土壤中总石油烃污染（TPH）的微生物降解与修复研究进展

微生物降解和修复是处理土壤中总石油烃(TPH)污染最简单、有效的方法之一.论文阐述了土壤TPH污染的产生、危害以及物理、化学、生物等修复方法的各自特点,其中重点介绍了微生物修复方法,论述了土壤中TPH在微生物表面的吸附、转运,在微生物体内的降解以及相关降解酶及基因;详细介绍了电子受体、温度、pH、营养元素等外界因素对微生物修复TPH污染的影响,在此基础上对土壤TPH污染的微生物修复现状和发展趋势进行了讨论.     

基于高通量测序技术的铬污染农田土壤菌群多样性及修复菌株的筛选

菌种资源筛选是铬污染土壤生物修复的基础.以铬污染农田土壤为研究对象,采用高通量测序方法分析土壤细菌多样性特征,并根据多样性分析结果,采用选择性培养基和培养方法快速筛选对铬具有适应性和去除能力的细菌,以寻找能在铬污染农田土壤原位修复中具有较大应用潜力的菌种资源.结果显示:受铬污染的土壤细菌群落丰富度和多样性均低于未受铬污染土壤.门水平上,铬污染土壤中放线菌门(Actinobacteria)细菌丰度显著高于未受铬污染的土壤,是两种生境丰度差异最大的门.属水平上,芽孢杆菌属(Bacillus)是铬污染土壤中丰度最高的优势属,显著高于未受铬污染的土壤.从铬污染土壤中共分离到6株能够耐受1 000μg/mL铬的细菌. 6株菌都具有一定的六价铬Cr(VI)去除能力,其中Cr1、Cr3和Cr8能在72 h内将500μg/mL铬培养基中的Cr(VI)全部去除,Cr8能在72 h内将1 000μg/mL铬培养基中的Cr(VI)去除61.2%. 16S rDNA测序结果表明,6株菌中有5株属于厚壁菌门芽孢杆菌属,1株属于放线菌门纤维微菌属(Cellulosimicrobium).结合菌体及菌落形态特征和序列分析结果,铬去除能力最高的Cr8菌可初步被确定为C. aquatile.本研究表明铬污染降低土壤中细菌多样性,根据高通量测序结果有选择性地快速筛选铬污染修复菌株具有可行性,Cr8菌是国内首次分离到的具有铬污染修复功能的纤维微菌属菌株.(图11表5参40)     

北固山芦苇湿地土壤对铜铬（Ⅵ）的吸附研究

北固山芦苇(Phragmites communis)湿地是长江中下游典型湿地类型之一,沿江工业化和城市化的快速发展使其面临严重的重金属污染威胁。然而,目前有关湿地重金属污染的吸附尤其竞争吸附的研究还少见报道。该文以北固山芦苇湿地为对象,采用平衡法对Cu2 、Cr(VI)在湿地土壤中的吸附行为进行了研究,旨在服务于湿地重金属污染的修复与生物学效应评价。研究结果表明:(1)湿地土壤吸附Cu2 、Cr(VI)的过程符合Langmuir等温模型;二者的表观最大吸附量(xm)分别为36.10g·kg-1和178.57g·kg-1(初始液质量浓度c0<500g·m-3),平均吸附率分别达到99.82%±0.35%和93.17%±1.14%。(2)无论单一吸附或竞争吸附体系,当c0(Cu2 )>250g·m-3时,平衡液Cu2 质量浓度快速升高。(3)c0相等的Cu2 、Cr(VI)竞争吸附体系中,平衡液中Cu2 质量浓度升高,Cr(VI)质量浓度下降;但xm的变化表现为Cu2 增加了2.7倍,Cr(VI)降低了2.4倍。(4)Cu2 、Cr(VI)的竞争吸附体系中,随Cr(VI)初始液质量浓度的变化(c0(Cu2 )恒定),Cr(VI)的xm下降至其单一吸附时的6%;而随Cu2 初始液质量浓度的变化(c0(Cr(VI))恒定),Cu2 的xm仅为其单一吸附时的1/3。     

