有机污染物湿地生物降解实验规律研究

本文以苯，甲苯和萘为对象，通过实验研究，测定有机污染物的土壤－水吸附平衡过程，在水溶液中生物降解过程以及在湿地系统（即土壤－水－微生物系统）中生物降解过程，并以质量守恒定律为基础，建立有机污染物湿地生物降解过程综合数学模型，数学模型通过实验验证，利用模型，定量预测了污染物生物降解所需的时间和程度，并提出动力学因子FK，判断污染物湿地生物降解速度的控制因素，定量预测了污染物在土壤固相的浓度分布规律。     

影响有机污染物在土壤中的迁移、转化行为的因素

本文介绍了有机污染物在土壤中的吸附与解吸附、渗滤、挥发和降解等行为过程。探讨了吸附与解吸附机理、土壤有机质含量和类型、水分含量及温度等对此过程的影响。依据某些典型的化合物行为模型,论述了影响土壤中有机污染物渗滤的因素。有机污染物需要先从土壤深层迁移至地表,然后挥发至大气,在土壤中迁移的速率较慢,控制着整个挥发过程,可用Ｆｉｃｋ 第二定律来描述。有机污染物在土壤中的非生物降解主要包括氧化－ 还原、光解和水解等反应。土壤中的Ｏ２ 含量、土壤有机质成分和含量、辐射强度、光谱分布、土壤水分含量、温度和ｐＨ 值等都会影响非生物降解过程。其中有些因素通过影响微生物的生物活性,还影响有机污染物的生物降解     

潜流湿地对典型选控性有机污染物去除的预测

建立潜流湿地有机污染物迁移转化模型,采用多孔介质模型描述潜流湿地的水力特性,并引入Monod方程相耦合,实现对湿地系统内部流场及水质浓度的同时模拟。通过实验,校核模型参数,并验证模型。结果表明,该模型能较好模拟潜流湿地中有机污染物的去除效果;计算条件下,在不同基质填料的潜流湿地中都会出现滞水区和快速通道,影响水力效率与污染物去除效果;预测了不同填料系统中7种典型选控性有机污染物的去除效果,其处理效率:苯胺苯酚二甲苯甲苯苯硝基苯氯苯,可通过优选填料提高吸附量和延长停留时间来提高选控性有机物的处理效果。     

人工湿地系统微生物去除污染物的研究进展

人工湿地污水处理系统具有净化效果显著、建设和运行费用低廉、管理简便等优点,近年来越来越受到人们的重视。人工湿地是利用介质、植物和微生物构成的复合系统来处理污水。微生物在人工湿地系统净化污水过程中发挥着重要作用。介绍了人工湿地系统中微生物去除污染物的研究进展,重点讨论了人工湿地对污染物和特殊有机污染物的去除以及系统基质中微生物的种群和活性等内容,并结合我国研究现状展望了该领域的研究前景。人工湿地系统微生物对污染物去除将成为人工湿地生态系统服务功能评价、人工湿地生态系统健康与稳定的诊断的重要组成部分。     

污染物的原位生物处理—生物清消技术

生物清消技术是一种迅速发展的污染物处理的生物技术,用于处理分散在土壤、地下水、海洋和湖泊中的污染物。生物清消技术通过向环境供给营养物、共作基质和供氧,并依靠有机污染物自身的碳源促进天然微生物群体的生长繁殖,也可进一步向污染环境中补充在实验中筛选和增殖的微生物(强化技术)稳定和加速生物降解过程。本文介绍了生物清消的几种方法:生物促进法、生物耕作法、固相清消法、土壤堆制法、生物泥浆法,还介绍了强化技术应用的几个方面。     

石油烃在不同土壤中的气相自然衰减规律

挥发性有机物(VOCs)在包气带中的迁移扩散是土壤和地下水中可挥发污染物自然衰减的重要机制,也与蒸气入侵暴露和风险评估密切相关。采用微宇宙实验对12种挥发性石油烃(正戊烷、正己烷、正庚烷、正辛烷、环戊烷、环己烷、环庚烷、环辛烷、苯、甲苯、乙苯、对二甲苯)在4种土壤(黑土、黄土、红土、石英砂)中的气相自然衰减机制和气态生物降解动力学规律进行了研究。结果表明,正构烷烃、环烷烃和苯系物蒸气在4种土壤中的气相自然衰减去除率都遵循黑土>黄土>红土>石英砂的规律;黑土中生物降解对污染物去除率的贡献高于黄土,而红土和石英砂中的生物降解速率极低;4种苯系物的自然衰减和生物降解潜力远高于正构烷烃和环烷烃;苯系物气相生物降解速率排序为：甲苯>苯>乙苯>对二甲苯。本研究结果可为蒸气入侵定量风险评估和石油污染场地自然衰减速率定量评估提供参考。     

