Application of source removal and natural attenuation remediation strategies at MGP sites in Wisconsin

This article presents site closure strategies of source material removal and dissolved‐phase groundwater natural attenuation that were applied at two manufactured gas plant (MGP) sites in Wisconsin. The source removal actions were implemented in 1999 and 2000 with groundwater monitoring activities preceding and following those actions. Both of these sites have unique geological and hydrogeological conditions. The article briefly presents site background information and source removal activities at both of these sites and focuses on groundwater analytical testing data that demonstrate remediation of dissolved‐phase MGP‐related groundwater impacts by natural attenuation. A statistical evaluation of the data supports a stable or declining MGP parameter concentration trend at each of the sites. A comparison of the site natural attenuation evaluation is made to compare with the requirements for site closure under the Wisconsin Department of Natural Resources regulations and guidance. © 2003 Wiley Periodicals, Inc.     

A deterministic approach to evaluate and implement monitored natural attenuation for chlorinated solvents

A US EPA directive and related technical protocol outline the information needed to determine if monitored natural attenuation (MNA) for chlorinated solvents is a suitable remedy for a site. For some sites, conditions such as complex hydrology or perturbation of the contaminant plume caused by an existing remediation technology (e.g., pump‐and‐treat) make evaluation of MNA using only field data difficult. In these cases, a deterministic approach using reactive transport modeling can provide a technical basis to estimate how the plume will change and whether it can be expected to stabilize in the future and meet remediation goals. This type of approach was applied at the Petro‐Processors Inc. Brooklawn site near Baton Rouge, Louisiana, to evaluate and implement MNA. This site consists of a multicomponent nonaqueous‐phase source area creating a dissolved groundwater contamination plume in alluvial material near the Mississippi River. The hydraulic gradient of the groundwater varies seasonally with changes in the river stage. Due to the transient nature of the hydraulic gradient and the impact of a hydraulic containment system operated at the site for six years, direct field measurements could not be used to estimate natural attenuation processes. Reactive transport of contaminants were modeled using the RT3D code to estimate whether MNA has the potential to meet the site‐specific remediation goals and the requirements of the US EPA Office of Solid Waste and Emergency Response Directive 9200.4‐17P. Modeling results were incorporated into the long‐term monitoring plan as a basis for evaluating the effectiveness of the MNA remedy. As part of the long‐term monitoring plan, monitoring data will be compared to predictive simulation results to evaluate whether the plume is changing over time as predicted and can be expected to stabilize and meet remediation goals. This deterministic approach was used to support acceptance of MNA as a remedy. © 2007 Wiley Periodicals, Inc.     

Insufficient source area remediation results in the rebound of TCE breakdown products in groundwater

In the early 1990s, a soil removal action was completed at a former disposal pit site located in southern Michigan. This action removed waste oil, cutting oil, and chlorinated solvents from the unsaturated zone. To contain groundwater contaminant migration at the site, a groundwater pump‐and‐treat system comprised of two extraction wells operating at a combined flow of 50 gallons per minute, carbon treatment, and a permitted effluent discharge was designed, installed, and operated for over 10 years. Groundwater monitoring for natural attenuation parameters and contaminant attenuation modeling demonstrated natural attenuation of the contaminant plume was adequate to attain site closure. As a result of incomplete contaminant source removal, a rebound of contaminants above the levels established in the remedial action plan (RAP) has occurred in the years following system shutdown and site closure. Groundwater concentrations have raised concerns regarding potential indoor air quality at adjacent residential properties constructed in the past 9 to 10 years. The only remedial option available in the original RAP is to resume groundwater pump‐and‐treat. To remediate the source area, an alternate remediation strategy using an ozone sparge system was developed. The ozone sparge remediation strategy addresses the residual saturated zone contaminants beneath the former disposal pit and reestablishes site closure requirements without resumption of the pump‐and‐treat system. A pilot study was completed successfully; and the final system design was subsequently approved by the Michigan Department of Environmental Quality. The system was installed and began operations in July 2010. As of the January 2011 monitoring event, the system has shown dramatic improvement in site contaminant concentrations. The system will continue to operate until monitoring results indicate that complete treatment has been obtained. The site will have achieved the RAP objectives when the system has been shut down and meets groundwater residential criteria for four consecutive quarters. © 2011 Wiley Periodicals, Inc.     

