Remediation of BTEX and trichloroethene

The widespread use of industrial chemicals in our highly industrialized society has often caused contamination of large terrestrial and marine areas due to the deliberate and accidental release of organic pollutants into the soil and groundwater. In this review, environmental problems arising from the use of chlorinated solvents and BTEX compounds are described, and an overview about active management strategies for remediation with special emphasis on phytoremediation are presented to achieve a reduction of the total mass of chlorinated solvents and BTEX compounds in contaminated areas. Phytoremediation has been proposed as an efficient, low-cost remediation technique to restore areas contaminated with chlorinated solvents and BTEX compounds. The feasibility of phytoremediation as a remediation tool for these compounds is discussed with particular reference to the uptake and metabolism of these compounds, and a future perspective on the use of phytoremediation for the removal of chlorinated solvents and BTEX compounds is given.     

Impact of injection system design on ISCO performance with permanganate--mathematical modeling results

In situ chemical oxidation (ISCO) using permanganate (MnO(4)(-)) can be a very effective technique for remediation of soil and groundwater contaminated with chlorinated solvents. However, many ISCO projects are less effective than desired because of poor delivery of the chemical reagents to the treatment zone. In this work, the numerical model RT3D was modified and applied to evaluate the effect of aquifer characteristics and injection system design on contact and treatment efficiency. MnO(4)(-) consumption was simulated assuming the natural oxidant demand (NOD) is composed of a fraction that reacts instantaneously and a fraction that slowly reacts following a 2nd order relationship where NOD consumption rate increases with increasing MnO(4)(-) concentration. MnO(4)(-) consumption by the contaminant was simulated as an instantaneous reaction. Simulation results indicate that the mass of permanganate and volume of water injected has the greatest impact on aquifer contact efficiency and contaminant treatment efficiency. Several small injection events are not expected to increase contact efficiency compared to a single large injection event, and can increase the amount of un-reacted MnO(4)(-) released down-gradient. High groundwater flow velocities can increase the fraction of aquifer contacted. Initial contaminant concentration and contaminant retardation factor have only a minor impact on volume contact efficiency. Aquifer heterogeneity can have both positive and negative impacts on remediation system performance, depending on the injection system design.     

Surface catalyzed Fenton treatment of bis(2-chloroethyl) ether and bis(2-chloroethoxy) methane

This study examined the feasibility of using surface catalyzed Fenton treatment to remediate soil and groundwater contaminated by the chlorinated ethers, bis(2-chloroethyl) ether (BCEE) and bis(2-chloroethoxy) methane (BCEM). Parameters that affect the contaminant loss rate such as porewater pH, hydrogen peroxide concentration, and solid/water ratio were systematically evaluated. Batch reactors were set-up utilizing either contaminated or uncontaminated soil, obtained from an industrial site in Moss Point, MS, that was mixed with synthetic groundwater containing the contaminants of interest. The results show an increase in contaminant reduction with a decrease in pH, an increase in hydrogen peroxide concentration, or an increase in the solid/water ratio. For a similar set of conditions, contaminant reduction was greater for systems utilizing contaminated soil as compared to the systems containing uncontaminated soil. In addition, specific oxygen uptake rates (SOURs) were measured for biomass, collected from an activated sludge plant, exposed to different dilutions of untreated and surface catalyzed Fenton treated water to evaluate whether residual BCEE, BCEM, and their co-contaminants as well as their oxidation by-products were potentially inhibitory or can potentially serve as a substrate for the biomass. The measured SOURs show that the surface catalyzed Fenton treatment enhanced the biodegradability of the contaminated groundwater and served as a substrate for the biomass.     

Allocating Remedial Costs at Superfund Sites with Commingled Groundwater Contaminant Plumes

Remedial efforts at Superfund sites across the country focus on groundwater contaminant plumes that have been produced by contributions from multiple parties. Allocating cleanup costs between the parties in a fair and equitable manner can be a problem of substantial complexity. Considerable time and money may be spent determining the amount of contamination attributable to each party in order to apportion liability. Contaminant plumes that have evolved over long periods of time may affect large volumes of groundwater and require extensive remediation. Pump and treat remedial costs are driven by both the volume of water extracted and the mass of contaminants removed. Allocation methods based solely on the mass of contaminants contributed by each party are inadequate in this setting since they do not account for both components of the remedial costs. This paper presents an approach for equitably allocating remedial costs when addressing overlapping or commingled groundwater plumes. The method accounts for the major elements driving the costs of remediating dispersed contaminant plumes.     

