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.     

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.     

1,4‐Dioxane Treatment Technologies

The chlorinated solvent stabilizer 1,4‐dioxane (DX) has become an unexpected and recalcitrant groundwater contaminant at many sites across the United States. Chemical characteristics of DX, such as miscibility and low sorption potential, enable it to migrate at least as far as the chlorinated solvent from which it often originates. This mobility and recalcitrance has challenged remediation professionals to redesign existing treatment systems and monitoring networks to accommodate widespread contamination. Furthermore, remediation technologies commonly applied to chlorinated solvent co‐contaminants, such as extraction and air stripping or in situ enhanced reductive dechlorination, are relatively ineffective on DX removal. These difficulties in treatment have required the industry to identify, develop, and demonstrate new and innovative technologies and approaches for both ex situ and in situ treatment of this emerging contaminant. Great strides have been made over the past decade in the development and testing of remediation technologies for removal or destruction of DX in groundwater. This article briefly summarizes the fate and transport characteristics of DX that make it difficult to treat, and presents technologies that have been demonstrated to be applicable to groundwater treatment at the field scale.  ©2016 Wiley Periodicals, Inc.     

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.     

Comparing PFAS to other groundwater contaminants: Implications for remediation

Established groundwater contaminants such as chlorinated solvents and hydrocarbons have impacted groundwater at hundreds of thousands of sites around the United States and have been responsible for multibillion dollar remediation expenditures. An important question is whether groundwater remediation for the emerging contaminant class comprised of per‐ and polyfluoroalkyl substances (PFAS) will be a smaller, similar, or a larger‐scale problem than the established groundwater contaminants. A two‐pronged approach was used to evaluate this question in this paper. First, nine quantitative scale‐of‐remediation metrics were used to compare PFAS to four established contaminants: chlorinated solvents, benzene, 1,4‐dioxane, and methyl tert‐butyl ether. These metrics reflected the prevalence of the contaminants in the U.S., attenuation potential, remediation difficulty, and research intensity. Second, several key challenges identified with PFAS remediation were evaluated to see similar situations (qualitative analogs) that have been addressed by the remediation field in the past. The results of the analysis show that four out of nine of the evaluated quantitative metrics (production, number of potential sites, detection frequency, required destruction/removal efficiency) indicate that the scale of PFAS groundwater remediation may be smaller compared to the current scale of remediation for conventional groundwater contaminants. One attenuation metric, median plume length, suggests that overall PFAS remediation could pose a greater challenge compared to hydrocarbon sites, but only slightly larger than chlorinated volatile organic compounds sites. The second attenuation metric, hydrophobic sorption, was not definitive regarding the potential scale of PFAS remediation. The final three metrics (regulatory criteria, in‐situ remediation capability, and research intensity) all indicate that PFAS remediation might end up being a larger scale problem than the established contaminants. An assessment of the evolution of groundwater remediation capabilities for established contaminants identified five qualitative analogs for key PFAS groundwater remediation issues: (a) low‐level detection analytical capabilities; (b) methods to assess the risk of complex chemical mixtures; (c) nonaqueous phase dissolution as an analog for partitioning, precursors, and back diffusion at PFAS sites; (d) predictions of long plume lengths for emerging contaminants; and (e) monitored natural attenuation protocols for other non‐degrading groundwater contaminants. Overall the evaluation of these five analogs provided some comfort that, while remediating the potential universe of PFAS sites will be extremely challenging, the groundwater community has relevant past experience that may prove useful. The quantitative metrics and the qualitative analogs suggest a different combination of remediation approaches may be needed to deal with PFAS sites and may include source control, natural attenuation, in‐situ sequestration, containment, and point‐of‐use treatment. However, as with many chlorinated solvent sites, while complete restoration of PFAS sites may be uncommon, it should be possible to prevent excessive exposure of PFAS to human and ecological receptors.     