Comparing PFAS to other groundwater contaminants: Implications for remediation

Established groundwater contaminants such as chlorinated solvents and hydrocarbons have impacted groundwater at hundreds of thousands of sites around the United States and have been responsible for multibillion dollar remediation expenditures. An important question is whether groundwater remediation for the emerging contaminant class comprised of per‐ and polyfluoroalkyl substances (PFAS) will be a smaller, similar, or a larger‐scale problem than the established groundwater contaminants. A two‐pronged approach was used to evaluate this question in this paper. First, nine quantitative scale‐of‐remediation metrics were used to compare PFAS to four established contaminants: chlorinated solvents, benzene, 1,4‐dioxane, and methyl tert‐butyl ether. These metrics reflected the prevalence of the contaminants in the U.S., attenuation potential, remediation difficulty, and research intensity. Second, several key challenges identified with PFAS remediation were evaluated to see similar situations (qualitative analogs) that have been addressed by the remediation field in the past. The results of the analysis show that four out of nine of the evaluated quantitative metrics (production, number of potential sites, detection frequency, required destruction/removal efficiency) indicate that the scale of PFAS groundwater remediation may be smaller compared to the current scale of remediation for conventional groundwater contaminants. One attenuation metric, median plume length, suggests that overall PFAS remediation could pose a greater challenge compared to hydrocarbon sites, but only slightly larger than chlorinated volatile organic compounds sites. The second attenuation metric, hydrophobic sorption, was not definitive regarding the potential scale of PFAS remediation. The final three metrics (regulatory criteria, in‐situ remediation capability, and research intensity) all indicate that PFAS remediation might end up being a larger scale problem than the established contaminants. An assessment of the evolution of groundwater remediation capabilities for established contaminants identified five qualitative analogs for key PFAS groundwater remediation issues: (a) low‐level detection analytical capabilities; (b) methods to assess the risk of complex chemical mixtures; (c) nonaqueous phase dissolution as an analog for partitioning, precursors, and back diffusion at PFAS sites; (d) predictions of long plume lengths for emerging contaminants; and (e) monitored natural attenuation protocols for other non‐degrading groundwater contaminants. Overall the evaluation of these five analogs provided some comfort that, while remediating the potential universe of PFAS sites will be extremely challenging, the groundwater community has relevant past experience that may prove useful. The quantitative metrics and the qualitative analogs suggest a different combination of remediation approaches may be needed to deal with PFAS sites and may include source control, natural attenuation, in‐situ sequestration, containment, and point‐of‐use treatment. However, as with many chlorinated solvent sites, while complete restoration of PFAS sites may be uncommon, it should be possible to prevent excessive exposure of PFAS to human and ecological receptors.     

Historical analysis of monitored natural attenuation: A survey of 191 chlorinated solvent sites and 45 solvent plumes

A survey of experts in the application of natural attenuation was conducted to better understand how monitored natural attenuation (MNA) is being applied at chlorinated solvent sites. Thirty‐four remediation professionals provided general information for 191 sites where MNA was evaluated, and site‐specific data for 45 chlorinated solvent plumes being remediated by MNA. Respondents indicated that MNA was precluded as a remedy at only 23 percent of all sites where evaluated as a remedial option. Leading factors excluding MNA as a remedial approach were the presence of an expanding plume and an unreasonably long estimated remediation time frame. MNA is being used as the sole remedy at about 30 percent of the sites, and 33 percent are implementing MNA in conjunction with source zone remediation. The remaining sites are implementing MNA with plume remediation (13 percent), source containment (9 percent), or some other strategy (16 percent). © 2004 Wiley Periodicals, Inc.     

