Interaction of dissolution,sorption and biodegradation on transport of BTEX in a saturated groundwater system: Numerical modeling and spatial moment analysis

Interaction of various physical, chemical and biological transport processes plays an important role in deciding the fate and migration of contaminants in groundwater systems. In this study, a numerical investigation on the interaction of various transport processes of BTEX in a saturated groundwater system is carried out. In addition, the multi-component dissolution from a residual BTEX source under unsteady flow conditions is incorporated in the modeling framework. The model considers Benzene, Toluene, Ethyl Benzene and Xylene dissolving from the residual BTEX source zone to undergo sorption and aerobic biodegradation within the groundwater aquifer. Spatial concentration profiles of dissolved BTEX components under the interaction of various sorption and biodegradation conditions have been studied. Subsequently, a spatial moment analysis is carried out to analyze the effect of interaction of various transport processes on the total dissolved mass and the mobility of dissolved BTEX components. Results from the present numerical study suggest that the interaction of dissolution, sorption and biodegradation significantly influence the spatial distribution of dissolved BTEX components within the saturated groundwater system. Mobility of dissolved BTEX components is also found to be affected by the interaction of these transport processes.     

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     

Natural Attenuation of Fuel Hydrocarbon Contaminants:Correlation of Biodegradation with Hydraulic Conductivity in a Field Case Study

Two biodegradation models are developed torepresent natural attenuation of fuel－hydrocarbon contaminants as observed in a comprehensive natural-gradient tracer test in a heterogeneous aquifer on the Columbus Air Force Basein Mississippi,USA．The first, a first-order mass loss model,describes the irreversible losses of BTEX and its individual components, i．e．,benzene（B）,toluene（T）,ethyl benzene（E）,and xylene（X）．The second, a reactive pathway model,describe ssequential degradation pathways for BTEX utilizing multiple electron acceptors,including oxygen,nitrate,iron and sulfate,and via methanogenesis．The heterogeneous aquifer is represented by multiple hydraulic conductivity（ K） zones delineated on the basis of numerous flowmeter K measurements．A direct propagation artificial neural network（DPN）is used as an inverse modeling tool to estimate the biodegradation rate constants associated with each of the K zones．In both the mass loss model and the reactive pathway model,the biodegradation rate constants show an increasing trend with the hydraulic conductivity．The finding of correlation between biodegradation kinetics and hydraulic conductivity distributions is of general interest and relevance to characterization and modeling of natural attenuation of hydrocarbons in other petroleum-product contaminated sites．     

岩溶裂隙含水层中石油类有机物的自然衰减机制

石油类有机物污染是地下水环境领域亟须解决的关键课题.本次研究耦合数值模拟和水文地球化学技术模拟岩溶裂隙含水层中石油类有机物的自然衰减过程并定量计算其自然衰减机制.基于BIOSCREEN模型的模拟计算可知,近30年对流、弥散、稀释等物理过程和生物降解过程对石油类有机物衰减贡献率的平均值分别为31.53%和68.47%,生物降解作用是岩溶裂隙含水层自然修复能力的主要机制.利用质量守恒定律分析水化学（HCO₃-、NO₃-）和同位素（δ15N_NO3、δ18O_NO3和δ13C_DIC）之间的相关关系可知石油类有机物生物降解贡献地下水HCO₃-的平均值为33.93%;石油类有机物生物降解消耗主要电子受体NO₃-贡献地下水δ13C_DIC的百分率为30.77%且其占总生物降解的90.69%.      

