多环芳烃污染土壤的生物修复

综述了土壤环境中多环芳烃的来源、归宿、生物转化机理、影响因素及生物修复技术研究进展,提出了利用生物技术治理土壤环境中多环芳烃的思路及方法。     

多环芳烃污染土壤的微生物与植物联合修复研究进展

本文综述了多环芳烃(PAHs)污染土壤中微生物降解途径、机理及生物反应器的应用,并从植物修复角度,进一步阐述了与微生物联合作用促进污染土壤中PAHs降解的途径、机理及其应用。提出了利用微生物共代谢降解及其与植物联合修复PAHs污染土壤环境的生物修复技术未来研究课题。     

多环芳烃长期污染土壤的微生物强化修复初步研究

本研究通过室内模拟试验,以急性毒性较强的菲(Phe)和遗传毒性较强的苯并[a]芘(B[a]P)为代表性多环芳烃(PAHs)污染物,以不同C源、通气状况和水分条件为调控因子,对PAHs长期污染土壤的土著微生物强化修复进行初步研究。结果表明,搅动处理使污染土壤中Phe和B[a]P的降解率分别达59.44%和26.14%,而淹水处理使两者降解率分别达46.48%和13.27%。添加C源(淀粉和葡萄糖)处理提高了土壤中PAHs的降解率,且随着C源的施用量而增加。同时也发现污染土壤中PAHs降解菌和微生物总量呈正相关,并随着PAHs降解菌数量的增加,土壤中PAHs降解率也随之提高。可见,土壤中PAHs降解速率主要决定于PAHs的降解菌数量。     

生物表面活性剂强化微生物修复多环芳烃污染土壤的初探

通过温室盆栽实验,单独或联合接种多环芳烃专性降解菌(DB)和添加生物表面活性剂-鼠李糖脂(RH),研究了生物表面活性剂强化微生物修复多环芳烃(PAHs)长期污染土壤的效果。结果表明,添加RH和接种DB能明显促进土壤中PAHs总量和各组分PAHs的降解。经过90 d培养后,添加RH、DB和RH+DB处理的PAHs的降解率分别为21.3%、32.6%、36.0%,较对照分别提高了333.0%、563.3%、633.0%。此外,随着苯环数的增加,土壤中15种PAHs平均降解率逐渐降低。同时也发现DB、RH+DB处理土壤中脱氢酶活性、多酚氧化酶活性和PAHs降解菌数量显著高于CK、RH处理,但是CK与RH处理没有显著差异,说明DB、RH在促进土壤中PAHs的降解方面有不同的机制。     

多环芳烃污染土壤的植物-微生物联合修复初探

在温室盆栽条件下,通过种植紫花苜蓿单独或联合接种菌根真菌(Glomus caledonium L.)(AM)和多环芳烃专性降解菌(DB),研究了利用植物-微生物强化修复多环芳烃(PAHs)长期污染土壤的效果。试验结果表明,接种菌根真菌和PAHs专性降解菌能促进紫花苜蓿的生长和土壤中PAHs的降解。经过90天修复试验,种植紫花苜蓿接种AM、DB和DB+AM处理的PAHs的降解率分别为47.9%、49.6%、60.1%,均高于只种植紫花苜蓿的对照处理(CK)(21.7%)。另外,随着PAHs苯环数的增加,其平均降解率逐渐降低,但是接种PAHs专性降解菌能够提高4环和5环PAHs的降解率。同时也发现土壤中脱氢酶活性和PAHs降解菌数量越高的处理,土壤PAHs的降解率也越高,这也是种植紫花苜蓿接种微生物能够有效促进土壤PAHs降解的原因。     

