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%。     

石油降解菌的筛选优化及其对油污土壤的修复特性

分别以牛肉膏蛋白胨-布氏哈斯培养基、蓝色凝胶培养基作为初筛和复筛培养基,从石油污染土壤中筛选出2株可产生微生物表面活性剂的石油烃降解菌。并将菌株投加到油污土壤中进行修复研究,考查了不同影响因素对修复效果的影响。研究结果表明,(1)2株菌对中度石油污染土壤有较好的修复效果,向油污土壤中直接投加菌株修复70 d时对石油烃的去除率为52%;(2)向油污土壤中投加降解菌并同时补充氮营养液,修复70 d时对土壤中总石油烃的去除率可达到75%;对土壤中正构烷烃的去除率为66%;(3)与土壤的含水率及土著菌的降解效果相比,向油污土壤中投加降解菌以及补充氮磷营养液是影响石油污染土壤修复效果的关键因素。     

降解菌ZQ5与紫茉莉对芘污染土壤的联合修复

在温室盆栽条件下,通过单独种植紫茉莉、单独接种多环芳烃(PAHs)模式化合物芘的专性降解菌ZQ5和两者的联合修复的3种处理,对芘污染土壤的修复效果进行了研究。结果表明,经90 d修复后,植物-微生物联合修复可将人工污染土壤中的芘降解81.1%,将石油污染土壤中的芘降解50.3%,其修复效率明显高于其他2种处理,是紫茉莉修复的1.98倍,是降解菌ZQ5修复的1.39倍。ZQ5的不同接菌量对于修复60 d后的降解率影响不大。外源生物修复条件下,10～20 cm土壤的修复效率要高于5 cm土壤;自然降解条件下,5 cm土层降解率略高于其他土层。     

植物-固体菌剂联合修复石油污染土壤的基础研究

以高效石油降解菌N_2、KB为目的菌种,玉米粉、麸皮和锯末为载体制备固体菌剂,并测定了这3种载体的饱和持水量、pH值和吸菌量。以吸菌量为评价指标,结合经济性综合选择最优载体,同时还考察了温度、pH值和料水比对最优载体吸菌量的影响。通过测定微生物数量和石油降解率的变化,考察了植物微生物联合修复效果。结果表明,与玉米粉和麸皮相比,锯末饱和持水量更大、吸菌量较大。锯末是木材厂的下脚料,可以实现高价值资源化利用。在温度30℃,pH为7,料水比1∶1.5的最适培养条件下,固体菌剂中N_2和KB两种细菌的活菌数量分别高达1.00×109CFU·g~(-1)和1.58×109CFU·g~(-1)。采用生物菌剂和柳枝稷对石油污染土壤进行植物-微生物联合修复实验,100 d后石油降解率可达到50.5%。     

一株多环芳烃降解菌的筛选及其降解特性

微生物修复是治理土壤多环芳烃(polycyclic aromatic hydrocarbons, PAHs)污染的主要方法,而高效降解菌筛选是微生物修复技术的重要基础。从北京焦化厂土壤中筛选分离得到一株PAHs降解菌Q3,通过生理生化和16S rDNA等分析手段鉴定其为Rhodococcus rhodochrous。结果表明:该菌株对芘的耐受能力较强,可降解初始浓度为200 mg·L~(-1)的芘;该菌株具有降解广谱性,可利用苯并[a]芘、苯并[b]荧蒽、二苯并[a,h]蒽、苯并[g,h,i]苝等9种PAHs为唯一碳源进行代谢,特别是对苯并[a]芘等高环PAHs具有较好的降解效果;此外,该菌株可有效降解模拟液中的混合PAHs,并且对野外被PAHs长期污染的土壤具有较好的强化修复效果。投加菌株处理后的处理组与对照组相比,土壤PAHs总去除率提高了24%。以上结果表明该菌株对环境中被PAHs污染的土壤具有较好的强化修复潜力,可为PAHs污染土壤的微生物修复技术提供技术参考。     

