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.     

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

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

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.     

In situ remediation of PCE at a site with clayey lithology and a significant smear zone

Groundwater at the former Serry's Dry Cleaning site in Corvallis, Oregon, was impacted by chlorinated volatile organic compounds (CVOCs). The primary CVOCs impacting the site include tetrachloroethene, trichloroethene, dichloroethene, and vinyl chloride, which were detected at concentrations up to 22,000, 1,700, 3,100, and 7 μg/L, respectively, prior to treatment. Large seasonal fluctuations in groundwater CVOC concentrations indicated that a significant fraction of the CVOC mass was present in the smear zone. Field‐scale pilot tests were performed for the Oregon Department of Environmental Quality's Dry Cleaner Program to evaluate the performance of EHC® in situ chemical reduction (ISCR) technology. The pilot study involved evaluating field performance and physical distribution into low‐permeability soil using basic Geoprobe® injection tooling. The testing results confirmed that bioremediation enhanced by ISCR supported long‐term treatment at the site. This article describes the implementation and results of the tests. Performance data are available from a three‐year period following the injections, allowing for a discussion about sustained performance and reagent longevity. © 2010 Wiley Periodicals, Inc.     

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.     

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.     

Use of bio‐traps with multiple substrates and electron acceptors to optimize remediation

Bio‐Traps® were used to investigate biodegradation of benzene, methyl tertiary butyl ether (MTBE), and tertiary butyl alcohol (TBA) under different conditions at a fractured rock site to aid the selection of a bioremediation approach. The Bio‐Traps were amended with the ¹³C‐labeled constituent of interest and sampled sequentially at 15‐, 30‐, 60‐, and 90‐day intervals. The conditions tested were biodegradation during operation of an air sparge system, amendment with nitrate during the air sparge operation, anaerobic biodegradation with the system turned off, and anaerobic biodegradation with nitrate amendment. There was increased biomass with nitrate amendment whether the air sparge system was on or off for all the constituents of interest. The diversity of the microbial community, determined by phospholipid fatty acid analysis, decreased with nitrate amendment as more specialized degraders were selected. The most negative indicators of potential biodegradation performance were observed with the anaerobic control. There was less biomass overall, less incorporation of ¹³C into biomass, and decreased membrane permeability. As testing with additional amendments continues at the site, it is not yet certain which treatment might be selected for bioremediation, but the Bio‐Trap tests thus far have identified that the in situ, natural attenuation condition is least favorable for biodegradation. © 2009 Wiley Periodicals, Inc.     

Evolution of predictive tools for in situ bioremediation and natural attenuation evaluations

Proving the viability of in situ bioremediation technologies and gathering data for its full‐scale implementation typically involves collecting multiple rounds of data and often completing microcosm studies. Collecting these data is cumbersome, time‐consuming, costly, and typically difficult to scale. A new method of completing microcosm studies in situ using an amendable sampling device deployed and incubated in groundwater monitoring wells provides actionable data to expedite site cleanup. The device, referred to as a Bio‐Trap® sampler, is designed to collect actively colonizing microbes and dissolved organic compounds from groundwater for analysis using conventional analytical techniques and advanced diagnostic tools that can answer very specific design and viability questions relating to bioremediation. Key data that can be provided by in situ microcosm studies using Bio‐Trap® samplers include definitively demonstrating contaminant destruction by using compound‐specific isotope analysis and providing data on the mechanism of the degradation by identifying the responsible microbes. Three case studies are presented that demonstrate the combined flexibility of Bio‐Trap® samplers and advanced site diagnostics. The applications include demonstrating natural attenuation of dissolved chlorinated solvents, demonstrating natural attenuation of dissolved petroleum compounds, and using multiple Bio‐Trap® samplers to comparatively assess the viability of bioaugmentation at a chlorinated solvent release site. At each of these sites, the in situ microcosm studies quickly and cost‐effectively answered key design and viability questions, allowing for regulatory approval and successful full‐scale implementation. © 2010 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.     

