浅层地下水氯代烃污染天然生物降解的判别依据

天然条件下氯代烃生物降解的判别, 是确定氯代烃污染天然衰减恢复治理技术是否可以采用的关键, 可为天然衰减恢复治理技术的应用提供技术支持.通过分析氯代烃生物降解的特性发现, 地下水环境中氯代烃的生物降解, 必然伴随有第一基质、电子受体、中间产物以及有关的一些间接性指标, 在污染羽状体不同位置及污染羽状体内外产生明显变化, 这些指标的变化均可以不同程度地指示氯代烃生物降解的产生.据此总结出氯代烃生物降解衰减的判别依据分别为电子受体、第一基质(能源和碳源) 及降解中间产物三类指标.      

纳米镍/铁去除氯代烃影响因素的探讨

氯代烃是地下水中最常检出的有机污染物之一,传统的处理方法去除率很低。近年来随着铁还原技术的发展,纳米铁和纳米双金属也成为一个活跃的研究领域。利用批实验的研究方法以四氯乙烯(PCE)和四氯化碳(CT)为目标污染物,研究纳米镍/铁在去除PCE过程中的影响因素。实验结果表明,在碱性条件下,纳米Ni/Fe对PCE脱氯速率比在酸性和中性条件下脱氯速率更快;纳米Ni/Fe对初始浓度为6·51mg/L的PCE溶液脱氯速率是对初始浓度为20·56mg/L的PCE溶液脱氯速率的1·8倍;对于氯代程度相同的CT和PCE,对CT的脱氯速率明显快于对PCE。     

纳米镍-铁去除四氯乙烯的影响因素

氯代烃是地下水中最常检出的有机污染物之一,传统的处理方法需要很长时间与大量经费。本文利用批实验的研究方法以四氯乙烯(PCE)为目标污染物,研究纳米镍铁在去除PCE过程中的影响因素。实验结果表明,暴露后的纳米镍铁脱氯速率比不暴露时速率降低约4倍;反应温度是影响反应速率的重要因素之一,每升高10℃,反应速率常数kSA提高2～3倍;在一定范围内,镍/铁质量比越高,越利于脱氯反应的快速进行,镍/铁的质量比为8%左右时,对氯代烃脱氯速率最快;反应液中的溶解氧不利于纳米颗粒对氯代烃的降解。     

天然地下水环境四氯乙烯的强化生物降解

采用批实验方法, 以天然地下水为基础培养液, 利用在实验室条件下培养驯化的微生物, 以醋酸作为共代谢基质, 加入酵母粉提供氮源, 研究了四氯乙烯(PCE) 的降解效果.研究表明, 通过强化影响PCE降解的某些因素, 在20℃的地下水环境中, PCE可以很快转化为三氯乙烯(TCE), 并可以进一步转化为二氯乙烯(DCEs), 但没有检测到DCEs的脱氯产物.PCE的脱氯速率为0.1848d-1, 半衰期为3.75d.亦研究了低温环境下PCE的降解效果.结果表明, 在低温环境下, PCE也可以发生生物降解, 但是脱氯速率相对较慢, 为0.0761d-1, 半衰期为9.11d, 且终产物为TCE.      

纳米镍/铁去除四氯乙烯的影响因素

氯代烃是地下水中最常检出的有机污染物之一,传统的处理方法需要很长时间与经费。近年来随着铁还原技术的发展,纳米铁和纳米双金属也是一个活跃的研究领域。本文利用批实验的研究方法以四氯乙烯(PCE)为目标污染物,研究纳米镍/铁在去除PCE过程中的影响因素。实验结果表明,暴露后的纳米Ni/Fe脱氯速率比不暴露时速率降低约4倍;反应温度是影响反应速率的一个重要因素之一,每升高10℃,反应速率常数kSA提高2~3倍;在一定范围内,Ni/Fe质量比越高,越利于脱氯反应的快速进行,当Ni/Fe的质量百分比为8%左右时,对氯代烃脱氯速率最快;反应液中的溶解…     

零价铁降解水中氯代烃的实验室研究

由于氯代有机溶剂的大量使用和使用氯气对饮用水消毒 ,致使四氯化碳 (CT)和四氯乙烯 (PCE)成为地下水和饮用水中常见的污染物 .利用廉价铁屑对CT和PCE进行还原性脱氯 ,对其动力学过程进行初步研究 ,并对影响反应速率的因素进行探讨 .结果表明 ,零价铁对氯代烃有明显的脱氯作用 ,相同氯代程度的烷烃和烯烃 ,烷烃的脱氯速度快 ,反应符合一级反应动力学方程 ,反应是准一级反应 ,反应速率受到传质速率即零价铁比表面积的影响 .     

