表面活性剂增效电动技术修复多环芳烃污染土壤

研究了电动修复过程中修复时间和表面活性剂Triton X-100、鼠李糖脂对多环芳烃芘污染土壤的修复效果的影响。结果表明,在电动修复过程中,随着修复时间的增加,芘的去除率相应提高。通过向电解液中添加表面活性剂Triton X-100,芘的去除率从11.64%提高到了23.42%,当在电解液中添加浓度为40倍CMC的鼠李糖脂后去除率升高至36.29%,阳极附近土壤甚至达到了92.49%,这表明Triton X-100和鼠李糖脂均能促进土壤中芘的溶解和迁移,鼠李糖脂的促进作用高于Triton X-100。     

Using nanoscale zero-valent iron for the remediation of polycyclic aromatic hydrocarbons contaminated soil

The sites contaminated with recalcitrant organic compounds, such as polycyclic aromatic hydrocarbons (PAHs) with multiple benzene rings, are colossal and ubiquitous environmental problems. They are relatively nonbiodegradable and mutagenic, and 16 of them are listed in the U.S. Environment Protection Agency priority pollutants. Thus, the efficient and emerging remediation technologies for removal of PAHs in contaminated sites have to be uncovered urgently. In this decade, the zero-valent iron (ZVI) particles have been used successfully in the laboratory, pilot, and field, such as degradation of chlorinated hydrocarbons and remediation of the other pollutants. Nevertheless, as far as we know, little research has investigated for soil remediation; this study used nanoscale ZVI particles to remove pyrene in the soil. The experimental variables were determined, including reaction time, iron particle size, and dosage. From the results, both the micro- and nanoscales of ZVI were capable of removing the target compound in soil, but the higher removal efficiencies were by nanoscale ZVI because of the massive specific surface area. The optimal operating conditions to attain the best removal efficiency of pyrene were obtained while adding nanoscale ZVI 0.1 g/g soil within 60 min and 150 rpm of mixing. Thus, nanoscale ZVI has proved to be a promising remedy for PAH-contaminated soil in this study, as well as an optimistically predictable application for additional pilot and field studies.     

Anaerobic biodegradation of polycyclic aromatic hydrocarbon in soil

Known concentrations of phenanthrene, pyrene, anthracene, fluorene and acenapthene were added to soil samples to investigate the anaerobic degradation potential of polycyclic aromatic hydrocarbon (PAH). Consortia-treated river sediments taken from known sites of long-term pollution were added as inoculum. Mixtures of soil, consortia, and PAH (individually or combined) were amended with nutrients and batch incubated. High-to-low degradation rates for both soil types were phenanthrene > pyrene > anthracene > fluorene > acenaphthene. Degradation rates were faster in Taida soil than in Guishan soil. Faster individual PAH degradation rates were also observed in cultures containing a mixture of PAH substrates compared to the presence of a single substrate. Optimal incubation conditions were noted as pH 8.0 and 30 degrees C. Degradation was enhanced for PAH by the addition of acetate, lactate, or pyruvate. The addition of municipal sewage or oil refinery sludge to the soil samples stimulated PAH degradation. Biodegradation was also measured under three anaerobic conditions; results show the high-to-low order of biodegradation rates to be sulfate-reducing conditions > methanogenic conditions > nitrate-reducing conditions. The results show that sulfate-reducing bacteria, methanogen, and eubacteria are involved in the PAH degradation; sulfate-reducing bacteria constitute a major component of the PAH-adapted consortia.     