多环芳烃污染土壤生物联合强化修复研究进展

多环芳烃(polycyclic aromatic hydrocarbons,PAHs)是广泛存在于环境中的一类有毒有机污染物。在PAHs污染土壤修复领域中,运用一些生物化学的方式来强化生物联合修复技术可以有效缩短生物修复的时间,大大提高修复效率,最具发展前景和应用价值。本文主要以植物-微生物、植物-微生物-土壤动物两种生物联合修复方式为对象,结合各自的特点、机理和实例,推断了其修复机制的内在原因,总结了影响土壤中PAHs降解效率的主要因素(包括:PAHs的浓度水平、根系分泌物的种类、外源添加降解菌和土壤动物的数量和种类、菌属或土壤动物之间的种间竞争和部分环境因素等);同时通过综述近年来国内外强化生物联合修复PAHs污染土壤的技术原理、应用成果和存在的一些问题,指出了不同情况下制约PAHs强化降解进程的潜在限制因子(包括:表面活性剂和固定化微生物的添加量、不同表面活性剂的适度混合、载体材料的性质、固定化方式的选取、土壤养分和水分含量等);并强调在进行强化修复的过程中,要注重现场应用和安全性评价,为多环芳烃污染土壤的生物联合强化修复研究提供了理论依据和技术参考。     

降解菌对堆肥中多环芳烃降解作用的初步研究

通过在堆肥中加入经过驯化的降解菌这种土壤有机污染生物修复技术,以超声波提取－高效液相色谱（ＨＰＬＣ）分离测定的方法,对堆肥材料中多环芳烃的浓度变化进行监测,从而了解降解解菌对堆肥中多环芳烃的降解作用。实验结果表明,降解菌对堆肥中的多环芳烃有明显的降解作用。     

土地生物处理过程中多环芳烃降解模型及应用

土地生物处理能有效降解土壤中有机污染物多环芳烃 (PAHs) ,构建的基于土壤屏蔽反应机理的数学模型能较好的描述该降解过程 ,从而可以预测降解土壤生态系统中PAHs所需的时间、降解程度以及降解结束后被土壤所屏蔽的PAHs的量 ,数学模型在美国Alcoa公司LTU基地的大型土地生物处理工程中得到了验证。利用该数学模型 ,预测了 3,4,5和 6-环 -PAHs的土地生物处理过程及规律     

根系分泌物及其在修复多环芳烃污染土壤中的应用

修复被多环芳烃污染的土壤是目前环境和生态领域的一个前沿课题,植物修复是一种经济廉价、可操作性强、美化景观的绿色技术,而根系分泌物在植物修复污染土壤过程中有着重要的意义。总结了近年来国内外植物根系分泌物研究的主要成果,系统介绍了根系分泌物的定义、组成、影响因素及其收集和分离纯化方法,综述了近年来根系分泌物在植物修复技术中的应用情况,以期为进一步开展多环芳烃污染土壤植物修复研究提供实践参考和理论依据。     

土壤环境中多环芳烃研究的回顾与展望——基于Web of Science大数据的文献计量分析

为深入了解土壤环境中多环芳烃研究的全球状况和前沿动态,客观反映相关国家、机构和个人在该领域的科学能力和影响,采用ISI Web of Knowledge的Web of Science引文数据库,对1900―2014年间该库收录的土壤环境中多环芳烃研究领域的相关文献进行了计量分析。结果表明,该领域全球发文量总体呈持续快速上升趋势,美国的发文量、总被引频次和H指数均居榜首,中国的发文量和总被引频次居次席,但篇均被引频次明显偏低;中国科学院和英国兰卡斯特大学的发文量和H指数居研究机构的前两位,篇均被引频次排名最高的研究机构是美国马萨诸塞大学;英国兰卡斯特大学的Jones K C等两位学者发文量和H指数最高,北达克科特大学Hawthorne S B的篇均被引频次最高,国内学者中北京大学的陶澍和浙江大学的朱利中最有影响力;该领域的主要期刊有Environmental Science & Technology、Chemosphere和Environmental Pollution等;该领域的研究热点多集中于土壤环境中多环芳烃的降解及生物修复、多环芳烃在各介质中的溶解与吸附、以及多环芳烃的源解析等方向,“中国”相关研究在近5年中占重要地位。     

