Sustainable remediation at the Massachusetts Military Reservation

When does remediation do more harm than good? After conducting a sustainability analysis on a large pump‐and‐treat site at the Massachusetts Military Reservation (MMR), the Air Force Center for Engineering and the Environment (AFCEE) found evidence suggesting that the remediation systems were creating more pollution than they were remediating. For several years, the AFCEE/MMR has had an aggressive “better, cheaper, faster” optimization program intended to expedite aquifer restoration, reduce costs to the taxpayers, and reduce cleanup time frames. An initial sustainability analysis was conducted in 2005 as part of this program. The analysis identified several concerns, one of which was the indirect generation of air emissions from conventional fossil fuel–based power plants used to power the remediation systems. In addition to the environmental impact of these air emissions, the cost of electricity continues to increase. The AFCEE/MMR evaluated options for addressing both of these concerns and opted to employ renewable energy technology in the form of a utility‐scale wind turbine. This case study presents a more sustainable approach to remediation at the MMR through the use of renewable energy, in the form of a 1,500‐kW wind turbine. Power costs for operating the treatment systems, which processed up to 16 million gallons per day, amounted to over $2.2 million in 2008. The wind turbine is anticipated to reduce the program's electricity costs and offset air emissions, generated indirectly through the use of electricity from fossil fuel–based power plants, by approximately 25 to 30 percent. Based on a range of utility cost projections and an estimate of the turbine's energy production, the $4.6 million project is anticipated to have a payback period between six and eight years. © 2010 Wiley Periodicals, Inc. *

1 This article is a U.S. Government work and, as such, is in the public domain of the United States of America.

     

Using wind to power a groundwater circulation well—preliminary results

In areas of the country where the U.S. Department of Energy has classified the available wind resources as Class 3 or greater, the use of wind turbines to provide power to relatively small remediation systems such as groundwater circulation wells may be technically and economically feasible. Groundwater circulation wells are a good candidate technology to couple with renewable energy, because the remediation system removes contamination from the subject aquifer with no net loss of the groundwater resource, while the wind turbine does not create potentially harmful air emissions. Wind data collected in the vicinity of the former Nebraska Ordnance Plant Superfund site were used to select a wind turbine system to provide a portion of the energy necessary to power a groundwater circulation well located in an area of high trichloroethylene groundwater contamination. Because utility power was already installed at the remediation system, a 10 kW grid inter‐tie wind turbine system supplements the utility system without requiring batteries for energy storage. The historical data from the site indicate that the quantity of energy purchased correlates poorly with the quantity of groundwater treated. Preliminary data from the wind turbine system indicate that the wind turbine provides more energy than the remediation system treatment components and the well submersible pump require on a monthly average. The preliminary results indicate that the coupling of wind turbines and groundwater circulation wells may be an attractive alternative in terms of the system operation time, cost savings, and contaminant mass removal. © 2004 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.     

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.     

Environmental Effects Monitoring in Sydney Harbor During Remediation of One of Canada's Most Polluted Sites: A Review and Lessons Learned

This article reviews a comprehensive marine environmental effects monitoring program (MEEMP) comprised of components capable of detecting changes in the marine environment over short or extended temporal scales during remediation of one of Canada's most polluted sites at the Sydney Tar Ponds. The monitoring components included: water and sediment quality, amphipod toxicity testing, mussel tissue, crab hepatopancreas tissue, and benthic community assessments. The MEEMP was designed to verify the impact predictions for the remediation project (i.e., no immediate damage to the marine ecosystem through remediation activities). Some components were capable of providing conclusive data (e.g., sediment and water quality), while others only yielded data that were inconclusive or difficult to attribute to remediation activities (e.g., intertidal community assessments and amphipod toxicity testing). Components that provided only inconclusive results or were difficult to attribute to remediation activities were discontinued, resulting in substantial cost savings during the project, but without compromising the overall objectives of the program, which was to monitor for potential adverse environmental effects of remediation on the marine environment in Sydney Harbor and to verify environmental effects predictions made in the Environmental Impact Statement for the project. The rationale for discontinuing certain MEEMP components and discussion of conclusive results are incorporated into “lessons learned” for environmental remediation practitioners and regulators working on similar large‐scale multiyear remediation projects. © 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.     

