DNAPL Source Depletion: 2. Attainable Goals and Cost–Benefit Analyses

It is difficult to quantify the range in source strength reduction (MdR) that may be attainable from in situ remediation of a dense nonaqueous‐phase liquid (DNAPL) site given that available studies typically report only the median MdR without providing insights into site complexity, which is often a governing factor. An empirical study of the performance of in situ remediation at a wide range of DNAPL‐contaminated sites determined MdRs for in situ bioremediation (EISB), in situ chemical oxidation (ISCO), and thermal treatment remedies. Median MdR, geometric mean MdR, and lower/upper 95 percent confidence interval for the mean were: 49x, 105x, 20x/556x, respectively, for EISB; 9x, 21x, and 4x/110x for ISCO; and 19x, 31x, and 6x/150x for thermal treatment. Lower MdR values were determined for large, complex sites and for sites with DNAPL pool‐dominated source zones. A feasibility analysis of partial DNAPL depletion is described for a pool‐dominated source zone. Back‐diffusion from low‐hydraulic conductivity units within a pool‐dominated source zone is shown to potentially sustain a secondary source for more than 1,000 years, indicating that aggressive source treatment may not reduce the remediation timeframe. Estimated plume response demonstrates there may be no reduction in cost associated with aggressive treatment, and little difference in risk reduction associated with the various alternatives. Monitored natural attenuation (MNA) for the source zone is shown to be a reasonable alternative for the pool‐dominated source zone considered in this example. It is demonstrated that pool‐dominated source zones with a large range in initial DNAPL mass (250 to 1,500 kg) may correspond to a narrow range in source strength (20 to 30 kg/year). This demonstrates that measured source strength is nonunique with respect to DNAPL mass in the subsurface and, thus, source strength should not be used as the sole basis for predicting how much DNAPL mass remains or must be removed to achieve a target goal. If aggressive source zone treatment is to be implemented due to regulatory requirements, strategic pump‐and‐treat is shown to be most cost effective. These remedial decisions are shown to be insensitive to a range of possible DNAPL pool conditions. At sites with an existing pump‐and‐treat system, a significant increase in mass removal and source strength reduction may be achieved for a low incremental cost by strategic placement of extraction wells and pumping rate selection. © 2014 Wiley Periodicals, Inc.     

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.     

Successful ISCR‐enhanced bioremediation of a TCE DNAPL source utilizing EHC® and KB‐1®

Remediation of chlorinated solvent DNAPL sites often meets with mixed results. This can be attributed to the diametrically opposed nature of the impacts, where the disparate dissolved‐phase plume is more manageable than the localized, high‐concentration source area. A wide range of technologies are available for downgradient plume management, but the relative mass of contaminants in a DNAPL source area generally requires treatment for such technologies to be effective over the long term. In many cases, the characteristics of DNAPL source zones (e.g., depth, soil heterogeneity, structural limitations) limit the available options. The following describes the successful full‐scale implementation of in situ chemical reduction (ISCR) enhanced bioremediation of a TCE DNAPL source zone. In this demonstration, concentrations of TCE were rapidly reduced to below the maximum contaminant level (MCL) in less than six months following implementation. The results described herein suggest that ISCR‐enhanced bioremediation is a viable remedial alternative for chlorinated solvent source zones. © 2010 Wiley Periodicals, Inc.     

Enhanced anaerobic bioremediation in a multicontaminant plume

The potential application of enhanced in situ bioremediation (EISB) for treatment of a plume containing high concentrations of 1,2‐dichloroethane (1,2‐DCA), as well as lower concentrations of other chlorinated ethanes, chlorinated methanes, and chlorinated ethenes was evaluated through the implementation of four field trials. The field trials confirmed that EISB is an effective technology for treating multiple contaminants, with estimated mass removal rates on the order of several kilograms per day and groundwater concentration reductions nearing 100 percent of the initial concentrations. The field trials also demonstrated that engineering controls could be effectively used to overcome potential inhibitions related to high concentrations of 1,2‐DCA. © 2008 Wiley Periodicals, Inc.     