土壤环境中多环芳烃研究的回顾与展望——基于WebofScience大数据的文献计量分析

为深入了解土壤环境中多环芳烃研究的全球状况和前沿动态,客观反映相关国家、机构和个人在该领域的科学能力和影响,采用ISI Web of Knowledge的Web of Science引文数据库,对1900—2014年间该库收录的土壤环境中多环芳烃研究领域的相关文献进行了计量分析。结果表明,该领域全球发文量总体呈持续快速上升趋势,美国的发文量、总被引频次和H指数均居榜首,中国的发文量和总被引频次居次席,但篇均被引频次明显偏低;中国科学院和英国兰卡斯特大学的发文量和H指数居研究机构的前两位,篇均被引频次排名最高的研究机构是美国马萨诸塞大学;英国兰卡斯特大学的Jones K C等两位学者发文量和H指数最高,北达克科特大学Hawthorne S B的篇均被引频次最高,国内学者中北京大学的陶澍和浙江大学的朱利中最有影响力;该领域的主要期刊有Environmental ScienceTechnology、Chemosphere和Environmental Pollution等;该领域的研究热点多集中于土壤环境中多环芳烃的降解及生物修复、多环芳烃在各介质中的溶解与吸附、以及多环芳烃的源解析等方向,“中国”相关研究在近5年中占重要地位。     

SYNOPSIS Polycyclic Aromatic Hydrocarbons (PAHs) in Soil — a Review

PAHs are mainly produced by combustion processes and consist of a number of toxic compounds. While the concentrations of individual PAHs in soil produced by natural processes (e.g., vegetation fires, volcanic exhalations) are estimated to be around 1—10 μg kg⁻¹, recently measured lowest concentrations are frequently 10 times higher. Organic horizons of forest soils and urban soils may even reach individual PAH concentrations of several 100 μg kg⁻¹. The PAH mixture in temperate soils is often dominated by benzofluoranthenes, chrysene, and fluoranthene. The few existing studies on tropical soils indicate that the PAH concentrations are relatively lower than in temperate soils for most compounds except for naphthalene, phenanthrene, and perylene suggesting the presence of unidentified PAH sources. PAHs accumulate in C‐rich topsoils, in the stemfoot area, at aggregate surfaces, and in the fine‐textured particle fractions, particularly the silt fraction. PAHs are mainly associated with soil organic matter (SOM) and soot‐like C. Although the water‐solubility of PAHs is low, they are encountered in the subsoil suggesting that they are transported in association with dissolved organic matter (DOM). The uptake of PAHs by plants is small. Most PAHs detected in plant tissue are from atmospheric deposition. However, earthworms bioaccumulate considerable amounts of PAHs in short periods. The reviewed work illustrates that there is a paucity of data on the global distribution of PAHs, particularly with respect to tropical and southern hemispheric regions. Reliable methods to characterize bioavailable PAH pools in soil still need to be developed.     

Changes in Polycyclic Aromatic Hydrocarbons (PAHs) and Soil Biological Parameters in a Revegetated Coal Mine Spoil

Coal mining leads to severe land degradation and creates huge amounts of mine spoil. Coal mine spoil contains toxic polycyclic aromatic hydrocarbons (PAHs) derived from coal, which can be alleviated through revegetation with suitable tree species. The present study was aimed at evaluating the impact of different tree species (Albizia lebbeck , Cassia siamea , Delonix regia , and Dalbergia sissoo ) on the quality of coal mine spoil and changes in PAH concentration. Soil samples were collected from the revegetated coalmine overburden dumps of Jharia coalfield, Dhanbad, India and analysed by GC‐MS for 16 priority PAHs and soil quality parameters were analyzed by standard analytical protocols. Reclamation improved the biological properties of the mine spoil: microbial biomass (+59–176%), dehydrogenase activity (+46–198%), fluorescein diacetate hydrolase activity (+104–127%), phenol oxidase activity (+150–250%), and peroxidase activity (+93–181%). PAH concentration in revegetated mine spoil ranged from 0 · 51 to 1 · 35 mg kg⁻¹, with a significance reduction in total as well as individual PAHs. For individual tree species, total PAH reduction decreased in the order: C. siamea (81 · 6%) > A. lebbeck (55 · 6%) > D. regia (51 · 9%) > D. sissoo (51 · 5%). Correlation analysis showed significant association between the degradation of PAHs and soil biological properties of revegetated site. Microbial biomass carbon and soil enzymes were negatively correlated with PAH content in the mine spoil. But microbial stress indicators like respiration/microbial carbon ratio were not correlated, which revealed no adverse effect of PAH on soil microbes. Principal component analysis revealed that most of the biological parameters were closely associated with the degradation of low molecular weight PAHs. Copyright © 2016 John Wiley & Sons, Ltd.     