Metrics for integrating sustainability evaluations into remediation projects

The US Sustainable Remediation Forum (SURF) created a compilation of metrics (Metrics Toolbox) in response to a need for a broad set of metrics that could be used to assess and monitor the effectiveness of remedies in achieving sustainability goals. Metrics are the key impacts, outcomes, or burdens that are to be assessed or balanced to determine the influences and impacts of a remedial action. Metrics can reflect any of the three aspects of sustainability (i.e., environmental, social, or economic) or a combination of these aspects. Regardless, metrics represent the most critical sustainable outcomes from the perspective of the key stakeholders. The Metrics Toolbox is hosted online at www.sustainableremediation.org/library/guidance‐tools‐and‐other‐resources . By selecting metrics from the Metrics Toolbox as a starting point and considering a potentially wider suite of metrics in remedial program decisions, appropriate assessments can be made. Qualitative and quantitative metrics are tabulated for each remedial phase: remedial investigation, remedy selection, remedial design, remedial construction, operation and maintenance, and closure. Attributes for each metric are described so that remediation practitioners and key stakeholders can view the universe of metrics available and select the most relevant, site‐specific metrics for a particular site. For this reason, SURF recommends that remediation practitioners consider the metrics compiled in the Metrics Toolbox as a companion to the sustainable remediation framework published elsewhere in this journal and other sustainability evaluations. © 2011 Wiley Periodicals, Inc.     

Guidance for performing footprint analyses and life‐cycle assessments for the remediation industry

The US Sustainable Remediation Forum (SURF) proposes a nine‐step process for conducting and documenting a footprint analysis and life‐cycle assessment (LCA) for remediation projects. This guidance is designed to assist remediation practitioners in evaluating the impacts resulting from potential remediation activities so that preventable impacts can be mitigated. Each of the nine steps is flexible and scalable to a full range of remediation projects and to the tools used by remediation practitioners for quantifying environmental metrics. Two fictional case studies are presented to demonstrate how the guidance can be implemented for a range of evaluations and tools. Case‐study findings show that greater insight into a study is achieved when the nine steps are followed and additional opportunities are provided to minimize remediation project footprints and create improved sustainable remediation solutions. This guidance promotes a consistent and repeatable process in which all pertinent information is provided in a transparent manner to allow stakeholders to comprehend the intricacies and tradeoffs inherent in a footprint analysis or LCA. For these reasons, SURF recommends that this guidance be used when a footprint analysis or LCA is completed for a remediation project. © 2011 Wiley Periodicals, Inc.     

Framework for integrating sustainability into remediation projects

The US Sustainable Remediation Forum (SURF) created this Framework to enable sustainability parameters to be integrated and balanced throughout the remediation project life cycle, while ensuring long‐term protection of human health and the environment and achieving public and regulatory acceptance. Parameters are considerations, impacts, or stressors of environmental, social, and economic importance. Because remediation project phases are not stand‐alone entities but interconnected components of the wider remediation system, the Framework provides a systematic, process‐based approach in which sustainability is integrated holistically and iteratively within the wider remediation system. By focusing stakeholders on the preferred end use or future use of a site at the beginning of a remediation project, the Framework helps stakeholders form a disciplined planning strategy. Specifically, the Framework is designed to help remediation practitioners (1) perform a tiered sustainability evaluation, (2) update the conceptual site model based on the results of the sustainability evaluation, (3) identify and implement sustainability impact measures, and (4) balance sustainability and other considerations during the remediation decision‐making process. The result is a process that encourages communication among different stakeholders and allows remediation practitioners to achieve regulatory goals and maximize the integration of sustainability parameters during the remediation process. © 2011 Wiley Periodicals, Inc.     

Trends In Regulatory Acceptance Of Risk-Based Cleanup Goals And Natural Attenuation For Site Closure

Since 1994, there has been a significant regulatory shift toward risk-based cleanup standards based on the site-specific risk of the more toxic and mobile compounds; namely, benzene, ethyl benzene, toluene, and xylene (BTEX). This regulatory shift has been accompanied by a growing acceptance of natural attenuation as an important component of petroleum site remediation. This article briefly reviews regulatory progress toward risk-based remediation and describes the successful application of risk-based corrective actions (RBCAs) at two fuel contaminated sites on Air Force installations. By developing site-specific cleanup goals, and combining natural attenuation, source reduction, and land use controls, innovative risk-based closure plans have been implemented on these sites.     

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.     

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.     

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.     

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.     