Microbial responses to in situ chemical oxidation,six‐phase heating,and steam injection remediation technologies in groundwater

The evaluation of microbial responses to three in situ source removal remedial technologies—permanganate‐based in situ chemical oxidation (ISCO), six‐phase heating (SPH), and steam injection (SI)—was performed at Cape Canaveral Air Station in Florida. The investigation stemmed from concerns that treatment processes could have a variety of effects on the indigenous biological activity, including reduced biodegradation rates and a long‐term disruption of community structure with respect to the stimulation of TCE (trichloroethylene) degraders. The investigation focused on the quantity of phospholipid fatty acids (PLFAs) and its distribution to determine the immediate effect of each remedial technology on microbial abundance and community structure, and to establish how rapidly the microbial communities recovered. Comprehensive spatial and temporal PLFA screening data suggested that the technology applications did not significantly alter the site's microbial community structure. The ISCO was the only technology found to stimulate microbial abundance; however, the biomass returned to predemonstration values shortly after treatment ended. In general, no significant change in the microbial community composition was observed in the SPH or SI treatment areas, and even small changes returned to near initial conditions after the demonstrations. © 2004 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.     

Kinetic study of permanganate oxidation of tetrachloroethylene at a high pH under acidic conditions

Since carbon compounds are the main component of dense nonaqueous phase liquids (DNAPLs), the end products of all in situ chemical oxidation (ISCO) will include carbon dioxide. If the production rate of carbon dioxide exceeds the capacity of water to remove the carbon dioxide, degassing will occur. The uncontrolled carbon dioxide gas may change the flow patterns, remobilize the pooled DNAPL, transport DNAPL vapor, and reduce the relative permeability to the aqueous phase. Under high pH buffered conditions, most of the carbon dioxide will be dissolved in water. In this study, potassium permanganate oxidation of tetrachloroethylene (PCE) was conducted using a sodium carbonate buffered solution (1 g/L, pH = 10.6 ± 0.1) at three different temperatures (5, 10, and 20°C) and three potassium permanganate concentrations (0.2, 1, and 5 g/L). Extensive kinetic studies suggest that the overall oxidation is a second‐order reaction and pseudo‐first‐order with respect to PCE and potassium permanganate, respectively. The second‐order rate constant and the activation energy were 0.028 ± 0.001 M^?1s^?1 at 20°C and 43.9 ± 2.85 kJ/M, respectively. This study provides a base for further experimental and field studies on potassium permanganate oxidation of PCE under natural or artificial high pH buffered conditions. © 2004 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.     

Successful unsaturated zone treatment of PCE with sodium permanganate

In situ chemical oxidation (ISCO) with permanganate has been widely used for soil and groundwater treatment in the saturated zone. Due to the challenges associated with achieving effective distribution and retention in the unsaturated zone, there is a great interest in developing alternative injection technologies that increase the success of vadose‐zone treatment. The subject site is an active dry cleaner located in Topeka, Kansas. A relatively small area of residual contamination adjacent to the active facility building has been identified as the source of a large sitewide groundwater contamination plume with off‐site receptors. The Kansas Department of Health and Environment (KDHE) currently manages site remedial efforts and chose to pilot‐test ISCO with permanganate for the reduction of perchloroethene (PCE) soil concentrations within the source area. KDHE subsequently contracted Burns & McDonnell to design and implement an ISCO pilot test. A treatability study was performed by Carus Corporation to determine permanganate‐soil‐oxidant‐demand (PSOD) and the required oxidant dosing for the site. The pilot‐test design included an ISCO injection approach that consisted of injecting aqueous sodium permanganate using direct‐push technology with a sealed borehole. During the pilot test, approximately 12,500 pounds of sodium permanganate were injected at a concentration of approximately 3 percent (by weight) using the methods described above. Confirmation soil sampling conducted after the injection event indicated PCE reductions ranging from approximately 79 to more than 99 percent. A follow‐up treatment, consisting of the injection of an additional 6,200 pounds of sodium permanganate, was implemented to address residual soil impacts remaining in the soil source zone. Confirmation soil sampling conducted after the treatment indicated a PCE reduction of greater than 90 percent at the most heavily impacted sample location and additional reductions in four of the six samples collected. © 2009 Wiley Periodicals, Inc.     