固定化微生物修复石油污染土壤影响因素研究

针对石油污染土壤修复,利用实验室已筛选的高效石油降解单菌SM-3,以天然有机材料为载体,吸附法制备固定化微生物。将游离与固定化微生物应用于室内花盆模拟修复石油污染土壤,对C/N/P、微生物投加量、石油含量、氧化剂和表面活性剂设计5因素4水平正交实验,探讨不同修复时期各影响因素的重要性顺序,最佳条件下各菌株的修复效果。结果表明,不同微生物在不同降解时期,各影响因素的重要性会发生变化;经过21 d的修复,固定化单菌SM-3石油降解率为22.77%,修复过程中,接种量是最重要的影响因素,营养元素N、P投加影响较大,表面活性剂和氧化剂影响次之。     

石油烃对翅碱蓬生理特性的影响及植物-微生物联合降解

通过盆栽实验,测定在低浓度石油烃浓度下翅碱蓬的生长生理指标及沉积物和翅碱蓬中石油烃含量的变化,研究石油烃对翅碱蓬生理特性和抗氧化酶系统的影响及植物-微生物联合修复效果。结果表明,翅碱蓬抗氧化酶能够快速提高活性来抵御逆境,植株还可通过增加其叶绿素含量等来适应或补偿逆境造成的损失。同时还发现,当植物处于石油烃污染沉积物时,它体内污染物的分布会与自然情况下有所不同,自然情况下分布为茎>叶>根,受污染时分布为根>茎>叶,该结果可以作为判断沉积物是否受到污染的依据。实验的不同处理(加植物加菌组、只加菌未种植物组、种植物未加菌组)去除率分别为70.87%、63.66%和60.26%,翅碱蓬-降解菌处理的沉积物中石油烃残留浓度最低、去除量最高,表明植物-微生物联合作用更有利于石油烃污染沉积物的修复。     

不同处理条件对石油污染土壤植物修复的影响

针对石油烃植物修复过程中的主要影响因素,研究了不同植物种类、不同土壤调理剂和菌剂使用等不同条件对土壤中石油烃植物修复效果的影响.结果表明,不同种类的植物修复可使总石油烃的年降解率达到37.8％ ～ 73.98％,其中大豆和碱蓬具有较好的修复效果;3种不同土壤调理剂对石油烃污染土壤修复的效果为商业添加剂＞牛粪＞蛭石;先微生物修复后种植植物的处理要优于单独的微生物修复及微生物、植物修复同步进行的处理.     

喹啉降解菌的降解效果考察

为了探索石油污染土壤中含氮杂环化合物的降解情况,在考察石油污染土壤理化性质的基础上,选择喹啉作为目标污染物,采用选择性富集培养的方法,从45份石油污染土壤样品中,分离得到155株降解喹啉污染物的高效降解菌株,从中选择降解效率较高的2株喹啉降解菌命名为Q5和Q24,进行喹啉的降解性能研究,比较了单一优势菌株、人工复合菌群和土壤中的自然菌群对喹啉的降解情况。实验结果表明,石油污染土壤中自然菌群对喹啉的降解效果好于单一的优势菌株和人工复合菌群。     

柴油降解菌的筛选、菌群构建及其对柴油和十五烷的降解机理

针对柴油污染土壤生物修复技术效率低的问题,通过构建高效降解菌群修复柴油污染的土壤,采用组合优化和正交实验构建最佳组合与接种比例的菌群,并研究其柴油降解特性。结果表明,通过筛选、鉴定并命名的4株柴油降解菌为Bacillus sp. VOC18-L1、 Enterococcus faecalis-L2、 Lysinibacillus-L3、 Rhodococcus equi-L4;当4株菌接种比例为3∶1∶3∶4,pH=7.0,30℃,转速150 r·min~(-1)时,柴油降解的效果最佳,14 d对7.0 mL·L~(-1)的柴油降解率达到89.0%。通过气相色谱质谱联用仪(GC-MS)检测柴油降解产物,发现该混合菌株能将柴油中的烷烃降解为短链烷烃,最终转化为小分子物质。同时利用KEGG数据库获得代谢丰度图并初步预测每种菌的功能,根据微生物多样性测试结果,进一步证明了混合菌对柴油完全降解的效果优于单种菌种。通过人工构建的微生物菌群可以有效地应用于柴油污染土壤的修复。     

