Simple Modeling Tool for Reconstructing Source History Using High Resolution Contaminant Profiles From Low‐k Zones

An innovative but simple analytical modeling tool for reconstructing contaminant concentration versus time trends (i.e., “source history”) for a site using high‐resolution contaminant profiles from low permeability (low‐k) zones was developed and tested. Migration of contaminants into low‐k zones via diffusion (and possibly slow advection) produce concentration versus depth profiles that can be used to understand temporal concentration trends at the interface with overlying transmissive zones, including evidence of attenuation over time due to source decay. A simple transport‐based spreadsheet tool for generating source history estimates fit to the profiles was developed and applied to published soil concentration versus depth data from five distinct areas of four different sites contaminated with chlorinated ethenes. Using the root mean square error as an optimization metric, strong fits between measured and model‐predicted soil data were obtained in the majority of cases using site‐specific values for input parameters. In general, significant improvements could not be obtained by varying these parameters. As a result, the source history estimates generated by the tool were similar to those that had already been generated using more intensive analytical or numerical inverse modeling approaches. This included confirmation of constant source histories at locations where dense nonaqueous‐phase liquid was present (or suspected to be present), and declining source histories for locations where source isolation and/or attenuation had occurred. The advantage of the modeling tool described here is that it provides a simpler yet more dynamic method for understanding source behavior over time than existing approaches. ©2015 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.     

Combined MODFLOW‐FRACTRAN Application to Assess Chlorinated Solvent Transport and Remediation in Fractured Sedimentary Rock

Detailed field investigations and numerical modeling were conducted to evaluate transport and fate of chlorinated solvent contamination in a fractured sedimentary bedrock aquifer (sandstone/siltstone/mudstone) at a Superfund site in central New Jersey. Field investigations provided information on the fractured rock system hydrogeology, including hydraulic gradients, bulk hydraulic conductivity, fracture network, and rock matrix, and on depth discrete contaminant distribution in fractures (via groundwater sampling) and matrix (via detailed subsampling of continuous cores). The numerical modeling endeavor involved application of both an equivalent porous media (EPM) model for flow and a discrete fracture network (DFN) model for transport. This combination of complementary models, informed by appropriate field data, allowed a quantitative representation of the conceptual site model (CSM) to assess relative importance of various processes, and to examine efficacy of remedial alternatives. Modeling progressed in two stages: first a large‐scale (20 km x 25 km domain) 3‐D EPM flow model (MODFLOW) was used to evaluate the bulk groundwater flow system and contaminant transport pathways under historic and current aquifer stress conditions and current stresses. Then, results of the flow model informed a 2‐D DFN transport model (FRACTRAN) to evaluate transport along a 1,000‐m flowpath from the source represented as a 2‐D vertical cross‐section. The combined model results were used to interpret and estimate the current and potential future extent of rock matrix and aqueous‐phase contaminant conditions and evaluate remedial strategies. Results of this study show strong effects of matrix diffusion and other processes on attenuating the plume such that future impacts on downgradient well fields under the hydraulic stresses modeled should be negligible. Results also showed futility of source remediation efforts in the fractured rock, and supported a technical impracticability (TI) waiver for the site. © 2013 Wiley Periodicals, Inc.     

The use of zero‐valent iron injection to remediate groundwater: Results of a pilot test at the Marshall Space Flight Center

In situ treatability studies are being conducted to evaluate various in situ technologies to manage groundwater contamination at the NASA Marshall Space Flight Center in Huntsville, Alabama. The focus of these studies is to evaluate remediation options for contaminated (mostly aerobic) groundwater occurring within the basal portion of a clayey residuum called the rubble zone. The tension‐saturated media and unsaturated media lying above the rubble zone are also being treated where they make up a significant component of the contaminant mass. An in situ chemical reduction field pilot test was implemented (following bench‐scale tests) during July and August 2000. The test involved the injection of zero‐valent iron powder in slurry form, using the Ferox^SM process patented by ARS Technologies, Inc. The pilot test focused on trichloroethene (TCE)‐contaminated groundwater within the rubble zone. Maximum pre‐injection concentrations of about 72,800 micrograms per liter (μg/l) were observed and no secondary sources are believed to exist beneath the area. The potential presence of unexploded ordnance forced an implementation strategy where source area injections were completed, as feasible, followed by overlapping injections in a down gradient alignment to create a permeable reactive zone for groundwater migration. Eight post‐injection rounds of groundwater performance monitoring were completed. The results are encouraging, in terms of predicted responses and decreasing trends in contaminant levels. © 2003 Wiley Periodicals, Inc.     

