Surfactant-enhanced remediation of DNAPL zones in granular aquifer systems

Dense nonaqueous phase liquids (DNAPLs), in particular chlorinated solvents such as trichloroethene, pose groundwater contamination problems at hazardous waste sites across North America. The mobility of DNAPLs in the subsurface, their low aqueous solubility, and the heterogeneity of typical aquifer systems combine to create conditions that inhibit the rapid remediation of DNAPL sites by traditional pump-and-treat methods. Surfactant-enhanced methods for DNAPL-site remediation accelerate the pace of remediation in granular aquifer systems, e.g., alluvium and outwash. The importance of adequate hydraulic conductivity and aquitard conditions is stressed in the application of surfactant-enhanced aquifer remediation (SEAR).     

Coupling surfactants/cosolvents with oxidants for enhanced DNAPL removal: A review

Surfactants and cosolvents are useful for enhancing the apparent solubility of dense nonaqueous‐phase liquid (DNAPL) compounds during surfactant‐enhanced aquifer remediation (SEAR). In situ chemical oxidation (ISCO) with permanganate, persulfate, and catalyzed hydrogen peroxide has proven to be a cost‐effective and viable remediation technology for the treatment of a wide range of organic contaminants. Coupling compatible remedial technologies either concurrently or sequentially in a treatment train is an emerging concept for more effective cleanup of DNAPL‐contaminated sites. Surfactants are effective for DNAPL mass removal but not useful for dissolved plume treatment. ISCO is effective for plume control and treatment but can be less effective in areas where large masses of DNAPL are present. Therefore, coupling SEAR with ISCO is a logical next step for source‐zone treatment. This article provides a critical review of peer‐reviewed scientific literature, nonreviewed professional journals, and conference proceedings where surfactants/cosolvents and oxidants have been utilized, either concurrently or sequentially, for DNAPL mass removal. © 2010 Wiley Periodicals, Inc.     

Mobility control: How injected surfactants and biostimulants may be forced into low‐permeability units

Recovering dense nonaqueous‐phase liquid (DNAPL) remains one of the most difficult problems facing the remediation industry. Still, the most common method of recovering DNAPL is to physically remove the contaminants using common technologies such as total fluids recovery pumps, vacuum systems, and “pump‐and‐treat.” Increased DNAPL removal can be attained using surfactants to mobilize and/or solubilize the pollutants. However, very little is understood of the methods developed by petroleum engineers beginning in the 1960s to overcome by‐passed, low‐permeability zones in heterogeneous oil reservoirs. By injecting or causing the formation of viscous fluids in the subsurface, petroleum engineers caused increased in‐situ pressures that forced fluid flow into low permeability units as well as the higher permeability thief zones. Polymer flooding involves injecting a viscous aqueous polymer solution into the contaminated aquifer. Foam flooding involves injecting surfactant to decontaminate the high‐permeability zones and then periodic pulses of air to cause a temporary viscous foam to form in the high‐permeable zones after all DNAPL is removed. Later surfactant pulses are directed by the foam into unswept low‐permeable units. These methods have been applied to DNAPL removal using surfactants but they can also be applied to the injection of bio‐amendments into low‐permeability zones still requiring continued remediation. Here we discuss the principles of mobility control as practiced in an alluvial aquifer contaminated with chlorinated solvent and coal tar DNAPLs as well as some field results. © 2003 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.     

Natural attenuation with varying degrees of aquifer heterogeneity: Implications for groundwater monitoring

This study evaluated the effect of heterogeneity in hydraulic conductivity on the tendency for contaminant plumes to attenuate via dilution, hydrodynamic dispersion, and molecular diffusion in simulated aquifers. Simulations included one homogeneous and four increasingly heterogeneous hydraulic conductivity fields. A numerical mass transport model generated an initial contaminant plume for each case; all initial plumes had the same mass. Next, the model simulated plume migrations through the simulated aquifers. Results suggest that highly heterogeneous settings are potentially effective at plume attenuation. Low‐velocity zones in heterogeneous settings delay plume travel, enabling more time for natural processes to lower contaminant concentrations in groundwater. © 2012 Wiley Periodicals, Inc.     

