地下水中BTEX的原位生物修复研究进展

BTEX是苯、甲苯、乙苯和二甲苯的统称,存在于原油和石油产品中,其作为化工原料,广泛应用于农药、塑料及合成纤维等制造业.BTEX已成为地下水中普遍存在的污染物,自然衰减或生物修复工程已成功应用于地下水中BTEX的去除.自然衰减受BTEX污染的地下水具有良好的效果,但相比之下,生物修复工程更快、更有效.综述了在好氧和厌氧条件下,地下水中BTEX原位生物修复过程的微生物降解机制.     

Developing slow-release persulfate candles to treat BTEX contaminated groundwater

The development of slow-release chemical oxidants for sub-surface remediation is a relatively new technology. Our objective was to develop slow-release persulfate-paraffin candles to treat BTEX-contaminated groundwater. Laboratory-scale candles were prepared by heating and mixing Na₂S₂O₈ with paraffin in a 2.25 to 1 ratio (w/w), and then pouring the heated mixture into circular molds that were 2.38 cm long and either 0.71 or 1.27 cm in diameter. Activator candles were prepared with FeSO₄ or zerovalent iron (ZVI) and wax. By treating benzoic acid and BTEX compounds with slow-release persulfate and ZVI candles, we observed rapid transformation of all contaminants. By using ¹⁴C-labeled benzoic acid and benzene, we also confirmed mineralization (conversion to CO2) upon exposure to the candles. As the candles aged and were repeatedly exposed to fresh solutions, contaminant transformation rates slowed and removal rates became more linear (zero-order); this change in transformation kinetics mimicked the observed dissolution rates of the candles. By stacking persulfate and ZVI candles on top of each other in a saturated sand tank (14 × 14 × 2.5 cm) and spatially sampling around the candles with time, the dissolution patterns of the candles and zone of influence were determined. Results showed that as the candles dissolved and persulfate and iron diffused out into the sand matrix, benzoic acid or benzene concentrations (C_o = 1 mM) decreased by >90% within 7 d. These results support the use of slow-release persulfate and ZVI candles as a means of treating BTEX compounds in contaminated groundwater.     

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。     

农药污染地下水的微生物治理及含水层渗透性变化研究

采用了从农药厂阿特拉津生产车间排污口污泥中分离出的菌种AT菌 ,进行了农药阿特拉津污染地下水微生物治理的模拟实验研究 ,在实验条件 (T =10℃ ,pH =7.5 )与野外含水层的条件基本一致情况下 ,难于生物降解的污染质阿特拉津的一次投菌降解率可达 3 1.0 8% ;设计了两种有效细菌的投放方式以模拟野外条件下的菌种投加条件。另外 ,AT菌的作用会造成被治理含水层的渗透性能降低 ,两种投菌方式下 ,实验后含水层的渗透系数分别下降 60 .5 4%和 3 4 5 6%。清水冲洗 10d的渗透性恢复率分别为 48.96%及 81.3 6% ,说明清水渗透恢复的方法效果明显     

Enhanced bioremediation of soil from Tianjin,China, contaminated with polybrominated diethyl ethers

This work aimed to evaluate the effectiveness of nutrients, H₂O₂, and tourmaline on the bioremediation of fields where the soil was contaminated with polybrominated diethyl ethers (PBDEs). The results showed that 39.2, 38.3, and 48.1 % of total PBDE removal was observed in microcosms with the addition of nutrients, such as NaNO₃, NH₄Cl, and NH₄NO₃, respectively, compared to only 15.2 and 5.8 % of PBDE removal from soil with added Aspergillus niger and control soil, respectively, after 50 days of incubation. In addition, 50.8 and 56.5 % of total PBDE removal were observed in microcosms with 0.5 and 1 μL H₂O₂. The addition of tourmaline increased total PBDE removal to 32.4 %. Significant increases in soil enzymatic activity with PBDE degraders and bacterial communities were observed using polymerase chain reaction (PCR)—denaturing gradient gel electrophoresis (DGGE). These observations suggested that the combination of inorganic nutrients with chemical, mineral, and biological treatment could improve the PBDE removal efficiency. However, the combination of H₂O₂ and biological treatment processes is the most efficient technology. This combination of technologies would not cause adverse effects on the subsequent bioremediation process. Therefore, this work offers a potential alternative for the remediation of soil contaminated with PBDE pollutants.     