Removal of PCBs in contaminated soils by means of chemical reduction and advanced oxidation processes

Although the chemical reduction and advanced oxidation processes have been widely used individually, very few studies have assessed the combined reduction/oxidation approach for soil remediation. In the present study, experiments were performed in spiked sand and historically contaminated soil by using four synthetic nanoparticles (Fe⁰, Fe/Ni, Fe₃O₄, Fe_3???x Ni _x O₄). These nanoparticles were tested firstly for reductive transformation of polychlorinated biphenyls (PCBs) and then employed as catalysts to promote chemical oxidation reactions (H₂O₂ or persulfate). Obtained results indicated that bimetallic nanoparticles Fe/Ni showed the highest efficiency in reduction of PCB28 and PCB118 in spiked sand (97 and 79 %, respectively), whereas magnetite (Fe₃O₄) exhibited a high catalytic stability during the combined reduction/oxidation approach. In chemical oxidation, persulfate showed higher PCB degradation extent than hydrogen peroxide. As expected, the degradation efficiency was found to be limited in historically contaminated soil, where only Fe⁰ and Fe/Ni particles exhibited reductive capability towards PCBs (13 and 18 %). In oxidation step, the highest degradation extents were obtained in presence of Fe⁰ and Fe/Ni (18–19 %). The increase in particle and oxidant doses improved the efficiency of treatment, but overall degradation extents did not exceed 30 %, suggesting that only a small part of PCBs in soil was available for reaction with catalyst and/or oxidant. The use of organic solvent or cyclodextrin to improve the PCB availability in soil did not enhance degradation efficiency, underscoring the strong impact of soil matrix. Moreover, a better PCB degradation was observed in sand spiked with extractable organic matter separated from contaminated soil. In contrast to fractions with higher particle size (250–500 and <500 μm), no PCB degradation was observed in the finest fraction (≤250 μm) having higher organic matter content. These findings may have important practical implications to promote successively reduction and oxidation reactions in soils and understand the impact of soil properties on remediation performance.     

Treatment of polychlorinated biphenyls in two surface soils using catalyzed H₂O₂ propagations

Two surface soils contaminated with polychlorinated biphenyls (PCBs) collected from Superfund sites in the New England region of the United States, Fletcher Paints and Merrimack Industrial Metals, were evaluated for field treatment at the bench level using catalyzed H₂O₂ propagations (CHP—modified Fenton’s reagent). The two soils were first evaluated for the potential for in situ treatment based on two criteria: (1) temperature (<40 °C after CHP reagent addition), and (2) hydrogen peroxide longevity (>24 h). In situ CHP remediation was more applicable to the Fletcher soil, while the Merrimack soil was better suited to ex situ treatment based on temperature increases and hydrogen peroxide lifetimes. Using the highest hydrogen peroxide concentrations appropriate for in situ treatment in each soil, PCB destruction was 94% in the Fletcher soil but only 48% in the Merrimack soil. However, 98% PCB destruction was achieved in the Merrimack soil using conditions more applicable to ex situ treatment (higher hydrogen peroxide concentrations with temperatures >40 °C). Analysis of degradation products by gas chromatography/mass spectroscopy showed no detectable chlorinated degradation products, suggesting that the products of PCB oxidation were rapidly dechlorinated and degraded. The results of this research document that the two PCB-contaminated soils studied can be effectively treated using aggressive CHP conditions, and that such a detailed bench study provides important information before implementing field treatment.     

Physicochemical and biological quality of soil in hexavalent chromium-contaminated soils as affected by chemical and microbial remediation

