天然有机质对纳米零价铁去除水中六价铬的影响

应用纳米零价铁进行地下水污染治理是近年迅速发展的环境修复新技术,但在实际应用中,纳米零价铁的反应活性受到环境条件的影响,其中自然界中广泛存在的天然有机质就是重要影响因素。通过批实验研究腐殖酸(天然有机质代表物)对纳米零价铁去除水中六价铬的影响,结果表明,腐殖酸的存在能够极大地抑制纳米铁去除六价铬的反应速度和去除效率,原因在于纳米铁对腐殖酸具有一定的吸附作用,从而减少了纳米铁表面的有效活性位点,降低了对六价铬的作用。此外发现,水体中溶解氧的存在有利于纳米铁对六价铬的去除。关于腐殖酸-纳米零价铁-六价铬的相互作用研究,对于进一步揭示修复体系作用机制具有重要的理论和应用价值。     

Dechlorination of perchloroethylene using zero-valent metal and microbial community

This research evaluates an integrated technique for the degradation of perchloroethylene (PCE) using a combination of zero-valent metal and an anaerobic microbial community. The microbial community was obtained from river sediment through a series of cultivation and enrichment processes, and was able to successfully convert PCE to ethylene. The degradation tests were carried out in five groups of reactors, i.e. Zn (zero-valent zinc), Fe (zero-valent iron), MB (a microbial community), ZnMB (zinc and a microbial community) and FeMB (iron and a microbial community). The results suggested that the FeMB system had the highest efficiency in removing PCE (about 99.9% after 24 days), followed by Zn (98.5%), ZnMB (84.8%), Fe (76.9%) and MB (49.6%). The degradation kinetics of PCE could be described by a pseudo-first-order reaction; the apparent reaction rate constants were 0.231, 0.187, 0.135, 0.076, 0.031 days⁻¹ for the Zn, FeMB, ZnMB, Fe, and MB systems, respectively. Much more Cl⁻ was detected as a by-product in the degradation tests using FeMB or ZnMB than using Fe or Zn. The results implied that not only PCE, but also the reaction intermediates, e.g., trichloroethylene (TCE) and dichloroethylenes (DCE isomers) may have been dechlorinated in the FeMB and ZnMB systems. Results suggest that the presence of the microbial community in the FeMB and ZnMB systems may not only affect the removal efficiency of PCE, but can also change the reaction pathways in the dechlorination process. The integrated technique combining the iron and the microbial community showed better degradation efficiency than the others; it may be viewed as an environmentally desirable remediation.     

Effect of metal content on chlorophyll fluorescence and chlorophyll degradation in lichen Pyxine cocoes (Sw.) Nyl.: a case study from Uttar Pradesh,India

The major aim of the present study is to identify the relationship of physiological parameters of the photosynthetic system with the elemental content of the naturally growing lichen Pyxine cocoes. The epiphytic foliose lichen P. cocoes was used as biomonitoring indicator and effect of atmospheric pollutants on physiological integrity was examined. Potential quantum yield of Photosystem II (fluorescence ratio Fv/Fm), chlorophyll degradation ratio and quantitative estimation of Al, As, Cd, Cr, Cu, Pb, Fe and Zn contained in the lichen thallus were ascertained. Statistical analysis revealed significantly positive correlations between Fv/Fm and element contents (Al and Cr). The chlorophyll degradation as well as alteration in the pigment content was found to be the most sensitive parameters to assess the vitality of lichen thallus against polluted environment. The species accumulated higher amounts of elements (Al, As, Cu, Fe and Zn) in the polluted sites as compared to the non polluted sites. It was also evident from this study that vehicular emission played a significant role in the release of elements as pollutants in the surrounding environment. The effectiveness of this lichen could be further investigated by comparing this species with other biomonitors.     

纳米铁还原高浓度硝基苯的实验

采用液相还原法制备纳米铁粒子,粒径约为50 nm,主要成分为ɑ-Fe。实验研究了纳米铁还原高浓度硝基苯的效果及反应动力学。结果表明:自制的纳米铁具有很高的活性,短时间内能将高浓度硝基苯彻底还原,效果远优于普通铁粉。当摩尔比满足n纳米铁∶n硝基苯=4∶1时,纳米铁还原硝基苯属于一级反应动力学,反应速率常数和半衰期分别为0.159 3 h-1和4.351 2 h。整个实验过程中,ρ(DO)在0.5 mg/L以下,pH值约为9.0,体系呈弱碱性的厌氧环境,有利于厌氧微生物的生长。纳米铁反应后的产物为Fe6(OH)12CO3和MgFe3O4,且以Fe6(OH)12CO3为主。纳米铁反应后较以前比粒径变化不大,分散性较好,但表面被严重腐蚀。     

