Co-contamination of water with chlorinated hydrocarbons and heavy metals: challenges and current bioremediation strategies

Chlorinated hydrocarbons can cause serious environmental and human health problems as a result of their bioaccumulation, persistence and toxicity. Improper disposal practices or accidental spills of these compounds have made them common contaminants of soil and groundwater. Bioremediation is a promising technology for remediation of sites contaminated with chlorinated hydrocarbons. However, sites co-contaminated with heavy metal pollutants can be a problem since heavy metals can adversely affect potentially important biodegradation processes of the microorganisms. These effects include extended acclimation periods, reduced biodegradation rates, and failure of target compound biodegradation. Remediation of sites co-contaminated with chlorinated organic compounds and toxic metals is challenging, as the two components often must be treated differently. Recent approaches to increasing biodegradation of organic compounds in the presence of heavy metals include the use of dual bioaugmentation; involving the utilization of heavy metal-resistant bacteria in conjunction with an organic-degrading bacterium. The use of zero-valent irons as a novel reductant, cyclodextrin as a complexing agent, renewable agricultural biosorbents as adsorbents, biosurfactants that act as chelators of the co-contaminants and phytoremediation approaches that utilize plants for the remediation of organic and inorganic compounds have also been reported. This review provides an overview of the problems associated with co-contamination of sites with chlorinated organics and heavy metals, the current strategies being employed to remediate such sites and the challenges involved.     

发扬地学学科优势,形成具有国土资源部门特色的土壤修复理论与技术体系

岩石圈是土壤重金属元素的根本来源,是其迁移转化和生物-地球化学循环的场所,也是重金属元素的最后归宿,因此地质学、岩石学、矿物学和地球化学在重金属污染土壤修复中具有基础性的重要指导意义。国土资源部门已经在土壤重金属调查、溯源和风险评价上发挥了重要作用,还可以在探索研究灾害链的组成、影响因素和阻断途径的基础上,形成有地学特色的修复理论和技术。目前,国土资源部门的修复理论研究成果主要集中在缓变型地球化学灾害理论和地球化学工程学方面,在所属研究机构已经形成了若干种土壤修复剂,通过小试、中试和典型示范,验证了这些修复剂具有优异的修复性能与效果,是落实"土十条"和生态文明建设的一支重要力量。     

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。     

土壤修复过程中重金属形态的研究综述

重金属污染土壤的修复是现阶段污染土壤治理中的难点之一,在土壤修复过程中对重金属的形态研究已在多个领域中开展,并且在重金属形态及其与生物有效性和毒性等研究领域取得了一定的成果。本文综述了现阶段在污染土壤修复过程中对重金属形态研究的主要领域,分析研究重金属形态的必要性,总结出土壤修复过程中重金属形态方面应当从重金属在土壤与植物中的存在形态入手,研究重金属元素在不同界面间的迁移转化规律,通过阻断重金属元素在污染源、土壤、生物之间的传递链条,以阻止重金属对生物体造成危害,从而为土壤重金属污染的治理修复提供理论基础。     

对重金属和辐射污染的土壤和地下水的微生物修复

由重金属和辐射产生的环境污染在世界范围内产生了一系列问题.利用特殊的微生物如金属还原和耐金属细菌对环境中的金属和辐射污染进行处理具有非常好的前景.现场的生物修复的成功应用将对清除污染环境中的重金属和辐射提供潜在方法.最近的研究还关注于了解在微生物群体内重金属和辐射对微生物的作用.生物毯和生物膜是在生物修复中具有代表性的两种微生物群落的机能.金属的种类和价态变化、转移过程以及微生物代谢作用是对金属和辐射生物修复的三种重要的组成部分.结合以上三方面,可以更好的了解自然中的微生物和生物修复过程之间的关系.     