不同基质共代谢降解地下水中四氯乙烯的研究

文中以甲醇、乙醇、甲酸盐、乙酸盐、乳酸盐和葡萄糖作为共代谢基质,利用某污水处理厂厌氧池中的污水(泥)作为接种物,对厌氧微生物进行培养和驯化,降解四氯乙烯(PCE)。实验结果表明,在厌氧污水(泥)和土壤混合环境下培养的微生物,以COD为培养指标,11d可培养成熟。6种基质均能使PCE还原脱氯降解成三氯乙烯(TCE)和1,1-二氯乙烯(1,1-DCE),PCE的降解均符合一级反应动力学方程,反应速率常数大小依次为K乙酸盐>K葡萄糖>K乳酸盐>K乙醇>K甲酸盐>K甲醇,其中乙酸盐是最有效的共代谢基质,其反应速率常数为0·6632d-1。     

应用质量通量评估地下水中BTEX和乙醇的自然衰减

近年来,应用于修复石油烃污染地下水的监测自然衰减技术得到了广泛深入研究,同时质量通量方法已逐渐成为评 估地下水燃油污染场地自然衰减监测修复效能的重要手段。通过在室内砂槽中添加乙醇汽油组分,监测其自然衰减,利用 质量通量方法,得出了BTEX和乙醇的质量减少率、自然衰减速率常数K;结合非反应示踪剂溴离子,评价了BTEX和乙醇 自然衰减因素中吸附和微生物的联合降解效应。结果表明,自然衰减是地下水中燃油组分修复的重要机制,质量通量方法 是评估自然衰减的有效方法之一。BTEX和乙醇在自然衰减过程中被去除的比例分别为78.88%和98.71%,其中约98%的 BTEX 因吸附和生物降解联合作用被去除,接近100%的乙醇因内在生物降解作用被去除;BTEX 的自然衰减速率为 0.077d-1~0.167d-1,乙醇为0.353d-1,自然条件下乙醇比BTEX更容易衰减。     

基于砂槽电化学-水动力学循环系统氯代烃反应迁移实验与模拟研究

在室内砂槽实验尺度,建立了潜水-微承压含水层中电化学-水动力循环系统下混合氯代烃生物降解的反应迁移模型,求取了混合氯代烃体系中各组分的反应动力学参数,并基于模型探究了含水层性质及工艺参数对该修复过程的影响机制.研究结果表明:（1）增大抽水流量可加快反应速率常数大的污染物降解,同时也会抑制反应速率常数较小的污染物去除.（2）增大电流强度和井内电极对氯代烃的好氧降解和厌氧脱氯过程分别具有促进和抑制作用.（3）含水层非均质性越强,氯代烃降解速率越小,这尤其体现在低渗区,且含水层非均质性对易降解污染物修复效果的影响较小.      

浅层地下水中氯代烷烃生物降解的地下水化学 响应规律研究

以东北某油田石油污染场地多期地下水化学监测数据为基础,分析氯代烷烃自然生物降解中充当第一基质、电子受体、中间产物的水化学组分及相关地球化学参数在污染晕演化的不同时段、不同部位的变化趋势,了解氯代烷烃生物降解的地下水化学响应特征,并以此为依据对污染场地浅层地下水氯代烷烃生物降解程度进行定性评价。结果表明:2010年6月,事故发生约1年之际,在ZK1—ZK3—ZK6纵向剖面上生物降解过程中充当电子受体的水化学组分(SO42–)、第一基质(CH2Cl2、CHCl3)和代表地下水环境的主要理化指标(pH、Eh)从上游到下游均呈递增规律,而相关还原产物(Fe2+、Mn2+、HCO3–)则呈递减规律,这也表明天然微生物降解具有一定的滞后性。2010年6月氯代烷烃天然生物降解评价表明ZK1属微生物降解证据充足;ZK3观测井属微生物降解证据有限;ZK6观测井属微生物降解证据不足。而2011年5月,事故发生约2年之际,封堵污染源后随污染晕中心的向下游迁移,ZK3观测井中生物降解作用逐渐明显,在ZK3—ZK6纵向剖面上地下水化学指标呈现上述响应规律,而ZK1观测井诸多水化学指标经上游未污染地下水的补充更新,逐渐趋向污染前的背景值。     

Field investigation of the natural attenuation and intrinsic biodegradation rates at an underground storage tank site