Applying chemical oxidation technologies at NAPL‐impacted sites to facilitate risk‐based closure

In situ chemical oxidation (ISCO) has found widespread remedial application at sites that lack nonaqueous‐phase liquid (NAPL) or have a relatively small amount of contaminant mass. Historically, its use has been limited at sites with large amounts of NAPL, primarily because of cost considerations. Proper application of ISCO can expand its use at sites with substantial amounts of NAPL—particularly where it is being used to selectively remediate higher toxicity fractions or reduce the mobility of the NAPL itself through artificial weathering. Alone or in conjunction with conventional technologies, chemical oxidation provides a means for reducing the risk associated with NAPL and potentially closing impacted sites without completely removing NAPL. © 2010 Wiley Periodicals, Inc.     

Designing funnel‐and‐gate groundwater remediation systems near property corners

Numerical models were used to simulate alternative funnel‐and‐gate groundwater remediation structures near property corners in hypothetical homogeneous and heterogeneous unconfined aquifers. Each structure comprised a highly permeable central gate (hydraulic conductivity = 25 m/d) and soil‐bentonite slurry walls (hydraulic conductivity = 0.00009 m/d). Gates were perpendicular to regional groundwater flow and approximately 5 m from a contaminant plume's leading tip. Funnel segments collinear to the central gate reached property boundaries; additional funnel segments followed property boundaries in the most hydraulically upgradient direction. Structures were 1 m thick and anchored into the base of the aquifer. Two structures were simulated for each aquifer: one with a 3.0‐m‐long central gate and funnels on either side; and a second with a 1.5‐m‐long central gate, funnels on either side, and 0.75‐m‐long end gates. Funnels were lengthened in successive simulations, until a structure contained a contaminant plume. Results suggest that, for the same total gate length, one‐gate structures may facilitate more rapid remediation, up to 44 percent less time in trials conducted in this study, than multiple‐gate structures constructed near property corners. However, in order to effectively contain a plume, one‐gate structures were up to 46 percent larger than multiple‐gate structures. © 2011 Wiley Periodicals, Inc.     

Interconnectivity between the Superficial Aquifer and the Deep Confined Aquifers of the Gnangara Mound, Western Australia

Perth groundwater resources are obtained from three major aquifers that occur beneath the Perth metropolitan area: the Superficial aquifer, Leederville aquifer and Yarragadee aquifer. Each aquifer has a unique seasonal water level pattern controlled by soils, geomorphology and geology. Landuse is mainly responsible for variations in recharge; however, the hydraulic properties control aquifer response and water level pattern to a greater degree. Groundwater in the three aquifers is generally of very good quality except in localised areas. Salinity increases with depth and in direction of groundwater flow in the three aquifers. The best water quality is in the Superficial aquifer in the Wanneroo well field area. The geochemistry and stable isotope signatures from the three major aquifers revealed distinct water types that suggest very little hydraulic connection or mixing of waters between these aquifers at the present abstraction and recharge regimes. The results also show that the Leederville and Yarragadee aquifers were recharged during earlier cooler times while the Superficial aquifer is being recharged at present.     

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.     

In‐Canal Stabilization/Solidification of NAPL‐Impacted Sediments

In situ solidification (ISS) has been used with increasing frequency as a remedial technology for source area treatment at upland sites impacted with a variety of organic contaminants, including coal tar, creosote, and other nonaqueous phase liquids (NAPLs). With several large, complex, urban water ways and rivers impacted with NAPLs, ISS is more recently being considered as a technology of choice to help reduce remedial costs, minimize short‐ and long‐term impacts of mobile NAPL, and lower the carbon footprint. This article presents the results of a successful pilot study of ISS at the Gowanus Canal Superfund site in Brooklyn, New York. This represents the first major sediment ISS field demonstration project in a saline environment and the first project to evaluate large‐scale implementation of ISS from a barge and through overlaying sediment. ©2016 Wiley Periodicals, Inc.     