Remedial options for chlorinated volatile organics in a partially anaerobic aquifer

A laboratory study was conducted for the selection of appropriate remedial technologies for a partially anaerobic aquifer contaminated with chlorinated volatile organics (VOCs). Evaluation of in situ bioremediation demonstrated that the addition of electron donors to anaerobic microcosms enhanced biological reductive dechlorination of tetrachloroethene (PCE), trichloroethene (TCE), and 1,1,1‐trichloroethane (1,1,1‐TCA) with half‐lives of 20, 22, and 41 days, respectively. Nearly complete reductions of PCE, TCE, 1,1,1‐TCA, and the derivative cis‐dichloroethene were accompanied by a corresponding increase in chloride concentrations. Accumulation of vinyl chloride, ethene, and ethane was not observed; however, elevated levels of ¹⁴CO₂ (from ¹⁴C‐TCE spiked) were recovered, indicating the occurrence of anaerobic oxidation. In contrast, very little degradation of 1,2‐dichloropropane (1,2‐DCP) and 1,1‐dichlorethane (1,1‐DCA) was observed in the anaerobic microcosms, but nutrient addition enhanced their degradation in the aerobic biotic microcosms. The aerobic degradation half‐lives for 1,2‐DCP and 1,1‐DCA were 63 and 56 days, respectively. Evaluation of in situ chemical oxidation (ISCO) demonstrated that chelate‐modified Fenton's reagent was effective in degrading aqueous‐phase PCE, TCE, 1,1,1‐TCA, 1,2‐DCP, etc.; however, this approach had minimal effects on solid‐phase contaminants. The observed oxidant demand was 16 g‐H₂O₂/L‐groundwater. The oxidation reaction rates were not highly sensitive to the molar ratio of H₂O₂:Fe²⁺:citrate. A ratio of 60:1:1 resulted in slightly faster removal of chemicals of concern (COCs) than those of 12:1:1 and 300:1:1. This treatment resulted in increases in dissolved metals (Ca, Cr, Mg, K, and Mn) and a minor increase of vinyl chloride. Treatment with zero‐valent iron (ZVI) resulted in complete dechlorination of PCE, and TCE to ethene and ethane. ZVI treatment reduced 1,1,1‐TCA only to 1,1‐DCA and chloroethane (CA) but had little effect on reducing the levels of 1,2‐DCP, 1,1‐DCA, and CA. The longevity test showed that one gram of 325‐mesh iron powder was exhausted in reaction with > 22 mL of groundwater. The short life of ZVI may be a barrier to implementation. The ZVI surface reaction rates (k_sa) were 1.2 × 10^?2 Lm^?2h^?1, 2 × 10^?3 Lm^?2h^?1, and 1.2 × 10^?3 Lm^?2h^?1 for 1,1,1‐TCA, TCE, and PCE, respectively. Based upon the results of this study, in situ bioremediation appeared to be more suitable than ISCO and ZVI for effectively treating the groundwater contamination at the site. © 2004 Wiley Periodicals, Inc.     

Planning‐level source decay models to evaluate impact of source depletion on remediation time frame