地下水污染场地污染的控制与修复

我国存在大量的地下水污染场地,给地下水资源的使用带来了严重威胁。将地下水污染场地划分为4大类,15个亚类,为制定不同地下水污染场地的管理、控制和修复规定提供了依据;对地下水污染防治规划的内容和方法技术进行了论述。提出了建立地下水污染的预警系统,为污染的预防奠定基础;介绍了地下水污染的控制与修复技术,并对地下水污染防控和治理的基本原则进行了探讨。     

Impact of land use types on the concentrations of metals in soils of urban environment in Nigeria

The concentrations of metals (Cd, Pb, Ni, Cr, Cu, Fe, Mn and Zn) were determined in soils under different land use types in an urban environment in order to study the impact of land uses on the concentrations of metals in the soils. The mean concentration range of metals for all land use types were 42.1 to 410, 11.2 to 118.2, 4388.2 to 31891.1, 9.7 to 65.4, 0.1 to 1.8, 4.7 to 35.2, 2.0 to 16.8 and 77.9 to 881.7 mg/kg, for Mn, Pb, Fe, Cu, Cd, Cr, Ni and Zn, respectively. The computed multiple pollution index (MPI) indicated that 67 % of the examined sites had MPI values between 1 and 20 i.e. at the pollution range, while 33 % of sites had MPI values of zero which indicated that these sites were not polluted with the studied metals. Zinc had the highest impact on the multiple pollution index values. Three main principal components were identified from the principal component analysis which include (i) Cu, Zn, Pb, Cr and Ni originating from both industrial and agricultural sources, and as well as automobile exhausts; (ii) Fe and Mn which originated from both natural and anthropogenic sources; (iii) Cd which its anthropogenic origin is different from components I and II. This study provided information on the sources of metals in the urban environment and extent of contamination associated with each land use, which are useful in the ranking of contaminated sites, environmental quality management, environmental forensic studies and guidance for remediation/redevelopment of contaminated land.     

电化学循环井驱动模拟含水层化学氧化降解三氯乙烯

传统原位化学氧化地下水修复技术存在氧化剂迁移距离短和利用率低等问题。本研究在双井循环模式促进传质的基础上,通过注水井中的地下水电解原位提供O₂和H₂,配合乙二胺四乙酸(ethylenediamine tetraacetic acid,EDTA)络合溶解出含水层Fe(Ⅱ),活化O₂产生羟基自由基(•OH),实现地下水三氯乙烯(TCE)的氧化降解。在填充了砂土和黏土互层的二维砂槽中,设置电流为0.2 A、流速为72 cm/d、初始TCE浓度为3 mg/L,经过9 d的连续通电处理后,TCE浓度降低到1 mg/L,降解率达到67%。通电前投加0.5 mmol/L EDTA,经过1 d水流循环后含水层中溶解态Fe(Ⅱ)浓度从02 mg/L增加到414 mg/L,黏土区域较高。通电过程中,循环井促进O₂、Fe(Ⅱ)-EDTA和TCE的有效接触与反应,使TCE氧化降解。通电初期,黏土区域Fe(Ⅱ)氧化速率、TCE降解速率较周围慢,后期差异逐渐减小。未通电时加入醋酸钠可促进Fe(Ⅲ)还原,使含水层中铁循环利用。该修复过程通过循环井提升了氧化剂迁移距离,使用源于含水层的Fe(Ⅱ)-EDTA和稳定性较好的O₂提高了氧化剂利用率,有望应用于有机污染地下水修复。     

改性Mg(OH)2对多种重金属污染土壤的修复效果

为了研究一种高效的多种重金属污染土壤修复剂,本文采用了一种具有OH^-缓释功能的改性Mg（OH）₂,通过重金属污染土壤稳定化修复实验,探讨了改性Mg（OH）₂对污染土壤中多种重金属（Pb、Cd、Cu、Zn）的稳定效率及对多种重金属形态分布的影响。结果表明,投加改性Mg（OH）₂对土壤中多种重金属均有稳定作用,对Pb、Cd、Cu、Zn的稳定效率分别为72.42%、34.53%、87.64%和97.65%,且改性Mg（OH）₂的投加使重金属交换态质量明显减少、残渣态质量增加,进一步提高了重金属的稳定性,降低了重金属生物有效性;另外,改性Mg（OH）₂具有OH^-缓释性,可使土壤长期保持一定的碱性,是一种经济有效的土壤修复剂。     

Influence Factors on the In-situ Remediation of Halogenated Organic Compounds by Nanoscale Zerovalent Iron