Technical Challenges to In-situ Remediation of Polluted Sites

Throughout the world, subsurface contamination has become a widespread and pervasive problem. Toxic chemicals such as heavy metals and organic compounds are commonly used in a myriad of industries. However, largely through inadvertent or accidental release, these chemicals are presently polluting sites across the United States. In order to protect public health and the environment, further pollution must be prevented and sites with existing contamination urgently need remediation. Unfortunately, remediating subsurface contamination has proved to be a daunting task. Heavy metals and organic compounds often coexist and their distribution within the subsurface is highly dependent on particle and macro-scale heterogeneities. Vast resources have been invested to develop efficient remediation technologies, yet very few of these technologies have been successful. In-situ remediation is often preferred due to minimal site disturbance, safety, simplicity, and cost-effectiveness. The effectiveness of in-situ remediation technologies depends largely on the contaminant chemistry and subsurface heterogeneities (including particle-scale heterogeneities such as fine-grained soils, soils with reactive minerals, and/or soils rich in organic matter as well as macro-scale heterogeneities such as irregular soil layers and/or lenses). Under such heterogeneous conditions, integrated electrokinetic remediation technology has great potential. As a safe and economical remedial option for so many contaminated sites, the application of integrated electrokinetic remediation offers enormous public health, environmental, and financial benefits.     

纳米材料在土壤重金属污染修复中的应用

重金属污染土壤的修复一直是国内外环境研究者关注的重点环境问题之一.近年来,纳米材料在土壤重金属污染修复中的应用也受到了越来越多的关注.综述了主要纳米材料及其改性材料修复土壤重金属的应用、纳米材料的组合技术应用以及影响纳米材料修复土壤重金属效果的主要因素,提出了今后该领域应重点加强研发新的纳米材料,同时提高其在土壤中的扩散能力,研究从室内实验到田间实验的应用;进一步深入探讨了纳米材料在土壤中的环境行为及相关机理等,以期充分理解并进一步推动纳米材料在土壤重金属污染修复中的应用.      

污染土壤植物修复中螯合诱导和转基因技术的应用现状与前景

近年来,螯合诱导技术和转基因技术作为强化植物吸收重金属的两种技术备受关注。文中系统地介绍了植物对重金属的解毒机理、植物的基因改良以及螯合诱导技术和转基因技术在提高植物修复能力中的应用等有关内容,最后探讨了螯合诱导技术和转基因技术的发展方向,认为这两项技术不失为大有潜力的土壤重金属污染修复技术,具有着广阔的应用前景。     

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).     

生物炭修复重金属污染土研究进展

随着城市化进程的加快及工业生产的迅速发展,土壤重金属污染日益加剧,对生态环境造成严重的危害。生物炭是缺氧或限氧条件下加热生物质制得的高度芳香化富含碳的固态物质,其在重金属污染土修复方面具有显著效果,受到广泛关注。基于近些年来国内外围绕生物炭修复重金属污染土所取得的研究成果,分别从生物炭的制备及性质、修复效果及其影响因素、修复机理等方面总结了该领域的研究现状及进展,取得如下主要认识:（1）生物炭具有价格低廉,修复效率高,改良土壤、环境友好等优势;（2）生物炭的理化性质主要受原材料和热解温度的影响,采用活化、磁化、氧化和消化等方法能改善生物炭的性质,提高修复效率;（3）生物炭对土壤中重金属迁移性和生物有效性的影响包括两个方面:固定重金属减少生物有效性或者迁移重金属增加生物有效性,后者可通过改性方法来降低重金属的迁移性和生物有效性;（4）生物炭对土体的固化效果一般,但可与其他固化材料共同使用,以改善土体的力学性质;（5）生物炭修复机理固定重金属的效果为:沉淀作用>络合作用>静电作用,离子交换>物理吸附。最后,针对该领域的研究现状,提出了未来的研究重点和方向,主要包括:建立划分生物炭的统一标准;探讨生物炭对多种重金属共同污染的修复效率;阐明生物炭吸附重金属的机理及其贡献率;扩大研究尺度;开展基于生物炭的固化试验及力学性质研究。     