A recent United States Environmental Protection Agency (US EPA) Expert Panel on Dense Nonaqueous Phase Liquid (DNAPL) Source Remediation concluded that the decision‐making process for implementing source depletion is hampered by quantitative uncertainties and that few useful predictive tools are currently available for evaluating the benefits. This article provides a new planning‐level approach to aid the process. Four simple mass balance models were used to provide estimates of the reduction in the remediation time frame (RTF) for a given amount of source depletion: step function, linear decay, first‐order decay, and compound. As a shared framework for assessment, all models use the time required to remediate groundwater concentrations below a particular threshold (e.g., goal concentration or mass discharge rate) as a metric. This value is of interest in terms of providing (1) absolute RTF estimates in years as a function of current mass discharge rate, current source mass, the remediation goal, and the source‐ reduction factor, and (2) relative RTF estimates as a fraction of the remediation time frame for monitored natural attenuation (MNA). Because the latter is a function of the remediation goal and the remaining fraction (RF) of mass following remediation, the relative RTF can be a valuable aid in the decision to proceed with source depletion or to use a long‐term containment or MNA approach. Design curves and examples illustrate the nonlinear relationship between the fraction of mass remaining following source depletion and the reduction in the RTF in the three decay‐based models. For an example case where 70 percent of the mass was removed by source depletion and the remediation goal (C_g/C₀) was input as 0.01, the improvement in the RTF (relative to MNA) ranged from a 70 percent reduction (step function model) to a 21 percent reduction (compound model). Because empirical and process knowledge support the appropriateness of decay‐based models, the efficiency of source depletion in reducing the RTF is likely to be low at most sites (i.e., the percentage reduction in RTF will be much lower than the percentage of the mass that is removed by a source‐depletion project). Overall, the anticipated use of this planning model is in guiding the decision‐making process by quantifying the relative relationship between RTF and source depletion using commonly available site data. © 2005 Wiley Periodicals, Inc.     

TCE plume remediation via ISCR‐enhanced bioremediation utilizing EHC® and KB‐1®

Groundwater below an operating manufacturing facility in Portland, Oregon, was impacted by chlorinated volatile organic compounds (CVOCs), with concentrations indicative of a dense, nonaqueous‐phase liquid (DNAPL) release. The downgradient plume stretched under the adjacent Willamette River, intersecting zones of legacy impacts from a former manufactured gas plant (MGP). An evaluation of source‐area and downgradient plume treatment remedies identified in situ bioremediation as most likely to be effective for the CVOC plume, while leaving the legacy impacts for other responsible parties. With multiple commercially available products to choose from, the team developed and implemented a bench test to identify the most appropriate technology, which was further evaluated in a field pilot study. The results of the testing demonstrated conclusively that bioremediation enhanced by in situ chemical reduction (ISCR) using EHC® and KB‐1® was most appropriate for this site, providing outstanding results. The following describes the implementation and results of the tests. © 2008 Wiley Periodicals, Inc.     

ERD of Residual TCE DNAPL Achieving Nondetect from a Single Injection of Food‐Grade Waste

Residual dense nonaqueous phase liquid (DNAPL) composed of trichloroethene (TCE) was identified in a deeper interval of an overburden groundwater system at a manufacturing facility located in northern New England. Site hydrostratigraphy is characterized by two laterally continuous and transmissive zones consisting of fully‐saturated fine sand with silt and clay. The primary DNAPL source was identified as a former dry well with secondary contributions from a proximal aboveground TCE storage tank. A single additive‐injection mobilization in 2001 utilizing a food‐grade injectate formulated with waste dairy product and inactive yeast enhanced residual TCE DNAPL destruction in situ by stimulating biotic reductive dechlorination. The baseline TCE concentration was detected up to 97,400 μg/L in the deeper interval of the overburden groundwater system, and enhanced reductive dechlorination (ERD) achieved >99 percent reduction in TCE concentrations in groundwater over nine years with no evidence of sustained rebound. TCE concentrations have remained nondetect below 2.0 μg/L for the last five consecutive sampling rounds between 2013 and 2015. ERD utilizing a food‐grade injectate is a green remediation technology that has destroyed residual DNAPL at the site and achieved similar results at other residual DNAPL sites during both pilot‐ and full‐scale applications. ©2016 Wiley Periodicals, Inc.     