Enhanced degradation of chlorinated ethylenes in groundwater from a paint contaminated site by two-stage fluidized-bed reactor

Groundwater, used in this study, contaminated predominantly with aromatic compounds, was biologically treated in a fluidized-bed reactor (FBR) with immobilized cells. The aromatics were completely decomposed, while cis-1,2-dichloroethylene (cis-DCE) and trichloroethylene (TCE) were decomposed only approximately 20% and 5%, respectively. In these studies a significant improvement of the decomposition efficiency for chlorinated ethylenes was achieved by utilizing cometabolism. Methanol (MeOH) and toluene were used as the substrate in the case of one-stage reactor (Single Reactor). MeOH (187 mg l(-1)) increased the decomposition efficiency up to 40% and 60% for cis-DCE and TCE, respectively, while toluene (20 mg l(-1)) increased the decomposition efficiency of cis-DCE to 92% and the decomposition efficiency of TCE to 76%. In the case of two-stage reactor system (Reactor 1 and Reactor 2), MeOH and methane (CH4) were used as the substrate. In this system, cells grown on MeOH or CH4 in the Reactor 1 were continuously fed into Reactor 2 and groundwater was fed into Reactor 2 only. When MeOH (384 mg l(-1) d(-1)) was used as substrate the decomposition efficiency of cis-DCE and TCE were 60% and 70%, respectively. Similar decomposition efficiency was observed for a small amount of CH4 (19.3 mg l(-1) d(-1)).     

In situ sequenced bioremediation of mixed contaminants in groundwater

A mixture of chlorinated solvents (about 0.5-10 mg/l), including tetrachloroethene (PCE) and carbon tetrachloride (CT), together with a petroleum hydrocarbon, toluene (TOL), were introduced into a 24 m long x 2 m wide x 3 m deep isolated section (henceforth called a gate) of the Borden aquifer and subjected to sequential in situ treatment. An identical section of aquifer was similarly contaminated and allowed to self-remediate by natural attenuation, thus serving as a control. The control presents a rare opportunity to critically assess the performance of the treatment systems, and represents the first such study for sequenced in situ remediation. The first treatment step was anaerobic bioremediation. This was accomplished using a modified nutrient injection wall (NIW) to pulse benzoate and a nutrient solution into the aquifer, maximizing mixing by dispersion and minimizing fouling near the injection wells. In the anaerobic bioactive zone that developed, PCE, CT and chloroform (CF), a degradation product of CT, degraded with a half-lives of about 59, 5.9 and 1.7 days, respectively. The second step was aerobic bioremediation, using a biosparge system. TOL and cis-1,2 dichloroethene (cDCE), from PCE degradation, were found to degrade aerobically with half-lives of 17 and 15 days, respectively. Compared to natural attenuation, PCE and TOL removal rates were significantly better in the sequenced treatment gate. However, CT and CF were similarly and completely attenuated in both gates. It is believed that the presence of TOL helped sustain the reducing environment needed for the reduction of these two compounds.     

表面活性剂强化甲基营养型芽孢杆菌修复柴油污染土壤

使用吐温80（Tween80）、鼠里糖脂（RL）、十二烷基苯磺酸钠（SDBS）和十二烷基苯硫酸钠（SDS）强化甲基营养型芽孢杆菌（Bacillus methylotrophicus）修复柴油污染土壤,研究了表面活性剂对甲基营养型芽孢杆菌的影响。结果表明：甲基营养型芽孢杆菌可以较好地降解柴油,但由于土壤的吸附,土壤中柴油的修复效率较低,仅为22.68%;因此,需要使用表面活性剂进行强化。浓度为3 000 mg·L-1的SDBS和SDS、2 000 mg·L-1的Tween80、500 mg·L-1的RL具有较好的洗脱效果。微生物毒性实验表明,Tween80和RL对甲基营养型芽孢杆菌具有促进作用,可以用于强化修复柴油污染土壤。2 000 mg·L-1 Tween80强化甲基营养型芽孢杆菌修复柴油土壤的修复效果（46.11%）优于500 mg·L-1 RL的修复效果（45.32%）,同时具有较好的经济性,具有较好的应用前景。     

砷污染土壤微生物修复机制及其研究进展

土壤砷污染是一个全球性问题。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。微生物修复是目前研究的热点,也是治理砷污染土壤的主要手段之一。综述了土壤中砷污染现状及其赋存形式,重点分析讨论了砷污染土壤的微生物修复机制以及提高微生物修复效率的方法。土壤砷污染修复是一项复杂的系统工程,单一的修复技术很难实现显著的效果。只有建立在以微生物修复为主的基础上,辅之以物理化学、植物及农业生态等措施,才能大大提高微生物修复效率。总结了近年来国内外微生物修复砷污染土壤技术的研究进展,以期为深入研究微生物代谢砷的机制及其在砷污染治理中的应用提供参考。     

Pilot-scale constructed wetlands for petroleum-contaminated groundwater.

