ART in‐well technology proves effective in treating 1,4‐dioxane contamination

A common industrial solvent additive is 1,4‐dioxane. Contamination of dissolved 1,4‐dioxane in groundwater has been found to be recalcitrant to removal by conventional, low‐cost remedial technologies. Only costly labor and energy‐intensive pump‐and‐treat remedial options have been shown to be effective remedies. However, the capital and extended operation and maintenance costs render pump‐and‐treat technologies economically unfeasible at many sites. Furthermore, pump‐and‐treat approaches at remediation sites have frequently been proven over time to merely achieve containment rather than site closure. A major manufacturer in North Carolina was faced with the challenge of cleaning up 1,4‐dioxane and volatile organic compound–impacted soil and groundwater at its site. Significant costs associated with the application of conventional approaches to treating 1,4‐dioxane in groundwater led to an alternative analysis of emerging technologies. As a result of the success of the Accelerated Remediation Technologies, LLC (ART) In‐Well Technology at other sites impacted with recalcitrant compounds such as methyl tertiarybutyl ether, and the demonstrated success of efficient mass removal, an ART pilot test was conducted. The ART Technology combines in situ air stripping, air sparging, soil vapor extraction, enhanced bioremediation/oxidation, and dynamic subsurface groundwater circulation. Monitoring results from the pilot test show that 1,4‐dioxane concentrations were reduced by up to 90 percent in monitoring wells within 90 days. The removal rate of chlorinated compounds from one ART well exceeded the removal achieved by the multipoint soil vapor extraction/air sparging system by more than 80 times. © 2005 Wiley Periodicals, Inc.     

Best Available Treatment Technologies Applied to Groundwater Circulation Wells

Groundwater circulation wells (GCWs) are a quasi‐in‐situ method for remediating groundwater in areas where remediation techniques that limit the water available for municipal, domestic, industrial, or agricultural purposes are inappropriate. The inherently resource‐conservative nature of groundwater circulation wells is also philosophically appealing in today's culture, which is supportive of green technologies. Groundwater circulation wells involve the circulation of groundwater through a dual‐screen well, with treatment occurring between the screens. The wells are specifically designed so that one well screen draws in groundwater and the second returns the groundwater after it has been treated within the well. Historically, the treatment has been performed with specialized equipment proprietary to GCW vendors. Two full‐scale pilot systems at a formerly used Defense Superfund site in Nebraska used best available technologies for treatment components. A multiple‐tray, low‐profile air stripper typically used for pump‐and‐treat remediation systems was successfully adapted for the GCW pilot system located in a trichloroethylene (TCE) hot spot. An ultraviolet water disinfection system was successfully adapted for the GCW pilot system located in a hot spot contaminated with the explosive compound hexhydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX). The pilot systems showed that GCW technology is competitive with a previously considered pump‐and‐treat alternative for focused extraction, and the regulatory community was supportive of additional GCW applications. A remedial design for the site includes 12 more GCW systems to complete focused remediation requirements. © 2002 Wiley Periodicals, Inc.     

Ex situ treatment of MTBE‐containing groundwater by a UV peroxide system

This article describes the design, implementation, and operating results for an ex situ ultraviolet/hydrogen peroxide (UVP) system to treat methyl tert‐butyl ether (MTBE) in extracted groundwater. The UVP modification was designed to reduce the operation and maintenance costs of an existing groundwater pump‐and‐treat treatment system that relied on air stripping and carbon adsorption. The UVP system is relatively inexpensive and can easily be scaled to cope with different groundwater extraction rates up to 80 gpm by adding UV lamps in series or in parallel at the higher groundwater extraction rates. The MTBE concentration in the effluent from the UVP system to the carbon vessels decreased from an average of 590 μg/L to approximately 2 μg/L on average over 33 months of operation of the UVP. Incorporation of this UVP modification as a second‐stage treatment to the groundwater pump‐and‐treat/soil vapor extraction system, after the air stripper and prior to the carbon vessels, significantly increased the usable life of the carbon (from two months previously to about two years after installation) and completely resolved the issue of frequent MTBE breakthroughs of the carbon that had plagued the remediation system since its inception. © 2006 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.     