The pollution of soil and groundwater by halogenated organic compounds (HOCs) is more and more severe. HOCs are of strong toxicity and difficult to be biodegraded. Due to its unique advantages, nanoscale zerovalent iron (NZVI) has become a hot research topic in the field of in situ remediation around the world. In this paper, basic reaction theories and kinetics of HOCs degradation by NZVI are briefly summarized. The influence factors on the in situ remediation of HOCs by NZVI are comprehensively discussed. The influence factors include the intrinsic properties of NZVI due to its different preparation and modification methods, and environment factors, such as pH, dissolved oxygen, ionic species, metals, nonreactive hydrophobic and natural organic compounds, concentrations and components of HOCs, microorganisms and subsurface heterogeneity. The effects of all these factors on NZVI stability, deliverability, targeting ability, and reactivity during in situ remediation are emphasized. Finally, the practical application of this technology are summarized and prospected.     

地下水硝酸盐污染与治理研究进展综述

地下水的硝酸盐污染是全球所面临的一个日益严重的问题,对硝酸盐污染的地下水修复技术的研究也自然成为近年来国内外学者研究的热点。就地下水硝酸盐污染的机理和途径、对人体及其它生物的危害以及修复技术等方面作了详细介绍,另外,就地下水硝酸盐污染的治理引用了工程实际加以说明。最后指出了未来地下水硝酸盐污染治理研究的方向。     

微生物修复石油污染地下水的实验研究

为修复陕北黄土区石油污染地下水,采用优化土著微生物菌群的生物技术,进行了地下水中石油的降解与修复实验研究。在实验装置内加入了1.5%的优化菌群制剂,优化出的菌群初步鉴定主要有:假单胞菌属、微球菌属、放线菌属、真菌类的青霉属和曲霉属等。实验结果显示,在实验装置中人为添加石油含量为182.5 mg/l、862.5 mg/l、1695.0 mg/l时,经过28~37 d的微生物修复,地下水中石油的降解率为27.47%~92.46%,而无菌对照中的石油含量变化在5%以内,说明在无菌条件下地下水中石油降解缓慢。该实验过程验证了微生物修复技术在地下水石油污染修复中的有效性,探索了应用的可行性。     

Chemical treatments for mobilizing arsenic from contaminated aquifer solids to accelerate remediation

Arsenic is a prevalent contaminant at US Superfund sites where remediation by pump and treat systems is often complicated by slow desorption of As from Fe and Al (hydr)oxides in aquifer solids. Chemical amendments that either compete with As for sorption sites or dissolve Fe and Al (hydr)oxides can increase As mobility and improve pump and treat remediation efficiency. The goal of this work was to determine optimal amendments for improving pump and treat at As contaminated sites such as the Vineland Chemical Co. Superfund site in southern New Jersey. Extraction and column experiments were performed using As contaminated aquifer solids (81 ± 1 mg/kg), site groundwater, and either phosphate (NaH₂PO₄·H₂O) or oxalic acid (C₂H₂O₄·2H₂O). In extraction experiments, phosphate mobilized between 11% and 94% of As from the aquifer solids depending on phosphate concentration and extraction time (1 mM–1 M; 1–24 h) and oxalic acid mobilized between 38% and 102% depending on oxalic acid concentration and extraction time (1–400 mM; 1–24 h). In column experiments, phosphate additions induced more As mobilization in the first few pore volumes but oxalic acid was more effective at mobilizing As overall and at lower amendment concentrations. At the end of the laboratory column experiments, 48% of As had been mobilized from the aquifer sediments with 100 mM phosphate and 88% had been mobilized with 10 mM oxalic acid compared with 5% with ambient groundwater alone. Furthermore, simple extrapolations based on pore volumes suggest that chemical treatments could lower the time necessary for clean up at the Vineland site from 600 a with ambient groundwater alone to potentially as little as 4 a with 10 mM oxalic acid.     

Risk characterization and surface water quality assessment of Manas River,Assam (India) with an emphasis on the TOPSIS method of multi-objective decision making

The present study centers on the investigation of surface water quality with the aid of quality indices and explores the application of a multi-objective decision-making method (TOPSIS) in arranging decisions for policy makers on the basis of overall ranking of the sampling locations. A case study has been performed on the Manas River, Assam (India). Water Quality Index (WQI) involving physico-chemical parameters, and heavy metal pollution index (HPI) and contamination index (CI) involving heavy metal influences were employed for water quality assessment. WQI graded two sampling locations “very poor” and all other locations “poor”. HPIs of all the locations were below the critical value of 100, but the CI depicted that two locations were “moderately contaminated”. Risk assessment to human health was done using hazard quotient and hazard index. Cluster analysis (CA) demonstrated site similarity by grouping the relatively more polluted and less polluted (LP) sites into two major clusters. However, there surfaced difficulty in discerning the overall water quality, as all the three quality indices included different parameters and contradicted each other. A multi-objective decision-making tool, TOPSIS was therefore employed for ranking the locations on the basis of their relative pollution levels. The novelty of the study reflects in the identification of the relatively more or relatively less polluted sites within the same cluster in CA by the application of TOPSIS. The study justifies the effectiveness of TOPSIS method in prioritizing decisions in complex scenarios for policy makers.     