汽油污染含水层中芳香烃的自然去除与生物降解特征

石油烃污染地下水是一个普遍而严重的环境问题.用砂卵石、中粗砂、细砂、粉砂和粘土等在实验室内按照自然界沉积物层序制作了一个含水层物理模型,具有给水、排水、监测、抽提、淋滤与注入等功能.利用该模型开展石油烃污染地下水的特征研究结果表明,苯、甲苯、乙苯和二甲苯(benzene,toluene,ethylbenzene,xylene;BTEX)各溶解组分能够被自然去除,其中甲苯自然衰减的速率系数为0.057 5～0.150 4 d-1,二甲苯为0.068 3～0.104 6 d,乙苯大约为0.047 8 d,苯为O.017 8～0.040 6 d.甲苯与二甲苯容易被去除,然而苯的去除则需要较长的时间.作为BTEX去除反应的电子受体,溶解氧、硝酸盐在需氧或厌氧条件下具有优先利用的机会,而硫酸盐则缺乏优先利用的机会.BTEX溶解组分浓度的降低,加上电子受体浓度的降低,可以表明含水层存在需氧条件与硝酸盐还原条件下的内在生物降解作用.其意义在于通过增加含水层中电子受体的浓度,将有助于内在生物降解能力的增强,从而能够提高含水层中污染物去除的效果.     

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。     

含水层非均质性不同刻画方法对地下水流和溶质运移预测的影响

为探讨含水层非均质性不同刻画方法对地下水流和溶质运移预测的影响,基于非均质含水层砂箱实验,分别用传统等效均质模型、克立金插值和水力层析刻画含水层渗透系数场,并探讨了先验信息对水力层析结果的影响.将不同方法估算的渗透系数场用以预测地下水流和溶质运移过程,以此判断不同方法估算结果的优劣,分析含水层非均质性对地下水流和溶质运移的影响.结果表明:与克立金插值法相比,水力层析法可以更好地刻画含水层非均质性,较准确地预测地下水流和溶质运移过程;钻孔岩心渗透系数样本值作为先验信息可以提高水力层析法估算结果的精度;传统等效均质模型无法准确预测地下水流和溶质运移过程.含水层非均质性的增强将导致溶质污染羽分布形态和运移路径的空间变异性增强,并且优势通道直接决定溶质的分布及运移路径.      

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.     

含水层层状非均质对地下水流系统的影响

区域尺度上含水层非均质具有复杂的结构性和随机性,难以准确刻画,造成非均质对区域地下水流系统的影响机制研究不够深入。本文以鄂尔多斯盆地白垩系地下水流系统为研究实例,选择典型剖面,采用剖面二维随机数值模拟方法,通过对比不同非均质刻画方法下地下水流场的变化,探讨含水层层状非均质对地下水流系统的影响机制。结果显示,均质条件下模型各向异性（含水层水平和垂向渗透系数比值Kh/Kv）取值为1000时,地下水流场与实际条件较为接近;非均质条件下,渗透系数方差取值0.91,水平相关长度取值5000 m,Kh/Kv取值150时,接近实际条件。研究表明,在大尺度地下水流模拟研究中,采用水平相关长度、渗透系数方差和各向异性值三个变量生成的随机场能很好地刻画含水层的层状非均质特征及其对水流系统的影响控制作用。由于含水层不同尺度层状非均质的叠加效应,采用均质各向异性介质等效概化含水层层状非均质性会造成等效各向异性值偏大失真的效应。     

某石化污染场地含水层自然降解BTEX能力评估

地下水污染问题是国家关注的重要环境问题之一,监测与评估含水层自然降解污染物能力是防治地下水污染的基本手段,也是国外地下水中修复技术研究热点课题。以华北平原某石油化工类场地为案例,通过调查场地水文地质条件、土壤及地下水污染现状,监测场地地下水中苯系物(BTEX)浓度及相关化学参数变化,运用微生物水文地球化学方法和水文地质方法,估算了该场地含水层自然降解苯系物量。这一研究成果为评估我国石油类场地地下水污染的自然修复能力提供了实证和基础数据。     

Pumping-induced Well Hydraulics and Groundwater Budget in a Leaky Aquifer System with Vertical Heterogeneity in Aquitard Hydraulic Properties