Cyclodextrin‐enhanced remediation of organic and metal contaminants in porous media and groundwater

Heavy metals and toxic organic contaminants are found at numerous industrial and military sites. The generally poor performance of conventional pump‐and‐treat schemes has made the development of improved methods for contaminated site remediation a significant environmental priority. One such innovative method is cyclodextrin‐enhanced flushing of the contaminated porous media and groundwater. Cyclodextrin is a glucose‐based molecule that is produced on industrial scales by microorganisms. Over the last years, several cyclodextrin derivatives have received extensive research interest. It was shown that cyclodextrins can significantly enhance the solubility of toxic organics, and in some cases, heavy metals and radioactive isotopes. As a sugar, cyclodextrin is considered relatively non‐toxic to humans, plants, and soil microbes. Thus, there are minimal health‐related concerns associated with the injection of cyclodextrin into the subsurface, which is an inherent advantage for use of cyclodextrins as a remediation agent. This paper provides a review of the available literature concerning use of cyclodextrin for remediation of groundwater and soil.     

Vegetative remediation process offers advantages over traditional pump-and-treat technologies

The use of bioremediation technologies to clean up contaminated soil and groundwater is increasingly winning favor over more costly and often ineffective mechanical approaches. One new type of bioremediation process, known as TreeMediation^TM, uses trees and other vegetation to remediate soil by acting as a natural pump to extract and remediate contaminated groundwater in aquifers less than 30 feet deep. This article describes this innovative treatment method, shows its advantages over traditional pump and-treat techniques, and explains how TreeMediation is being used to extract nitrate and ammonium contamination from an aquifer in New Jersey.     

Treatment technology for remediation of wood preserving sites: Overview

This is the first in a series of five articles describing the applicability, performance, and cost of technologies for the remediation of contaminated soil and water at wood preserving sites. Site‐specific treatability studies conducted under the supervision of the United States Environmental Protection Agency (US EPA), National Risk Management Research Laboratory (NRMRL), from 1995 through 1997 constitute much of the basis for the evaluations presented, although data from other treatability studies, literature sources, and actual site remediations have also been included to provide a more comprehensive evaluation of remediation technologies. This article provides an overview of the wood preserving sites studied, including contaminant levels, and a summary of the performance of the technologies evaluated. The subsequent articles discuss the performance of each technology in more detail. Three articles discuss technologies for the treatment of soils, including solidification/stabilization, biological treatment, solvent extraction and soil washing. One article discusses technologies for the treatment of liquids, water and nonaqueous phase liquids (NAPLS), including biological treatment, carbon adsorption, photolytic oxidation, and hydraulic containment. The reader should be aware that other technologies including, but not limited to, incineration, thermal desorption, and base catalyzed dehalogenation, also have application for treating contaminants on wood preserving sites. They are not discussed in these five articles since the focus was to evaluate lesser known and hopefully lower cost approaches. However, the reader should include consideration of these other technologies as part of any evaluation or screening of technologies applicable to remediation of wood preserving sites.     

Treatment technologies for 1,4‐Dioxane: Fundamentals and field applications

1,4‐Dioxane is a synthetic industrial chemical frequently found at contaminated sites where 1,1,1‐trichloroethane was used for degreasing. It is a probable human carcinogen and has been found in groundwater at sites throughout the United States. The physical and chemical properties and behavior of 1,4‐dioxane create challenges for its characterization and treatment. It is highly mobile and has not been shown to readily biodegrade in the environment. In December 2006, the U.S. Environmental Protection Agency's Office of Superfund Remediation and Technology Innovation (OSRTI) prepared a report titled “Treatment Technologies for 1,4‐Dioxane: Fundamentals and Field Applications.” The report provides information about the chemistry of dioxane, cleanup goals, analytical methods, available treatment technologies, and site‐specific treatment performance data. The information may be useful to project managers, technology providers, consulting engineers, and members of academia faced with addressing dioxane at cleanup sites or in drinking water supplies. This article provides a synopsis of the US EPA report, which is available at http://cluin.org/542R06009 . © 2007 Wiley Periodicals, Inc.     