Operating windows to assess whether monitored natural attenuation is a technically feasible remediation option for BTEX‐contaminated groundwater

When used in combination with source management strategies, monitored natural attenuation (MNA) is likely to be a technically feasible remediation option if the contaminant persistence time along the flow path is less than (a) the transport time to the compliance point and (b) the time available for groundwater remediation objectives to be achieved. Biodegradation is often the most significant natural attenuation process for benzene, toluene, ethylbenzene, and xylenes (BTEX) in groundwater. While BTEX transport rates increase with groundwater velocity, examination of data obtained from the published literature for seven sites undergoing MNA revealed significant positive correlations between groundwater velocity and first‐order biodegradation rates for toluene (r = 0.83, P < 0.05), ethylbenzene (r = 0.93, P < 0.01), m‐ and p‐xylene (r = 0.96, P < 0.01), and o‐xylene (r = 0.78, P < 0.05). This is attributed to increased dispersion at higher velocities leading to more mixing of electron acceptors with the contaminant plume. There was no positive correlation between groundwater velocity and first‐order biodegradation rates for benzene due to noise in the relationship caused by variations in (a) the concentrations of electron acceptors in the uncontaminated groundwater and (b) the proportions of benzene in the total BTEX concentration in the source area. A regression model of the relationship between groundwater velocity and the first‐order biodegradation rate can be used to delineate operating windows for groundwater velocity within which the contaminant persistence time is less than the transport and remediation times for a given source concentration, target concentration, distance to compliance point, retardation factor, and remediation time. The operating windows can provide decision makers with a rapid indication of whether MNA is likely to be a technically feasible remediation option at a given site. © 2005 Wiley Periodicals, Inc.     

Evaluating a Site for Natural Attenuation: EPA Region IV's New Guidance

Natural attenuation has recently been recognized by the U.S. Environmental Protection Agency (EPA) as an appropriate remedy for sites contaminated with chlorinated solvents. Because natural attenuation does not require active remediation, it is considerably less expensive than other groundwater remedies. However, as laid out in EPA's recently released guidance, careful, systematic evaluation of natural attenuation must be conducted to ensure that the remedial approach is appropriate for a given site. The guidance requires that data be collected to demonstrate that natural attenuation is occurring and a fate-and-transport model must be conducted to estimate the extent to which a contaminated plume will ultimately migrate. Finally, the proponent of natural attenuation must be prepared to conduct long-term groundwater monitoring to verify that natural attenuation is controlling plume migration and that human health and the environment are not adversely affected.     

Modeling remediation time using natural attenuation at a dry‐cleaner site

Contaminants from dry‐cleaning sites, primarily tetrachloroethene (PCE), trichloroethene (TCE), cis‐dichloroethene (cis‐DCE), and vinyl chloride (VC), have become a major concern because of the limited funds and regulatory programs to address them. Thus, natural attenuation and its effectiveness for these sites needs to be evaluated as it might provide a less costly alternative to other remediation methods. In this research, data from a site in Texas were analyzed and modeled using the Biochlor analytical model to evaluate remediation times using natural attenuation. It was determined that while biodegradation and source decay were occurring at the site, the resulting attenuation rates were not adequate to achieve cleanup in a reasonable time frame without additional source remediation or control strategies. Cleanup times exceeded 100 years for all constituents at the site boundary and 800 years at the source for PCE, assuming cleanup levels of 0.005 mg/L for PCE and TCE and 0.07 mg/L and 0.002 mg/L for cis‐DCE and VC, respectively. © 2005 Wiley Periodicals, Inc.     