Challenges of soil mixing using catalyzed hydrogen peroxide with rotating dual axis blending technology

Although known to be one of the most effective oxidants for treatment of organic contaminants, catalyzed hydrogen peroxide (CHP) is typically not used for soil mixing applications because of health and safety concerns related to vapor generation and very rapid rates of reaction in open excavations. In likely the first large‐scale in situ CHP soil mixing application, an enhanced CHP, modified Fenton's reagent (MFR), was applied during soil mixing at the Kearsarge Metallurgical Superfund Site in New Hampshire. An innovative rotating dual‐axis blender (DAB) technology was used to safely mix the MFR into low‐plasticity silt and clay soils to remediate residual 1,1,1‐trichloroethane (111TCA); 1,1‐dichloroethene (11DCE); and 1,4‐dioxane (14D). It was expected that the aggressive treatment approach using relatively “greener” hydrogen peroxide (HP) chemistry would effectively treat Site contaminants without significant byproduct impacts to groundwater or the adjacent pond. The remediation program was designed to treat approximately 3,000 cubic yards of residual source area soil in situ by aggressively mixing MFR into the soils. The subsurface interval treated was from 7 to 15 feet below ground surface. To accurately track the soil mixing process and MFR addition, the Site was divided into 109 10‐foot square treatment cells that were precisely located, dosed, and mixed using the DAB equipped with an on‐board GPS system. The use of stabilizing agents along with careful calculation of the peroxide dose helped to ensure vapor‐free conditions in the vicinity of the soil mixing operation. Real‐time sampling and monitoring were critical in identifying any posttreatment exceedences of the cleanup goals. This allowed retreatment and supplemental testing to occur without impacting the soil mixing/in situ chemical oxidation (ISCO) schedule. Posttreatment 24‐hr soil samples were collected from 56 random locations after ensuring that the HP had been completely consumed. The posttreatment test results showed that 111TCA and 11DCE concentrations were reduced to nondetect (ND) or below the cleanup goals of 150 μg/kg for 111TCA and 60 μg/kg for 11DCE. Supplemental posttreatment soil samples, collected six months after treatment, showed 100 percent compliance with the soil treatment goals. Groundwater samples collected one year after the MFR soil mixing treatment program showed either ND or low concentrations for 111TCA, 11DCE, and 14D. Successful stabilization and site restoration was performed after overcoming considerable challenges associated with loss of soil structure, high liquid content, and reduced bearing capacity of the blended soils.     

Surfactant‐Oxidant Co‐Application for Soil and Groundwater Remediation

In situ chemical oxidation (ISCO) typically delivers oxidant solutions into the subsurface for contaminant destruction. Contaminants available to the oxidants, however, are limited by the mass transfer of hydrophobic contaminants into the aqueous phase. ISCO treatments therefore often leave sites with temporarily clean groundwater which is subject to contaminant rebound when sorbed and free phase contaminants leach back into the aqueous phase. Surfactant Enhanced In situ Chemical Oxidation (S‐ISCO^®) uses a combined oxidant‐surfactant solution to provide optimized contaminant delivery to the oxidants for destruction via desorption and emulsification of the contaminants by the surfactants. This article provides an overview of S‐ISCO technology, followed by an implementation case study at a coal tar contaminated site in Queens, New York. Included are data points from the site which demonstrate how S‐ISCO delivers desorbed contaminants without uncontrolled contaminant mobilization, as desorbed and emulsified contaminants are immediately available to the simultaneously injected oxidant for reaction. ©2016 Wiley Periodicals, Inc.     