A study of treatment options to remediate explosives and perchlorate in soils and groundwater at Camp Edwards,Massachusetts

The Army National Guard initiated an Innovative Technology Evaluation (ITE) Program in March 2000 to study potential remedial technologies for the cleanup of explosives‐contaminated soil and groundwater at the Camp Edwards site on the Massachusetts Military Reservation. The soil technologies chosen for the ITE program were: soil washing, chemical oxidation, chemical reduction, thermal desorption/destruction (LTTD), bioslurry, composting, and solid phase bioremediation. The technologies were evaluated based on their ability to treat both washed and untreated soil. A major factor considered was the ability to degrade explosives, such as RDX, found in particulate form in the soils. The heterogeneous nature of explosives in soils dictates that the preferred technology must be able to treat explosives in all forms, including the particulate form. Groundwater remediation technologies considered include: in situ cometabolic reduction, two forms of in situ chemical oxidation, Fenton‐like oxidation and potassium permanganate. This article presents the results of each of the remedial technologies evaluated and discusses which technologies met the established ITE performance goals. © 2003 Wiley Periodicals, Inc.     

Developing Effective Decision Support for the Application of “Gentle” Remediation Options: The GREENLAND Project

Gentle remediation options (GRO) are risk management strategies/technologies that result in a net gain (or at least no gross reduction) in soil function as well as risk management. They encompass a number of technologies, including the use of plant (phyto‐), fungi (myco‐), and/or bacteria‐based methods, with or without chemical soil additives or amendments, for reducing contaminant transfer to local receptors by in situ stabilization, or extraction, transformation, or degradation of contaminants. Despite offering strong benefits in terms of risk management, deployment costs, and sustainability for a range of site problems, the application of GRO as practical on‐site remedial solutions is still in its relative infancy, particularly for metal(loid)‐contaminated sites. A key barrier to wider adoption of GRO relates to general uncertainties and lack of stakeholder confidence in (and indeed knowledge of) the feasibility or reliability of GRO as practical risk management solutions. The GREENLAND project has therefore developed a simple and transparent decision support framework for promoting the appropriate use of gentle remediation options and encouraging participation of stakeholders, supplemented by a set of specific design aids for use when GRO appear to be a viable option. The framework is presented as a three phased model or Decision Support Tool (DST), in the form of a Microsoft Excel‐based workbook, designed to inform decision‐making and options appraisal during the selection of remedial approaches for contaminated sites. The DST acts as a simple decision support and stakeholder engagement tool for the application of GRO, providing a context for GRO application (particularly where soft end‐use of remediated land is envisaged), quick reference tables (including an economic cost calculator), and supporting information and technical guidance drawing on practical examples of effective GRO application at trace metal(loid) contaminated sites across Europe. This article introduces the decision support framework. ©2015 Wiley Periodicals, Inc.     

Biogeochemical gradients as a framework for understanding waste‐site evolution

The migration of biogeochemical gradients is a useful framework for understanding the evolution of biogeochemical conditions in groundwater at waste sites contaminated with metals and radionuclides. This understanding is critical to selecting sustainable remedies and evaluating sites for monitored natural attenuation, because most attenuation mechanisms are sensitive to geochemical conditions, such as pH and redox potential. Knowledge of how gradients in these parameters evolve provides insights into the behavior of contaminants with time and guides characterization, remedy selection, and monitoring efforts. An example is a seepage basin site at the Savannah River Site in South Carolina where low‐level acidic waste has seeped into groundwater. The remediation of this site relies, in part, on restoring the natural pH of the aquifer by injecting alkaline solutions. The remediation will continue until the pH upflow of the treatment zone increases to an acceptable value. The time required to achieve this objective depends on the time it takes the trailing pH gradient, the gradient separating the plume from influxing natural groundwater, to reach the treatment zone. Predictions of this length of time will strongly influence long‐term remedial decisions. © 2008 Wiley Periodicals, Inc.     