Performance evaluation of an in situ source area combined remedy for the remediation of commingled chlorinated ethanes and ethenes

The chlorinated volatile organic compounds (CVOCs), tetrachloroethene (PCE), trichloroethene (TCE), and 1,1,1‐trichloroethane (1,1,1‐TCA), often found as commingled contaminants of concern (COCs) in groundwater, can degrade via a variety of biotic and abiotic reductive pathways. In situ remediation of a groundwater contaminant source area containing commingled 1,1,1‐TCA, PCE, and TCE was conducted using a combined remedy/treatment train approach. The first step was to create geochemically reducing conditions in the source area to degrade the CVOCs to lesser chlorinated CVOCs (i.e., 1,1‐dichloroethane [1,1‐DCA], 1,1‐dichlorethene [1,1‐DCE], cis‐1,2‐dichoroethene [cis‐1,2‐DCE], and vinyl chloride [VC]) via enhanced reductive dechlorination (ERD). Carbon substrates were injected to create microbial‐induced geochemically reducing conditions. An abiotic reductant (zero‐valent iron [ZVI]) was also used to further degrade the CVOCs, minimizing the generation of 1,1‐DCE and VC, and co‐precipitate temporarily mobilized metals. An in situ aerobic zone was created downgradient of the treatment zone through the injection of oxygen. Remaining CVOC degradation products and temporarily mobilized metals (e.g., iron and manganese) resulting from the geochemically reducing conditions were then allowed to migrate through the aerobic zone. Within the aerobic zone, the lesser chlorinated CVOCs were oxidized and the solubilized metals were precipitated out of solution. The injection of a combination of carbon substrates and ZVI into the groundwater system at the site studied herein resulted in the generation of a geochemically reducing subsurface treatment zone that has lasted for more than 4.5 years. Mass concentrations of total CVOCs were degraded within the treatment zone, with near complete transformation of chlorinated ethenes and a more than 90 percent reduction of CVOC mass concentrations. Production of VC and 1,1‐DCE has been minimized through the combined effects of abiotic and biological processes. CVOC concentrations have declined over time and temporarily mobilized metals are precipitating out of the dissolved phase. Precipitation of the dissolved metals was mitigated using the in situ oxygenation system, also resulting in a return to aerobic conditions in downgradient groundwater. Chloroethane (CA) is the dominant CVOC degradation product within the treatment zone and downgradient of the treatment zone, and it is expected to continue to aerobically degrade over time. CA did not accumulate within and near the aerobic oxygenation zone. The expectations for the remediation system are: (1) the concentrations of CVOCs (primarily in the form of CA) will continue to degrade; (2) total organic carbon concentrations will continue to decline to pre‐remediation levels; and, (3) the groundwater geochemistry will experience an overall trend of transitioning from reducing back to pre‐remediation mildly oxidizing conditions within and downgradient of the treatment zone.     

Re‐evaluation of treatment approach for a site contaminated with Freon‐113 and 1,1,1‐trichloroethane

This study demonstrates a remedial approach for completing the remediation of an aquifer contaminated with 1,1,2‐trichlorotrifluoroethane (Freon‐113) and 1,1,1‐trichloroethane (TCA). In 1987, approximately 13,000 pounds of Freon‐113 were spilled from a tank at an industrial facility located in the state of New York. The groundwater remediation program consisted of an extraction system coupled with airstripping followed by natural attenuation of residual contaminants. In the first phase, five recovery wells and an airstripping tower were operational from April 1993 to August 1999. During this time period over 10,000 pounds of CFC‐13 and 200 pounds of TCA were removed from the groundwater and the contaminant concentrations decreased by several orders of magnitude. However, the efficiency of the remediation system to recover residual Freon and/or TCA reduced significantly. This was evidenced by: (1) low levels (< 10 ppb) of Freon and TCA captured in the extraction wells and (2) a slight increase of Freon and/or TCA in off‐site monitoring wells. A detailed study was conducted to evaluate the alternative for the second‐phase remediation. Results of a two‐year groundwater monitoring program indicated the contaminant plume to be stable with no significant increase or decrease in contaminant concentrations. Monitored geochemical parameters suggest that biodegradation does not influence the fate and transport of these contaminants, but other mechanisms of natural attenuation (primarily sorption and dilution) appear to control the fate and transport of these contaminants. The contaminants appear to be bound to the soil matrix (silty and clay units) with limited desorption as indicated by the solid phase analyses of contaminant concentrations. Results of fate and transport modeling indicated that contaminant concentrations would not exceed the action levels in the wells that showed a slight increase in contaminant concentrations and in the downgradient wells (sentinel) during the modeled timeframe of 30 years. This feasibility study for natural attenuation led to the termination of the extraction system and a transaction of the property, resulting in a significant financial benefit for the original site owner. © 2003 Wiley Periodicals, Inc.     