微生物砷代谢机制的研究进展（Progress in Study of Mechanisms of Microbial Arsenic Transformation in Environment）

环境砷污染是一个全球性问题.研究砷的生物地球化学循环可以明确环境中砷的来源及其转化特征,为探索砷污染治理的方法提供参考.越来越多的研究表明,自然界中的微生物在砷的迁移转化过程中发挥了重要作用.根据微生物对砷的代谢机制不同将其分为:砷氧化微生物、砷还原微生物和砷甲基化微生物.砷氧化微生物可以将环境中的As(Ⅲ)氧化为毒性较弱并且容易被铁铝矿物吸附固定的As(Ⅴ),因此对降低环境中的砷毒性具有重要作用;微生物对砷的甲基化作用的产物通常为毒性较低的有机砷,因此也被认为是理想的修复环境砷污染的生物手段之一;然而在还原环境中,砷还原微生物却可以将游离态和结合态的As(Ⅴ)还原为毒性更强的As(Ⅲ),从而加重环境中的砷污染状况.由此可见,明确微生物的砷代谢机制及其对砷污染环境中砷迁移转化的影响,是实现生物修复砷污染环境的必要前提.论文总结了近年来国内外微生物砷代谢机制的研究进展,以期为深入研究微生物代谢砷的机理及其在砷污染治理中的应用提供参考.     

铬污染土壤的微生物修复

采用淋溶实验研究微生物对铬污染土壤中Cr(Ⅵ)的修复,研究培养基成分、培养基添加量及淋溶液pH值对修复效果的影响.结果表明,培养基淋溶能完全修复铬污染土壤中水溶性Cr(Ⅵ),浸出液中Cr(Ⅵ)浓度由初始的700.3mg·L-1降低至检出限以下.单独加入碳源作为培养基时,土壤中Cr(Ⅵ)不能得到完全修复,碳源与氮源结合作...     

重金属污染土壤的微生物生态效应及其修复研究进展

污染土壤微生物生物修复技术是一项非常有应用前景的环保新技术。本文综述了近年来重金属对土壤微生物生物量、种群及生化过程的影响以及微生物对重金属污染土壤的修复机理和修复研究进展,较全面的分析了重金属对土壤微生物的生态效应。     

北固山芦苇湿地土壤对铜铬(VI)的吸附研究

北固山芦苇(Phragmites communis)湿地是长江中下游典型湿地类型之一,沿江工业化和城市化的快速发展使其面临严重的重金属污染威胁.然而,目前有关湿地重金属污染的吸附尤其竞争吸附的研究还少见报道.该文以北固山芦苇湿地为对象,采用平衡法对Cu2+、Cr(VI)在湿地土壤中的吸附行为进行了研究,旨在服务于湿地重金属污染的修复与生物学效应评价.研究结果表明(1)湿地土壤吸附Cu2+、Cr(VI)的过程符合Langmuir等温模型;二者的表观最大吸附量(xm)分别为36.10 g·kg-1和178.57 g·kg-1(初始液质量浓度c0＜500 g·m-3),平均吸附率分别达到99.82%± 0.35%和93.17%±1.14%.(2)无论单一吸附或竞争吸附体系,当c0(Cu2+)＞250 g·m-3时,平衡液Cu2+质量浓度快速升高.(3)c0相等的Cu2+、Cr(VI) 竞争吸附体系中,平衡液中Cu2+质量浓度升高,Cr(VI)质量浓度下降;但xm的变化表现为Cu2+增加了2.7倍,Cr(VI)降低了2.4倍.(4)Cu2+、Cr(VI) 的竞争吸附体系中,随Cr(VI)初始液质量浓度的变化(c0(Cu2+)恒定),Cr(VI)的xm下降至其单一吸附时的6%;而随Cu2+初始液质量浓度的变化(c0(Cr(VI))恒定),Cu2+的xm仅为其单一吸附时的1/3.     