1,4‐Dioxane: Emerging technologies for an emerging contaminant

The synthetic chemical, 1,4‐dioxane, is classified by the U.S. Environmental Protection Agency (EPA) as a probable human carcinogen. Between 2013 and 2015, the EPA detected 1,4‐dioxane in public drinking water supplies in 45 states at concentrations up to 33 µg/L and in groundwater from releases at hazardous waste sites across the United States. Although a Federal maximum contaminant level drinking water standard has not yet been proposed, state‐specific standards and criteria are as low as 0.3 µg/L. 1,4‐Dioxane is a recalcitrant chemical in that applications of conventional treatment technologies have had limited success in reducing concentrations in water to meet current and proposed health‐protective levels. Although mainly used as a stabilizer for the solvent 1,1,1‐trichloroethane, it has been used in other industrial processes and has been detected in a variety of consumer products, such as foods, pharmaceuticals, cosmetics, and detergents. The high aqueous solubility of 1,4‐dioxane coupled with limited solubility of chlorinated solvents typically found in conjunction with 1,4‐dioxane contamination is the primary reason for its treatment challenges. In the last several years, an alternative, cost‐effective technology has been developed that has demonstrated treatment to levels significantly lower than the Federal and state‐specific goals. This article provides a Federal and state‐by‐state summary of 1,4‐dioxane‐specific drinking water and groundwater concentration criteria and qualitative comparison of the effectiveness of conventional treatment technologies compared to the effectiveness of an alternative treatment technology. A case study is also provided to present details regarding the application of an alternative treatment technology at an active groundwater remediation site in California.     

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

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

Recent Developments in Cleanup Technologies

Although the reaction mechanics are somewhat mysterious, the use of iron for in situ groundwater treatment has recently gained considerable attention and respect in the remediation industry. The basic scientific principles of both applications of iron have been known for over a century; however, both were nearly unheard of as remediation technologies five years ago. Both technologies have a strong potential for widespread use. They are commercially available, have been proven in field studies, are less expensive than traditional pump and treat technologies, and, in many types of groundwater systems, may be able to meet difficult-to-achieve groundwater treatment standards. As these technologies continue to undergo development, there could be considerably more aggressive applications used to treat ground-water containing high concentrations of chlorinated organics and DNAPLs.     

The in situ treatment of TCE and PFAS in groundwater within a silty sand aquifer

Chlorinated ethenes such as trichloroethene (TCE), cis‐1,2‐dichloroethene (cis‐1,2‐DCE), and vinyl chloride along with per‐ and polyfluoroalkyl substances (PFAS) have been identified as chemicals of concern in groundwater; with many of the compounds being confirmed as being carcinogens or suspected carcinogens. While there are a variety of demonstrated in‐situ technologies for the treatment of chlorinated ethenes, there are limited technologies available to treat PFAS in groundwater. At a former industrial site shallow groundwater was impacted with TCE, cis‐1,2‐DCE, and vinyl chloride at concentrations up to 985, 258, and 54 µg/L, respectively. The groundwater also contained maximum concentrations of the following PFAS: 12,800 ng/L of perfluoropentanoic acid, 3,240 ng/L of perfluorohexanoic acid, 795 ng/L of perfluorobutanoic acid, 950 ng/L of perfluorooctanoic acid, and 2,140 ng/L of perfluorooctanesulfonic acid. Using a combination of adsorption, biotic, and abiotic degradation in situ remedial approaches, the chemicals of concern were targeted for removal from the groundwater with adsorption being utilized for PFAS whereas adsorption, chemical reduction, and anaerobic biodegradation were used for the chlorinated ethenes. Sampling of the groundwater over a 24‐month period indicated that the detected PFAS were treated to either their detection, or below the analytical detection limit over the monitoring period. Postinjection results for TCE, cis‐1,2‐DCE, and vinyl chloride indicated that the concentrations of the three compounds decreased by an order of magnitude within 4 months of injection, with TCE decreasing to below the analytical detection limit over the 24‐month monitoring period. Cis‐1,2‐DCE, and vinyl chloride concentrations decreased by over 99% within 8 months of injections, remaining at or below these concentrations during the 24‐month monitoring period. Analyses of Dehalococcoides, ethene, and acetylene over time suggest that microbiological and reductive dechlorination were occurring in conjunction with adsorption to attenuate the chlorinated ethenes and PFAS within the aquifer. Analysis of soil cores collected pre‐ and post‐injection, indicated that the distribution of the colloidal activated carbon was influenced by small scale heterogeneities within the aquifer. However, all aquifer samples collected within the targeted injection zone contained total organic carbon at concentrations at least one order of magnitude greater than the preinjection total organic carbon concentrations.     

