灰漂珠吸附剂的除氟机制.结果表明:①初始ρ（F-）和吸附温度对改性粉煤灰漂珠吸附水中F-的去除率有显著影响,当pH为5.0、初始ρ（F-）为125 mg/L、吸附温度为40℃时,改性粉煤灰漂珠对水中F-的吸附效果最佳.②动力学试验显示,改性粉煤灰漂珠对水中F-的吸附过程符合准二级动力学模型,说明该吸附过程主要以化学吸附为主;与Langmuir和Freundlich吸附等温模型相比,Temkin吸附等温模型更适合于描述该吸附平衡过程.③SEM、EDS和BET比表面积分析显示,改性后的粉煤灰漂珠内部生成了具有不规则表面和多孔结构的含钙团簇物质,从而增加了BET比表面积,改善了孔隙结构.XRD分析显示,钙改性粉煤灰漂珠主要通过离子交换作用吸附去除水中的F-.研究显示,以工业废物为原料制备的钙改性粉煤灰漂珠吸附剂的最大除氟率为93.59%,是一种具有应用潜力的低成本吸附材料.      

演马矿煤矸石堆周围环境中重金属分布特征

以焦作市演马矿煤矸石堆为对象,检测分析其周围土壤、地下水和植物中的重金属含量,并结合当地的地形地貌、土壤性质和地下水动力条件,研究煤矸石堆放与环境污染之间的联系. 根据地形地貌、地下水流向和风向,在演马矿煤矸石堆周围布置土壤、地下水和植物采样点,检测分析pH和重金属(如Pb,Mn,Zn,Cu,Cr和Cd)含量及分布规律. 结果表明:煤矸石堆放是造成周围环境污染的重要因素,煤矸石释放的重金属大部分被土壤所吸附,所检测的6种重金属在土壤中均被检出,其中部分点位的Zn和Cd含量已经超过土壤环境质量标准(GB15618-1995)中的二级标准;土壤中重金属可以进一步向地下水和植物传递,地下水中Mn含量与煤矸石堆的距离呈负相关,植物叶中Pb的含量最高,叶和茎中重金属含量表现出与煤矸石堆的相关性;矿坑排水、锅炉房飘尘也是造成周围环境重金属污染的重要来源.      

F-对Al在土壤中吸附-解吸行为的影响

研究了F-对Al在土壤中吸附-解吸行为的影响.结果表明,F-可以通过两种方式来影响土壤对Al的吸附.加入的F-与Al形成F-Al络合物后将减少土壤对铝的吸附量;土壤吸附F-时释放的OH-则将提高土壤对铝的吸附量,一定程度上抑制了前一种方式的影响,但F-将降低土壤对Al的吸附量这一规律没有改变.由于土壤对Al有很强的亲合力,能被1.0M KCl解吸下来的铝数量很小,F-对铝的解吸行为没有产生明显的影响.     

酸热活化、有机化、柱撑改性海泡石对土壤中钒的吸附固定

采用酸热活化、巯基有机化、羟基铁铝柱撑3种方法对天然海泡石进行改性,研究不同改性方法对海泡石结构及比表面积的影响,并将其作为吸附剂加入土壤,采用批量吸附试验考察吸附剂添加量、吸附时间、初始钒V（Ⅴ）离子浓度等因素对吸附效果的影响,探究添加改性海泡石的土壤对V（Ⅴ）的吸附效果及机理。研究结果表明:改性后海泡石比表面积增大,部分结构发生改变,吸附能力增强;添加羟基铁铝柱撑、酸热活化、巯基有机化改性海泡石的土壤对V（Ⅴ）的最大吸附量分别为2159.71,1619.57,936.57 mg/kg;吸附方式为单分子层物理吸附;解吸试验表明,添加羟基有机化改性海泡石的土壤解吸率最高,酸热活化和羟基铁铝柱撑海泡石次之。添加柱撑及酸热活化海泡石的土壤对V的吸附效果较好,用量5%时对V（Ⅴ）的固化率分别为30.24%、22.67%,但柱撑海泡石的稳定性仍有待提升。     