Surfactant-enhanced remediation of contaminated soil: a review

Extracting aqueous solutions with or without additives are employed to solubilize contaminants in soil. Since water solubility is the controlling removing mechanism, additives are used to enhance efficiencies. These additives can reduce the time to treat a site compared to the use of water alone. Additives must be of low toxicity and biodegradable. The research in this area has focussed mainly on halogenated volatile organic compounds (VOCs) and is still quite limited for metal removal. Additives include surfactants, organic and inorganic acids, sodium hydroxide, which can dissolve organic soil matter, water-soluble solvents such as methanol, displacement of cations with nontoxic ones, complexing agents such as EDTA, acids in combination with complexing agents or oxidizing/reducing agents. Cationic, anionic and nonionic surfactants are particularly used for soil washing or flushing. They contain both hydrophobic and hydrophilic portions, making them ideal for solubilization of hydrophobic compounds. Numerous studies have indicated that surfactants enhance recoveries of non-aqueous phase liquids (NAPLs). There have also been indications that pretreatment of soil with surfactant washing to solubilize hydrophobic compounds such as PAHs enhances biodegradation of these contaminants. A few in situ field studies have been performed with surfactants. Large-scale treatment has been done mostly for organic removal. Soil pH, soil type, cation exchange capacity (CEC), particle size, permeabilities and contaminants all affect removal efficiencies. High clay and organic matter contents are particularly detrimental. Understanding the chemistry of the binding of the contaminant and the hydrogeology of the site are very important. Once the water is pumped from the soil, it must be extracted and then treated to remove the hydrocarbons and metals. Several technologies exist such as sodium hydroxide or sodium sulfide precipitation, ion exchange, activated carbon adsorption, ultrafiltration, reverse osmosis, electrodialysis and biological processes. Recycling of the surfactants is desired to decrease treatment costs.

This paper will provide an overview of the laboratory research, field demonstration and full-scale application of surfactants for the remediation of contaminated soil. The majority of pilot scale in situ flushing tests, particularly in the United States, have involved the use of surfactants and co-solvents. There are only a few full-scale projects however. Recent laboratory scale efforts by the authors concerning the use of biosurfactants, biologically produced surfactants, to enhance the removal of copper, cadmium and zinc from contaminated soils and sediments are discussed. Three types of biosurfactants were evaluated for their effectiveness. They included a lipopeptide called surfactin from Bacillus subtilis, a rhamnolipid from Pseudomonas aeruginosa and a sophorolipid from Torulopsis bombicola. The results indicated the feasibility of removing the metals with the anionic biosurfactants even though the exchangeable fractions were not significant.     

南方某工业区大气总悬浮颗粒物重金属来源解析及其对土壤环境质量的影响

解析大气总悬浮颗粒物(TSP)的重金属来源可为重金属生态风险评价和环境修复提供理论依据。本文研究了中国南方某工业城市冶炼厂周边冬季TSP和表层土壤(0~20 cm)中的重金属环境效应。采用大气主动采样技术收集TSP样品,原子荧光光谱法和电感耦合等离子体质谱法测定其中重金属的含量,结合富集因子法和Pearson系数法分析重金属含量特征及其来源。结果表明,研究区TSP中Zn、Pb、Cd含量最高达到30809.06×10-6、9902.91×10-6、1011.21×10-6,分别是中国土壤背景值的201.43、222.53、5616.20倍,属于污染严重级别;Ni、Cr含量分别是中国土壤背景值的1.83倍和2.96倍。冶炼厂、火力发电厂和化工厂等人为源是Zn、Pb、Cd、Hg、As等重金属富集的主导因素;土壤重金属含量与TSP重金属含量呈显著正相关,可判定研究区土壤的重金属来源主要为大气沉降。     

环境矿物材料治理镉（Cd^2＋）污染研究进展

近年来,环境矿物材料以其经济、有效、无二次污染等特点,在重金属废水处理和土壤修复方面显示出了众多优势,可替代传统的镉污染处理方法。本文综述了国内外环境矿物材料在处理镉污染方面的研究进展,并对今后应用环境矿物材料治理镉污染提出了一些建议。     

被污染土壤的植物修复研究

植物修复是利用植物吸收、降解、挥发、根滤、稳定、泵吸等作用机理,达到去除土壤、水体中污染物,或使污染物固定以减轻其危害性,或使污染物转化为毒性较低化学形态的现场治理技术.植物修复对于重金属污染土壤的治理修复具有重要意义.已有研究在累积与超累积植物的寻找筛选、植物对重金属等有害物的耐毒和解毒机理、植物修复现场环境调控及根际处理技术等方面取得了大量成果.现代分子生物学、基因工程技术发展有可能使植物修复技术取得重大突破.     