Synthetic Media: A Promising New Treatment Technology for 1,4‐Dioxane

1,4‐Dioxane (14DX) is classified as a probable human carcinogen by the US Environmental Protection Agency (EPA), and it has toxic effects on the kidney and liver. EPA's Health Advisory Level (HAL) for 14DX is 0.35 micrograms per liter (μg/L). Accordingly, several states have lowered their drinking water advisory levels and site cleanup levels. The widespread occurrence of 14DX in contaminated groundwater has contributed to a growing demand for remediation services. Treating 14DX is a challenge due to its very low Henry's law constant, low sorption potential, and strong ether linkages. The primary solution for 14DX remediation has been various forms of advanced oxidation processes (AOP), namely pump and treat followed by ex situ treatment with catalyzed ultraviolet light oxidation or ozone‐peroxidation. Many of the available advanced oxidation systems are complex, requiring careful monitoring and maintenance to adjust for variable source water and operating conditions. Synthetic media is a relatively new 14DX treatment technology that overcomes many of the operating challenges faced by existing technologies. AMBERSORB? 560 (AMBERSORB) has recently demonstrated the effective removal of 14DX over a wide range of concentrations and operating conditions, including those created by in situ thermal remediation. Consistent and reliable treatment down to sub‐0.3 μg/L levels differentiates synthetic media technology from other 14DX treatment technologies. AMBERSORB provides a solution to the problem of “stranded capital” by offering a 14DX treatment system capable of meeting regulatory standards today and in the foreseeable future. © 2014 Wiley Periodicals, Inc.     

Case study of ex situ remediation and conversion to a combined in situ/ex situ bioremediation approach at an oxygenated gasoline release site

In response to an oxygenated gasoline release at a gas station site in New Hampshire, a temporary treatment system consisting of a single bedrock extraction well, a product recovery pump, an air stripper, and carbon polishing units was installed. However, this system was ineffective at removing tertiary butyl alcohol from groundwater. The subsequent remedial system design featured multiple bedrock extraction wells and an ex situ treatment system that included an air stripper, a fluidized bed bioreactor, and carbon polishing units. Treated effluent was initially discharged to surface water. Periodic evaluation of the remediation system performance led to system modifications, which included installing an additional extraction well to draw contaminated groundwater away from an on‐site water supply well, adding an iron and manganese pretreatment system, and discharge of treated effluent to an on‐site drywell. Later, the air stripper and carbon units were eliminated, and an infiltration gallery was installed to receive treated, oxygenated effluent in order to promote flushing of the smear zone and in situ bioremediation in the source area. This article discusses the design, operation, performance, and modifications to the remediation system over time, and provides recommendations for similar sites. © 2007 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.     

Technology review and evaluation of different chemical oxidation conditions on treatability of PFAS

Per‐ and polyfluoroalkyl substances (PFAS) are a class of stable compounds widely used in diverse applications. These emerging contaminants have unique properties due to carbon–fluorine (C–F) bonds, which are some of the strongest bonds in chemistry. High energy is required to break C–F bonds, which results in this class of compounds being recalcitrant to many degradation processes. Many technologies studied that have shown treatment effectiveness for PFAS cannot be implemented in situ. Chemical oxidation is a demonstrated remediation technology for in situ treatment of a wide range of organic environmental contaminants. An overview of relevant literature is presented, summarizing the use of single or combined reagent chemical oxidation processes that offer insight into oxidation–reduction chemistries potentially capable of PFAS degradation. Based on the observations and results of these studies, bench‐scale treatability tests were designed and performed to establish optimal conditions for the formation of specific free radical species, including superoxide and sulfate radicals, via various combinations of oxidants, catalysts, pH buffers, and heat to assess PFAS treatment by chemical oxidants. The study also suggests the possible abiotic transformations of some PFAS when chemical oxidation is or was used for treatment of primary organic contaminants (e.g., petroleum or chlorinated organic compounds) at a site. The bench‐scale tests utilized field‐collected samples from a firefighter training area. Much of the available data related to chemical oxidation of PFAS has only been reported for one or both of the two more commonly discussed PFAS (perfluorooctane sulfonic acid and/or perfluorooctanoic acid). In contrast, this treatability study evaluates oxidation of a diverse list of PFAS analytes. The results of this study and published literature conclude that heat‐activated persulfate is the oxidation method with the best degradation of PFAS. Limited reduction of reported PFAS concentrations in this study was observed in many oxidation reactors; however, unknown mass of PFAS (such as precursors of perfluoroalkyl acids) that cannot be identified in a field collected sample complicated quantification of how much oxidative destruction of PFAS actually occurred.     

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.     

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.     

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.     