A pilot study was conducted to determine the feasibility of using constructed treatment wetlands to remediate recovered groundwater from the subsurface of a former refinery site. The pilot system consisted of four subsurface flow treatment cells operated in an upward vertical flow mode and equipped with subsurface aeration lines. The treatment system showed minimal capability for methyl-tert-butyl ether removal, but did effectively remove total petroleum hydrocarbons-deisel range organics and total benzene, toluene, ethylbenzene, and o-, m-, and p-xylenes (total BTEX). Effluent benzene concentrations were less than 0.05 mg/L in 70% of the samples from a treatment cell using subsurface aeration and a wetland sod amendment. Based on 1 year of operating data, cumulative mass removal approached 80% for benzene and 88% for total BTEX.     

Effect of vegetation in pilot-scale horizontal subsurface flow constructed wetlands treating sulphate rich groundwater contaminated with a low and high chlorinated hydrocarbon

In order to characterize the effect of vegetation on performance of constructed wetlands (CWs) treating low and high chlorinated hydrocarbon, two pilot-scale horizontal subsurface flow (HSSF) CWs (planted with Phragmites australis and unplanted) treating sulphate rich groundwater contaminated with MCB (monochlorobenzene, as a low chlorinated hydrocarbon), (about 10 mg L⁻¹), and PCE (perchloroethylene, as a high chlorinated hydrocarbon), (about 2 mg L⁻¹), were examined. With mean MCB inflow load of 299 mg m⁻² d⁻¹, the removal rate was 58 and 208 mg m⁻² d⁻¹ in the unplanted and planted wetland, respectively, after 4 m from the inlet. PCE was almost completely removed in both wetlands with mean inflow load of 49 mg m⁻² d⁻¹. However, toxic metabolites cis-1,2-DCE (dichloroethene) and VC (vinyl chloride) accumulated in the unplanted wetland; up to 70% and 25% of PCE was dechlorinated to cis-1,2-DCE and VC after 4 m from the inlet, respectively. Because of high sulphate concentration (around 850 mg L⁻¹) in the groundwater, the plant derived organic carbon caused sulphide formation (up to 15 mg L⁻¹) in the planted wetland, which impaired the MCB removal but not statistically significant. The results showed significant enhancement of vegetation on the removal of the low chlorinated hydrocarbon MCB, which is probably due to the fact that aerobic MCB degraders are benefited from the oxygen released by plant roots. Vegetation also stimulated completely dechlorination of PCE due to plant derived organic carbon, which is potentially to provide electron donor for dechlorination process. The plant derived organic carbon also stimulated dissimilatory sulphate reduction, which subsequently have negative effect on MCB removal.     

The variability and intrinsic remediation of a BTEX plume in anaerobic sulphate-rich groundwater

Data from long-term groundwater sampling, limited coring, and associated studies are synthesised to assess the variability and intrinsic remediation/natural attenuation of a dissolved hydrocarbon plume in sulphate-rich anaerobic groundwater. Fine vertical scale (0.25- and 0.5-m depth intervals) and horizontal plume-scale (>400 m) characteristics of the plume were mapped over a 5-year period from 1991 to 1996. The plume of dissolved BTEX (benzene, toluene, ethylbenzene, xylene) and other organic compounds originated from leakage of gasoline from a subsurface fuel storage tank. The plume was up to 420 m long, less than 50 m wide and 3 m thick. In the first few years of monitoring, BTEX concentrations near the point of leakage were in approximate equilibrium with non-aqueous phase liquid (NAPL) gasoline. NAPL composition of core material and long-term trends in ratios of BTEX concentrations in groundwater indicated significant depletion (water washing, volatilisation and possibly biodegradation) of benzene from residual NAPL after 1992. Large fluctuations in BTEX concentrations in individual boreholes were shown to be largely attributable to seasonal groundwater flow variations. A combination of temporal and spatial groundwater quality data was required to adequately assess the stationarity of plumes, so as to allow inference of intrinsic remediation. Contoured concentration data for the period 1991 to 1996 indicated that plumes of toluene and o-xylene were, at best, only partially steady state (pseudo-steady state) due to seasonal groundwater flow changes. From this analysis, it was inferred that significant remediation by natural biodegradation was occurring for BTEX component plumes such as toluene and o-xylene, but provided no conclusive evidence of benzene biodegradation. Issues associated with field quantification of intrinsic remediation from groundwater sampling are highlighted. Preferential intrinsic biodegradation of selected organic compounds within the BTEX plume was shown to be occurring, in parallel with sulphate reduction and bicarbonate production. Ratios of average hydrocarbon concentrations to benzene for the period 1991 to 1992 were used to estimate degradation rates (half-lives) at various distances along the plume. The estimates varied with distance, the narrowest range being, for toluene, 110 to 260 days. These estimates were comparable to rates determined previously from an in situ tracer test and from plume-scale modelling.     