Biotechnological advances in bioremediation of heavy metals contaminated ecosystems: an overview with special reference to phytoremediation

The ability of heavy metals bioaccumulation to cause toxicity in biological systems—human, animals, microorganisms and plants—is an important issue for environmental health and safety. Recent biotechnological approaches for bioremediation include biomineralization (mineral synthesis by living organisms or biomaterials), biosorption (dead microbial and renewable agricultural biomass), phytostabilization (immobilization in plant roots), hyperaccumulation (exceptional metal concentration in plant shoots), dendroremediation (growing trees in polluted soils), biostimulation (stimulating living microbial population), rhizoremediation (plant and microbe), mycoremediation (stimulating living fungi/mycelial ultrafiltration), cyanoremediation (stimulating algal mass for remediation) and genoremediation (stimulating gene for remediation process). The adequate restoration of the environment requires cooperation, integration and assimilation of such biotechnological advances along with traditional and ethical wisdom to unravel the mystery of nature in the emerging field of bioremediation. This review highlights better understanding of the problems associated with the toxicity of heavy metals to the contaminated ecosystems and their viable, sustainable and eco-friendly bioremediation technologies, especially the mechanisms of phytoremediation of heavy metals along with some case studies in India and abroad. However, the challenges (biosafety assessment and genetic pollution) involved in adopting the new initiatives for cleaning-up the heavy metals-contaminated ecosystems from both ecological and greener point of view must not be ignored.     

土壤-水稻系统中重金属元素与其他元素之间的相互作用

通过相关关系的统计分析,探讨了四川省61件水稻籽实及其根系土中重金属元素与其他元素间的相互关系。研究结果表明:①水稻籽实对重金属元素、微量元素、大量元素的富集系数差异很大,元素富集系数之间具有显著的相关性;②水稻籽实中重金属元素的含量与土壤中部分元素的含量之间存在着显著的相关关系;③水稻籽实重金属元素的含量与籽实中其他元素含量之间的相关关系显著。结合元素之间的相互作用对元素地球化学行为的影响,评价了作物籽实中重金属元素的危害程度,为土壤修复提供了新思路。     

微生物诱导碳酸盐岩沉淀过程及作用机理

微生物诱导碳酸钙沉淀(microbially induced calcium carbonate precipitation, MICP)是一种在自然界中广泛存在的生物矿化过程。由于MICP具有反应速度快、环境条件要求低、应用范围广、温室气体减排效应显著等特点,在地质、土木、水利、环境多个领域中广泛推广应用。文章在分析国内外相关研究成果的基础上,归纳整理出反硝化过程、硫酸盐还原作用、尿素分解作用等多种微生物诱导下碳酸钙矿化途径和作用机制。以尿素分解菌为代表,重点讨论微生物诱导碳酸盐沉淀过程中pH、温度、离子浓度等环境因素对生成矿物晶型晶貌等方面的影响,总结了MICP的环境应用机制,即环境中的重金属元素通过替换作用替换矿化矿物中的Ca2+或CO₃2?从而被固定。MICP作为一种简单高效的地质环境过程,在生态环境修复领域具有广阔的应用前景。      

地浸采铀矿山地下水环境修复研究进展

地浸采铀技术已成为世界采铀的主流工艺,采区退役后地下水环境修复亦为人们所关注的热点。文章简要介绍了碱法、中性和酸法三种典型地浸采铀技术的特点,系统分析了地浸采铀对地下水环境的影响,并以酸法地浸铀矿山地下水环境修复技术为例,重点介绍了物理化学修复技术和生物修复技术及其原理与应用,归纳总结了其优缺点,并对未来的研究方向进行了展望。指出下一步应加强在酸性与氧化环境中能使铀固定并长期稳定的新技术,高活性、强适应性修复菌群的选育、驯化技术,地下水异位-原位协同生物修复技术,以及放射性核素及重金属在铀矿地浸地下水环境中的吸附-解吸、氧化-还原、溶解-沉淀等行为与机理及其主控因素等方面的研究。     