Allocating Remedial Costs at Superfund Sites with Commingled Groundwater Contaminant Plumes

Remedial efforts at Superfund sites across the country focus on groundwater contaminant plumes that have been produced by contributions from multiple parties. Allocating cleanup costs between the parties in a fair and equitable manner can be a problem of substantial complexity. Considerable time and money may be spent determining the amount of contamination attributable to each party in order to apportion liability. Contaminant plumes that have evolved over long periods of time may affect large volumes of groundwater and require extensive remediation. Pump and treat remedial costs are driven by both the volume of water extracted and the mass of contaminants removed. Allocation methods based solely on the mass of contaminants contributed by each party are inadequate in this setting since they do not account for both components of the remedial costs. This paper presents an approach for equitably allocating remedial costs when addressing overlapping or commingled groundwater plumes. The method accounts for the major elements driving the costs of remediating dispersed contaminant plumes.     

Isotopes as tracers in a contaminated fractured chalk aquitard

Clusters of industrial plants often generate contaminant plumes with several potential sources. Prevention of further pollution and designing suitable remedial measures require identification of the contributing source among all potential ones and the sorting of currently active sources from historical ones. In the study area, an industrial complex in the Negev desert, Israel, contaminants could not serve as indicators for the contamination sources because of their extensive spatial distribution across the site. However, stable isotopes of oxygen, hydrogen and sulfur, as well as tritium, proved to be efficient tools for this task. The isotopic characterization of the potential end members provided the criteria for constraining a contaminating source when several alternative sources appeared viable. The isotopic fractionation of oxygen and hydrogen isotopes could be tied to the various disposal phases of the industrial wastewater. The three case studies presented here confirm the important role of isotopes as tracers in contaminated sites.     

Contaminated site remedial investigation and feasibility removal of chlorinated volatile organic compounds from groundwater by activated carbon fiber adsorption

Groundwater contaminated by dense, non-aqueous phase liquids (DNAPLs) such as chlorinated solvents has become a serious problem in some regions of Taiwan. The sources of these contaminants are due to industrial discharges. These chlorinated volatile organic compounds (VOCs) have been proven to be carcinogenic to humans. The groundwater is used for domestic drinking water supply in some cities of Taiwan and the severely contaminated groundwater has to be treated in order to meet the requirement of drinking water standards. This study covers two areas of work. In the first part, polluted groundwater samples were collected from the contaminated site and analytical results indicated measurable concentrations of 12 representative chlorinated VOCs in water samples. The primary VOCs detected included trichloroethene (TCE), tetrachloroethene (PCE), 1,1,2-trichloroethane (1,1,2-TCA), and 1,1-dichloroethene (1,1-DCE). Second, to remove VOCs groundwater was treated using adsorption on activated carbon fiber (ACF). This involved pumping groundwater through vessels containing ACF. Most VOCs, including TCE, PCE, 1,1,2-TCA, and DCE, were readily adsorbed onto ACF and are removed from the water stream. Our study showed that the technology was able to significantly reduce chlorinated VOCs concentrations in groundwater.     

Attenuation reactions in a multiple contaminated aquifer in Bitterfeld (Germany)

Large-scale contaminated sites with multiple contaminants in the groundwater present a challenge to risk assessment and remediation. Attenuation reactions take place in the subsurface and act to contain contaminants, but must be thoroughly investigated on a site-specific basis. Field data from monitoring wells at a contaminated industrial site in Bitterfeld, Germany, are presented and analyzed for evidence of the prevalent biodegradation reactions. The groundwater in the Tertiary aquifer is contaminated with large quantities of chlorinated aliphatic compounds, in addition to chlorobenzenes and BTEX. In this strictly anaerobic environment, geochemical indications for several microbial processes were found, including methanogenesis, sulfate and iron reduction as well as reductive dechlorination of the chlorinated hydrocarbons. Direct evidence for the latter degradation reaction was observed along the flowpath due to the appearance of intermediates and an increase in the degree of dechlorination.     

Transport and fate of organic wastes in groundwater at the Stringfellow hazardous waste disposal site, southern California