Life cycle based risk assessment of recycled materials in roadway construction

This paper uses a life-cycle assessment (LCA) framework to characterize comparative environmental impacts from the use of virgin aggregate and recycled materials in roadway construction. To evaluate site-specific human toxicity potential (HTP) in a more robust manner, metals release data from a demonstration site were combined with an unsaturated contaminant transport model to predict long-term impacts to groundwater. The LCA determined that there were reduced energy and water consumption, air emissions, Pb, Hg and hazardous waste generation and non-cancer HTP when bottom ash was used in lieu of virgin crushed rock. Conversely, using bottom ash instead of virgin crushed rock increased the cancer HTP risk due to potential leachate generation by the bottom ash. At this scale of analysis, the trade-offs are clearly between the cancer HTP (higher for bottom ash) and all of the other impacts listed above (lower for bottom ash). The site-specific analysis predicted that the contaminants (Cd, Cr, Se and Ag for this study) transported from the bottom ash to the groundwater resulted in very low unsaturated zone contaminant concentrations over a 200 year period due to retardation in the vadose zone. The level of contaminants predicted to reach the groundwater after 200 years was significantly less than groundwater maximum contaminant levels (MCL) set by the US Environmental Protection Agency for drinking water. Results of the site-specific contaminant release estimates vary depending on numerous site and material specific factors. However, the combination of the LCA and the site specific analysis can provide an appropriate context for decision making. Trade-offs are inherent in making decisions about recycled versus virgin material use, and regulatory frameworks should recognize and explicitly acknowledge these trade-offs in decision processes.     

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.     

Advanced site diagnostic tool 3D‐CSIA for in situ remediation

In situ remediation is inherently considered “green remediation.” The mechanisms of destruction by in situ technologies, however, are often unseen and not well understood. Further, physical effects of amendment application affect concentration data in an identical manner as the desired reactive mechanism. These uncertainties have led to the weight‐of‐evidence approach when proving viability: multiple rounds of data collection, bench studies, pilot studies, and so on. Skipping these steps has resulted in many failed in situ applications. Traditional assessment data are often tangential to the desired information (e.g., “Is contaminant being destroyed or just being pushed around and diluted?” and “What is the mechanism of the destruction and can it be monitored directly?”). An advanced site diagnostic tool, “Three‐Dimensional Compound Specific Stable Isotope Analysis” (3D‐CSIA), can assess the viability of in situ technologies by providing definitive data on contaminant destruction that are not concentration‐related. The 3D‐CSIA tool can also locate source zones and apportion remediation cost by identifying plumes of different isotope signatures and fractionation trends. Further, use of the 3D‐CSIA tool allows remediation professionals to evaluate effectiveness of treatment and make better decisions to expedite site closure and minimize costs. This article outlines the fundamentals of advanced site diagnostic tool 3D‐CSIA in detail, and its benefit is highlighted through a series of case studies at chlorinated solvent–contaminated sites. © 2010 Wiley Periodicals, Inc.     

In-situ bioremediation of hanford groundwater

The U.S. Department of Energy has generated liquid wastes containing radioactive and hazardous chemicals throughout the more than forty years of operation at its Hanford site in Washington State. Many of the waste components, including nitrate and carbon tetrachloride (CCl₄), have been detected in the Hanford groundwater. In-situ bioremediation of CCl₄ and nitrate is being considered to clean the aquifer. Preliminary estimates indicate that this technology should cost significantly less than ex-situ bioremediation and about the same as air stripping/granular activated carbon. In-situ bioremediation has the advantage of providing ultimate destruction of the contaminant and requires significantly less remediation time. Currently, a test site is under development. A computer-aided design tool is being used to design optimal remediation conditions by linking subsurface transport predictions, site characterization data, and microbial growth and contaminant destruction kinetics.     