有机污染土壤电动-微生物修复过程中的影响因素及优化措施

生物修复技术因其费用低、对环境不产生二次污染而被视为是一项具有广阔发展前景的技术。然而,一些强疏水性的有机污染物,生物可利用性很差,严重阻碍了其生物降解效率。电动与微生物联合修复技术(电动-微生物修复),在顽固性有机污染物的去除方面表现出巨大潜力。电场的施加可向土壤中分散外源物质、营养物质和微生物;或通过增强土壤中有机污染物与降解菌的传质过程,提高难降解有机物的生物可利用性;还可诱使土壤中的污染物产生电化学反应,增强污染物的去除效果。文章对有机污染土壤的电动-微生物修复过程的影响因素及优化措施进行了综述。文章认为,影响电动-微生物修复效率的因素主要有电场强度、污染物的生物可利用性、污染物结构和性质、微生物种群以及环境因素(如土壤pH值、土壤类型、营养物质、含水量等)。因此,在实施修复的过程中应根据污染场址的电化学特性选择合适的电流或电压梯度;另外,可通过施加表面活性剂、助溶剂或螯合剂,构建微生物群落,以及优化土壤环境条件,如调整土壤pH、提供营养物质、电子受体、共代谢基质等方式优化有机污染土壤电动-微生物修复的过程。深入研究有机污染土壤电动-微生物修复过程中的影响因素和优化措施,有望为电动-微生物修复技术在有机污染土壤的场地修复及过程调控中的应用提供一定的理论依据。     

重金属与多环芳烃复合污染土壤的分布特征及修复技术研究进展

土壤中污染物通常以复合污染的形式存在,各种污染物之间的相互作用增加了修复的难度,仅针对单一污染物进行治理通常难以达到土壤修复的要求。该文对重金属与多环芳烃复合污染的分布特征及两者之间的交互作用进行了总结,综述了几种复合污染土壤修复技术(淋洗法、植物修复、微生物修复和电动法)的作用机理及适用条件,并对该类型复合污染土壤修复技术的研究方向提出了展望。     

降雨条件下纳米零价铁镍对污染土壤中六价铬迁移的影响

通过模拟降雨进行土柱淋溶实验来研究降雨条件下纳米零价铁镍(nZVI/Ni)对污染土壤六价铬迁移的影响,并测定淋溶液的Cr(Ⅵ)浓度、pH、电导率和累积释放量.使用改进BCR连续提取法测定淋溶后各层土壤的铬形态分布,分析施加nZVI/Ni对土壤中铬形态的影响.结果表明,降雨条件下六价铬的释放过程主要分为快速和慢速释放两个阶段.随着淋溶体积的增加,土壤淋溶液的pH逐渐升高后最后趋于平稳,电导率和Cr(Ⅵ)浓度迅速下降后趋于平稳.模拟降雨条件下,土壤中投加nZVI/Ni显著降低了淋溶液中Cr(Ⅵ)的累积释放量.投加0.10%nZVI/Ni土壤淋溶液的Cr(VI)累积释放量低于空白对照57.53%.在nZVI/Ni投加量相同时,模拟降雨的pH值越低nZVI/Ni的修复效果越好;降雨的淋溶次数对修复效果基本无影响;采用均匀混合的方式投加nZVI/Ni有着更好的修复效果.在土壤中nZVI/Ni对Cr(Ⅵ)修复过程中,纳米铁材料起主要作用,Fe(Ⅱ)的贡献很小.土壤经nZVI/Ni修复后,可还原态铬含量减少,可氧化态铬含量增加,表明纳米零价铁镍可以降低土壤中铬的迁移性,降雨条件下对六价铬污染土壤具有一定的修复效果.     

Bioremediation of oily sludge-contaminated soil by stimulating indigenous microbes

In situ bioremediation of oily sludge-contaminated soil by biostimulation of indigenous microbes through adding manure was conducted at the Shengli oilfield in northern China. After bioremediation for 360 days, total petroleum hydrocarbon (TPH) content was reduced by 58.2% in the treated plots compared with only 15.6% in the control plot. Moreover, bioremediation significantly improved the physicochemical properties of the soil in the treated plot. Soil microbial counts and community-level physiological profiling were also examined. Manure addition increased TPH degraders and polycyclic aromatic hydrocarbon (PAH) degraders in the contaminated soil by one to two orders of magnitude. The activity and biodiversity of soil microbial communities also increased markedly in the treated plot compared with that of the control. Finally, biotoxicity was used to evaluate the soils and a sharp increase in the EC50 of the soil after bioremediation was observed, indicating that bioremediation had reduced the toxicity of the soil.     