微生物降解石油源多环芳香烃的研究进展

石油源多环芳香烃是存在于石油中的一类致畸、致癌污染物,具有以低环(2~3环)为主且取代基比例明显高于其他来源PAHs的组分特征。石油泄露引发的PAHs污染,其降解主要依赖于微生物的活动。本文对能够降解PAHs的微生物种类、降解机理、代谢途径及编码基因进行了概述。从PAHs作为碳源的角度将微生物降解机理划分为能以PAHs为唯一碳源进行生长的降解机理和共代谢机理。对与PAHs有关的好氧和厌氧微生物降解途径及对应的编码基因簇进行了总结。自然界中细菌、放线菌、真菌及藻类都能够降解PAHs,由加氧酶催化的苯环羟基化和还原酶介导的苯环脱芳烃化是好氧和厌氧降解途径的关键步骤,与降解有关的pca,cat,paa,nah,nah-like和bcr基因簇则分别调控好氧和厌氧降解过程。这些进展有助于系统了解石油源PAHs的降解过程、微生物作用机理和分子遗传机制,为进一步利用微生物促进环境生物修复提供理论依据。     

Comparison of Fenton's Reagent and Ozone Oxidation of Polycyclic Aromatic Hydrocarbons in Aged Contaminated Soils (7 pp)

Background, Aim and Scope   Polycyclic aromatic hydrocarbons (PAHs) are formed as a result of incomplete combustion and are among the most frequently occurring contaminants in soils and sediments. PAHs are of great environmental concern due to their ubiquitous nature and toxicological properties. Consequently, extensive research has been conducted into the development of methods to remediate soils contaminated with PAHs. Fenton's reagent or ozone is the most commonly studied chemical oxidation methods. However, the majority of remediation studies use soils that have been artificially contaminated with either one or a limited number of PAH compounds in the laboratory. Hence, it is essential to extend such studies to soils contaminated with multiple PAHs under field conditions. Objectives   The objective of this study is to investigate the capacity of Fenton's reagent and ozone to degrade PAHs in soils. The soils have been collected from a number of different industrial sites and, therefore, will have been exposed to different PAH compounds in varying concentrations over a range of time periods. The capacity of Fenton's reagent and ozone to degrade PAHs in industrially contaminated soils is compared to results obtained in studies using soils artificially contaminated with PAHs in the laboratory. Materials and Methods: Nine soil samples, contaminated with PAHs, were collected from five different industrial sites in Sweden. For the Fenton's reagent procedure, the pH of the soil slurry samples was adjusted to pH 3 and they were kept at a constant temperature of 70oC whilst H2O2 was added. For the ozone procedure, soil samples were mixed with 50% water and 50% ethanol and kept at a constant temperature of 45 oC. Ozone was then continually introduced to each soil sample over a period of four hours. Following the Fenton's reagent and ozone oxidation procedures, the samples were filtered to isolate the solid phase, which was then extracted using pressurized liquid extraction (PLE). The sample extracts were cleaned up using open columns and then analysed by gas chromatography-mass spectrometry (GC-MS). Results: The relative abundance of the detected PAHs varied between soils, associated with different industries. For example, low molecular weight (LMW) PAHs were more abundant in soil samples collected from wood impregnation sites and high overall PAH degradation efficiencies were observed in soils originating from these sites. In the contaminated soils studied, PAHs were more effectively degraded using Fenton's reagent (PAH degradation efficiency of 40-86%) as opposed to ozone (PAH degradation efficiency of 10-70%). LMW PAHs were more efficiently degraded, using ozone as the oxidizing agent, whereas the use of Fenton's reagent resulted in a more even degradation pattern for PAHs with two through six fused aromatic rings. Discussion: The degradation efficiency for both methods was largely dependent on the initial PAH concentration in the soil sample, with higher degradation observed in highly polluted soils. LMW PAHs are more susceptible to degradation than high molecular weight (HMW) PAHs. As a result of this the relative abundance of large (often carcinogenic) PAHs increased after chemical oxidation treatment, particularly after ozone treatment. Repeated Fenton's reagent treatment did not result in any further degradation of soil PAHs, indicating that residual soil PAHs are strongly sorbed. The effectiveness of the two oxidation treatment approaches differed between industrial sites, thus highlighting the importance of further research into the influence of soil properties on the sorption capacity of PAHs. Conclusions: This study demonstrates that the degree to which chemical oxidation techniques can degrade soil bound PAHs chemical degradation is highly dependent on both the concentration of PAHs in the soils and the compounds present, i.e. the various PAH profiles. Therefore, similarities in the PAH degradation efficiencies in the nine soil samples studied were observed with the two chemical oxidation methods used. However, the degradation performance of Fenton's reagent and ozone differed between the two methods. Overall, Fenton's reagent achieved the highest total PAH degradation due to stronger oxidation conditions. LMW PAHs showed higher susceptibility to oxidation, whereas high molecular weight (HMW) PAHs appear to be strongly sorbed to the soils and therefore less chemically available for oxidation. This study highlights the importance of including soils collected from a range of contaminated sites in remediation studies. Such soil samples will contain PAH contaminants of varying concentrations, chemical and physical properties, and have been aged under field conditions. In addition to the chemical and physical properties of the soils, these factors will all influence the chemical availability of PAHs to oxidation. Recommendations and Perspectives: We recommend including aged contaminated soils in chemical degradation studies. In future chemical remediation work, we intend to investigate the potential influence of the chemical and physical properties of PAHs and soil parameters potential influence on the chemical oxidation efficiency in aged contaminated soils. Due to the vast number of contaminated sites there is a great need of efficient remediation methods throughout the world. This study shows the difficulties which may be experienced when applying remediation methods to a variation of contaminated sites.     