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.     

In-Situ Fenton-Like Oxidation of Volatile Organics: Laboratory,Pilot, and Full-Scale Demonstrations

Laboratory, pilot, and full-scale experiments were used to evaluate and optimize the ISOTEC^SM remedial process at a warehousing facility in Union, New Jersey. Based on modified Fenton's oxidative chemistry, the ISOTEC^SM process uses a proprietary catalytic agent that delays formation of reactive hydroxyl radicals. This allows adequate dispersion of the hydroxyl radicals, which is an oxidizing agent, throughout a contaminant plume. Ground-water at the site was contaminated with high levels of gasoline and waste oil constituents, principally BTEX and MTBE. Bench scale microcosm studies were used to evaluate the appropriate site-specific stoichiometric relationships between catalyst, stabilizers, and oxidizers; the effect of contaminant type and concentration; and the pH optima. Based on results of the laboratory studies, a pilot-scale study was performed at the site. One injection point for catalyst, stabilizers, and oxidant was installed in the contaminated zone at the site, with one hydraulically connected downgradient well used for monitoring. A single treatment of the reagents in the optimal stoichiometry determined from the laboratory study was injected in-situ over a period of three days. A 98.5 percent reduction in volatile organics was observed in the area treated, with the radial extent of treatment estimated to be approximately 20 feet, based on the presence of hydroxyl radicals detected in hydraulically connected areas and at the surface. The full-scale process employed six injection points and three treatment cycles over a three-month period. Subsequent to treatment, contaminant levels were either nondetectable or were reduced to below applicable New Jersey groundwater standards, with regulatory closure on the site achieved in less than one year.     

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.     

Innovative applications of subgrade biogeochemical reactors: Three case studies

Subgrade biogeochemical reactors (SBGRs) are an in situ remediation technology shown to be effective in treating contaminant source areas and groundwater hot spots, while being sustainable and economical. This technology has been applied for over a decade to treat chlorinated volatile organic compound source areas where groundwater is shallow (e.g., less than approximately 30 feet below ground surface [ft bgs]). However, this article provides three case studies describing innovative SBGR configurations recently developed and tested that are outside of this norm, which enable use of this technology under more challenging site conditions or for treatment of alternative contaminant classes. The first SBGR case study addresses a site with groundwater deeper than 30 ft bgs and limited space for construction, where an SBGR column configuration reduced the maximum trichloroethene (TCE) groundwater concentration from 9,900 micrograms per liter (μg/L) to <1 μg/L (nondetect) within approximately 15 months. The second SBGR is a recirculating trench configuration that is supporting remediation of a 5.7‐acre TCE plume, which has significant surface footprint constraints due to the presence of endangered species habitat. The third SBGR was constructed with a new amendment mixture and reduced groundwater contaminant concentrations in a petroleum hydrocarbon source area by over 97% within approximately 1 year. Additionally, a summary is provided for new SBGR configurations that are planned for treatment of additional classes of contaminants (e.g., hexavalent chromium, 1,4‐dioxane, dissolved explosives constituents, etc.). A discussion is also provided describing research being conducted to further understand and optimize treatment mechanisms within SBGRs, including a recently developed sampling approach called the aquifer matrix probe.     

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.     

Phytoremediation of industrial sludge using vegetation‐assisted dewatering

With the emergence of risk‐based corrective action decisions, there is interest in the use of more natural techniques that may be as protective as the traditional removal, landfill, or capping approaches for impoundment closure. The use of phytoremediation is one of the more promising techniques. This article presents the results of a three‐year field‐pilot phytoremediation study that involved the use of plants to enhance sludge dewatering at an inactive natural gas‐cracking wastewater lagoon. The dewatering was accompanied by contaminant reduction of benzene, toluene, xylene (BTX), and naphthalene concentrations to below the cleanup goals. Meanwhile, the concentration reductions of three or more ring polynuclear aromatic hydrocarbons (PAHs) varied between 30 percent and 60 percent, except for dibenz[a,h]anthracene. The residual PAHs in the sludge are not leaching. Parallel laboratory studies suggest a reduced PAH availability and mobility in the unsaturated zone sludge. © 2002 Wiley Periodicals, Inc.     