Stable Isotope Probing to Confirm Field‐Scale Co‐Metabolic Biodegradation of 1,4‐Dioxane

1,4‐Dioxane, a common co‐contaminant with chlorinated solvents, is present in groundwater at Site 24 at Vandenberg Air Force Base in California. Historical use of chlorinated solvents resulted in concentrations of 1,4‐dioxane in groundwater up to approximately 2,000 μg/L. Starting in 2013, an in situ propane biosparge system operation demonstrated reductions in 1,4‐dioxane concentrations in groundwater. The work detailed herein extends the efforts of the first field demonstration to a second phase and confirms the biodegradation mechanism via use of stable isotope probing (SIP). After two months of operation, 1,4‐dioxane concentrations decreased approximately 45 to 83 percent at monitoring locations in the test area. The results of the SIP confirmed ¹³C‐enriched 1,4‐dioxane was transformed into dissolved inorganic carbon (suggesting mineralization to carbon dioxide) and incorporated into microbial biomass (likely attributed to metabolic uptake of biotransformation intermediates or of carbon dioxide).  ©2016 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.     

Natural attenuation of chlorinated solvent plumes at Texas dry cleaners

Dry cleaners are the largest users of perchloroethene (PCE) solvents in the United States. Releases from dry cleaners to soil and groundwater, however, remain largely unstudied. This article presents a database of 137 chlorinated solvent plumes at dry cleaners in Texas. The data indicate that PCE plumes are generally shorter in extent than those from industrial sites. Degradation products were observed at more than 80 percent of the sites with groundwater contamination. Calculated attenuation rates are on the order of one‐to‐three‐year half‐lives for PCE and its degradation products. The estimated cleanup timeframe for calculated attenuation rates is < 50 years. More research is needed to understand the presence of organic carbon sources at dry cleaners and its implications for natural attenuation. © 2004 Wiley Periodicals, Inc.     

Bench‐ and pilot‐scale applications of electrochemical peroxidation: A new remedial concept

Electrochemical peroxidation (ECP) is a proprietary process that utilizes sacrificial iron electrodes and stochiometrically balanced applications of hydrogen peroxide to efficiently destroy aqueous phase contaminants. In laboratory trials it has been successful in reducing, often to non‐detectable levels, BTEX, fuel additives, chlorinated solvents, and polychlorinated biphenyls in ground waters. The process has also been found effective in reducing the chemical and biological oxygen demand of industrial waste water. Agency‐approved pilot tests will be conducted at two gasoline spill sites during 2000 where traditional pump and treat methods have proven ineffectual because of ground water chemistry or subsurface hydrologic conditions. The ECP process utilizes a tripartite treatment strategy consisting of 1) ex situ chemical oxidation; 2) in situ oxidation by reinjection of treated water with residual oxidants at the head of the plume; and 3) reestablishment of aerobic biodegradation by alteration of subsurface redox conditions. In contrast to other in situ oxidation treatment methods, dissolved iron is derived electrochemically, negating the need for ferrous salt addition. Dilute hydrogen peroxide (3 percent) is incrementally added to maximize oxidation efficiency and eliminate safety and environmental concerns accompanying the use of highly concentrated solutions. Results of laboratory trials and the geological and geochemical considerations of upcoming pilot‐scale applications are presented. Other potential applications currently under investigation include combination with other remedial processes (e.g. permeable barriers and hydrogen release compounds) to insure complete and rapid contaminant mineralization.     

The Use of Natural Systems to Remediate Groundwater: Department of Energy Experience at the Savannah River Site

Natural remediation is moving toward the forefront as engineers clean groundwater at the Savannah River Site (SRS), a major Department of Energy (DOE) installation near Aiken, South Carolina. This article reviews two successful, innovative remediation methods currently being deployed: biosparging to treat chlorinated solvents and phytoremediation to address tritium in groundwater. The biosparging system reintroduces oxygen into the groundwater and injects nutrient compounds for in‐situ remediation. The system has greatly reduced the concentrations of trichloroethylene (TCE) and vinyl chloride in wells downgradient from a sanitary landfill (SLF). Phytoremediation is an emerging technology that promises effective and inexpensive cleanup of certain hazardous wastes. Using natural processes, plants can break down, trap and hold, or transpire contaminants. This article discusses the use of phytoremediation to reduce the discharge of tritium to an on‐site stream at SRS. © 2002 Wiley Periodicals Inc. *     

Successful solid-phase bioremediation of petroleum-contaminated soil

Biological processes have been used to remediate petroleum hydrocarbons, pesticides, chlorinated solvents, and halogenated aromatic hydrocarbons. Biological treatment of contaminated soils may involve solid-phase, slurry-phase, or in situ treatment techniques. This article will review the general principle of solid-phase bioremediation and discuss the application of this technique for the cleanup of total petroleum hydrocarbons on two sites. These remedial programs will reduce total petroleum hydrocarbon contamination from the mean concentration of 2,660 ppm to under the 200-ppm cleanup criteria for soil and under the 15-ppm cleanup criteria for groundwater. Over 32,000 yards of soil have been treated by solid-phase treatment to date. The in situ system operation is effectively producing biodegradation in the subsurface. The project is approximately one-third complete.     