Life‐cycle assessment of in situ thermal remediation

A detailed cradle‐to‐grave life‐cycle assessment (LCA) of an in situ thermal treatment remedy for a chlorinated‐solvent‐contaminated site was performed using process LCA. The major materials and activities necessary to install, operate, monitor, and deconstruct the remedy were included in the analysis. The analysis was based on an actual site remedy design and implementation to determine the potential environmental impacts, pinpoint major contributors to impacts, and identify opportunities for improvements during future implementation. The Electro‐Thermal Dynamic Stripping Process (ET‐DSP?) in situ thermal technology coupled with a dual‐phase extraction and treatment system was evaluated for the remediation of 4,400 yd³ of tetrachloroethene‐ and trichloroethene‐impacted soil, groundwater, and bedrock. The analysis was based on an actual site with an estimated source mass of 2,200 lbs of chlorinated solvents. The remedy was separated into four stages: remedy installation, remedy operation, monitoring, and remedy deconstruction. Environmental impacts were assessed using Sima Pro software, the ecoinvent database, and the ReCiPe midpoint and endpoint methods. The operation stage of the remedy dominated the environmental impacts across all categories due to the large amount of electricity required by the thermal treatment technology. Alternate sources of electricity could significantly reduce the environmental impacts of the remedy across all impact categories. Other large impacts were observed in the installation stage resulting from the large amount of diesel fuel, steel, activated carbon, and asphalt materials required to implement the technology. These impacts suggest where opportunities for footprint reductions can be found through best management practices such as increased materials reuse, increased recycled‐content materials use, and clean fuels and emission control technologies. Smaller impacts were observed in the monitoring and deconstruction stages. Normalized results show the largest environmental burdens to fossil depletion, human toxicity, particulate matter formation, and climate‐change categories resulting from activities associated with mining of fossil fuels for use in electricity production. In situ thermal treatment can reliably remediate contaminated source areas with contaminants located in low‐permeability zones, providing complete destruction of contaminants in a short amount of time, quick return of the site to productive use, and minimized quantities of hazardous materials stored in landfills for future generations to remediate. However, this remediation strategy can also result in significant emissions over a short period of time. It is difficult to quantify the overall value of short‐term cleanups with intense treatment emissions against longer‐term cleanups with lower treatment emissions because of the environmental, social, and economic trade‐offs that need to be considered and understood. LCA is a robust, quantitative tool to help inform stakeholder discussions related to the remedy selection process, trade‐off considerations, and environmental footprint‐reduction opportunities, and to complement a broader toolbox for the evaluation of sustainable remediation strategies. © 2012 Wiley Periodicals, Inc.     

Sustained treatment: Implications for treatment timescales associated with source‐depletion technologies

Sustained treatment is an emerging concept used to describe enhancements in attenuation capacity after the conclusion of the active treatment period for a given source‐depletion technology. The term includes mechanisms that lead to contaminant transformation or destruction over extended periods of time, such as endogenous biomass decay, slow diffusion of remedial amendments from low‐permeability zones, and the formation of reactive mineral species. This “value‐added” treatment continues after the end of capital expenditures at a site, and it provides additional insight in determining if monitored natural attenuation is a viable long‐term option for a site. This article identifies several sustained treatment mechanisms, examines technology‐specific factors that contribute to sustained treatment, and explores the potential timescales of sustained treatment relative to active treatment. As demonstrated in post‐treatment site data obtained during a comprehensive source‐depletion technology performance survey, enhanced bioremediation is the most promising in promoting sustained treatment, and this beneficial effect can extend for several years due to factors such as slow biomass decay. There is little evidence that other commonly used technologies (thermal treatment, in situ chemical oxidation, surfactant‐enhanced remediation, or cosolvent flushing) result in any significant sustained treatment. An exception would be a cosolvent flushing project where large quantities of biodegradable cosolvent are left in the subsurface at the end of the project, which could result in sustained long‐term dechlorination activity. In the case of in situ chemical oxidation, factors that contribute to a higher incidence of concentration rebound mask any potential sustained treatment effects. © 2011 Wiley Periodicals, Inc.     