 Contamination of groundwater by petroleum-hydrocarbons is a widespread environmental problem. Natural attenuation is a passive remedial approach to degrade and dissipate contaminants in soil and groundwater. In this study, a mass flux approach was used to calculate the contaminant mass reduction and field-scale decay rate at a gasoline spill site. The mass flux technique is accomplished using the differences in total contaminant mass flux across two cross sections of the contaminant plume. The mass flux calculation shows that up to 88% of the dissolved BTEX (benzene, toluene, ethylbenzene, and xylene isomers) removal was observed by natural attenuation processes. The efficiency of intrinsic biodegradation was evaluated by the in situ tracer method. A first-order decay model was applied for the natural attenuation and intrinsic biodegradation rate calculation. Results reveal that intrinsic biodegradation process was the major cause of the BTEX reduction among the natural attenuation mechanisms, and iron reduction was the dominant biodegradation pattern within the plume. Approximately 87% of the BTEX removal was caused by intrinsic biodegradation processes. The calculated BTEX natural attenuation and intrinsic biodegradation rates were 0.24 and 0.16% l/day, respectively. Results suggest that natural attenuation mechanisms can effectively contain the plume, and the mass flux method is useful in assessing the efficiency of the natural attenuation. Received: 6 December 1999 · Accepted: 11 July 2000     

The effect of aquifer heterogeneity on natural attenuation rate of BTEX

Monitored natural attenuation can be a viable option for remediation of groundwater contamination by BTEX compounds. Under the field conditions, the rate of contaminant mass attenuation through natural processes, such as biodegradation, to a large extent affected by the groundwater flow regime, which is primarily controlled by the aquifer heterogeneity. Numerical simulation techniques were used to describe quantitatively the relationship between biodegradation rate of BTEX and aquifer heterogeneity. Different levels of aquifer heterogeneity were described by random hydraulic conductivity fields (K) having different statistical parameters, the coefficient of variation (CV) and the correlation length (h). The Turning Bands Algorithm was used to generate such K fields. Visual MODFLOW/RT3D was used to simulate the fate and transport of dissolved BTEX plume within heterogeneous aquifers. The multispecies reactive transport approach described BTEX degradation using multiple terminal electron-accepting processes. First-order biodegradation rate constants were calculated from simulated BTEX plumes in heterogeneous flow fields. The results showed that aquifer heterogeneity significantly affected biodegradation rate; it decreased with increasing CV when h was in the range of up to 12 m, whereas it increased with increasing CV when h was greater than about 12 m. For well characterized aquifers, this finding could be of great value in assessing the effectiveness of natural attenuation during feasibility studies at BTEX contaminated sites.     

Hydrogeological modeling constraints provided by geophysical and geochemical mapping of a chlorinated ethenes plume in northern France

A methodological approach is described which combines geophysical and geochemical data to delineate the extent of a chlorinated ethenes plume in northern France; the methodology was used to calibrate a hydrogeological model of the contaminants’ migration and degradation. The existence of strong reducing conditions in some parts of the aquifer is first determined by measuring in situ the redox potential and dissolved oxygen, dissolved ferrous iron and chloride concentrations. Electrical resistivity imaging and electromagnetic mapping, using the Slingram method, are then used to determine the shape of the pollutant plume. A decreasing empirical exponential relation between measured chloride concentrations in the water and aquifer electrical resistivity is observed; the resistivity formation factor calculated at a few points also shows a major contribution of chloride concentration in the resistivity of the saturated porous medium. MODFLOW software and MT3D99 first-order parent–daughter chain reaction and the RT3D aerobic–anaerobic model for tetrachloroethene (PCE)/trichloroethene (TCE) dechlorination are finally used for a first attempt at modeling the degradation of the chlorinated ethenes. After calibration, the distribution of the chlorinated ethenes and their degradation products simulated with the model approximately reflects the mean measured values in the observation wells, confirming the data-derived image of the plume.     

Modeling in situ benzene bioremediation in the contaminated Liwa aquifer (UAE) using the slow-release oxygen source technique