Geochemical evaluation of metals in groundwater at long‐term monitoring sites and active remediation sites

At many sites, long‐term monitoring (LTM) programs include metals as chemicals of concern, although they may not be site‐related contaminants and their detected concentrations may be natural. At other sites, active remediation of organic contaminants in groundwater results in changes to local geochemical conditions that affect metal concentrations. Metals should be carefully considered at both types of sites, even if they are not primary contaminants of concern. Geochemical evaluation can be performed at LTM sites to determine if the monitored metals reflect naturally high background and, hence, can be removed from the analytical program. Geochemical evaluation can also be performed pre‐ and post‐treatment at active remediation sites to document the effects of organics remediation on metals and identify the processes controlling metal concentrations. Examples from both types of sites are presented in this article. © 2008 Wiley Periodicals, Inc.     

Constant Head Injection for Enhanced In Situ Chemical Oxidation

With the successful implementation of in situ chemical oxidation (ISCO) programs to remediate contaminated soil and groundwater aquifers worldwide, ISCO has become established as a traditional remediation technique. On the basis of historical success, expanded ISCO practices are now routinely applied to increasingly difficult geologic environments, including formerly problem locations such as those containing nonaqueous‐phase liquid, fractured bedrock, low‐conductivity media, and highly layered and/or heterogeneous aquifers. Effective delivery of amendment, however, remains the single most important aspect of successful remediation, particularly given the range of potentially applicable delivery methods and site complexities. Selecting the most appropriate technique for any specific site depends upon a clear understanding of the variety of site constraints, including factors such as site conditions, underlying geology, contaminant distribution, technology limitations, and other project‐specific factors. Because the injection program is often the largest cost associated with implementation of an ISCO project, it is critical to develop a cost‐effective injection method for each site. Constant head injection provides a cost‐effective alternative for sites with low‐conductivity lithology(ies). Constant head injection employs a continuous low‐pressure application method to deliver ISCO agents over a long period of time. This synergistic method complements the existing site conditions and heterogeneity, working with the natural conditions, rather than trying to overcome or destroy the site geology using highly aggressive delivery techniques. © 2014 Wiley Periodicals, Inc.     

Closing the mass balance at chlorinated solvent sites: Sources and attenuation processes

Using detailed mass balance and simple analytical models, a spreadsheet‐based application (BioBalance) was developed to equip decision makers with a predictive tool that can provide a semiquantitative projection of source‐zone concentrations and provide insight into the long‐term behavior of the associated chlorinated solvent plume. The various models were linked in a toolkit in order to predict the composite impacts of alternative source‐zone remediation technologies and downgradient attenuation processes. Key outputs of BioBalance include estimates of maximum plume size, the time frame for plume stabilization, and an assessment of the sustainability of anaerobic natural attenuation processes. The toolkit also provides spatial and temporal projections of integrated contaminant flux and plume centerline concentrations. Results from model runs of the toolkit indicate that, for sites trying to meet traditional, “final” remedial objectives (e.g., two to three orders of magnitude reduction in concentration with restoration to potable limits), “dispersive” mechanisms (e.g., heterogeneous flow and matrix diffusion) can extend remedial time frames and limit the benefits of source remediation in reducing plume sizes. In these cases, the removal of source mass does not result in a corresponding reduction in the time frame for source remediation or plume stabilization. However, this should not discourage practitioners from implementing source‐depletion technologies, since results from the toolkit demonstrate a variety of measurable benefits of source remediation. Model runs suggest that alternative, “intermediate” performance metrics can improve and clarify source remediation objectives and better monitor and evaluate effectiveness. Suggested intermediate performance metrics include reduction in overall concentrations or mass within the plume, reduction of flux moving within a plume, and reduction in the potential for risk to a receptor or migration of a target concentration of contaminant beyond a site boundary. This article describes the development of two key modules of the toolkit as well as illustrates the value of using intermediate performance metrics to evaluate the performance of a source‐remediation technology. © 2010 Wiley Periodicals, Inc.     