In situ thermal remediation of DNAPL and LNAPL using electrical resistance heating

Electrical resistance heating (ERH) is an in situ treatment for soil and groundwater remediation that can reduce the time to clean up volatile organic compounds (VOCs) from years to months. The technology is now mature enough to provide site owners with both performance and financial certainty in their site‐closure process. The ability of the technology to remediate soil and groundwater impacted by chlorinated solvents and petroleum hydrocarbons regardless of lithology proves to be beneficial over conventional in situ technologies that are dependent on advective flow. These conventional technologies include: soil vapor recovery, air sparging, and pumpand‐treat, or the delivery of fluids to the subsurface such as chemical oxidization and bioremediation. The technology is very tolerant of subsurface heterogeneities and actually performs as well in low‐permeability silts and clay as in higher‐ permeability sands and gravels. ERH is often implemented around and under buildings and public access areas without upsetting normal business operations. ERH may also be combined with other treatment technologies to optimize and enhance their performance. This article describes how the technology was developed, how it works, and provides two case studies where ERH was used to remediate complex lithologies. © 2005 Wiley Periodicals, Inc.     

Remediation of Persistent Organic Pollutants Using a Novel Two-Phase Soil Washing Biosorption Process

A two-phase soil washing biosorption process was developed for the remediation of p,p-DDT-contaminated soil. The process involved desorption of contaminants from soil using dilute primary alcohols (40% 1-propanol) followed by contaminant removal from cosolvent solutions using fungal biosorption. Bench scale remediation studies were preformed to simulate ex situ (recycling experiment) or in situ (soil column study) treatment strategies. Both systems were effective at cleaning the soil to below Australian regulatory p,p-DDT levels. After 50–80 hours of soil washing, over 93% of p,p-DDT was removed from the soil(990 mg kg^-1 to <65 mg kg^-1) using either of these methods.p,p-DDT was removed from the cosolvent phase by sorption onto the fungal biomass. This resulted in only low levels of p,p-DDT remaining in the cosolvent solution(<1.5 mg l^-1). The application of both treatment strategies resulted in the rapid clean up of p,p-DDT-contaminated soil and the potential to recycle cosolvent solutions. The ability to recycle cosolvent solutions provides a mechanism for cost reductions of the remediation strategy.     

CSIA of TCE and Daughter Products With Multiple Sources,Multiple Attenuation Mechanisms,and Low Ethene

One of the most often asked questions from regulators considering monitored natural attenuation (MNA) for a site is if there are mechanisms in situ that can completely detoxify the contaminant of concern. This article describes a method that uses data derived from compound‐specific isotope analysis (CSIA) to investigate if complete in situ degradation of trichloroethene (TCE) has occurred. MNA was the selected remediation strategy at the former England Air Force Base (fEAFB) in Louisiana. Previously declining concentrations of TCE, 1,2‐cis‐dichloroethene, and vinyl chloride had increased in selected wells, and less ethene was observed than expected on the basis of mass balance. Reductive dechlorination, partial or otherwise, could not explain observed trends, so the question at fEAFB had become: Was there an in situ mechanism for complete TCE detoxification (i.e., complete degradation to innocuous end products) at the site? CSIA was used for investigating this question at fEAFB. A previously developed formalism was adapted to interpret the CSIA data to answer the question. Standard interpretation assuming only reductive dechlorination demonstrated detoxification in 9 of the 15 contaminated wells, whereas the interpretation developed here did so in 14. © 2014 Wiley Periodicals, Inc.     

Biochemical Treatment of Hydraulically Complex Hexavalent Chromium and Chlorinated Volatile Organic Plumes

Groundwater contaminated with hexavalent chromium (Cr⁺⁶) and chlorinated volatile organic compounds (cVOCs) presents unique in situ remedial challenges in an oxygen‐rich environment. On one hand, chemical oxidation would be effective in treating the cVOCs; however, it would not be appropriate to treat Cr⁺⁶. Biological treatment may be appropriate to treat the Cr⁺⁶; however, the cVOC degradation pathway within these mixed plumes is currently following an abiotic pathway with little to no daughter‐product production. Thus, a blended approach was needed to treat both constituents in situ in an effort to avoid a long‐term, costly pump‐and‐treat solution. This article evaluates an in situ biogeochemical stabilization/reduction strategy by injecting an inorganic carbon‐based remedial additive into the geologic and hydrogeologic environment to decrease concentrations within the commingled Cr⁺⁶ and cVOC plume. The concept involves creating favorable redox reducing conditions to shift the groundwater geochemical equilibrium from the more toxic Cr⁺⁶ to the less toxic trivalent chromium (Cr⁺³), with the final outcome being a conversion to chrome oxide that molecularly fixes to the soil grains. In addition, reducing conditions developed for chromium reduction should result in an increase in the available natural formation iron that should further enhance the natural abiotic reduction of cVOCs. © 2013 Wiley Periodicals, Inc.