How much heterogeneity? Flow versus area from a big data perspective

Over the past 10 years, there has been an increased recognition that matrix diffusion processes are a significant factor controlling the success of groundwater remediation. New field techniques and modeling tools have, consequently, been developed to understand how contaminants diffuse into and then out of low‐permeability (“low‐k”) zones and assess the resulting impact on groundwater quality. Matrix diffusion, in turn, is driven by one key factor: geologic heterogeneity. The importance of heterogeneity is being emphasized in the groundwater field by general rules of thumb such as “90% of the mass flux occurs in 10%‐20% of the cross‐sectional area” and conceptual models that show most of the groundwater flow occurs through the aquifer's “mobile porosity” which just a small fraction of commonly used effective porosity values (between 0.02 and 0.10 for mobile porosity vs. 0.25 for effective porosity). For this study, 141 boring logs from 43 groundwater remediation sites were evaluated to develop an empirically based estimate of the groundwater flow versus aquifer cross‐sectional area to confirm or reject the general flow versus area rules of thumb. This study indicated that at these 43 sites, an average of 30% of the cross‐sectional area carried 90% of the groundwater flow. Our flow‐only analysis does provide moderate (but not confirmatory) support for the “mobile porosity” concept with an estimated representative mobile porosity value of about 0.11 at the 43 sites.     

Remediating TCE‐contaminated groundwater in low‐permeability media using hydraulic fracturing to emplace zero‐valent iron/organic carbon amendment

A field pilot test in which hydraulic fracturing was used to emplace granular remediation amendment (a mixture of zero‐valent iron [ZVI] and organic carbon) into fine‐grained sandstone to remediate dissolved trichloroethene (TCE)‐contaminated groundwater was performed at a former intercontinental ballistic missile site in Colorado. Hydraulic fracturing was used to enhance the permeability of the aquifer with concurrent emplacement of amendment that facilitates TCE degradation. Geophysical monitoring and inverse modeling show that the network of amendment‐filled fractures extends throughout the aquifer volume targeted in the pilot test zone. Two years of subsequent groundwater monitoring demonstrate that amendment addition resulted in development of geochemical conditions favorable to both abiotic and biological TCE degradation, that TCE concentrations were substantially reduced (i.e., greater than 90 percent reduction in TCE mass), and that the primary degradation processes are likely abiotic. The pilot‐test data aided in re‐evaluating the conceptual site model and in designing the full‐scale remedy to address a larger portion of the TCE‐contaminated groundwater plume. © 2012 Wiley Periodicals, Inc.     

Using an integrated approach for quantifying VOC source areas for site remediation

Locating and quantifying free-phase volatile organic compounds (VOCs) in the subsurface represent one of the more difficult challenges facing hazardous waste site remediation programs. Successful remediation programs require reliable data on the size and extent of potential VOC contamination sources. Improving subsurface quantification of VOCs requires a large number of reliable low-cost samples. Satisfying this objective relies on improved sampling techniques, field analysis of samples, and a modified quality assurance program. This paper describes an integrated approach using conventional split-spoon samplers, microcore sampling, hexane extractions, and a field gas chromatograph with an autosampler as part of a technical demonstration for innovative remediation technologies. Using this approach, it was possible to delineate a subsurface source of free-phase VOCs at a cost of $15 per sample. The distribution of dense nonaqueous phase liquid determined by this sampling approach agreed with the conceptual model for the site.     

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.     

Techniques for rapidly evaluating the progress of in-situ remediation

Although standard methods of monitoring the progress of in-situ remediation may provide general results for the most permeable zones affected by soil vapor extraction or bioventing, they are essentially unsuccessful at providing information on the degree of heterogeneity within the remediation zone and on the existence of “hot spots.” Data are presented that suggest that monitoring the concentrations of fixed and biogenic gases and measuring soil permeability on a small-scale basis may circumvent the common problems associated with assessing the progress of in-situ remediation. The costs of these monitoring techniques are minor compared to those of designing and operating an in-situ remediation system, and may save additional time and costs by identifying problem areas early in the cleanup process.     