Application of an Adapted Version of MT3DMS for Modeling Back‐Diffusion Remediation Timeframes

Simulation of back‐diffusion remediation timeframe for thin silt/clay layers, or when contaminant degradation is occurring, typically requires the use of a numerical model. Given the centimeter‐scale vertical grid spacing required to represent diffusion‐dominated transport, simulation of back‐diffusion in a 3‐D model may be computationally prohibitive. Use of a local 1‐D model domain approach for simulating back‐diffusion is demonstrated to have advantages but is limited to only some applications. Incorporation of a local domain approach for simulating back‐diffusion in a new model, In Situ Remediation‐MT3DMS (ISR‐MT3DMS) is validated based on a benchmark with MT3DMS and comparisons with a highly discretized finite difference numerical model. The approach used to estimate the vertical hydrodynamic dispersion coefficient is shown to have a significant influence on the simulated flux into and out of silt/clay layers in early time periods. Previously documented back‐diffusion at a Florida site is modeled for the purpose of evaluating the sensitivity of the back‐diffusion controlled remediation timeframe to various site characteristics. A base case simulation with a clay lens having a thickness of 0.2 m and a length of 100 m indicates that even after 99.96 percent aqueous TCE removal from the clay lens, the down‐gradient concentrations still exceed the MCL in groundwater monitoring wells. This shows that partial mass reduction from a NAPL source zone via in situ treatment may have little benefit for the long‐term management of contaminated sites, given that back‐diffusion will sustain a groundwater plume for a long period of time. Back‐diffusion model input parameters that have the greatest influence on remediation timeframe and thus may warrant more attention during field investigations, include the thickness of silt/clay lenses, retardation coefficient representing sorbed mass in silt/clay, and the groundwater velocity in adjacent higher permeability zones. Therefore, pump‐and‐treat systems implemented for the purpose of providing containment may have an additional benefit of reducing back‐diffusion remediation timeframe due to enhanced transverse advective fluxes at the sand/clay interface. Remediation timeframes are also moderately sensitive to the length of the silt/clay layers and transverse vertical dispersivity, but are less sensitive to degradation rates within silt/clay, contaminant solubility, contact time, tortuosity coefficient, and monitoring well‐screen length for the scenarios examined. ©2015 Wiley Periodicals, Inc.     