Bioremediation of 3,4-dichloroaniline and 2,4,6-trinitrotoluene in soil in the presence of natural adsorbents

The use of some adsorbents may decrease the toxicity of organic pollutants to microbes and plants during soil bioremediation. Experiments were conducted with 3,4-dichloroaniline (DCA) and 2,4,6-trinitrotoluene (TNT). Here we demonstrate that activated carbon can reduce the toxicity of readily available chemicals in soil by transferring them to a less available fraction. This process results in accelerated biodegradation of dichloroaniline by the inoculated Paracoccus denitrificans st. 3XA. In the case of TNT, activated carbon promotes strong binding through accelerated microbial reduction of its nitro-groups and catalytic chemical oxidation of the methyl-group and polymerisation or binding of the products formed.     

Coordination chemistry and the carcinogenicity and mutagenicity of chromium(VI)

Chromate is a known carcinogen, it is only in recent years that the molecular mechanisms by which this toxicity may be expressed have been investigated. The toxicity of chromate may be mediated by the reaction of chromium(VI) with glutathione (GSH) to generate relatively stable chromium(V) complexes and other more reactive intermediates. The conditions favouring the formation of such complexes have been studied. Reactive intermediates generated during the reduction of chromate by GSH include thionyl radicals and at least two relatively stable chromium(V) species (g -1.996 and g -.986). Mixtures of chromium(VI) and glutathione and a chromium(V) complex of glutathione, which we have isolated from the reaction (g = 1.996), are capable of causing strand breaks in bacteriophage PM2 DNA. In contrast a chromium(III) complex of GSSG, one of the final products of the reaction between GSH and chromium(VI), does not damage DNA in closed circle assays. These observations support the suggestion that reactive intermediates generated during the reduction of chromium(VI) provide one route by which the genotoxicity of chromate may be expressed.     

不同价态铬在不同水分条件下的生物有效性及其对水稻的毒性

氧化还原过程在铬的形态转化中起了重要作用,而铬形态的转化能够影响其生物有效性及毒性。通过温室土培试验研究了六价铬(Cr(Ⅵ))与三价铬(Cr(Ⅲ))在淹水与不淹水条件下在土壤溶液中的动态变化及水稻对其吸收的变化。结果表明,土壤中添加Cr(Ⅲ)时,土壤溶液中检测不出Cr;而随着土壤中添加Cr(Ⅵ)浓度的增加,土壤溶液中Cr(Ⅵ)的浓度增加,但是溶液中检测不出Cr(Ⅲ);淹水处理总体上降低了土壤溶液中Cr(Ⅵ)的浓度。而土壤添加Cr(Ⅲ)、Cr(Ⅵ)和水分处理对土壤溶液p H没有显著影响,p H在7.08.0之间变动。土壤添加Cr(Ⅵ)处理的水稻中,只有90 mg·kg-1Cr(Ⅵ)淹水处理的水稻成活,而其余处理水稻没有成活。土壤中添加Cr(Ⅲ)处理,水稻幼苗生物量随Cr(Ⅲ)浓度的增加而显著降低;除了200mg·kg-1Cr(Ⅲ)处理外,其余淹水处理的水稻幼苗生物量明显高于不淹水处理的。土壤添加Cr(Ⅲ)处理的水稻,在不淹水条件下水稻空壳率比较高,淹水条件下,随着土壤中添加Cr(Ⅲ)浓度水平的增加,水稻各部位Cr含量有增加的趋势,但增加不显著,秸秆最高Cr含量达到33.80 mg·kg-1,籽粒中Cr含量最高0.30 mg·kg-1。土壤固定Cr(Ⅲ)的能力远强于Cr(Ⅵ),添加Cr(Ⅵ)处理的土壤溶液中Cr(Ⅵ)的浓度很高,对水稻表现出较强的生长抑制。     