The in situ treatment of PFAS within porewater at the air–water interface of a PFAS source zone

The treatment of per- and polyfluoroalkyl substances (PFAS) within groundwater is an emerging topic, with various technologies being researched and tested. Currently, PFAS-impacted groundwater is typically treated ex situ using sorptive media such as activated carbon and ion exchange resin. Proven in situ remedial approaches for groundwater have been limited to colloidal activated carbon (CAC) injected into aquifers downgradient of the source zones. However, treatment of groundwater within the source zones has not been shown to be feasible to date. This study evaluated the use of CAC to treat dissolved PFAS at the air–water interface within the PFAS source zone. Studies have shown that PFAS tends to preferentially accumulate at the air–water interface due to the chemical properties of the various PFAS. This accumulation can act as a long-term source for PFAS, thus making downgradient treatment of groundwater a long-term requirement. A solution of CAC was injected at the air–water interface within the source zone at a site with PFAS contamination using direct push technology. A dense injection grid that targeted the interface between the air and groundwater was used to deliver the CAC. Concentrations of PFAS within the porewater and groundwater were collected using a series of nine lysimeters installed within the vadose and saturated water columns. A total of six PFAS were detected in the porewater and groundwater including perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA). Detectable concentrations of PFAS within the pore and groundwater before treatment ranged from values greater than 300 µg/L for PFPeA to less than 3 µg/L for PFNA. Following the injection of the CAC, monitoring of the porewater and groundwater for PFAS was conducted approximately 3, 6, 9, 12, and 18 months postinjection. The results indicated that the PFAS within the porewater and groundwater at and near the air–water interface was effectively attenuated over the 1.5-year monitoring program, with PFAS concentrations being below the method detection limits of approximately 10 ng/L, with the exception of PFPeA, which was detected within the porewater during the 18-month sampling event at concentrations of up to 55 ng/L. PFPeA is a five carbon-chained PFAS that has been shown to have a lower affinity for sorption onto activated carbon compared to the longer carbon-chained PFAS such as PFOA. Examination of aquifer cores in the zone of injection indicated that the total organic carbon concentration of the aquifer increased by five orders of magnitude postinjection, with 97% of the samples collected within the target injection area containing activated carbon, indicating that the CAC was successfully delivered into the source zone.     

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.     

Pollutant source identification and allocation: Advances in hydrocarbon fingerprinting

Often liability for environmental damage and cleanup of contaminated sites is made difficult, especially with chemically complex environments containing different pollutants, by the inability to differentiate potential sources (or “owners”) of pollutants from each other. As a result, unnecessary costs may be associated with having to assume financial responsibility for alleged contamination of a site. This article reviews the advances in chemical fingerprinting as a tool in identifying and differentiating sources of hydrocarbon pollutants in chemically complex environments. Appropriate hydrocarbon target analytes and required analytical methods for hydrocarbon fingerprinting are discussed, and new interpretative tools are presented that may be applied to contaminated soil, sediment, and groundwater environmental situations. With these analytical and interpretative techniques, an appropriate allocation of chemical contamination and costs at a site can be made.     

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.