多环芳烃污染土壤生物修复的强化方法

生物降解是去除环境中多环芳烃(PAHs)的重要途径,通过采取一些强化措施,如使用表面活性剂,添加营养物质和提供共代谢底物等,可显著提高PAHs降解速度和程度,为生物修复技术的成功应用提供前提。在分析中,对近年来国内外在PAHs污染土壤生物修复强化方面的研究进展进行了综述。     

Slurry-phase ozonation for remediation of sediments contaminated by polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbons (PAHs) are a group of toxic, persistent, bioaccumulating organic compounds containing two or more fused aromatic rings. They are listed by the U.S. Environmental Protection Agency as priority pollutants because of their carcinogenicity and toxicity. Employing ozonation as a remediation technique, this work investigated the treatability of a sediment sample from a freshwater boat slip subjected to coal tar contamination over a long period. The contaminated sediment sample contained high levels of PAHs in the forms of naphthalene, phenanthrene, pyrene, and benzo[a]pyrene, among other byproducts present in the humic and solid phases of the sediment. The objectives of this work were to examine (1) the degradation of PAHs in the contaminated sediment as treated by ozonation in the slurry form, (2) the effects of ozonation upon the soil matrix and the biodegradability of the resultant PAH intermediates, and (3) the feasibility of a combined technique using O3 as a pretreatment followed by biological degradation. The sediment was made into 3% w/w soil slurries and ozonated in a 1.7-L semi-batch, well-stirred reactor equipped with pH control and a cold trap for the gaseous effluent. Samples were collected after different ozonation durations and tested for biochemical oxygen demand (BOD), chemical oxygen demand (COD), UV absorbance, and toxicity, along with quantitative and qualitative determinations of the parent and daughter intermediates using gas chromatography/flame ionization detection (GC/FID), GC/mass spectrometry (MS), and ion chromatography (IC) techniques. The GC/MS technique identified 16 compounds associated with the humic and solid phases of the sediment. Intermediates identified at different ozonation times suggested that the degradation of PAHs was initiated by an O3 attack resulting in ring cleavage, followed by the intermediates' oxidation reactions with O3 and the concomitant OH radical toward their mineralization. Results suggested that ozonation for 2 hr removed 50-100% of various PAHs in the solid and liquid phases (as well as the aqueous and gaseous media resulting from the treatment process) of the sediment sample and that organic and inorganic constituents of the sediment were also altered by ozonation. Measurements and comparisons of BOD, COD, UV absorbance, and toxicity of the samples further suggested that ozonation improved the bioavailability and biodegradability of the contaminants, despite the increased toxicity of the treatment effluent. An integrated chemical-biological system appeared to be feasible for treating recalcitrant compounds.     

Remediation of polycyclic aromatic hydrocarbon (PAH) contaminated soil through composting with fresh organic wastes

Introduction  

Composting may enhance bioremediation of PAH-contaminated soils by providing organic substrates that stimulate the growth of potential microbial degraders. However, the influence of added organic matter (OM) together with the microbial activities on the dissipation of PAHs has not yet been fully assessed.     

生物柴油基微乳液的制备及其对钢铁厂多环芳烃污染土壤的修复性能

针对场地土壤中高浓度多环芳烃较难去除的问题,利用微乳液具有界面张力低、增溶能力强和体系稳定的特点,制备了污染土壤淋洗修复剂。采用表面活性剂、助表面活性剂、生物柴油为主要组分制备微乳液,优化微乳液最佳组分配比及制备条件,并比较表面活性剂、复配表面活性剂、生物柴油和微乳液等不同类型淋洗剂对钢铁厂污染土壤中多环芳烃的去除效果。结果表明,最佳微乳液组分及pH条件为：7.7% Tween-80、7.7% TX-100、15.4%正丁醇、20.5%生物柴油、pH=7。在不同类型的淋洗剂中,微乳液淋洗剂对多环芳烃的去除率最高(89.7%),显著高于其他类型淋洗剂的效果。多环芳烃的去除率与淋洗剂和土壤的液固比、洗脱振荡时间等有关,确定的微乳液最佳修复条件为：液固比为4∶1、洗脱振荡时间为8 h。按混合表面活性剂与生物柴油比为6∶4制备的微乳液洗脱效果最佳。本研究结果可为高效去除污染土壤中多环芳烃打下基础。     