大型水生植物在水污染治理中的应用研究进展

大型水生植物在水污染治理中可以发挥多种作用。通过自身的生长代谢可以大量吸收氮、磷等水体中的营养物质 ,而其中一些种类还可以富集不同类型的重金属或吸收降解某些有机污染物 ;通过促进微生物的生长代谢 ,可以使水中大部分可生物降解有机物 (BOD)降解 ;通过抑制低等藻类的生长 ,控制富营养化的表现形式等。根据不同的生活型特点 ,利用大型水生植物进行污水处理和水体修复的方式也多种多样 ,主要包括 :以漂浮植物为主的塘系统和以挺水植物为主的人工湿地系统等。本文从生态功能发挥的角度探讨了植物对污染物降解的机理 ,并对以大型水生植物为核心的各种污水处理系统的研究进展与现状进行了综述 ,指出了利用大型水生植物进行水污染治理的研究与应用中存在的问题和发展方向     

苯污染地下水系统反硝化菌分布及其净化过程

生物降解作用是地下水系统有机污染物自然衰减过程中最重要的破坏性衰减机制。在分析中,以我国某受苯污染水源地的地下水系统为对象,研究了该地下水中反硝化菌的分布,筛选出2株土著反硝化菌,通过生物降解实验证明其具有降解苯的能力,同时结合水源地历年的水质监测数据,首次从地球化学及生物学2个方面说明了该地下水中存在反硝化菌对苯的生物净化作用,为进一步研究该地下水中苯自然衰减规律奠定基础。     

大型水生植物在水污染治理中的应用研究进展

大型水生植物在水污染治理中可以发挥多种作用。通过自身的生长代谢可以大量吸收氨、磷等水体中的营养物质，而其中一些种类还可以富集不同类型的重金属或吸收降解某些有机污染物；通过促进微生物的生长代谢，可以使水中大部分可生物降解有机物（BOD）降解；通过抑制低等藻类的生长，控制富营养化的表现形式等。根据不同的生活型特点，利用大型水生植物进行污水处理和水体修复的方式也多种多样，主要包括：以漂浮植物为主的塘系统和以挺水植物为主的人工湿地系统等。本文从生态功能发挥的角度探讨了植物对污染物降解的机理，并对以大型水生植物为核心的各种污水处理系统的研究进展与现状进行了综述，指出了利用大型水生植物进行水污染治理的研究与应用中存在的问题和发展方向。     

表面活性剂冲洗修复多氯联苯污染土壤多相流研究

多氯联苯(PCBs)是一种具有持久性、抗生物降解性、脂肪溶性和明显的生物毒性等特性的持久性有机污染物,PCBs在土壤中难于准确定位、难被分解和强烈吸附,去除土壤中PCBs比较困难.表面活性剂冲洗法可以通过提高PCBs溶解度和降低水-PCBs界面张力来实现PCBs从土壤中去除;表面活性剂冲洗PCBs污染土壤涉及气相、水相、NAPLs相和固相等物质,是多相共存并相互发生作用的过程,发生相对渗透率、饱和度和毛细压力的变化;另外,为研究表面活性剂冲洗土壤中PCBs的去除机理,并降低PCBs对研究人员的危害,采用微观孔隙结构网络模型是一种较新颖的和效果显著的研究方法.开展表面活性剂冲洗PCBs污染土壤多相流研究,可以为PCBs污染场地修复提供理论基础和实验支持,并促进我国POPs履约工作的顺利进行.     

Monitoring aromatic hydrocarbon biodegradation by functional marker genes

The development of biological treatment technologies for contaminated environments requires tools for obtaining direct information about the biodegradation of specific contaminants. The potential of functional gene array analysis to monitor changes in the amount of functional marker genes as indicators of contaminant biodegradation was investigated. A prototype functional gene array was developed for targeting key functions in the biodegradation of naphthalene, toluene and xylenes. Internal standard probe based normalization was introduced to facilitate comparison across multiple samples. Coupled with one-colour hybridization, the signal normalization improved the consistency among replicate hybridizations resulting in better discrimination for the differences in the amount of target DNA. During the naphthalene biodegradation in a PAH-contaminated soil slurry microcosm, the normalized hybridization signals in naphthalene catabolic gene probes were in good agreement with the amount of naphthalene-degradation genes and the production of 14CO2. Gene arrays provide efficient means for monitoring of contaminant biodegradation in the environment.     