Vermiculite bio-barriers for Cu and Zn remediation: an eco-friendly approach for freshwater and sediments protection

The increase in heavy metal contamination in freshwater systems causes serious environmental problems in most industrialized countries, and the effort to find eco-friendly techniques for reducing water and sediment contamination is fundamental for environmental protection. Permeable barriers made of natural clays can be used as low-cost and eco-friendly materials for adsorbing heavy metals from water solution and thus reducing the sediment contamination. This study discusses the application of permeable barriers made of vermiculite clay for heavy metals remediation at the interface between water and sediments and investigates the possibility to increase their efficiency by loading the vermiculite surface with a microbial biofilm of Pseudomonas putida, which is well known to be a heavy metal accumulator. Some batch assays were performed to verify the uptake capacity of two systems and their adsorption kinetics, and the results indicated that the vermiculite bio-barrier system had a higher removal capacity than the vermiculite barrier (+34.4 and 22.8 % for Cu and Zn, respectively). Moreover, the presence of P. putida biofilm strongly contributed to fasten the kinetics of metals adsorption onto vermiculite sheets. In open-system conditions, the presence of a vermiculite barrier at the interface between water and sediment could reduce the sediment contamination up to 20 and 23 % for Cu and Zn, respectively, highlighting the efficiency of these eco-friendly materials for environmental applications. Nevertheless, the contribution of microbial biofilm in open-system setup should be optimized, and some important considerations about biofilm attachment in a continuous-flow system have been discussed.     

Biogeochemistry of landfill leachate plumes

The literature has been critically reviewed in order to assess the attenuation processes governing contaminants in leachate affected aquifers. Attenuation here refers to dilution, sorption, ion exchange, precipitation, redox reactions and degradation processes. With respect to contaminants, focus is on dissolved organic matter, xenobiotic organic compounds, inorganic macrocomponents as anions and cations, and heavy metals. Laboratory as well as field investigations are included. This review is an up-date of an earlier comprehensive review. The review shows that most leachate contamination plumes are relatively narrow and do not in terms of width exceed the width of the landfill. The concept of redox zones being present in the plume has been confirmed by the reported composition of the leachate contaminated groundwater at several landfills and constitutes an important framework for understanding the behavior of the contaminants in the plume as the leachate migrates away from the landfill. Diverse microbial communities have been identified in leachate plumes and are believed to be responsible for the redox processes. Dissolved organic C in the leachate, although it appears to be only slowly degradable when the volatile organic acids are gone, apparently acts as substrate for the microbial redox processes. Several xenobiotic organic compounds have been found to be degradable in leachate contaminated groundwater, but degradation rates under anaerobic redox conditions have only been determined in a few cases. Apparently, observations in actual plumes indicate more extensive degradation than has been documented in the laboratory. The behavior of cations in leachate plumes is strongly influenced by exchange with the sediment, although the sediment often is very coarse and sandy. Ammonium seems to be subject to anaerobic oxidation, but the mechanisms are not yet understood. Heavy metals do not seem to constitute a significant pollution problem at landfills, partly because the heavy metal concentrations in the leachate often are low, and partly because of strong attenuation by sorption and precipitation. Although complexation of heavy metals with dissolved organic matter is significant, the heavy metals are in most cases still strongly attenuated in leachate-polluted aquifers. The information available on attenuation processes has increased dramatically during the last 15 a, but the number of well-documented full scale leachate plumes are still few and primarily from sandy aquifers. Thus, the diversity of attenuation processes in leachate plumes is probably not yet fully understood. Apparently, the attenuation processes in leachate plumes may for many contaminants provide significant natural remediation, limiting the effects of the leachate on the groundwater to an area usually not exceeding 1000 m from the landfill.