Chemical and microbial methods are the main remediation technologies for chromium-contaminated soil. These technologies have progressed rapidly in recent years; however, there is still a lack of methods for evaluating the chemical and biological quality of soil after different remediation technologies have been applied. In this paper, microbial remediation with indigenous bacteria and chemical remediation with ferrous sulphate were used for the remediation of soils contaminated with Cr(VI) at two levels (80 and 1,276 mg kg^?1) through a column leaching experiment. After microbial remediation with indigenous bacteria, the average concentration of water-soluble Cr(VI) in the soils was reduced to less than 5.0 mg kg^?1. Soil quality was evaluated based on 11 soil properties and the fuzzy comprehensive assessment method, including fuzzy mathematics and correlative analysis. The chemical fertility quality index was improved by one grade using microbial remediation with indigenous bacteria, and the biological fertility quality index increased by at least a factor of 6. Chemical remediation with ferrous sulphate, however, resulted in lower levels of available phosphorus, dehydrogenase, catalase and polyphenol oxidase. The result showed that microbial remediation with indigenous bacteria was more effective for remedying Cr(VI)-contaminated soils with high pH value than chemical remediation with ferrous sulphate. In addition, the fuzzy comprehensive evaluation method was proven to be a useful tool for monitoring the quality change in chromium-contaminated soils.     

Detailed characterization of polar compounds of residual oil in contaminated soil revealed by Fourier transform ion cyclotron resonance mass spectrometry

Effects of remediation technologies on polar compounds of crude oil in contaminated soils have not been well understood when compared to hydrocarbons. In this study, ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to characterize the changes in NSO polar compounds of crude oil and residual oil after long-term natural attenuation, biostimulation and subsequent ozonation following biostimulation of contaminated soils. N₁ and O₁ species, which were abundant in the crude oil, were selectively biodegraded, and species with higher double bond equivalent values and smaller carbon numbers appeared to be more resistant to microbial alteration. O₂-O₆ species were enriched by biodegradation and contained a large number of compounds with a high degree of unsaturation. Ozone could react with a variety of polar compounds in residual oil after biodegradation and showed high reactivity with polar species containing aromatic or multi-aliphatic rings, including the residual N₁ and O₁ species, naphthenic acids and unsaturated O₃-O₆ compounds. Fatty acids and O₃-O₈ species dominated by saturated alkyl compounds were resistant to ozonation or the primarily incomplete ozonation products. Principal component analysis of identified peaks in the FT-ICR MS spectra provided a comprehensive overview of the complex samples at the molecular level and the results were consistent with the detailed analysis. Taken together, these results showed the high complexity of polar compounds in residual oils after biodegradation or ozonation in contaminated soil and would contribute to a better understanding of bioremediation and ozonation processes.     

Effects of chemical oxidation on sorption and desorption of PAHs in typical Chinese soils

In situ chemical oxidation is a commonly applied soil and groundwater remediation technology, but can have significant effects on soil properties, which in turn might affect fate and transport of organic contaminants. In this study, it was found that oxidation treatment resulted mainly in breakdown of soil organic matter (SOM) components. Sorption of naphthalene and phenanthrene to the original soils and the KMnO₄-treated soils was linear, indicating that hydrophobic partitioning to SOM was the predominant mechanism for sorption. Desorption from the original and treated soils was highly resistant, and was well modeled with a biphasic desorption model. Desorption of residual naphthalene after treating naphthalene-contaminated soils with different doses of KMnO₄ also followed the biphasic desorption model very well. It appears that neither changes of soil properties caused by chemical oxidation nor direct chemical oxidation of contaminated soils had a noticeable effect on the nature of PAH-SOM interactions.     

Atrazine degradation by fungal co-culture enzyme extracts under different soil conditions

This investigation was undertaken to determine the atrazine degradation by fungal enzyme extracts (FEEs) in a clay-loam soil microcosm contaminated at field application rate (5 μg g^?1) and to study the influence of different soil microcosm conditions, including the effect of soil sterilization, water holding capacity, soil pH and type of FEEs used in atrazine degradation through a 2⁴ factorial experimental design. The Trametes maxima–Paecilomyces carneus co-culture extract contained more laccase activity and hydrogen peroxide (H₂O₂) content (laccase = 18956.0 U mg protein^?1, H₂O₂ = 6.2 mg L^?1) than the T. maxima monoculture extract (laccase = 12866.7 U mg protein^?1, H₂O₂ = 4.0 mg L^?1). Both extracts were able to degrade atrazine at 100%; however, the T. maxima monoculture extract (0.32 h) achieved a lower half-degradation time than its co-culture with P. carneus (1.2 h). The FEE type (p = 0.03) and soil pH (p = 0.01) significantly affected atrazine degradation. The best degradation rate was achieved by the T. maxima monoculture extract in an acid soil (pH = 4.86). This study demonstrated that both the monoculture extracts of the native strain T. maxima and its co-culture with P. carneus can efficiently and quickly degrade atrazine in clay-loam soils.     