A steady state redox zone approach for modeling the transport and degradation of xenobiotic organic compounds from a landfill site

A redox zonation approach is used as a framework for obtaining biodegradation rate constants of xenobiotic compounds in a landfill plume (Grindsted, Denmark). The aquifer is physically heterogeneous in terms of a complex zonation of different geological units close to the landfill and biogeochemically heterogeneous in terms of a specified redox zonation. First-order degradation rates of six organic compounds (benzene, toluene, ethylbenzene, o-xylene, m/p-xylene, and naphthalene) were calculated in the methanogenic/sulfate- and Fe-reducing zones. The numerical simulations show that all compounds are anaerobically biodegraded, but at very different rates. High rates of biodegradation of most of the compounds (except benzene) were found in the Fe-reducing zone. These rates generally agree with previously published rates. Only o-xylene and toluene were significantly biodegraded in the methanogenic/sulfate-reducing environment. All rates in this redox zone are generally much lower than previously published rates.     

Trimethylphenylammonium-Smectite as an Effective Adsorbent of Water Soluble Aromatic Hydrocarbons

Homoionic trimethylphenylammonium (TMPA)- and tetramethylammonium (TMA)-clays were prepared by Ion-exchange reactions using two smectite clays that differed in their cation exchange capacities and surface charge densities. These clays are referred to as a low-charge (SAC) and high-charge (SWa)-smectite. The organo-clays were evaluated as adsorbents of water soluble aromatic hydrocarbons including benzene, toluene, ethylbenzene, p-xylene, butylbenzene, and naphthalene. All of the aromatic hydrocarbons tested were effectively removed from water by the low-charge TMPA-smectite. The low-charge TMA-smectite was an effective adsorbent for benzene but was ineffective in the removal of the alkylbenzenes and naphthalene from water. The effect of surface charge on the adsorption properties of TMPA-smectite was pronounced. The uptake of benzene and toluene by the high-charge TMPA-smectite was greatly reduced as compared to the low-charge TMPAsmectite. These results suggest the utility of TMPA-smectite as a liner material for petroleum storage containers and waste disposal reservoirs. The use of TMPA-smectite in conjunction with Na-smectite would provide a barrier with the ability to impede the flow of water and to effectively adsorb dissolved organic contaminants.     

Trimethylphenylammonium-smectite as an effective adsorbent of water soluble aromatic hydrocarbons

Homoionic trimethylphenylammonium (TMPA)- and tetramethylammonium (TMA)-clays were prepared by ion-exchange reactions using two smectite clays that differed in their cation exchange capacities and surface charge densities. These clays are referred to as a low-charge (SAC) and high-charge (SWa)-smectite. The organo-clays were evaluated as adsorbents of water soluble aromatic hydrocarbons including benzene, toluene, ethylbenzene, p-xylene, butylbenzene, and naphthalene. All of the aromatic hydrocarbons tested were effectively removed from water by the low-charge TMPA-smectite. The low-charge TMA-smectite was an effective adsorbent for benzene but was ineffective in the removal of the alkylbenzenes and naphthalene from water. The effect of surface charge on the adsorption properties of TMPA-smectite was pronounced. The uptake of benzene and toluene by the high-charge TMPA-smectite was greatly reduced as compared to the low-charge TMPA-smectite. These results suggest the utility of TMPA-smectite as a liner material for petroleum storage containers and waste disposal reservoirs. The use of TMPA-smectite in conjunction with Na-smectite would provide a barrier with the ability to impede the flow of water and to effectively adsorb dissolved organic contaminants.     

Combined application of conservative transport modelling and compound-specific carbon isotope analyses to assess in situ attenuation of benzene, toluene, and o-xylene

In recent years, compound specific isotope analyses (CSIA) have developed into one of the most powerful tools for the quantification of in situ biodegradation of organic contaminants. In this approach, the calculation of the extent of biodegradation of organic contaminants in aquifers is usually based on the Rayleigh equation, and thus neglects physical transport processes such as dispersion that contribute to contaminant dilution in aquifers. Here we combine compound specific isotope analyses with a conservative transport model to study the attenuation of aromatic hydrocarbons at a former gasworks site. The conservative transport model was first used to simulate concentration reductions caused by dilution at wells downgradient of a BTEX source. In a second step, the diluted concentrations, together with the available stable carbon isotope ratios and carbon fractionation factors for benzene, toluene and o-xylene were applied in the Rayleigh equation to quantify the degree of biodegradation at each of those wells. At the investigated site, where other attenuation processes such as sorption and volatilisation were proven to be negligible, the combined approach is recommended for benzene, which represents a compound for which the effect of biodegradation is comparable to or less than the effect of dilution. As demonstrated for toluene and o-xylene, the application of the Rayleigh equation alone is sufficient if dilution can be proved to be insignificant in comparison to biodegradation. The analysis also suggests that the source width and the position of the observation wells relative to the plume center line are significantly related to the degree of dilution.     

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.     