Application of the operating window concept to remediation‐option selection

An Erratum has been published for this article in Remediation 14(4) 2004, 141. The selection of remediation options for the management of unacceptable risks at contaminated sites is hindered by insufficient information on their performance under different site conditions. Therefore, there is a need to define “operating windows” for individual remediation options to summarize their performance under a variety of site conditions. The concept of the “operating window” has been applied as both a performance optimization tool and decision support tool in a number of different industries. Remediation‐option operating windows could be used as decision support tools during the “options appraisal” stage of the Model Procedures (CLR 11), proposed by the Environment Agency (EA) for England and Wales, to enhance the identification of “feasible remediation options” for “relevant pollutant linkages.” The development of remediation‐option operating windows involves: 1) the determination of relationships between site conditions (“critical variables”) and option performance parameters (e.g., contaminant degradation or removal rates) and 2) the identification of upper‐ and lower‐limit values (“operational limits”) for these variables that define the ranges of site conditions over which option performance is likely to be sufficient (the “operating window”) and insufficient (the “operating wall”) for managing risk. Some research has used case study data to determine relationships between critical variables and subsurface natural attenuation (NA) process rates. Despite the various challenges associated with the approach, these studies suggest that available case study data can be used to develop operating windows for monitored natural attenuation (MNA) and, indeed, other remediation options. It is envisaged that the development of remediation‐option operating windows will encourage the application of more innovative remediation options as opposed to excavation and disposal to landfill and/or on‐site containment, which remain the most commonly employed options in many countries. © 2004 Wiley Periodicals, Inc.     

Chloroethene dechlorination in acidic groundwater: Implications for combining fenton's treatment with natural attenuation

A sulfuric acid leak in 1988 at a chloroethene‐contaminated groundwater site at the Naval Air Station Pensacola has resulted in a long‐term record of the behavior of chloroethene contaminants at low pH and a unique opportunity to assess the potential impact of source area treatment technologies, which involve acidification of the groundwater environment (e.g., Fenton's‐based in situ chemical oxidation), on downgradient natural attenuation processes. The greater than 75 percent decrease in trichloroethene (TCE) concentrations and the shift in contaminant composition toward predominantly reduced daughter products (dichloroethene [DCE] and vinyl chloride [VC]) that were observed along a 30‐m groundwater flow path characterized by highly acidic conditions (pH = 3.5 ± 0.4) demonstrated that chloroethene reductive dechlorination can continue to be efficient under persistent acidic conditions. The detection of Dehalococcoides‐type bacteria within the sulfuric acid/chloroethene co‐contaminant plume was consistent with biotic chloroethene reductive dechlorination. Microcosm studies conducted with ¹⁴C‐TCE and ¹⁴C‐VC confirmed biotic reductive dechlorination in sediment collected from within the sulfuric acid/chloroethene co‐contaminant plume. Microcosms prepared with sediment from two other locations within the acid plume, however, demonstrated only a limited mineralization to ¹⁴CO₂ and ¹⁴CO, which was attributed to abiotic degradation because no significant differences were observed between experimental and autoclaved control treatments. These results indicated that biotic and abiotic mechanisms contributed to chloroethene attenuation in the acid plume at NAS Pensacola and that remediation techniques involving acidification of the groundwater environment (e.g., Fenton's‐based source area treatment) do not necessarily preclude efficient chloroethene degradation. © 2007 Wiley Periodicals, Inc.     

Groundwater geochemistry diagnostics during in situ ERH remediation

In situ remediation represents a series of challenges in interpreting the monitoring data on remedial progress. Among these challenges are problems in determining the progress of the remediation and the mechanisms responsible, so that the process can be optimized. The release of organic pollutants to groundwater systems and in situ remediation technologies alter the groundwater chemistry, but outside of natural attenuation studies using inorganic chemical analyses as indicators of intrinsic biodegradation, typically little attention has been paid to the changes in inorganic groundwater chemistry. Smith (2008) noted that during an electrical resistance heating remediation that took place at a confidential site in Chicago, a two‐orders‐of‐magnitude increase in chloride concentrations occurred during the remediation. This increase in chloride resulted in a corresponding increase in calcium as a result of what is known as the common ion effect. Carbon dioxide is the gas found in highest concentrations in natural groundwater (Stumm & Morgan, 1981), and its fugacity (partial pressure) corresponds directly with calcium concentrations. Carbon dioxide at supersaturation in groundwater is capable of dissolving organic compounds, such as trichloroethene, facilitating removal of nonaqueous‐phase liquids at temperatures below the boiling point of water. One means of diagnosing these reactions is through the use of compound‐specific isotopic analysis, which is capable of distinguishing between evaporation, biodegradation, and differences in sources. The appropriate diagnosis has the potential to optimize the benefits from these reactions, lower energy costs for removal of nonaqueous‐phase liquids, and direct treatment where it is needed most. © 2010 Wiley Periodicals, Inc.     