Sustainable Remediation Considerations for Treatment of 1,4‐Dioxane in Groundwater

1,4‐Dioxane remediation is challenging due to its physiochemical properties and low target treatment levels. As such, applications of traditional remediation technologies have proven ineffective. There are a number of promising remediation technologies that could potentially be scaled for successful application to groundwater restoration. Sustainable remediation is an important consideration in the evaluation of remediation technologies. It is critically important to consider sustainability when new technologies are being applied or new contaminants are being treated with traditional technologies. There are a number of social, economic, and environmental drivers that should be considered when implementing 1,4‐dioxane treatment technologies. This includes evaluating sustainability externalities by considering the cradle‐to‐grave impacts of the chemicals, energy, processes, transportation, and materials used in groundwater treatment. It is not possible to rate technologies as more or less sustainable because each application is context specific. However, by including sustainability thinking into technology evaluations and implementation plans, decisions makers can be more informed and the results of remediation are likely to be more effective and beneficial. There are a number sustainable remediation frameworks, guidance documents, footprint assessment tools, life cycle assessment tools, and best management practices that can be utilized for these purposes. This paper includes an overview describing the importance of sustainability in technology selection, identifies sustainability impacts related to technologies that can be used to treat 1,4‐dioxane, provides an approximating approach to assess sustainability impacts, and summarizes potential sustainability impacts related to promising treatment technologies. ©2016 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.     

Advances in photocatalytic remediation technology

The cost of remediation at hazardous waste sites is estimated at billions of dollars annually. It is imperative that more cost‐effective remediation technologies be developed, particularly to address the more complex megasites. Chlorinated hydrocarbons represent the major contaminants at many such sites. It has long been recognized that chlorinated hydrocarbons can be destroyed by photocatalytic oxidation. Traditional photocatalysts, however, have often shown inadequate destruction activity, a loss of activity over time, and poor selectivity, thereby producing substantial amounts of phosgene and chloroform by‐products. This article presents results obtained using novel photocatalyst compositions. The results demonstrate the ability to achieve high photocatalytic destruction activity for chlorinated hydrocarbons with full retention of activity over extended time periods and with complete elimination of phosgene and chloroform by‐products. © 2006 Wiley Periodicals, Inc.     

Travis Air Force Base: A greener cleanups case study

Travis Air Force Base, California, has accelerated the pace of remediation while reducing long‐term costs and cutting greenhouse gas production. This has been achieved through optimizing existing systems and processes, adopting greener cleanups best management practices, and testing and implementing innovative “green” technologies. By optimizing and replacing existing systems that used energy‐intensive infrastructure, and by promoting the use of innovative in situ technologies, the US Air Force (Air Force) led team comprised of the Air Force Civil Engineer Center, the US Army Corps of Engineers, the performance‐based contractor CH2M, and the regulatory agencies consisting of the US Environmental Protection Agency, the California Water Board, and the California Department of Toxic Substances Control, has reduced annual system operation and maintenance costs by over $200,000 per year, while reducing annual carbon dioxide production by approximately 930 tons per year. As a result of these actions, chlorinated solvent source areas have been reduced by over 99 percent in some cases, and the predicted cleanup time frame for multiple sites has been reduced by several decades. This article provides a case study for implementation of cost‐effective greener cleanup actions, and summarizes the approach taken by the Air Force led team to complete the greener cleanups self‐declaration process consistent with the ASTM International's E‐2893 Standard Guide for Greener Cleanups.     

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.     