Stabilization of hexavalent chromium with pretreatment and high temperature sintering in highly contaminated soil

• Separate reduction and sintering cannot be effective for Cr stabilization. • Combined treatment of reduction and sintering is effective for Cr stabilization. • Almost all the Cr in the reduced soil is residual form after sintering at 1000°C. This study explored the effectiveness and mechanisms of high temperature sintering following pre-reduction with ferric sulfate (FeSO₄), sodium sulfide (Na₂S), or citric acid (C₆H₈O₇) in stabilizing hexavalent chromium (Cr(VI)) in highly contaminated soil. The soil samples had an initial total Cr leaching of 1768.83 mg/L, and Cr(VI) leaching of 1745.13 mg/L. When FeSO₄ or C₆H₈O₇ reduction was followed by sintering at 1000°C, the Cr leaching was reduced enough to meet the Safety Landfill Standards regarding general industrial solid waste. This combined treatment greatly improved the stabilization efficiency of chromium because the reduction of Cr(VI) into Cr(III) decreased the mobility of chromium and made it more easily encapsulated in minerals during sintering. SEM, XRD, TG-DSC, and speciation analysis indicated that when the sintering temperature reached 1000°C, almost all the chromium in soils that had the pre-reduction treatment was transformed into the residual form. At 1000°C, the soil melted and promoted the mineralization of Cr and the formation of new Cr-containing compounds, which significantly decreased subsequent leaching of chromium from the soil. However, without reduction treatment, chromium continued to leach from the soil even after being sintered at 1000°C, possibly because the soil did not fully fuse and because Cr(VI) does not bind with soil as easily as Cr(III).     

Role of the vitamin E model compound Trolox in the prevention of Cr(VI)-induced cellular damage

Given the wide industrial use of chromium (Cr) and its environmental contamination, chromium represents a risk to humans exposed to the metal. Considering that Cr(VI) is a potent oxidizing agent that increases intracellular oxidation and DNA damage, it would be worth considering the pretreatment of cells with antioxidants as a means of preventing Cr(VI)-induced toxicity. The objective of this study was to pretreat yeast cells with the water-soluble vitamin E analogue Trolox in an effort to increase cell tolerance against reactive chromium and reactive oxygen species formed during Cr(VI) reduction. Results revealed a decrease in Cr(VI)-induced cytotoxicity and mitotic gene conversions in Trolox-pretreated cells. The protective effect of Trolox in Cr(VI) induced genotoxicity was confirmed also with the prokaryotic Salmonella typhimurium SOS/umu test. Pretreatment of cells with Trolox (1) increased total Cr bioaccumulation, (2) decreased Cr(VI)-induced intracellular oxidation, (3) decreased Cr(V) persistence and (4) increased OH^? formation in yeast extracts. These findings might be useful in directing future investigations concerning the use of Trolox as a human antioxidant supplement, and in clinical applications related to Cr-induced genotoxicity in occupational and environmental situations where chromium is a problem.     

Chromium (VI) tolerance in two halotolerant strains of Nostoc

The present study reports on chromium (VI) tolerance of two cyanobacterial strains Nostoc linckia and Nostoc spongiaeforme isolated from salt affected soils using uni-algal and bi-algal systems. Besides distinct halophilism, the two strains exhibited remarkable tolerance to chromium (VI) and revealed 1.2 to 2.8 times more chlorophyll in the presence of the metal. While phycobilins and carotenoids also increased in Nostoc linckia with total dissolved salts (TDS) as well as metal, a decline was observed in Nostoc spongiaeforme in the presence of Cr (VI). Relative algal biomass (as % of control) showed significantly higher values (123-239) in Nostoc linckia in the presence of salt, metal and combination of the two. In Nostoc spongiaeforme it declined in the presence of metal (72-81) but increased in the presence of salts (143-249) and also in the binary systems (121-440). The bi-algal consortium showed relatively less tolerance to salt and metal stress. Nostoc linckia (20 day culture) showed upto 40% chromium removal whereas Nostoc spongiaeforme showed up to 12% removal, indicating greater suitability of the former for use in bioremediation studies.     