Assessment of heavy metal pollution in the urban stream sediments and its tributaries

Globally, aquatic ecosystems are highly polluted with heavy metals arising from anthropogenic and terrigenous sources. The objective of this study was to investigate the pollution of stream sediments and possible sources of pollutants in Nakivubo Channel Kampala, Uganda. Stream sediments were collected and analysed for heavy metal concentration using flame atomic absorption spectrophotometer. The degree of pollution in Nakivubo channelized stream sediments for lead, cadmium, copper, zinc, manganese and iron was assessed using enrichment factor, geo-accumulation index and pollution load index. The results indicated that (1) the sediments have been polluted with lead, cadmium and zinc and have high anthropogenic influences; (2) the calculation of geo-accumulation index suggest that Nakivubo stream sediments have background concentration for copper, manganese and Fe (I _geo ≤ 0); (3) factor analysis results reveal three sources of pollutants as explained by three factors (75.0 %); (i) mixed origin or retention phenomena of industrial and vehicular emissions; (ii) terrigenous and (iii) dual origin of zinc (vehicular and industrial). In conclusion, the co-precipitation (inclusion, occlusion and adsorption) of lead, cadmium and zinc with manganese and iron hydroxides, scavenging ability of other metals, very low dissolved oxygen and slightly acidic to slightly alkaline pH in stream water could account for the active accumulation of heavy metals in Nakivubo stream sediments. These phenomena may pose a risk of secondary water pollution under sediment disturbance and/or changes in the geo-chemistry of sediments.     

负载型纳米Pd/Fe对挥发性氯代烃的去除

氯代烃的污染治理已成为当今世界最热门的研究领域之一。以水体中最常见的氯代烃污染物1,1-二氯乙烯（1,1-DCE）、林丹（γ-HCH）为主要目标污染物,探讨了不同条件下负载型纳米Pd/Fe对氯代烃的去除效果。负载型纳米Pd/Fe采用浸渍→液相还原→还原沉淀的方法制备,透射电镜显示采用该方法制备的负载型金属钯和铁的平均粒径均在纳米级范围内。负载型纳米Pd/Fe具有较高的表面反应活性,当负载型纳米Pd/Fe 用量为40 g/L、反应时间达2 h时,1.1-二氯乙烯和林丹的去除率分别达到85%和100%。脱氯率与Pd/Fe投加量、钯含量、初始pH值、反应温度等因素有关,与溶液的初始浓度关系不大。负载型纳米Pd/Fe对11-DCE和γ-HCH去除均符合一级反应动力学方程,速率常数分别为0-528 3 h^-1及2-012 9 h^-1,反应的半衰期t1/2分别为1.31 h和0.34 h。推断在反应过程中,Fe腐蚀产生的H2为主要还原剂,Pd是良好的加氢催化剂,在金属颗粒表面形成高浓度反应相,使反应短时间内完成。     

Mathematical model for hydraulically aided electrokinetic remediation of aquifer and removal of nonanionic copper

One of the most cost-effective in situ technologies for soil and groundwater (i.e., aquifer) remediation is electrokinetic remediation. In electrokinetic remediation, electromigration due to electric field is combined with hydromigration due to hydraulic flow by purge water to remove pollutants from aquifers through the pore water. This study aims at investigating theoretically the role of electromigration (as active movement) of pollutants and the role of hydromigration (as passive movement) of pollutants in electrokinetic remediation, and making it clear that the control variables for electrokinetic remediation are the applied voltage and the hydraulic flow rate. These aims are pursued by construction of a mathematical model based on physico-chemical considerations and by model simulations of the electrokinetic remediation applied to the virtual aquifer polluted by heavy metals of copper sulfate. According to numerical simulations with the model: (1) heavy metal (nonanionic copper) is removed from the upstream anode region and accumulated in the downstream cathode region; (2) to carry away the heavy metal outside the aquifer (global removal), hydromigration by purge water flow is essential; and (3) electromigration contributes mainly to the redistribution of heavy metals within the aquifer (local removal and local accumulation).     