Pneumatic fracturing to remove VOCS

A new process for enhancing in-situ remediation of low-permeability soil and rock formations is presently under development at the Hazardous Substance Management Research Center (HSMRC). The patented process, known as ?pneumatic fracturing,”? consists of injecting high-pressure air or other gas into contaminated geologic formations at controlled flow rates and pressures. In fine-grained soils such as clay, pneumatic fracturing creates conductive channels in the formation, thereby increasing the permeability and exposed surface area of the contaminated soil. The potential benefits of pneumatic fracturing are significant, since in-situ remedial technologies are essentially limited by the pore gas exchange rate of the soil being treated. This article describes the results of a recent demonstration of pneumatic fracturing at an industrial site to enhance a volatile organic compound (VOC) extraction system. After establishing the baseline removal rate of soil gas effluent from the clay, soil surrounding the extraction system was fractured to enhance VOC with drawal. A substantial improvement in the VOC removal rate was observed, including: (1) flush effluent concentrations that increased up to 200 times; and (2) air flows in the formation that increased up to 1,000 times.     

Using pneumatic fracturing extraction to achieve regulatory compliance and enhance voc removal from low-permeability formations

The New Jersey Department of Environmental Protection and Energy (NJDEPE) has been developing cleanup regulations that focus on remediation, rather than extended delineation, and on integrating regulatory requirements with technological developments. To this end, the NJDEPE, under the regulatory aegis of the Environmental Cleanup and Responsibility Act (ECRA), is monitoring an innovative treatment technology pilot test at a TCE-contaminated ECRA site in Hillsborough, New Jersey. The purpose of the study is to determine the applicability of pneumatic fracturing extraction (PFE) as a source-removal technique for extracting volatile organic compounds (VOCs) trapped informations with low permeability. The technology being pilot tested is pneumatic fracturing extraction, a process for enhancing permeability to promote in-situ removal and treatment of VOCs. The patented process uses high-pressure air injected into an isolated subsurface zone at controlled rates and pressures. At a critical point, the geologic material ruptures, and fractures are created that radiate outward from the fracture location. At the pilot test site, formation air flow was increased from 400 percent to 700 percent. PFE is a key component of the overall remediation strategy at the Hillsborough site. Consistent with proposed NJDEPE regulations, a ground-water pump-and-treat system will be installed for plume migration control. Once the pump-and-treat system has been established and shown to be effective, a more aggressive source removal program will be implemented using PFE. This program will include construction of a vadose zone PFE system and evaluation of the use of pneumatic fracturing to remove saturated zone residual dense nonaqueous phase liquids (DNAPL). Preliminary calculations suggest that if source zone concentrations can be reduced to 10 ppm of TCE, then TCE groundwater concentrations may be reduced to background levels at the property boundary compliance points.     

The Hidden Potential of Mass‐based Treatment: A Method for Preventing Rebound

A major challenge for in situ treatment is rebound. Rebound is the return of contaminant concentrations to near original levels following treatment, and frequently occurs because much of the residual nonaqueous phase liquid (NAPL) trapped within the soil capillaries or rock fractures remains unreachable by conventional in situ treatment. Fine‐textured strata have an especially strong capacity to absorb and retain contaminants. Through matrix diffusion, the contaminants dissolve back into groundwater and return with concentrations that can approach pretreatment levels. The residual NAPL then serves as a continuing source of contamination that may persist for decades or longer. A 0.73‐acre (0.3‐hectare) site in New York City housed a manufacturer of roofing materials for approximately 60 years. Coal tar served as waterproofing material in the manufacturing process and releases left behind residual NAPL in soils. An estimated 47,000 pounds (21,360 kg) of residual coal tar NAPL contaminated soils and groundwater. The soils contained strata composed of sands, silty sands, and silty clay. A single treatment using the RemMetrik^® process and Pressure Pulse Technology^® (PPT) targeted the contaminant mass and delivered alkaline‐activated sodium persulfate to the NAPL at the pore‐scale level via in situ treatment. Posttreatment soil sampling demonstrated contaminant mass reductions over 90 percent. Reductions in posttreatment median groundwater concentrations ranged from 49 percent for toluene to 92 percent for xylenes. Benzene decreased by 87 percent, ethylbenzene by 90 percent, naphthalene by 80 percent, and total BTEX by 91 percent. Mass flux analysis three years following treatment shows sustained reductions in BTEX and naphthalene, and no rebound. ©2015 Wiley Periodicals, Inc.     