Successfully applying sparging technologies

Air sparging is an innovative methodology for remediating organic compounds present in contaminated, saturated soil zones. In the application of the technology, sparging (injection) wells are used to inject a hydrocarbon-free gaseous medium (typically air) into the saturated zone below or within the areas of contamination. Two major mechanisms of remediation are engaged/enhanced due to the sparging process. First, volatile organic compounds are dissolved in the groundwater and sorbed on the soil partition into the advective air phase, effectively simulating an in-situ air stripping system. The stripped contaminants are transported in the air phase to the vadose zone, generally within the radius of influence of a standard vapor extraction and vapor treatment system. Second, with optimal environmental conditions, volatile and semivolatile organic compounds may be biodegraded by utilizing the sparging process to oxygenate the groundwater, thereby enhancing the growth and activity of the indigenous bacterial community. Air sparging is a complex multifluid phase process which has been applied successfully in Europe since the mid-1980s. Major design considerations include site geology, contaminant type, gas injection pressures and flow rates, injection interval (areal and vertical), and site-specific biofeasibility parameters. Site-specific geology and biofeasibility are the dominant design parameters. Pilot testing and full-scale design considerations should also be addressed. Mathematical models have been developed to simulate the air flow field during the sparging process and to examine the limitations imposed by site geology. Correct design and operation of this technology have been demonstrated to achieve groundwater cleanup to low part-per-billion contaminant levels. Incorrect design and operation can introduce significant pollution liability through undesirable contaminant migration in both the dissolved and vapor phases.     

Stratigraphic flux—A method for determining preferential pathways for complex sites

Experience with groundwater remediation over several decades has demonstrated that successful outcomes depend on quantitative conceptual site models (CSMs). Over the last 30 years, we have progressed from groundwater pump‐and‐treat remedies, which were largely designed based on a water supply perspective, to in situ and combined remedy strategies, which are only beginning to benefit from understanding the aquifer architecture and distribution of contaminant mass to assess plume maturity, mass flux, and more reliable means of fate and transport assessment. The U.S. Air Force funded the development of the Stratigraphic Flux approach to provide a framework for understanding contaminant transport pathways at its complex sites and enable more reliable and cost‐effective remediation. Stratigraphic Flux enables the development of quantitative, flux‐based CSMs that are founded in sequence stratigraphy, and high‐resolution hydraulic conductivity and contaminant distribution measurements. The result is a three‐dimensional graphical mapping of relative contaminant flux and classification of transport potential that is easy for all stakeholders to understand. The Stratigraphic Flux graphical model is based on a hydrofacies classification system that describes transport potential in three segments of the aquifer: transport zones—where the majority of groundwater flow occurs and transport rates are measured in feet per day; slow advection zones—where transport rates are measured in feet per year; and storage zones—where typically less than 1% of flow occurs, and diffusion dominates contaminant transport. The hydrofacies architectures are based on stratigraphy and transport potential is defined by grouping facies by orders of magnitude classes in hydraulic conductivity. By combining the hydrofacies architecture with contaminant concentration distributions, one can map relative contaminant flux to define and target the complex pathways that control contaminant transport and cleanup behavior. In this article, we describe the Stratigraphic Flux framework, focusing on the key information needed and the methods of analysis. We illustrate the results of its application to evaluate migration pathways for trichlorethylene and chromium at a former chrome pit at Air Force Plant 4 in Fort Worth, Texas. A comprehensive guidance document that describes the approach with a broad spectrum of tools and several site examples can be requested from the authors.     