Application of algae in biomonitoring and phytoextraction of heavy metals contamination in urban stream water

Biological technologies for wastewater remediation techniques employed to remove contaminants in urban stream water are increasingly receiving attention worldwide. The purpose of this study was therefore to determine the concentrations of lead, cadmium, copper, zinc, manganese and iron in algal biomass and establish the feasibility of using algae in phytoextraction and bio-monitoring of environmental quality. Analysis of algal biomass samples in the Nakivubo urban stream ecosystem, Kampala, Uganda, showed that there was contamination by lead, cadmium, copper and zinc as indicated by enrichment factor and pollution load index values. It is suspected that industrial and vehicular emissions are the major sources of these pollutants. Calculated bio-concentration factor was >- 1000 but with low concentration thresholds in each element, suggesting that algal biomass was a very good heavy metal accumulator. The bio-concentration values in algal biomass were found to be in the order of copper > zinc > lead > cadmium in the Nakivubo Channelized stream. In conclusion, algae can be a promising aquatic bio-filter plant for phytoextraction and bio-monitoring of polluted urban stream ecosystems and wastewater.     

中国地下水污染修复方法和技术应用展望

[研究目的]:中国地下水污染调查和修复日益受到科学界的重视,了解和掌握地下水污染修复方法和技术有助于对污染场地进行科学修复.[研究方法]:本文在系统分析国内外地下水污染修复案例的基础上,对中国地下水污染修复现场实施的技术方法进行总结.[研究结果]:结合中国区域经济发展特征和地下水污染调查评价成果认为,复杂的水文地质条件...     

利用扫描电镜技术研究纳米Ni-Fe颗粒对四氯化碳快速脱氯的机理

纳米铁具有高的比表面积和高反应活性,能快速将氯代烯烃还原成无毒氯离子、乙烯和乙烷,但对于氯代烷烃的脱氯仍能产生大量的氯代中间或最终产物,可以通过合成制得纳米双金属提高脱氯速率和减少氯代中间产物。本文利用扫描电镜测得实验室制备的纳米Ni-Fe(2%,质量分数)颗粒直径为20~60 nm,通过批实验方式对纳米Ni-Fe降解四氯化碳的反应动力学性质、产物、持久性能和反应机理进行了探讨。结果表明,纳米Ni-Fe体系主要最终产物为42%CH4和17%CH2Cl2。与铸铁屑和纳米铁相比,纳米Ni-Fe由于催化脱氯加氢,显著提高了氯代烃脱氯速率,同时降低了有毒氯代产物的产量,且Ni作为催化剂不会进入水体引起二次污染。纳米Ni-Fe颗粒在空气中具有很好的稳定性,虽然降解四氯化碳的最终产物CH4与纳米Pd-Fe相比少13%,但由于价格便宜,有望在工程上应用于氯代有机化合物水土污染治理。     

Degradation of phenol and trichlorophenol by heterogeneous photo-Fenton process using Granular Ferric Hydroxide<Superscript>®</Superscript>: comparison with homogeneous system

The decomposition of phenol and trichlorophenol (TCP) by using granular ferric hydroxide (GFH) as a photo-Fenton catalyst was investigated and compared with homogeneous photo-Fenton process. Experiments were conducted in a batch mode, duplicate for the degradation of phenol and TCP in the presence of solar light for both the processes. The effect of operating variables for heterogeneous photo-Fenton process like pH, peroxide concentration and GFH concentration on the degradation of the model compounds was optimized by univariate approach. The optimum conditions for the degradation of phenol and TCP were pH 3.0 ± 0.2, peroxide concentration 29.4 mM for phenol and 14.7 mM for TCP at GFH concentration of 0.5 g/500 mL. At optimum conditions, the mineralization efficiency of phenol and TCP by heterogeneous process was compared with homogeneous process. The mineralization efficiency for phenol and TCP was 96 and 86 %, respectively, for heterogeneous photo-Fenton process, while almost complete mineralization (~96 %) was observed for homogeneous process. In heterogeneous photo-Fenton process, longer reaction time was witnessed for complete mineralization of the compounds studied. Low molecular weight aliphatic acids like oxalic acid, acetic acid and inorganic chloride ion (in case of TCP) were observed during both the processes. In these processes, the reaction proceeds by hydroxyl radical (·OH) abstraction of the model compound studied. The mineralization of phenol and TCP obeys pseudo-first-order kinetics irrespective of the processes studied. The results indicate that GFH can be an effective heterogeneous photo-Fenton catalyst for the degradation of phenol and TCP.