In groundwater hydrology, aquitard heterogeneity is often less considered compared to aquifers, despite its significant impact on groundwater hydraulics and groundwater resources evaluation. A semi-analytical solution is derived for pumping-induced well hydraulics and groundwater budget with consideration of vertical heterogeneity in aquitard hydraulic conductivity (K) and specific storage (Ss). The proposed new solution is innovative in its partitioning of the aquitard into multiple homogeneous sub-layers to enable consideration of various forms of vertically heterogeneous K or Ss. Two scenarios of analytical investigations are explored: one is the presence of aquitard interlayers with distinct K or Ss values, a common field-scale occurrence; another is an exponentially depth-decaying aquitard Ss, a regional-scale phenomenon supported by statistical analysis. Analytical investigations reveal that a low-K interlayer can significantly increase aquifer drawdown and enhance aquifer/aquitard depletion; a high-Ss interlayer can noticeably reduce aquifer drawdown and increase aquitard depletion. Locations of low-K or high-Ss interlayers also significantly impact well hydraulics and groundwater budget. In the context of an exponentially depth-decaying aquitard Ss, a larger decay exponent can enhance aquifer drawdown. When using current models with a vertically homogeneous aquitard, half the sum of the geometric and harmonic means of exponentially depth-decaying aquitard Ss should be used to calculate aquitard depletion and unconfined aquifer leakage.     

Numerical modeling of contaminant transport in a stratified heterogeneous aquifer with dipping anisotropy

The combined influence of dip angle and adsorption heterogeneity on solute transport mechanisms in heterogeneous media can be understood by performing simulations of steady-state flow and transient transport in a heterogeneous aquifer with dipping anisotropy. Reactive and non-reactive contaminant transport in various types of heterogeneous aquifer is studied by simulations. The hydraulic conductivity (K) of the heterogeneous aquifer is generated by HYDRO_GEN with a Gaussian correlation spectrum. By considering the heterogeneity of the adsorption distribution coefficient (K _d), a perfect negative correlation between lnK and lnK _d is obtained by using the spherical grains model. The generated K and K _d are used as input to groundwater flow and transport models to investigate the effects of dipping sedimentary heterogeneity on contaminant plume evolution. Simulation results showed that the magnitude of the dip angle strongly controls the plume evolution in the studied anisotropic and heterogeneous aquifer. The retarded average pore-water velocity (v/R) of the adsorption model significantly controls the horizontal spreading of the plume. The bottom plume is intensively retarded in the zones between the dipping lenses of lower hydraulic conductivity and the no-flow bottom boundary. The implications of these findings are very important for the management of contaminated heterogeneous aquifers.     

非均质含水层中渗流与溶质运移研究进展简

Natural aquifer heterogeneity controls the groundwater flow and solute transport, and how to accurately quantify the flow and solute transport in heterogeneous aquifers has received wide attention by many scholars, and has become a hot research topic in earth science. Theoretically, a systematic review is given by the following aspect: flow and solute transport model, moment analysis, multi scale analysis. The resolved and remained issues for scale conversion in hydrogeology research are pointed out. Secondly, recent advances of heterogeneous field test, uncertainty and velocity connectivity are analyzed. Finally, the geophysical inversion of aquifer heterogeneity, stochastic theory and development of stochastic simulation software, scale conversion and uncertainty of velocity connectivity, and the relationship between heterogeneity and hydrogeological condition on the major four aspects of the future research direction is pointed out.     

利用滨海地下水系统对双频潮汐的响应识别含水层压力传导系数

含水层的压力传导系数是地下水溶质运移及扩散的重要参数,通常压力传导系数由抽水试验确定,即通过抽水给地下水系统一个扰动,然后监测地下水水位的响应,进而计算压力传导系数.对滨海地区含水层来说,潮汐波动就是天然的抽(注)水试验.潮汐由不同频率的分潮构成,前两项主频潮汐基本可代表潮汐主要特征.利用地下水水位对潮汐的响应,识别含...     