Assessment of contaminant lability during phytoremediation of polycyclic aromatic hydrocarbon impacted soil

Polycyclic aromatic hydrocarbons (PAHs) are recalcitrant compounds, some of which are known carcinogens, often found in high residual soil concentrations at industrial sites. Recent research has confirmed that phytoremediation holds promise as a low-cost treatment method for PAH contaminated soil. In this study, the lability of soil bound PAHs in the rhizosphere was estimated using solid phase extraction resin. An extraction time of 14 days was determined to be appropriate for this study. Resin-extractable PAHs, which are assumed to be more bioavailable, decreased during plant treatments. Significant reductions in the labile concentrations of several PAH compounds occurred over 12 months of plant growth. The differences in concentration between the unplanted and the planted soil indicate that the presence of plant roots, in addition to the passage of time, contributes to reduction in the bioavailability of target PAHs.     

生物强化修复石油污染土壤

筛选高效石油降解菌,考察菌株的降解性能及降解机理,进行花盆模拟高效外源菌强化修复石油污染土壤实验,在降解后期添加激活剂H2O2以及木屑来试图改善微生物的修复环境,减缓微生物的衰亡,并考察修复效果。结果表明,菌株L-1的降解效果较好,其对pH和温度有较大范围的适应性,能分泌较多的表面活性物质,细胞疏水性较强。将其应用于土壤修复中,经过50 d的修复,石油残留率达到50.6%左右,生物强化比自然修复残留率降低了8%左右。在第45天添加激活剂能有效改善修复效果,70 d时添加外源菌的土样最小石油残留率达到37.9%。     

Fenton based remediation of polycyclic aromatic hydrocarbons-contaminated soils

This paper aims to review the applications of Fenton based treatments specifically for polycyclic aromatic hydrocarbons-contaminated soils. An overview of the background and principles of Fenton treatment catalysed by both homogenous (conventional and modified Fenton) and heterogeneous (Fenton-like) catalysts is firstly presented. Laboratory and field soil remediation studies are then discussed in terms of efficiency, kinetics and associated factors. Four main scopes of integrated Fenton treatments, i.e. physical-Fenton, biological-Fenton, electro-Fenton and photo-Fenton are also reviewed in this paper. For each of these integrated remediation technologies, the theoretical background and mechanisms are detailed alongside with achievable removal efficiencies for polycyclic aromatic hydrocarbons in contaminated soils compared to sole Fenton treatment. Finally, the environmental impacts of Fenton based soil treatments are documented and discussed.     

Improving rigor in polycyclic aromatic hydrocarbon source fingerprinting

Source identification of polycyclic aromatic hydrocarbons in environmental samples has advanced greatly in the last 20 years and continues to advance. To realize potential benefits and avoid possible pitfalls, however, great care is needed as one applies published diagnostic tools to data sets. This commentary reflects some recent observations, concerns, and recommendations.     

Oxidation of polycyclic aromatic hydrocarbons by fungal isolates from an oil contaminated refinery soil