淀粉对无芒雀麦修复煤矿区多环芳烃长期污染土壤的影响

采用温室盆栽试验,以无芒雀麦(W)为修复植物,研究淀粉(D)不同剂量与无芒雀麦组合对煤矿区多环芳烃(PAHs)长期污染农田土壤修复的影响。结果表明,在土壤中添加淀粉剂量D1、D2培养3个月后,显著促进了土著微生物对煤矿区长期污染农田土壤PAHs的降解。D1、D2处理土壤中16种PAHs总量降解率(16.82%,19.06%)分别比对照CK(11.12%)提高了51.26%和71.40%,尤其对6环PAHs的降解增效最为突出。D2处理对6环PAHs的降解达最高,为37.05%,比CK处理提高了241.01%,且为D1处理的1.77倍。在污染土壤中添加淀粉并种植无芒雀麦(D1+W,D2+W)后,与对照CK、淀粉(D)和种植无芒雀麦单一处理(W)相比,土壤中16种PAHs总量降解率有了明显增加,D1+W与D2+W处理下16种PAHs降解率分别为26.26%和28.39%;在PAHs不同环数中对5,6环PAHs的修复效果提升最为明显,对其它环数PAHs降解效果提升不显著,其中5环和6环PAHs降解率在D2+W组合处理下达到最高,为48.63%和58.32%,比CK处理提高了110.36%和436.82%,比无芒雀麦单一处理提高了27.50%和47.77%。从土壤酶活性角度,淀粉、无芒雀麦单一处理及其组合下的土壤过氧化氢酶活性差异不明显,但均显著高于对照CK处理;无芒雀麦对多酚氧化酶活性有明显的激活作用,且与淀粉组合进一步显著提升了该酶的活性,与D1+W与D2+W组合下的5,6环PAHs降解率达最高相一致。综上,利用淀粉与无芒雀麦的优化组合形式能明显提升煤矿区5,6环PAHs长期污染农田土壤的修复效果,可以作为该区污染土壤修复治理的一种选择。     

土壤中多环芳烃的分布特征及其来源分析

利用气相色谱法分析了南充市10个不同功能区表层土壤中美国环保署规定的16种优控多环芳烃（PAHs）的含量和组分特征,运用同分异构体比率揭示了其污染来源。研究表明,该区土壤中PAHs的含量在9.1～2269.1μg·kg-1之间,而且工业区的残留量大于农业区和居民区的残留量。按PAHs的环数来分,在工业污染区PAHs的含量总的趋势是四环〉二环〉三环〉五环〉六环;农业和居民区二环〉三环〉五环〉四环〉六环。该污染状况与国内外相关研究比较,处于中等污染水平。煤、木材和化石的燃烧是该地区土壤中PAHs污染的主要来源,苯并（a）蒽和菲是主要的超标化合物。