煤矸石矿井填充过程中微生物作用后发酵液对地下水的影响

煤矸石是排放量最大的工业固废之一,堆积在地面会对环境造成严重影响.对煤矸石矿井填充过程中微生物作用后发酵液对地下水的影响进行研究,对煤矸石井下填充的可行性和安全性具有十分重要的意义.文章以义马跃进矿的长焰煤、煤矸石、矿井水为研究对象,在添加接种物的情况下,以硫酸根、硝酸盐氮、氨氮、硫离子和pH值为研究指标,对发酵液进行测定,结果表明:(1)硫酸盐和产甲烷菌在一定条件下可以共存;(2)整个系统的pH值呈弱碱性;(3)浸泡时间的长短使各指标之间有明显差异,是影响地下水的重要因素.在此基础之上,应继续研究利用煤矸石进行矿井填充的可行性和安全性.     

季铵化改性稻草吸附去除水中SO42-的特性研究

采用NaOH、环氧氯丙烷和三甲胺改性稻草秸秆,制备出含季铵基的吸附剂,用以去除水中的硫酸根离子(SO2-4).通过SEM、元素分析、13C-NMR表征发现,稻草改性后表面纤维结构暴露,含氮量增加,引入了大量的季铵基,吸附潜力显著提高.吸附实验结果表明,改性稻草吸附去除SO42-平衡时间约20min,pH为3～8范围内吸附效果较好.采用Langmuir吸附模型可较好地描述改性稻草对SO2-4的吸附等温线,其最大单分子层吸附量Qmax为74.76mg·g-1,吸附能力远大于原稻草(11.68mg·g-1).     

改性凹凸棒土对土壤中Cd2+吸附解吸及钝化效果影响

以凹凸棒土为原材料进行了热改性、酸改性、壳聚糖负载改性,并采用SEM、FT-IR、XRD表征其结构变化。通过改性凹凸棒土对土壤Cd~(2+)吸附解吸及土柱淋溶实验表明:凹凸棒土及改性凹凸棒土均能有效提高土壤对Cd~(2+)的吸附容量,减少Cd~(2+)的纵向迁移,降低淋溶风险。改性凹凸棒土主要是通过降低土壤中Cd的交换态和碳酸结合态含量增加土壤中Cd的铁锰氧化结合态及有机态含量,达到钝化土壤中Cd效果,综合处理效果优劣顺序为热改性凹凸棒土>酸改性凹凸棒>凹凸棒土>壳聚糖改性凹凸棒土>空白。     

锑矿冶炼区周边土壤吸附Sb (V)的行为研究

本文通过吸附平衡和动力学实验方法对Sb（V）在锑矿冶炼区周边土壤表面开展吸附行为研究,用常用的等温吸附模型和动力学吸附模型分别对等温吸附曲线和动力学吸附曲线进行拟合。结果表明：Langmuir与Freundlich模型对荒地土和林地土吸附Sb（Ⅴ）的等温吸附曲线均有较好的拟合效果,拟合系数R²0.988。荒地土对Sb（Ⅴ）的吸附能力大于林地土,其吸附量是林地土的2.9±0.2倍,这与Langmuir模型预测的该两种土壤的吸附倍数相当,荒地土表现出强烈吸附Sb（Ⅴ）的能力,尤其在锑浓度较高的体系中更为明显。结合土壤基本理化性质及矿物学特征,认为土壤秥粒、铁矿物和碳酸钙是影响土壤吸附Sb（V）的主要因素。有机质对土壤吸附Sb（Ⅴ）有一定促进作用,但这种影响只表现在Sb（Ⅴ）初始浓度低的条件下;而在Sb（Ⅴ）初始浓度高的条件下,有机质对土壤吸附Sb（Ⅴ）的影响不明显。土壤吸附Sb（Ⅴ）的过程分为快速吸附和慢速吸附两个阶段,快速反应发生在70 min以内。初始浓度低（0.01 mmol/L）的条件下,Elovich方程能够很好地拟合荒地土和林地土吸附Sb（V）的动态曲线;初始浓度高（2 mmol/L）的条件下,双常数方程对荒地土吸附Sb（V）的拟合效果较好,拟一级动力学方程和拟二级动力学方程则适用于拟合林地土吸附Sb（V）的过程。     

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.     

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.