In January 1999, wastewater influent and effluent from the pretreatment plant at the Stringfellow hazardous waste disposal site were sampled along with groundwater at six locations along the groundwater contaminant plume. The objectives of this sampling and study were to identify at the compound class level the unidentified 40-60% of wastewater organic contaminants, and to determine what organic compound classes were being removed by the wastewater pretreatment plant, and what organic compound classes persisted during subsurface waste migration. The unidentified organic wastes are primarily chlorinated aromatic sulfonic acids derived from wastes from DDT manufacture. Trace amounts of EDTA and NTA organic complexing agents were discovered along with carboxylate metabolites of the common alkylphenolpolyethoxylate plasticizers and nonionic surfactants. The wastewater pretreatment plant removed most of the aromatic chlorinated sulfonic acids that have hydrophobic neutral properties, but the p-chlorobenzene-sulfonic acid which is the primary waste constituent passed through the pretreatment plant and was discharged in the treated wastewaters transported to an industrial sewer. During migration in groundwater, p-chlorobenzenesulfonic acid is removed by natural remediation processes. Wastewater organic contaminants have decreased 3- to 45-fold in the groundwater from 1985 to 1999 as a result of site remediation and natural remediation processes. The chlorinated aromatic sulfonic acids with hydrophobic neutral properties persist and have migrated into groundwater that underlies the adjacent residential community.     

Modelling of an enhanced PAH attenuation experiment and associated biogeochemical changes at a former gasworks site in southern Germany

Former manufactured gas plant sites often form a widespread contaminant source in the subsurface, leading to large plumes that contain a wide variety of tar-oil related compounds. Although most of these compounds eventually degrade naturally, the relevant processes tend to be slow and inefficient, often leaving active remediation as the only viable option to eliminate the risks of toxic substances to reach potential receptors such as surface waters or drinking water wells. In this study we use a reactive transport model to analyse the fate of a contaminant plume containing acenaphthene, methylbenzofurans and dimethylbenzofurans (i) prior to the installation of an active remediation scheme and (ii) for an enhanced remediation experiment during which O(2) and H(2)O(2) were added to the contaminated groundwater through a recirculation well. The numerical model developed for this study considers the primary contaminant degradation reactions (i.e., microbially mediated redox reactions) as well as secondary and competing mineral precipitation/dissolution reactions that affect the site's hydrochemistry and/or contaminant fate. The model was calibrated using a variety of constraints to test the uncertainty on model predictions resulting from the undocumented presence of reductants such as pyrite. The results highlight the important role of reactive transport modelling for the development of a comprehensive process understanding.     

Redistribution of contaminants by a fluctuating water table in a micro-porous, double-porosity aquifer: field observations and model simulations

Large seasonal fluctuations of the water table are characteristic of aquifers with a low specific yield, including those fractured, double-porosity aquifers that have significant matrix porosity containing virtually immobile porewater, such as the Chalk of northern Europe. Where these aquifers are contaminated, a strong relationship between water table elevation and contaminant concentration in groundwater is commonly observed, of significance to the assessment, monitoring, and remediation of contaminated groundwater. To examine the processes governing contaminant redistribution by a fluctuating water table within the 'seasonally unsaturated zone', or SUZ, profiles of porewater solute concentrations have been established at a contaminated site in southern England. These profiles document the contaminant distribution in porewater of the Chalk matrix over the SUZ at a greater level of detail than recorded previously. A novel double-porosity solute transport code has been developed to simulate the evolution of the SUZ matrix porewater contaminant profiles, given a fluctuating water table, when the groundwater is initially contaminated and the SUZ is initially free of contamination. The model is simply characterised by: the matrix-fracture porosity ratio, the matrix block geometry, and a characteristic diffusion time. De-saturation and re-saturation of fractures is handled by a new approximation method. Contaminant accumulates in the upper levels of the SUZ, where it is less accessible to mobile groundwater, and acts as a persistent secondary source of contamination once the original source of contamination has been removed or has become depleted. The 'SUZ process' first attenuates the progress of contaminants in groundwater, and subsequently controls the slow release of contamination back to the mobile groundwater, thus prolonging the duration of groundwater contamination by many years. The SUZ process should operate in any fractured, micro-porous lithology e.g. fractured clays and mudstones, making this approach widely applicable.     

Characteristics and applications of controlled-release KMnO4 for groundwater remediation

In situ chemical oxidation (ISCO) using potassium permanganate (KMnO4) has been widely used as a practical approach for remediation of groundwater contaminated by chlorinated solvents like trichloroethylene. The most common applications are active flushing schemes, which target the destruction of some contaminant source by injecting concentrated permanganate (MnO4(-)) solution into the subsurface over a short period of time. Despite many promising results, KMnO4 flushing is often frustrated by inefficiency associated with pore plugging by MnO2 and bypassing. Opportunities exist for the development of new ISCO systems based on KMnO4. The new scheme described in this paper uses controlled-release KMnO4 (CRP) as an active component in the well-based reactive barrier system. This scheme operates to control spreading of a dissolved contaminant plume. Prototype CRP was manufactured by dispersing fine KMnO4 granules in liquid crystal polymer resin matrix. Scanning electron microscope data verified the formation of micro-scale (ID=20-200 microm) secondary capillary permeability through which MnO4(-) is released by a reaction-diffusion process. Column and numerical simulation data indicated that the CRP could deliver MnO4(-) in a controlled manner for several years without replenishment. A proof-of-concept flow-tank experiment and model simulations suggested that the CRP scheme could potentially be developed as a practical approach for in situ remediation of contaminated aquifers. This scheme may be suitable for remediation of sites where accessibility is limited or some low-concentration contaminant plume is extensive. Development of delivery systems that can facilitate lateral spreading and mixing of MnO4(-) with the contaminant plume is warranted.     