Use of geostatistical models in DNAPL source zone architecture and dissolution profiles assessment in spatially variable aquifer

Following the accidental subsurface release of dense nonaqueous phase liquids (DNAPLs), spatial variability of physical and chemical soil/contaminant properties can exert a controlling influence on infiltration pathways and organic entrapment. DNAPL spreading, fingering, and pooling typically result in source zones characterized by irregular contaminated regions with complex boundaries. Spatial variability in aquifer properties also influences subsequent DNAPL dissolution and aqueous transport dynamics. An increasing number of studies have investigated the effects of subsurface heterogeneity on the fate of DNAPL; however, previous work was limited to the examination of the behavior of single-component DNAPL in systems with simple and well-defined aqueous and solid surface chemistry. From a DNAPL remediation point of view, such an idealized assumption will bring a large discrepancy between the designs based on the model simulation and the reality. The research undertaken in this study seeks to stochastically explore the influence of spatially variable porous media on DNAPL entrapment and dissolution profiles in the saturated groundwater aquifer. A 3D, multicomponent, multiphase, compositional model, UTCHEM, was used to simulate natural gradient water flooding processes in spatially variable soils. Porosity was assumed to be uniform or simulated using sequential Gaussian simulation (SGS) and sequential indicator simulation (SIS). Soil permeability was treated as a spatially random variable and modeled independently of porosity, and a geostatistical method was used to generate random distributions of soil permeability using SGS and SIS (derived from measured grain size distribution curves). Equally possible 3D ensembles of aquifer realizations with spatially variable permeability accounting of physical heterogeneity could be generated. Tetrachloroethene (PCE) was selected as a DNAPL representative as it was frequently discovered at many contaminated groundwater sites worldwide, including Thailand. The randomly generated permeability fields were incorporated into UTCHEM to simulate DNAPL source zone architecture under 96-L hypothetical PCE spill in heterogeneous media and stochastic analysis was conducted based on the simulated results. Simulations revealed considerable variations in the predicted PCE source zone architecture with a similar degree of heterogeneity, and complex initial PCE source zone distribution profoundly affected PCE recovery time in heterogeneous media when subject to natural gradient water flush. The necessary time to lower PCE concentrations below Thai groundwater quality standard ranged from 39 years to more than 55 years, suggesting that spatial variability of subsurface formation significantly affected the dissolution behavior of entrapped PCE. The temporal distributions of PCE saturation were significantly altered owing to natural gradient water flush. Therefore, soil heterogeneity is a critical factor to design strategies for characterization and remediation of DNAPL contaminated sites. The systematic and comprehensive design algorithm developed and described herein perhaps serves as a template for application at other DNAPL sites in Thailand.     

Potential of groundwater contamination by polybrominated diphenyl ethers (PBDEs) in a sensitive bedrock aquifer (Canada)

It is necessary to understand the presence, movement, and persistence of contaminants in aquifers to develop adequate groundwater protection plans. Fractured bedrock aquifers with thin overburden cover are very sensitive to contamination, and little is known about transport processes from the ground surface to depth in this setting. This study was undertaken to investigate the potential of groundwater contamination by polybrominated diphenyl ethers (PBDEs), which are flame retardants, in a natural fractured bedrock aquifer in Canada proven to be sensitive to contamination. PBDEs, which had not been previously measured in groundwater in detail, were detected in the study aquifer at concentrations greater than those observed in surface-water bodies. Potential sources include manure, septic tanks, and the atmosphere. From this scoping study, it is evident that additional surveys of PBDE concentrations in groundwater are warranted, especially in settings with high potential source concentrations coupled with sensitive aquifers.     

Numerical modelling of the saline interface in coastal karstic aquifers within a conceptual model uncertainty framework