Dissolved benzene was detected in the shallow unconfined Liwa aquifer, UAE, which represents the main freshwater source for the nearby residence Bu Hasa camp area. The main source of this contamination is believed to be the rejected water released from Bu Hasa liquid recovery plant. In this paper, a finite element model (METABIOTRANS) is used to simulate the fate and transport of the dissolved benzene plume in Liwa aquifer. Different remediation scenarios were simulated in which the slow-release oxygen source (SOS) technique is utilized to minimize benzene concentrations at the nearest camp supply wells downstream of the contamination zone. Results of the remediation scenarios show that the highest biodegradation rates occur when the oxygen source is placed near the plume center; where higher benzene concentrations exist. The nearest oxygen release source to the contamination zone caused higher stimulation to bacterial growth than further down-gradient oxygen sources. It also exhibited longer resident time of oxygen in the aquifer; and therefore, yielded higher reductions in benzene concentrations. However, using one central SOS proved to be insufficient as contaminant escaped laterally. Additional four transverse oxygen sources were necessary to capture benzene that laterally spread away from the contamination zone. These lateral SOSs were essential to reduce benzene concentrations at the supply wells that are located at the plume fringes. Finally, it was found that increasing oxygen release from one source did not always improve remediation; and that using several SOSs with lower release rates could be a more practical approach to enhance benzene biodegradation in the aquifer.     

Identifying sources of chlorinated aliphatic hydrocarbons in a residential area in Italy using the integral pumping test method

The results of integral pumping tests (IPTs) performed in the city of Fabriano, Italy, are presented. The IPT methodology was developed by the European Union project INCORE, as a tool for groundwater investigation and source localization in contaminated areas. This methodology consists of a multiple-well pumping test in which the wells are positioned along a control plane downstream of suspected contaminant source zones and perpendicular to the mean groundwater flow direction. During the pumping, concentration time series of target contaminants are measured. In Fabriano, two control planes were realized to identify a chlorinated aliphatic hydrocarbon plume, to estimate the mass fluxes and draw up a ranked list of the main contamination sources. A numerical flow model was implemented to support the IPT design and to interpret the results. This study revealed low-level trichloroethylene contamination (concentration below 8 μg/l), tetrachloroethylene contamination (mean concentration up to 500 μg/l) and a mass flow rate of about 300 g/day. Through the application of the IPT method, the mean contaminant concentrations, the spatial distribution of concentration values along the control planes, and the total contaminant mass flow rates were evaluated, and the investigation area was reduced for further and deeper investigation activities.     

High-resolution monitoring of biogeochemical gradients in a tar oil-contaminated aquifer

The detailed understanding of in situ biodegradation of petroleum hydrocarbons in porous aquifers requires knowledge on biogeochemical gradients, the distribution of individual redox species and microorganisms. The generally limited spatial resolution of conventional monitoring wells, however, hampers appropriate characterization of small-scale gradients and thus localization of the relevant processes. Groundwater sampling across a BTEX plume in a sandy aquifer by means of a novel high-resolution multi-level well (HR-MLW) is presented here. The presence of distinct and steep biogeochemical gradients is demonstrated in the centimeter and decimeter scale, which could not be resolved with a conventional multi-level well. The thin BTEX plume with a vertical extension of only 80 cm exhibited a decline of contaminant concentrations by two orders of magnitude within a few centimeters in the upper and lower fringe zone. The small-scale distribution of sulfate, sulfide and Fe(II) in relation to the contaminants and elevated δ³⁴S and δ¹⁸O values of groundwater sulfate strongly indicated sulfate and iron reduction to be the dominant redox processes involved in biodegradation. High microbial activities and biomass especially at the plume fringes and the slope of chemical gradients supported the concept that the latter are regulated by microbial processes and transverse dispersion, i.e. vertical mixing of electron donors and acceptors. Transverse dispersion therefore was suggested to be a driving factor controlling biodegradation in porous aquifers, but not exclusively limiting natural attenuation processes at this site. Broad overlapping zones of electron donors and electron acceptors point towards additional factors limiting anaerobic biodegradation in situ. The identification of small-scale gradients substantially contributed to a better understanding of biodegradation processes and hence is a prerequisite for the development of reliable predictive mathematical models and future remediation strategies.     

地下水苯系物微生物降解及其碳同位素标记

微生物降解是地下水中有机物自然衰减评估的关键,单体稳定同位素是一种有效的评估方法。在对某油罐泄露场地地下水流场识别的基础上,刻画不同地下水中污染物、微生物及电子受体特征,发现随着与污染源水力联系的减弱,污染物浓度明显减小,微生物群落结构和电子受体氧化还原作用类型与源相似的程度也逐渐减弱,呈现出“污染源-下游源区-下游污染羽-上游源区-侧翼污染羽”的空间变化规律。甲苯、间/对二甲苯碳的同位素标记结果发现,降解程度“侧翼污染羽﹥下游污染羽﹥下游源区”,与电子受体表征降解量的排序相反;该场地微生物降解符合一般化学反应“勒沙特列原理”:污染物浓度越高,降解量越大,但降解程度相对减小。