Temporal ecological assessment of oil contaminated soils before and after bioremediation

Ecotoxicity methods were used to assess different soil and oil combinations before, during and after laboratory bioremediation with associated hydrocarbon analysis. Heavy, medium and light crude oil (API gravity 14, 30, and 55) was spiked (ca. 5% w/w) into two sandy soils in the laboratory having organic carbon concentrations of 0.3 (Norwood) and 4.7% (Norwood/Baccto). The earthworm (Eisenia fetida) 14-d lethality assay, the modified Microbics Microtox Solid-Phase assay, and the 14-d plant seed germination and growth assays using corn, wheat and oats, were spiked and tested during a 360-d laboratory remediation. Eisenia was the most sensitive of the three methods utilized with survival increasing throughout bioremediation with fastest toxicity reduction in the high carbon Norwood/Baccto soils where LC50's were 100% or greater at the end of 90-d whereas, > 150-d were required to achieve a similar result in the low carbon soil. Analysis of the undiluted treatments with oily soil alone showed that earthworm survival was high after 90-d in all high organic carbon soils, and after eight months in the low carbon soils, except for the Norwood soil-light oil treatment, which required 360-d to achieve 100% survival. The Microtox assay was less sensitive with EC50's 100% or greater observed after 90-d in high carbon soils and after 240-d for all low carbon soils. After bioremediation, no effects on seed germination were observed, although some plant growth inhibition effects remained. There was no direct correlation between total petroleum hydrocarbon concentrations and toxicity.     

Enhanced phytoremediation of arsenic contaminated land

In an attempt to clean up arsenic (As) contaminated soil, the effects of phosphorus (P) fertilizer and rhizosphere microbes on arsenic accumulation by the silverback fern, Pityrogramma calomelanos, were investigated in both greenhouse and field experiments. Field experiments were conducted in Ron Phibun District, an As-contaminated area in Thailand. Soil (136-269 microg As g(-1)) was collected there and used in the greenhouse experiment. Rhizosphere microbes (bacteria and fungi) were isolated from roots of P. calomelanos growing in Ron Phibun District. The results showed that P-fertilizer significantly increased plant biomass and As accumulation of the experimental P. calomelanos. Rhizobacteria increased significantly the biomass and As content of the test plants. Thus, P-fertilizer and rhizosphere bacteria enhanced As-phytoextraction. In contrast, rhizofungi reduced significantly As concentration in plants but increased plant biomass. Therefore, rhizosphere fungi exerted their effects on phytostabilization.     

The application of the vermicomposting process in the bioremediation of diesel contaminated soils

Abstract

Polycyclic Aromatic Hydrocarbons (PAHs) are among the environmental pollutants that have very high carcinogenic and mutagenic activity. Among hundreds of different PAHs, 17 are considered priority pollutants and routinely monitored for regulatory purposes. Extended periods of exposure and expensive clean-up costs are typically associated with the vast majority of processes used for the remediation of areas contaminated with PAHs. The results of this study indicate that bioremediation via vermicomposting could be an effective method for remedying soils contaminated with toxic organic compounds, such as PAHs. This study was conducted over 90?days in the presence of various quantities of organic matter (cattle manure) to recover soils contaminated with PAHs. High-performance liquid chromatography (HPLC) was applied to identify PAHs. An evaluation of the toxicity of the final material and the transformation of the organic matter throughout the process was also conducted. The data presented here suggest a relationship between the molar mass of the PAHs and the ability of the vermicomposting process to promote biodegradation. These results suggest that vermicomposting has great potential to be utilized as a tool for the bioremediation of soils impacted by PAHs.     