Developed fungal–bacterial biofilms as a novel tool for bioremoval of hexavelant chromium from wastewater

Remediation measures for hexavalent chromium [Cr(VI)] are required for a safe environment. As a recent development in microbiology, bacterial biofilms are being studied as effective bioremediation agents. When bacteria are in fungal surface-attached biofilm mode, they are called fungal–bacterial biofilms (FBBs). They have not been tested for bioremediation so far. Hence, this study was conducted to develop FBBs and glass-wool-attached bacterial biofilms (BBs), and to evaluate Cr(VI) tolerability and removal of bacterial monocultures, BBs and FBBs. FBBs showed a significantly high level of Cr(VI) tolerance and resistance compared with its BBs or monocultures. After 10 days, up to 90% of Cr(VI) had been removed, which was significantly higher than that of BBs or its monocultures. Thus, it is clear that FBBs can be used as a novel tool to decontaminate Cr(VI) both in situ and ex situ.     

Chromium toxicity and tolerance in plants

Chromium (Cr) is the second most common metal contaminant in ground water, soil, and sediments due to its wide industrial application, hence posing a serious environmental concern. Among various valence states, Cr(III) and Cr(VI) are the most stable forms. Cr(VI) is the most persistent in the soil and is highly toxic for biota. Since Cr is a non-essential element for plants, there is no uptake mechanism; Cr is taken up along essential elements such as sulfate through sulfate transporters. Cr accumulation in plants causes high toxicity in terms of reduction in growth and biomass accumulation, and Cr induces structural alterations. Cr interferes with photosynthetic and respiration processes, and water and minerals uptake mechanism. Various enzymatic activities related to starch and nitrogen metabolism are decreased by Cr toxicity either by direct interference with the enzymes or through the production of reactive oxygen species. Cr causes oxidative damage by destruction of membrane lipids and DNA damage. Cr may even cause the death of plant species. Few plant species are able to accumulate high amount of Cr without being damaged. Such Cr-tolerant, hyperaccumulator plants are exploited for their bioremediation property. The present review discusses Cr availability in the environment, Cr transfer to biota, toxicity issues, effect on germination and plant growth, morphological and ultrastructural aberrations, biochemical and physiological alterations, effect on metabolic processes, Cr-induced alterations at the molecular level, Cr hyperaccumulation and Cr detoxification mechanism, and the role of arbuscular mycorrhizae in Cr toxicity, in plants.     

Microbial communities biostimulated by ethanol during uranium (VI) bioremediation in contaminated sediment as shown by stable isotope probing

Stable isotope probing (SIP) was used to identify microbes stimulated by ethanol addition in microcosms containing two sediments collected from the bioremediation test zone at the US Department of Energy Oak Ridge site, TN, USA. One sample was highly bioreduced with ethanol while another was less reduced. Microcosms with the respective sediments were amended with ¹³C labeled ethanol and incubated for 7 days for SIP. Ethanol was rapidly converted to acetate within 24 h accompanied with the reduction of nitrate and sulfate. The accumulation of acetate persisted beyond the 7 d period. Aqueous U did not decline in the microcosm with the reduced sediment due to desorption of U but continuously declined in the less reduced sample. Microbial growth and concomitant ¹³C-DNA production was detected when ethanol was exhausted and abundant acetate had accumulated in both microcosms. This coincided with U(VI) reduction in the less reduced sample. ¹³C originating from ethanol was ultimately utilized for growth, either directly or indirectly, by the dominant microbial community members within 7 days of incubation. The microbial community was comprised predominantly of known denitrifiers, sulfate-reducing bacteria and iron (III) reducing bacteria including Desulfovibrio, Sphingomonas, Ferribacterium, Rhodanobacter, Geothrix, Thiobacillus and others, including the known U(VI)-reducing bacteria Acidovorax, Anaeromyxobacter, Desulfovibrio, Geobacter and Desulfosporosinus. The findings suggest that ethanol biostimulates the U(VI)-reducing microbial community by first serving as an electron donor for nitrate, sulfate, iron (III) and U(VI) reduction, and acetate which then functions as electron donor for U(VI) reduction and carbon source for microbial growth.