BACKGROUND AND OBJECTIVE: Indigenous soil microorganisms are used for the biodegradation of petroleum hydrocarbons in oily waste residues from the petroleum refining industry. The objective of this investigation was to determine the potential of indigenous strains of fungi in soil contaminated with petroleum hydrocarbons to biodegrade polycyclic aromatic hydrocarbons (PAH). MATERIALS AND METHODS: Twenty one fungal strains were isolated from a soil used for land-farming of oily waste residues from the petrochemical refining industry in Singapore and identified to genus level using laboratory culture and morphological techniques. Isolates were incubated in the presence of 30 mg/L of phenanthrene over a period of 28 days at 30 degrees C. The most effective strain was further evaluated to determine its ability to oxidise a wider range of PAH compounds of various molecular weight i.e acenaphthene, fluorene, fluoranthene, chrysene, benzo(a)pyrene and dibenz(ah)anthracene RESULTS AND DISCUSSION: After 28 days of incubation, 18 of the 21 fungal cultures were capable of oxidising over 50% of the phenanthrene present in culture medium, relative to abiotic controls. Fungal isolate, Penicillium sp. 06, was able to oxidise 89% of the phenanthrene present. This isolate could also oxidise more than 75% of the acenaphthene, fluorene and fluoranthene after 30 days of incubation. However, the oxidation of high molecular weight PAH i.e. chrysene, benzo(a)pyrene and dibenz(ah)anthracene by the Penicillium sp. 06 isolate was limited, where the extent of oxidation was inversely proportional to PAH molecular weight. CONCLUSIONS: Fungal isolate, Penicillium sp. 06, was effective at oxidising a range of PAH in petroleum contaminated soils, but higher molecular weight PAH were more recalcitrant. RECOMMENDATIONS AND OUTLOOK: There is potential for the re-application of this fungal strain to soil for bioremediation purposes.     

污染土壤修复技术预测

土壤污染已成为世界性环境问题,我国土壤污染现状更为严峻。污染土壤修复技术已成为全球科技的研究重点。本研究基于该领域国内外的相关研究论文与专利,采用文献计量学的统计方法,结合国内外相关项目、计划和法规等信息,对比分析了国内外论文/专利发文量阶段变化、技术研究的首篇报道年、专利景观图等。研究结果表明,我国污染土壤修复技术研发起步较晚,与发达国家总体水平存在10~15年的差距,在产业化领域更为突出。提出了在兼顾系统集成与技术原创的条件下,我国污染土壤修复的重点研发技术,为我国土壤修复技术的发展布局与政策制定提供决策依据。     

鼠李糖脂协助下的土壤中镉电动修复

实验研究了重金属Cd在生物表面活性剂鼠李糖脂协助下的电动修复过程,通过不同方式、不同浓度、不同酸碱度的鼠李糖脂溶液的添加与空白处理对比,探讨了鼠李糖脂协助下电动修复过程中的Cd在土壤介质中的迁移转化和机理,分析了鼠李糖脂溶液作为电动修复添加剂的可行性。结果表明,中等浓度酸性的鼠李糖脂溶液(pH=4.78,浓度为0.5、1和2 g/L)能对土壤中的重金属Cd进行有效的富集,富集量均在初始值的4倍以上,且其可交换态比重均大于42.07%,非常有利于土壤进行二次修复。此外,以pH=4.78,浓度为0.5 g/L的鼠李糖脂溶液作为预处理剂的Ex-08中的重金属Cd并未出现富集现象,但其对重金属的Cd的总去除效率达到了49.27%。表明利用鼠李糖脂溶液作为电动修复添加剂进行土壤重金属修复是可行的。     

A column method for determination of leaching of polycyclic aromatic hydrocarbons from aged contaminated soil

In this study a column leaching method for investigation of hydrophobic organic contaminants (HOCs) leaching from soil was developed. The method set-up is based on a recycled flow of sterile water through a soil column with a sedimentation chamber mounted on top of the column, in connection with on-line filtration. The combination of a sedimentation chamber and an on-line filtration enables the measurement of leaching concentrations from contaminated materials consisting of very fine particle fractions. In addition, by using on-line solid phase extraction, minute amounts of leaching HOCs may be captured and quantified with high accuracy and reproducibility. The method was applied successfully on a contaminated aged soil sample and the leaching behavior of seven PAHs, with three to six aromatic rings, was monitored for more than 1600 h under saturated conditions. The tested PAHs were fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)pyrene and benzo(ghi)perylene. The method proved to be reliable and capable of providing data on leachable amounts of the PAHs under field-like conditions and over a longer period of time. The results indicated low availability of the studied contaminants since only a minor fraction (0.3%) of the initial amount of PAHs in the soil was removed during the experiment (liquid/solid-ratio of 700 l/kg). Thus PAHs in aged contaminated soil are not to be expected to be released to any great extent only by leaching with water.     