Evaluation of in situ catalysed hydrogen peroxide propagation (CHP) for phenanthrene and fluoranthene removals from soil and its associated impacts on soil functionality

Extensive contamination of soils by highly recalcitrant contaminants such as polycyclic aromatic hydrocarbons (PAHs) is an environmental problem arising from rapid industrialisation. This work focusses on the remediation of soil contaminated with 3- and 4-aromatic ring PAHs (phenanthrene (PHE) and fluoranthene (FLUT)) through catalysed hydrogen peroxide propagation (CHP). In the present work, the operating parameters of the CHP treatment in packed soil column was optimised with central composite design (H₂O₂/soil 0.081, Fe³⁺/soil 0.024, sodium pyrophosphate (SP)/soil 0.024, pH of SP solution 7.73). The effect of contaminant aging on PAH removals was also investigated. Remarkable oxidative PAH removals were observed for the short aging and extended aging period (up to 86.73 and 70.61 % for PHE and FLUT, respectively). The impacts of CHP on soil biological, chemical and physical properties were studied for both spiked and aged soils. Overall, the soil functionality analyses after the proposed operating condition demonstrated that the values for soil respiration, electrical conductivity, pH and iron precipitation fell within acceptable limits, indicating the compatibility of the CHP process with land restoration.     

Dynamics of PCB removal and detoxification in historically contaminated soils amended with activated carbon

Activated carbon (AC) can help overcome toxicity of pollutants to microbes and facilitate soil bioremediation. We used this approach to treat a Histosol and an Alluvial soil historically contaminated with PCB (4190 and 1585 mg kg⁻¹, respectively; primarily tri-, tetra- and pentachlorinated congeners). Results confirmed PCB persistence; reductions in PCB extractable from control and AC-amended soils were mostly due to a decrease in tri- and to some extent tetrachlorinated congeners as well as formation of a bound fraction. Mechanisms of PCB binding by soil and AC were different. In addition to microbial degradation of less chlorinated congeners, we postulate AC catalyzed dechlorination of higher chlorinated congeners. A large decrease in bioavailable PCB in AC-amended soils was demonstrated by greater clover germination and biomass. Phytotoxicity was low in treated soils but remained high in untreated soils for the duration of a 39-month experiment. These observations indicate the utility of AC for remediation of soils historically contaminated with PCB.     

The influence of association of plant growth-promoting rhizobacteria and zero-valent iron nanoparticles on removal of antimony from soil by Trifolium repens

Using association of plants, nanomaterials, and plant growth-promoting bacteria (PGPR) is a novel approach in remediation of heavy metal-contaminated soils. Co-application of nanoscale zerovalent iron (nZVI) and PGPR to promote phytoremediation of Sb-contaminated soil was investigated in this study. Seedlings of Trifolium repens were exposed to different regimes of nZVI (0, 150, 300, 500, and 1000 mg/kg) and the PGPR, separately and in combination, to investigate the effects on plant growth, Sb uptake, and accumulation and physiological response of the plant in contaminated soil. Co-application of nZVI and PGPR had positive effects on plant establishment and growth in contaminated soil. Greater accumulation of Sb in the shoots compared to the roots of T. repens was observed in all treatments. Using nZVI significantly increased accumulation capacity of T. repens for Sb with the greatest accumulation capacity of 3896.4 μg per pot gained in the “PGPR+500 mg/kg nZVI” treatment. Adverse impacts of using 1000 mg/kg nZVI were found on plant growth and phytoremediation performance. Significant beneficial effect of integrated use of nZVI and PGPR on plant photosynthesis was detected. Co-application of nZVI and PGPR could reduce the required amounts of nZVI for successful phytoremediation of metalloid polluted soils. Intelligent uses of plants in accompany with nanomaterials and PGPR have great application prospects in removal of antimony from soil.