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.     

污染土壤及地下水修复的PRB技术及展望

PRB技术是一类就地修复污染土壤及地下水的新型技术 ,主要由注入井、浸提井和监测井3部分所组成。污染地区的水文地质学研究 ,是实施该技术的关键 ;化学活性物质的筛选、注入的部位、浓度、速率以及是否均匀分布 ,是该技术是否有效的关键要素。胶态零价铁PRB技术 ,被证明是一项修复由卤代烃、卤代芳烃和有机氯农药以及一些有毒金属 (如铬、硒、铀、砷和锝等 )引起的土壤及地下水污染的有效技术。尽管这些技术存在一定的弊病 ,但与传统的处理方法相比 ,其技术上的优势是十分明显的。可以预料 ,这一技术在我国有良好的应用前景     

Risk assessment and prioritisation of contaminated sites on the catchment scale

Contaminated sites pose a significant threat to groundwater resources worldwide. Due to limited available resources a risk-based prioritisation of the remediation efforts is essential. Existing risk assessment tools are unsuitable for this purpose, because they consider each contaminated site separately and on a local scale, which makes it difficult to compare the impact from different sites. Hence a modelling tool for risk assessment of contaminated sites on the catchment scale has been developed. The CatchRisk screening tool evaluates the risk associated with each site in terms of its ability to contaminate abstracted groundwater in the catchment. The tool considers both the local scale and the catchment scale. At the local scale, a flexible, site specific leaching model that can be adjusted to the actual data availability is used to estimate the mass flux over time from identified sites. At the catchment scale, a transport model that utilises the source flux and a groundwater model covering the catchment is used to estimate the transient impact on the supply well. The CatchRisk model was tested on a groundwater catchment for a waterworks north of Copenhagen, Denmark. Even though data scarcity limited the application of the model, the sites that most likely caused the observed contamination at the waterworks were identified. The method was found to be valuable as a basis for prioritising point sources according to their impact on groundwater quality. The tool can also be used as a framework for testing hypotheses on the origin of contamination in the catchment and for identification of unknown contaminant sources.     

Root establishment of perennial ryegrass (L. perenne) in diesel contaminated subsurface soil layers

The efficiency of rhizosphere biodegradation of petroleum hydrocarbons heterogeneously distributed in soils is dependent on the ability of plant roots to prospect into contaminated zones. Rhizobox experiments were conducted to study the influence of diesel contaminated layers on the spatial distribution and the development of the roots of perennial ryegrass. Root distribution and root and shoot development were monitored over time. The final root and above ground biomass and the final TPH concentration were determined. The spatial distribution of the contaminant as well as the irrigation method used affected root distribution, plant development and TPH degradation and therefore ryegrass remediation potential. The results show that roots colonise fully uncontaminated soil and grow preferentially between zones of contamination. Conversely, when no immediate uncontaminated soil is available, roots grow through contaminated zones in order to prospect for uncontaminated soil.     

Quantification of groundwater contamination in an urban area using integral pumping tests

In this paper, the integral groundwater investigation method is used for the quantification of PCE and TCE mass flow rates at an industrialized urban area in Linz, Austria. In this approach, pumping wells positioned along control planes perpendicular to the groundwater flow direction are operated for a time period on the order of days and sampled for contaminants. The concentration time series of the contaminants measured during operation of the pumping wells are then used to determine contaminant mass flow rates, mean concentrations and the plume shapes and positions at the control planes. The three control planes used in Linz were positioned downstream of a number of potential source zones, which are distributed over the field site. By use of the integral investigation method, it was possible to identify active contaminant sources, quantify the individual source strength in terms of mass flow rates at the control planes and estimate the contaminant plume position relative to the control planes. The source zones emitting the highest PCE and TCE mass flow rates could be determined, representing the areas where additional investigation and remediation activities will be needed. Additionally, large parts of the area investigated could be excluded from further investigation and remediation activities.     