地下水PRB原位生物修复中一种释氧材料的改进技术及效果分析

释氧材料经济有效的释氧是地下水原位生物修复的关键因素。实验通过在释氧材料中加入膨润土、磷酸二氢钾和硫酸铵等,改进释氧材料的性能。柱实验结果显示,该释氧材料释氧速率缓慢,释氧时间长,可以使溶液中DO长期保持在5 mg/L以上;另外,释氧材料中添加的缓冲剂及天然含水层介质对pH值有较好的缓冲作用,可以使pH值达到后续生物修复的要求。     

Fenton和类Fenton氧化处理地下水中BTEX及其动力学

研究比较Fenton试剂和类Fenton试剂氧化处理地下水中苯、甲苯、乙苯和二甲苯(BTEX)的效果及动力学.结果表明,Fenton氧化处理BTEX较类Fenton效果好,且反应过程中体系均处于强氧化环境,pH值维持在3左右;Fenton和类Fenton氧化去除BTEX过程均符合二级反应动力学方程:1/C=kt+1/C...     

Engineered and subsequent intrinsic in situ bioremediation of a diesel fuel contaminated aquifer

A diesel fuel contaminated aquifer in Menziken, Switzerland was treated for 4.5 years by injecting aerated groundwater, supplemented with KNO3 and NH4H2PO4 to stimulate indigenous populations of petroleum hydrocarbon (PHC) degrading microorganisms. After dissolved PHC concentrations had stabilized at a low level, engineered in situ bioremediation was terminated. The main objective of this study was to evaluate the efficacy of intrinsic in situ bioremediation as a follow-up measure to remove PHC remaining in the aquifer after terminating engineered in situ bioremediation. In the first 7 months of intrinsic in situ bioremediation, redox conditions in the source area became more reducing as indicated by lower concentrations of SO4(2-) and higher concentrations of Fe(II) and CH4. In the core of the source area, strongly reducing conditions prevailed during the remaining study period (3 years) and dissolved PHC concentrations were higher than during engineered in situ bioremediation. This suggests that biodegradation in the core zone was limited by the availability of oxidants. In lateral zones of the source area, however, gradually more oxidized conditions were reestablished again, suggesting that PHC availability increasingly limited biodegradation. The total DIC production rate in the aquifer decreased within 2 years to about 25% of that during engineered in situ bioremediation and remained at that level. Stable carbon isotope analysis confirmed that the produced DIC mainly originated from PHC mineralization. The total rate of DIC and CH4 production in the source area was more than 300 times larger than the rate of PHC elution. This indicates that biodegradation coupled to consumption of naturally occurring oxidants was an important process for removal of PHC which remained in the aquifer after terminating engineered measures.     

Innovative technologies for contaminated site remediation: focus on bioremediation.

Bioremediation, the process by which hazardous substances are degraded by microorganisms, is at the forefront of a larger group of innovative remediation technologies being applied at hazardous waste sites worldwide. Although the process of bioremediation has been utilized for decades in the field of wastewater engineering, its application to soils and groundwater at hazardous waste sites is fairly new and still undergoing intensive development. This article is intended to provide both an overview of the state of practice of bioremediation in hazardous waste remediation operations, and an inventory of issues to consider when evaluating the use of this technology for a contaminated site. These topics will be the subject matter of a unique Bioremediation Satellite seminar to be broadcast on January 9, 1992. The seminar, a joint venture between the Air and Waste Management Association (A&WMA) and the Hazardous Waste Action Coalition (HWAC), is the first in a series of satellite seminars that will deal with innovative hazardous waste remediation technologies. The intent of these seminars is to design programs which will make hazardous waste practitioners more familiar with innovative remediation technologies so that they will consider using the technologies in future clean-up operations.     

Factors inhibiting bioremediation of soil contaminated with weathered oils and drill cuttings

Oily drill cuttings and a soil contaminated with weathered crude oils were treated by enhanced biodegradation under tropical conditions in industrial scaled experiments. Oil contaminants were characterized by gas chromatography and mass spectrometry. This allowed for the identification of a mixture of two crude oils in the contaminated soil. After 12 months of bioremediation process, the removal of hydrocarbons reached by biodegradation an extent of 60% although nutrient amendment with elevated concentration of N-urea had highly detrimental effects on the hydrocarbon degrading fungal populations due to the production of toxic concentration of ammonia gas by nitrification. The saturated hydrocarbons were extensively assimilated, though n-alkanes were not completely removed. Aromatic hydrocarbons were less degraded than saturated whereas resin and asphaltene fractions were, surprisingly, partly assimilated. In laboratory conditions, the residual hydrocarbons in the field-treated materials were 15-20% further degraded when metabolic byproducts resulting from biodegradation were diluted or removed.