铬污染土壤的还原稳定化修复

以湖南某工业场地的铬污染土壤为修复对象,投加不同比例的FeSO4·7H2O、FeSO4·7H2O和Ca（OH）2混合物及NaHSO3,通过测定土壤及浸出液中六价铬、总铬以及铬的形态,比较3种稳定剂对该污染土壤的还原稳定化作用。结果表明,FeSO4·7H2O和NaHSO3对铬污染土壤的还原稳定效果都较好,可以有效还原土壤中六价铬并能降低土壤中总铬的浸出浓度。当FeSO4·7H2O投加量为2%时,土壤六价铬和总铬浸出浓度降幅分别达到99.0%和57.5%;当NaHSO3投加量为0.8%时,六价铬和总铬浸出浓度降幅分别达到97.7%和42.2%,与前二者相比,FeSO4·7H2O和Ca（OH）2混合物还原稳定化效果较差。投加FeSO4·7H2O能够将土壤中活性大的可交换态和碳酸盐态铬转化为稳定的有机态和残渣态铬;而NaHSO3主要将可交换态和碳酸盐态铬转化为相对稳定的铁锰氧化态铬,其稳定化效果要差于FeSO4·7H2O。     

Mobilization of soil organic matter by complexing agents and implications for polycyclic aromatic hydrocarbon desorption

Complexing agents are frequently used in treatment technologies to remediate soils, sediments and wastes contaminated with toxic metals. The present study reports results that indicate that the rate and extent of soil organic matter (SOM) as represented by dissolved natural organic carbon (DNOC) and polycyclic aromatic hydrocarbon (PAH) desorption from a contaminated soil from a manufactured gas plant (MGP) site can be significantly enhanced with the aid of complexing agents. Desorption of DNOC and PAH compounds was pH dependent, with minimal release occurring at pH 2-3 and maximal release at pH 7-8. At pH-6, chelate solutions were shown to dissolve large amounts of humic substances from the soil compared to controls. The complexing agents mobilized polyvalent metal ions, particularly Fe and Al from the soil. Metal ion chelation may disrupt humic (metal ion)-mineral linkages, resulting in mobilization of SOM and accompanying PAH molecules into the aqueous phase; and/or reduce the degree of cross-linking in the soil organic matter phase, which could accelerate PAH diffusion.     

污染土壤修复的技术再造与展望

污染土壤的面积在迅速扩大,迫切需要修复、治理;随着土壤污染组分的日益复杂化,等待着全面、高效的修复技术的研制。对污染土壤修复相关技术现状进行剖析表明,现有的各种污染土壤修复技术由于存在着许多技术上难以克服的问题,需要从技术的现有进展和技术构想进行整体意义上的创新,即如何把现有的技术进行参数优化、改造后进行最佳组合与综合,才能取得该技术领域的重大突破。污染土壤的生态化学修复,其实质在于技术的再造,代表了21世纪污染土壤修复技术的发展方向。     

Formation of polycyclic aromatic hydrocarbon via gas phase benzyne

Gas phase benzyne generated from the high temperature pyrolysis of phthalic anhydride is reduced to benzene. This newly formed benzene is then free to react further with more benzyne to yield more complex aromatic hydrocarbons.     

石油污染土壤的植物与微生物修复技术

石油污染土壤的生物修复技术具有成本低、简便高效、对环境影响小等优点,正逐步成为石油污染治理研究的热点领域,具有广阔的发展前景.介绍了我国的石油污染概况及生物修复技术在石油污染治理中的应用,重点对石油污染土壤的微生物修复、植物修复、植物一微生物联合修复技术的研究进展及各自的优点、局限性进行了综述,并提出了石油污染土壤生物修复技术研究的重点领域.