Pilot‐scale evaluation using bioaugmentation to enhance PCE dissolution at dover AFB national test site

An Interstate Technology and Regulatory Council (ITRC) forum was recently held that focused on six case studies in which bioremediation of dense nonaqueous‐phase liquids (DNAPLs) was performed; the objective was to demonstrate that there is credible evidence for bioremediation as a viable environmental remediation technology. The first two case studies from the forum have been previously published; this third case study involves a pilot‐scale demonstration that investigated the effects of biological activity on enhancing dissolution of an emplaced tetrachloroethene (PCE) DNAPL source. It used a controlled‐release test cell with PCE as the primary DNAPL in a porous media groundwater system. Both laboratory tests and a field‐scale pilot test demonstrated that bioaugmentation can stimulate complete dechlorination to a nontoxic end product and that the mass flux from a source zone increases when biological dehalorespiration activity is enhanced through nutrient (electron donor) addition and bioaugmentation. All project goals were met. Important achievements include demonstrating the ability to degrade a PCE DNAPL source to ethene and obtaining significant information on the impacts to the microbial populations and corresponding isotope enrichments during biodegradation of a source area. © 2007 Wiley Periodicals, Inc.     

In situ chemical oxidation of residual LNAPL and dissolved‐phase fuel hydrocarbons and chlorinated alkenes in groundwater using activated persulfate

A treatablity study (TS) was conducted to evaluate the efficacy of in situ chemical oxidation (ISCO) using activated persulfate, alone and in combination with air sparging (AS), for treating a source area contaminated with residual light nonaqueous‐phase liquid (LNAPL), dissolved‐phase fuel hydrocarbons (HCs), and dissolved‐phase chlorinated alkenes at Edwards Air Force Base (AFB), California. The TS was implemented in two phases. Phase I included injecting a solution of sodium persulfate and sodium hydroxide (NaOH) into groundwater via an existing well where residual LNAPL and dissolved‐phase contaminants were present. Because the results of Phase I indicated a limited distribution of the activated persulfate, Phase II was performed to assess whether AS could enhance the distribution of the sodium persulfate. Each phase was followed by groundwater monitoring and sampling at the injection well and at three monitoring wells, located 20 to 44 feet from the injection well. Results from Phases I and II of the TS indicated that (1) alkaline‐activated persulfate was effective in promoting the dissolution of LNAPL and the degradation of dissolved‐phase contaminants, but only at the injection well; (2) the addition of AS was effective in enhancing the radius of persulfate distribution from less than 20 feet to greater than 44 feet, and (3) persulfate alone (i.e., not in an activated state) was effective in reducing the concentrations of dissolved‐phase fuel HC and chlorinated alkenes. © 2009 Wiley Periodicals, Inc.     

Detecting and quantifying reductive dechlorination under monitored natural attenuation conditions

Field sampling and testing were used to investigate the relationship between baseline geochemical and microbial community data and in situ reductive dechlorination rates at a site contaminated with trichloroethene (TCE) and carbon tetrachloride (CTET). Ten monitoring wells were selected to represent conditions along groundwater flow paths from the contaminant source zone to a wetlands groundwater discharge zone. Groundwater samples were analyzed for a suite of geochemical and microbial parameters; then push‐pull tests with fluorinated reactive tracers were conducted in each well to measure in situ reductive dechlorination rates. No exogenous electron donors were added in these tests, as the goal was to assess in situ reductive dechlorination rates under natural attenuation conditions. Geochemical data provided preliminary evidence that reductive dechlorination of TCE and CTET was occurring at the site, and microbial data confirmed the presence of known dechlorinating organisms in groundwater. Push‐pull tests were conducted using trichlorofluoroethene (TCFE) as a reactive tracer for TCE and, in one well, trichlorofluoromethane (TCFM) as a reactive tracer for CTET. Injected TCFE was transformed to cis‐ and trans‐dichlorofluoroethene and chlorofluoroethene, and, in one test, injected TCFE was completely dechlorinated to fluoroethene (FE). In situ TCFE transformation rates ranged from less than 0.005 to 0.004/day. In the single well tested, injected TCFM was transformed in situ to dichlorofluoromethane and chlorofluoromethane; the TCFM transformation rate was estimated as 0.001/day. The results indicate that it is possible to use push‐pull tests with reactive tracers to directly detect and quantify reductive dechlorination of chlorinated ethenes and ethanes under monitored natural attenuation conditions, which has not previously been demonstrated. Transformation rate estimates obtained with these techniques should improve the accuracy of contaminant transport modeling. © 2012 Wiley Periodicals, Inc.