Forensic Analysis of Chlorinated Hydrocarbon Plumes in Groundwater: a Multi-Site Perspective

Forensic analyses of chlorinated hydrocarbon plumes typically entail reviews of site records, flow and transport modeling, and analysis of indicator compounds to gain insights into the behavior of a contaminant plume in the subsurface. Such approaches are directed toward unraveling the specific circumstances associated with the disposal history and hydrogeology of a site. A complimentary approach is to compare the behavior of a particular plume with a population of plumes from other sites that may be influenced by similar mechanisms (e.g. transformation processes such as reductive dehalogenation). In other words, hypotheses pertaining to plume behavior can be tested against a knowledge base of what is typical behavior and what is not. To address this proposed methodology, three example applications of statistical techniques to a multi-site data set are presented to provide background for problems that may be pertinent to forensic analyses. These examples include measuring the frequency of association between selected chlorinated hydrocarbon compounds, assessing the effects of transformation processes on temporal concentration trends in populations of groundwater monitoring wells, and dating plumes, in a relative sense, by concentration correlation analyses. In each case, the results of the statistical analyses are consistent with expectation, indicating that meaningful trends in chlorinated hydrocarbon plume behavior may be discerned from a diverse multi-site data set.     

Liability Theories in Contaminated Groundwater Litigation

Disputes regarding contaminated sites have given rise to an explosion of federal and state court litigation. Congress enacted the Resource Conservation and Recovery Act of 1976 ("RCRA"), 42 U.S.C. §§6901 et seq. , as a contemplated "cradle to grave" regulatory scheme for solid waste, and passed the Comprehensive Environmental Response, Compensation, and Liability Act ("CERCLA"), 42 U.S.C. §§9601 et seq. , to address the investigation and remediation of contaminated sites. RCRA and CERCLA each contemplate a strict, joint and several regulatory liability scheme to address sites that have required billions of dollars to investigate and remediate, and which will require additional billions in order to complete the job. Federal and state law cases involving groundwater contamination cases have presented special challenges to litigants and the Courts. Determining the source of groundwater contamination is often a matter of technical dispute, particularly in the case of commingled plumes or older plumes where original point source locations can no longer be located or where there has been a significant amount of contaminant degradation over time. Contaminated plumes derived in whole or in part from potential continuing sources can present difficult remedy selection issues and uncertainty regarding future cost obligations. While a variety of federal and state law theories of liability are available to address groundwater contamination, each presents certain benefits and limitations. For example, CERCLA claims can cover a wide spectrum of potentially responsible parties and are based on strict liability; however, CERCLA excludes petroleum from the scope of its liability scheme and limits recovery to necessary response costs consistent with the National Contingency Plan. RCRA claims can include petroleum contamination, but cannot seek recovery of past costs. Common law theories such as nuisance, trespass and negligence can permit recovery of a broader scope of potential damages and provide for joint and several liability, but they are not based on notions of strict liability and sometimes present difficult statute of limitations problems. This article identifies federal and California state law liability theories addressing responsibility for groundwater contamination, and reviews the elements of liability, potential limitations on available relief, and recent case law developments under these theories.     

Influence of temporally variable groundwater flow conditions on point measurements and contaminant mass flux estimations

Monitoring of contaminant concentrations, e.g., for the estimation of mass discharge or contaminant degradation rates, often is based on point measurements at observation wells. In addition to the problem, that point measurements may not be spatially representative, a further complication may arise due to the temporal dynamics of groundwater flow, which may cause a concentration measurement to be not temporally representative. This paper presents results from a numerical modeling study focusing on temporal variations of the groundwater flow direction. “Measurements” are obtained from point information representing observation wells installed along control planes using different well frequencies and configurations. Results of the scenario simulations show that temporally variable flow conditions can lead to significant temporal fluctuations of the concentration and thus are a substantial source of uncertainty for point measurements. Temporal variation of point concentration measurements may be as high as the average concentration determined, especially near the plume fringe, even when assuming a homogeneous distribution of the hydraulic conductivity. If a heterogeneous hydraulic conductivity field is present, the concentration variability due to a fluctuating groundwater flow direction varies significantly within the control plane and between the different realizations. Determination of contaminant mass fluxes is also influenced by the temporal variability of the concentration measurement, especially for large spacings of the observation wells. Passive dosimeter sampling is found to be appropriate for evaluating the stationarity of contaminant plumes as well as for estimating average concentrations over time when the plume has fully developed. Representative sampling has to be performed over several periods of groundwater flow fluctuation. For the determination of mass fluxes at heterogeneous sites, however, local fluxes, which may vary considerably along a control plane, have to be accounted for. Here, dosimeter sampling in combination with time integrated local water flux measurements can improve mass flux estimates under dynamic flow conditions.