Isotope applications in environmental investigations: Theory and use in chlorinated solvent and petroleum hydrocarbon studies

Isotope applications are gaining acceptance for use in surface water and groundwater investigations, complementing traditional geochemistry and physical hydrology techniques. Recent developments in analytical methodologies and in the understanding of isotope dynamics now allow the use of isotopes to investigate sources and fate of common groundwater contaminants such as chlorinated solvents and petroleum hydrocarbons. Contaminants with unique isotopic signatures may facilitate the determination of contaminant sources in complex plumes. Degradation of chlorinated solvents and some petroleum hydrocarbons impart unique isotopic signatures on both the original contaminant and the degradation product or products that provide verification of degradation. Use of a Rayleigh‐type model may allow determination of degradation extent. Coupled with models of contaminant fate and transport, degradation extent may be useful for determining degradation rates. © 2001 John Wiley & Sons, Inc.     

Remediation of chlorinated ethenes,ethanes, and methanes in groundwater using carbon‐ and iron‐based electron donor

Field‐scale pilot tests were performed to evaluate enhanced reductive dechlorination (ERD) of dissolved chlorinated solvents at a former manufacturing facility located in western North Carolina (the site). Results of the site assessment indicated the presence of two separate chlorinated solvent–contaminated groundwater plumes, located in the northern and southern portions of the site. The key chlorinated solvents found at the site include 1,1,2,2‐tetrachloroethane, trichloroethene, and chloroform. A special form of EHC^® manufactured by Adventus Americas was used as an electron donor at this site. In this case, EHC is a pH‐buffering electron donor containing controlled release carbon and ZV Iron MicroSphere 200, a micronscale zero‐valent iron (ZVI) manufactured by BASF. Approximately 3,000 pounds of EHC were injected in two Geoprobe^® boreholes in the saprolite zone (southern plume), and 3,500 pounds of EHC were injected at two locations in the partially weathered rock (PWR) zone (northern plume) using hydraulic fracturing techniques. Strong reducing conditions were established immediately after the EHC injection in nearby monitoring wells likely due to the reducing effects of ZV Microsphere 200. After approximately 26 months, the key chlorinated VOCs were reduced over 98 percent in one PWR well. Similarly, the key chlorinated solvent concentrations in the saprolite monitoring wells decreased 86 to 99 percent after initial increases in concentrations of the parent chlorinated solvents. The total organic carbon and metabolic acid concentrations indicated that the electron donor lasted over 26 months after injection in the saprolite aquifer. © 2009 Wiley Periodicals, Inc.     

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

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

Interactions between biological and abiotic pathways in the reduction of chlorinated solvents

While biologically mediated reductive dechlorination continues to be a significant focus of chlorinated solvent remediation, there has been an increased interest in abiotic reductive processes for the remediation of chlorinated solvents. In situ chemical reduction (ISCR) uses zero‐valent iron (ZVI)–based technologies, such as nanoscale iron and bimetallic ZVI, as well as naturally occurring reduced minerals incorporating dual‐valent iron (DVI), such as magnetite, green rust, and iron sulfides that are capable of dechlorinating solvents. A more recent area of development in ISCR has been in combining biological and abiotic processes. There are several ways in which biological and abiotic processes can be combined. First, the interaction between the two may be “causative.” For example, the Air Force Center for Engineering and the Environment's biogeochemical reductive dechlorination (BiRD) technology combines a mulch barrier with hematite and gypsum to create an iron‐sulfide‐based reducing zone. Biodegradation under sulfate‐reducing conditions produces sulfide that combines with the hematite to form iron sulfides. As such, the BiRD technology is “causative”; the biological processes create reducing minerals. The biological generation of other reducing minerals such as magnetite, siderite, and green rust is feasible and is, with magnetite, observed in nature at some petroleum sites. A second type of interaction between abiotic and biotic processes is “synergistic.” For example, biological processes can enhance the activity of reduced metals/minerals. This is the basis of the EHC® ISCR technologies, which combine ZVI with a (slowly) degradable carbon substrate. This combination rapidly creates buffered, strongly reducing conditions, which result in more complete solvent degradation (i.e., direct mineralization). The extent and level of reducing activity commonly observed are much greater when both the carbon substrate and the ZVI are present. When the carbon substrate is expended, the reducing activity due to ZVI alone is much less. The understanding of biogeochemical processes and their impact on abiotic processes is still developing. As that understanding develops, new and improved methods will be created to enhance volatile organic compound destruction. © 2009 Wiley Periodicals, Inc.