Fugacity modelling to predict the distribution of organic contaminants in the soil:oil matrix of constructed biopiles

Level I and II fugacity approaches were used to model the environmental distribution of benzene, anthracene, phenanthrene, 1-methylphenanthrene and benzo[a]pyrene in a four phase biopile system, accounting for air, water, mineral soil and non-aqueous phase liquid (oil) phase. The non-aqueous phase liquid (NAPL) and soil phases were the dominant partition media for the contaminants in each biopile and the contaminants differed markedly in their individual fugacities. Comparison of three soils with different percentage of organic carbon (% org C) showed that the % org C influenced contaminant partitioning behaviour. While benzene showed an aqueous concentration worthy of note for leachate control during biopiling, other organic chemicals showed that insignificant amount of chemicals leached into the water, greatly reducing the potential extent of groundwater contamination. Level II fugacity model showed that degradation was the dominant removal process except for benzene. In all three biopile systems, the rate of degradation of benzo(a)pyrene was low, requiring more than 12 years for soil concentrations from a spill of about 25 kg (100 mol) to be reduced to a concentration of 0.001 microgg(-1). The removal time of 1-methylphenanthrene and either anthracene or phenanthrene was about 1 and 3 years, respectively. In contrast, benzene showed the highest degradation rate and was removed after 136 days in all biopile systems. Overall, this study confirms the association of risk critical contaminants with the residual saturation in treated soils and reinforces the importance of accounting for the partitioning behaviour of both NAPL and soil phases during the risk assessment of oil-contaminated sites.     

Inverse modeling of BTEX dissolution and biodegradation at the Bemidji, MN crude-oil spill site

The U.S. Geological Survey (USGS) solute transport and biodegradation code BIOMOC was used in conjunction with the USGS universal inverse modeling code UCODE to quantify field-scale hydrocarbon dissolution and biodegradation at the USGS Toxic Substances Hydrology Program crude-oil spill research site located near Bemidji, MN. This inverse modeling effort used the extensive historical data compiled at the Bemidji site from 1986 to 1997 and incorporated a multicomponent transport and biodegradation model. Inverse modeling was successful when coupled transport and degradation processes were incorporated into the model and a single dissolution rate coefficient was used for all BTEX components. Assuming a stationary oil body, we simulated benzene, toluene, ethylbenzene, m,p-xylene, and o-xylene (BTEX) concentrations in the oil and ground water, respectively, as well as dissolved oxygen. Dissolution from the oil phase and aerobic and anaerobic degradation processes were represented. The parameters estimated were the recharge rate, hydraulic conductivity, dissolution rate coefficient, individual first-order BTEX anaerobic degradation rates, and transverse dispersivity. Results were similar for simulations obtained using several alternative conceptual models of the hydrologic system and biodegradation processes. The dissolved BTEX concentration data were not sufficient to discriminate between these conceptual models. The calibrated simulations reproduced the general large-scale evolution of the plume, but did not reproduce the observed small-scale spatial and temporal variability in concentrations. The estimated anaerobic biodegradation rates for toluene and o-xylene were greater than the dissolution rate coefficient. However, the estimated anaerobic biodegradation rates for benzene, ethylbenzene, and m,p-xylene were less than the dissolution rate coefficient. The calibrated model was used to determine the BTEX mass balance in the oil body and groundwater plume. Dissolution from the oil body was greatest for compounds with large effective solubilities (benzene) and with large degradation rates (toluene and o-xylene). Anaerobic degradation removed 77% of the BTEX that dissolved into the water phase and aerobic degradation removed 17%. Although goodness-of-fit measures for the alternative conceptual models were not significantly different, predictions made with the models were quite variable.     

SITE Demonstration of Slurry-Phase Biodegradation of PAH Contaminated Soil

This paper summarizes a joint Superfund Innovative Technology Evaluation (SITE) project on slurry-phase biodegradation and a project to collect information for the data base on Best Demonstrated Available Technologies (BOAT). In this 12-week study, a creosote contaminated soil from the Burlington Northern Superfund site in Brainerd, Minnesota was used to evaluate the effectiveness of the bioslurry reactors. During the demonstration, five 64-liter stainless steel bioreactors, equipped with agitation, aeration and temperature controls were used. The pilot scale study employed a 30 percent slurry, an inoculum of indigenous polynuclear aromatic hydrocarbon (PAH) degraders, and inorganic nutrients.

Total PAH degradation averaged 93.4 ± 3.2 percent over all five operating reactors in the 12 weeks with 97.4 percent degradation of the 2- and 3-ring PAHs and 90 percent degradation of the 4- to 6-ring PAHs. A study of the air emissions, both semivolatile compounds such as naphthalene, anthracene, and phenanthrene and volatile compounds such as toluene, xylene, and benzene, from the units showed that the greatest amount of emissions occurred during the loading of the reactors and during the first few days of operation. Therefore, it may not be cost-effective to require elaborate emissions controls unless there are significant quantities of volatile compounds present in the soil or water to be treated in a bioslurry reactor system.