Accelerating environmental cleanup at DOE sites: Monitored natural attenuation/enhanced attenuation—A basis for a new paradigm

The U.S. Department of Energy is conducting a project to accelerate remediation through the use of monitored natural attenuation and enhanced attenuation for chlorinated ethenes in soils and groundwater. Better monitoring practices, improved scientific understanding, and an advanced regulatory framework are being sought through a team effort that engages technology developers from academia, private industry, and government laboratories; site cleanup managers; stakeholders; and federal and state regulators. The team works collaboratively toward the common goals of reducing risk, accelerating cleanup, reducing cost, and minimizing environmental disruption. Cutting‐edge scientific advances are being combined with experience and sound environmental engineering in a broadly integrated and comprehensive approach that exemplifies socalled “third‐generation R&D.” The project is potentially a model for other cleanup activities. © 2004 Wiley Periodicals, Inc.     

Coupling Flow Analysis With Geochemical and Microbiological Analyses to Assess the Bioremediation Feasibility of a Contaminated Aquifer

An integrated approach combining classic and molecular microbiological methods, “in vitro” bioremediation assays and groundwater numerical modeling, has been established to identify optimized solutions for remediating aquifers contaminated with organic pollutants. Bacteria have been isolated from an aquifer contaminated with toluene and methyl tert‐butyl ether (MTBE), selected for their growth with contaminants as a sole carbon source and identified through 16S rDNA partial sequencing. Successive biodegradation laboratory tests have been performed to determine which chemical conditions were more appropriate for the isolated bacteria to more efficiently oxidize toluene and MTBE. A groundwater model was created using FEFLOW code first to determine the movement of the plume front and second to simulate the impact of the biodegradation processes along the groundwater flow directions based on the bioremediation rates obtained in the laboratory. The results show that this innovative and interdisciplinary model can be used to assist in developing monitoring and remediation plans for cleaning up complex contaminated groundwater sites. This approach successfully combines the identification of the optimum biogeochemical conditions for bacterial biodegradation to occur with the predictability of the development of the process over time, ensuring decisive support in the management of contaminated sites. ©2016 Wiley Periodicals, Inc.     

Creosote DNAPL Recovery‐Well Design for Mass Removal

Sites with dense nonaqueous‐phase liquid (DNAPL) contamination present significant remediation challenges in terms of technical practicability and cost. Remedial approaches to DNAPL sites often follow a management approach rather than removal or eradication approaches, particularly due to the uncertainties associated with the benefits of partial source mass removal, as complete source removal is unlikely. Mass‐removal technologies should be evaluated for all DNAPL sites, although implementation of recovery technologies will be limited to a few sites based upon site‐specific factors. Sitewide remedial strategies that employ source reduction, where applicable, and incorporate associated risk‐reduction technologies, including monitored natural attenuation, are advised. Creosote DNAPL sites are particularly challenging, as they are predominantly composed of low‐solubility polycyclic aromatic hydrocarbons that form long‐term continuing sources. Additionally, the physical properties of creosote DNAPL, including high viscosity and relatively low density, result in significant migration potential and considerable dissolved‐phase groundwater impacts. An innovative creosote DNAPL source recovery well design was developed to achieve separate‐phase removal of pooled creosote DNAPL. The design presented herein employs modified circulation‐well technology to mobilize DNAPL to the engineered recovery well, where it is gravity‐settled into a sump to permit separate‐phase mass removal of the emplaced DNAPL source without groundwater production or treatment. A discharge mass flux protocol was developed to verify dissolved‐phase plume stability and the benefit of the source mass removal. © 2013 Wiley Periodicals, Inc.