Fracture Characterization Using Borehole Radar: Numerical Modeling

Forward modeling of borehole radar data for a series of synthetic discrete-fracture network (DFN) models provides a conceptual framework for interpreting experimental field data at fractured rock sites. A finite-difference time-domain (FDTD) radar wave propagation model was developed for this purpose. Synthetic examples demonstrate the utility of single-hole reflection-mode and cross-hole transmission-mode borehole radar for (1) identification of fracture location and orientation, and (2) identification of fracture pore-fluid properties, which might change as a result of tracer tests or flooding exercises in support of resource development or site remediation. A two-dimensional, synthetic DFN was generated statistically based on hypothetical distributions of fracture length, orientation, aperture, permeability, and inter-connectivity. The DFN includes a zone of permeable fractures embedded within a network of lower-permeability fractures and a low-permeability rock matrix. We modeled the unconnected and non-permeable fractures as being filled with freshwater. To simulate tracer experiments, contaminant releases, or engineered-remediation processes, we considered alternately the inter-connected, permeable fractures to be filled with freshwater air, or saline water (tracer). Synthetic radar data sets for both single-hole reflection and cross-hole transmission modes were generated. The features in synthetic radargrams were then examined and compared to the DFN model to evaluate the likelihood of identifying fracture location, orientation, and pore fluid in field situations. This comparison demonstrates that (1) the replacement of freshwater with saline water in permeable fractures generally increases the amplitude of reflections from permeable, connected fractures; and (2) in general, radar reflection-mode data contains more information about fracture properties than transmission-mode data.     

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.     

Smoldering Combustion (STAR) for the Treatment of Contaminated Soils: Examining Limitations and Defining Success

Smoldering combustion, commercially available as the Self‐sustaining Treatment for Active Remediation (STAR) technology, is an innovative technique that has shown promise for the remediation of contaminant source zones. Smoldering combustion is an exothermic reaction (net energy producing) converting carbon compounds and an oxidant (e.g., oxygen in air) to carbon dioxide, water, and energy. Thus, following ignition, the smoldering combustion reaction can continue in a self‐sustaining manner (i.e., no external energy or added fuel input following ignition) as the heat generated by the reacting contaminants is used to preheat and initiate combustion of contaminants in adjacent areas, propagating a combustion front through the contaminated zone provided a sufficient flux of air is supplied. The STAR technology has applicability across a wide‐range of hydrocarbons in a variety of hydrogeologic settings; however, there are limitations to its use. Impacted soils must be permeable enough to allow a sufficient flux of air to the combustion front and there exists a minimum required concentration of contaminants such that the soils contain sufficient fuel for the reaction to proceed in a self‐sustaining manner. Further limitations, as well as lessons learned and methods to mitigate these limitations, are presented through a series of case studies. In summary, the successful implementation of STAR will result in >99 percent reduction in contaminant concentrations in treated areas, limited residual contaminant mass, reduced groundwater contaminant mass flux which can be addressed through monitored natural attenuation; and an enhanced site exit strategy, reduced lifecycle costs, and reduced risk. ©2016 Wiley Periodicals, Inc.     

DNAPL Source Depletion: 1. Predicting Rates and Timeframes

Given the relatively rapid rate of dense nonaqueous‐phase liquid (DNAPL) ganglia depletion, source zones are generally dominated by horizontal layers of DNAPL after a release to the saturated zone. Estimating the time required to attain specific source strength reduction targets resulting from partial DNAPL source depletion is challenging due to a lack of available screening models, and because little has been done to synthesize available empirical data. Analytical and semi‐analytical models are used to study general DNAPL pool dissolution dynamics. The half‐life for the decline in DNAPL source strength (i.e., aqueous mass discharge) is demonstrated as proportional to the square root of the pool length, the thickness of the pool, and the solubility for single component DNAPLs. The through‐pool discharge is shown to be potentially significant for thin pools or in upper regions of thicker pools. An empirical analysis is used to evaluate average concentration decline rates for 13 in situ chemical oxidation (ISCO) and 16 enhanced in situ bioremediation (EISB) sites. Mean apparent decline rates, based on the time required to achieve the observed source strength reduction, are calculated for the ISCO and EISB sites (half‐lives of 0.39 year and 0.29 year, respectively). The empirical study sites are shown to have faster decline rates than for a large, complex study site where ISCO was implemented (half‐life of 2.5 years), and for a conceptual pool‐dominated trichloroethene source zone where EISB was simulated (half‐life of 2.5 years). Guidance is provided on using these findings in estimating timeframes for partial DNAPL depletion goals. © 2014 Wiley Periodicals, Inc.