Numerical modelling is increasingly used as a tool for improving management strategies in aquifers and to support the design of comprehensive projects considering natural and anthropogenic processes. Overall, numerical simulation in karstic aquifers poses a major scientific challenge due to the non-Darcian groundwater flow dynamics. In specific cases, the equivalent porous medium approach has shown acceptable results, particularly in poorly karstified aquifers with regional/subregional scales such as this case. The Yucatan coastal karstic aquifer (Mexico) has been defined as a complex regional heterogeneous system, partially confined, thus allowing the discussion of multiple conceptual models. In this research, a two-dimensional numerical model of flow and transport was implemented using SEAWAT for the NW Yucatan aquifer. Four likely conceptual models were audited, calibrated and verified using hydrogeological field data, to select the best one, considering their fit and complexity. The numerical model accuracy was evaluated using the root-mean-square error, Nash Sutcliffe efficiency and the Pearson coefficient. The Akaike information criterion and Bayesian information criterion were included for evaluating the complexity of the numerical models. In addition, the signal of tide propagation into the aquifer was assessed as a proxy to improve the numerical calibration process. Results show that the most complex numerical model has a better calibration than the simpler models, but the model accuracy is worse when compared to less complex numerical models in the verification exercise. This research offers enhancement in the knowledge of numerical modelling in heterogeneous coastal aquifers within a conceptual-model uncertainty setting.

     

Characterization of the hydrogeologic environment at a petroleum hydrocarbon contaminated site in Korea

The hydrogeologic environment of a petroleum hydrocarbon contaminated site in Korea is characterized by hydrogeologic field work and chemical analyses of groundwater. Quaternary alluvium is the main aquifer contaminated by petroleum hydrocarbons, mainly TEX (toluene, ethylbenzene and xylenes). Contamination at this site was derived from the leaking of petroleum storage tanks. The aquifer is highly permeable, but vertically heterogeneous. Water-table fluctuations reach up to 2 m during heavy rains. Contaminants migrated to the northwest along the main groundwater-flow direction. The concentration of hydrocarbons in groundwater is particularly high downgradient from the source area. The ubiquitous distribution of TEX was caused by the heterogeneity of the aquifer material and the significant fluctuation of the water-table. Chemical properties of the contaminated groundwater and field parameters indicate that intrinsic biodegradation, including aerobic respiration, nitrate reduction, iron reduction, manganese reduction, and sulfate reduction, occurs at this site. The dilution and mixing due to new groundwater recharge from rainfall is also identified as one of the major attenuation processes of TEX.     

Installation of a vertical slurry wall around an Italian quarry lake: complications arising and simulation of the effects on groundwater flow

Slurry walls are non-structural barriers that are constructed underground to impede groundwater flow or manage groundwater control problems. The study area is in the Piemonte plain (Italy), close to the River Po. Quarrying works carried out below the piezometric surface created two big quarry lakes. The local groundwater system is characterized by a lower semi-confined aquifer, which is overlain by a semi-permeable bed of clayey peat (aquitard) and an upper unconfined aquifer. Locally, the peat fades away and the granulometry of this horizon becomes silty sandy. A planned enlargement of the quarry will increase the size and depth of the quarry lakes. So the aquitard bed between the two aquifers will be damaged, creating a mixing rate of groundwater. Such a procedure would not be compatible with the presence of two municipal wells upstream from the quarries. Consequently, the installation of a vertical diaphragm (slurry wall) is recommended to separate the aquifers and to act as a filter for the groundwater flowing from the unconfined to the semi-confined aquifer. To predict the consequences caused by the installation of the vertical diaphragm separating the unconfined aquifer and the semi-confined one, a specifically adjusted finite-difference model was used. The model showed a maximum rising of the water table equal to 12 cm, just upstream of the diaphragm and for a distance of about 100 m, and a maximum lowering of 2 cm just downstream of the diaphragm. However, the slurry wall would not cause any change in the piezometric head in the area where there are municipal wells and, hence, will not have any negative effect on the functionality of the municipal wells. Moreover, the migration of water from the unconfined aquifer through the vertical diaphragm will stimulate a series of attenuation and auto-depuration processes of eventual contaminants. These processes are due to the higher crossing time that the groundwater flow takes to go through the vertical barrier (t _a = 96.5 days, whereas for the horizontal semi-permeable layer t _a = 9.6 days). So, the vertical diaphragm can be a resolutive element, representing a mediation and separation factor between the unconfined and the semi-confined aquifers along the border of the quarrying areas, and a protective barrier for the water quality of the quarry lake and the semi-confined aquifer.