Sustainable soil remediation by refrigerated condensation at sites with “high‐concentration” recalcitrant compounds and NAPL: Two case studies

Remediation of recalcitrant compounds at sites with high concentrations of volatile organic compounds (VOCs) or nonaqueous‐phase liquids (NAPLs) can present significant technical and financial (long‐term) risk for stakeholders. Until recently, however, sustainability has not been included as a significant factor to be considered in the feasibility and risk evaluation for remediation technologies. The authors present a framework for which sustainability can be incorporated into the remediation selection criteria focusing specifically on off‐gas treatment selection for soil vapor extraction (SVE) remediation technology. SVE is generally considered an old and standard approach to in situ remediation of soils at a contaminated site. The focus on off‐gas treatment technology selection in this article allows for more in‐depth analysis of the feasibility evaluation process and how sustainable practices might influence the process. SVE is more commonly employed for recovery of VOCs from soils than other technologies and generally employs granular activated carbon (GAC), catalytic, or thermal oxidation, or an emerging alternative technology known as cryogenic‐compression and condensation combined with regenerative adsorption (C3–Technology). Of particular challenge to the off‐gas treatment selection process is the potential variety of chemical constituents and concentrations changing over time. Guidance is available regarding selection of off‐gas treatment technology (Air Force Center for Environmental Excellence, 1996; U.S. Environmental Protection Agency, 2006). However, there are common shortcomings of off‐gas treatment technology guidance and applications; practitioners have rarely considered sustainability and environmental impact of off‐gas treatment technology selection. This evaluation includes consideration of environmental sustainability in the selection of off‐gas treatment technologies and a region‐specific (Los Angeles, California) cost per pound and time of remediation comparisons between GAC, thermal oxidation, and C3–Technology. © 2008 Wiley Periodicals, Inc.     

Insights from years of performance that are shaping injection‐based remediation systems

Research and field experience from the past 15 years has allowed remediation professionals to purposefully design injection‐based remediation systems with a high potential for success. Industry professionals can now claim a number of achievements that were unthinkable just a few years ago: (1) we have demonstrated that maximum contaminant levels (MCLs) can be achieved for multiple contaminants; (2) we have successfully targeted dense nonaqueous‐phase liquid (DNAPL) source zones; (3) we have expanded our understanding of injection hydraulics to treat large plumes; and (4) we have collected sufficient data on rates of treatment to be more predictive regarding outcomes. The next decade will continue to evolve the design and execution of these types of systems for application to more complex problems. At this point on the timeline, questions regarding the mechanisms of treatment have largely been addressed, allowing a shift in focus to operational enhancements. Specific operational insights arising from the body of work to date that arguably will continue to shape and influence the design and execution of injection‐based remediation systems include: (1) the fact that delivery does not always equal distribution, (2) treatment optimization requires aquifer tuning, and (3) life‐cycle costs can be reduced with remedy‐optimized investigation. The number of examples that support these concepts and their ramifications to future technology refinement is already increasing, demonstrating how the refinements that can be made around these areas of focus will enhance our ability to effectively tackle larger and more complicated plumes, and do so with maximum efficiency. © 2011 Wiley Periodicals, Inc.