Resilience: A New Consideration for Environmental Remediation in an Era of Climate Change

There has been a growing movement within the environmental industry to develop more sustainable approaches in environmental remediation. These have generally included carbon footprint analysis, life cycle assessment, and best management practices to reduce the overall net environmental, social, and economic impacts of investigation and remediation activities. One of the foundational reasons net environmental impacts are currently evaluated is to identify and, subsequently, reduce contributions to climate change, primarily greenhouse gas emissions. While this trend toward sustainability and reduction in impact to the global environment is both important and admirable, the approach to remediation design and long‐term planning now needs to evolve further to better incorporate climate resilience into sustainable remediation design and implementation: designing remediation solutions that account for the projected impacts of climate change, as well as have the capacity to adapt to changing conditions. As a global population, we are now beyond the point of being able to prevent climate change and instead need to plan for adapting to it. In remediation, the effects of climate change create both risks and opportunities which should be considered during remedial design and long‐term planning. Responsible parties may see the push for—and management of—these considerations through their internal corporate risk management. The authors of this paper propose a simple framework for climate adaptation and resilience evaluations and plan development for remediation projects. ©2015 Wiley Periodicals, Inc.     

Stratigraphic flux—A method for determining preferential pathways for complex sites

Experience with groundwater remediation over several decades has demonstrated that successful outcomes depend on quantitative conceptual site models (CSMs). Over the last 30 years, we have progressed from groundwater pump‐and‐treat remedies, which were largely designed based on a water supply perspective, to in situ and combined remedy strategies, which are only beginning to benefit from understanding the aquifer architecture and distribution of contaminant mass to assess plume maturity, mass flux, and more reliable means of fate and transport assessment. The U.S. Air Force funded the development of the Stratigraphic Flux approach to provide a framework for understanding contaminant transport pathways at its complex sites and enable more reliable and cost‐effective remediation. Stratigraphic Flux enables the development of quantitative, flux‐based CSMs that are founded in sequence stratigraphy, and high‐resolution hydraulic conductivity and contaminant distribution measurements. The result is a three‐dimensional graphical mapping of relative contaminant flux and classification of transport potential that is easy for all stakeholders to understand. The Stratigraphic Flux graphical model is based on a hydrofacies classification system that describes transport potential in three segments of the aquifer: transport zones—where the majority of groundwater flow occurs and transport rates are measured in feet per day; slow advection zones—where transport rates are measured in feet per year; and storage zones—where typically less than 1% of flow occurs, and diffusion dominates contaminant transport. The hydrofacies architectures are based on stratigraphy and transport potential is defined by grouping facies by orders of magnitude classes in hydraulic conductivity. By combining the hydrofacies architecture with contaminant concentration distributions, one can map relative contaminant flux to define and target the complex pathways that control contaminant transport and cleanup behavior. In this article, we describe the Stratigraphic Flux framework, focusing on the key information needed and the methods of analysis. We illustrate the results of its application to evaluate migration pathways for trichlorethylene and chromium at a former chrome pit at Air Force Plant 4 in Fort Worth, Texas. A comprehensive guidance document that describes the approach with a broad spectrum of tools and several site examples can be requested from the authors.     

Ecofriendly Zinc Oxide-Decorated Poly-3-hydroxyalkanoate—graft—Poly-Methyl Acrylate Copolymer Film for Photocatalysis-Mediated Water Treatment

Journal of Polymers and the Environment - The application of microbiologically produced polymer, i.e., medium-chain-length poly-3-hydroxyalkanoate (mcl-PHA), in environmental remediation technology...     

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.     

Performance evaluation of an in situ source area combined remedy for the remediation of commingled chlorinated ethanes and ethenes

The chlorinated volatile organic compounds (CVOCs), tetrachloroethene (PCE), trichloroethene (TCE), and 1,1,1‐trichloroethane (1,1,1‐TCA), often found as commingled contaminants of concern (COCs) in groundwater, can degrade via a variety of biotic and abiotic reductive pathways. In situ remediation of a groundwater contaminant source area containing commingled 1,1,1‐TCA, PCE, and TCE was conducted using a combined remedy/treatment train approach. The first step was to create geochemically reducing conditions in the source area to degrade the CVOCs to lesser chlorinated CVOCs (i.e., 1,1‐dichloroethane [1,1‐DCA], 1,1‐dichlorethene [1,1‐DCE], cis‐1,2‐dichoroethene [cis‐1,2‐DCE], and vinyl chloride [VC]) via enhanced reductive dechlorination (ERD). Carbon substrates were injected to create microbial‐induced geochemically reducing conditions. An abiotic reductant (zero‐valent iron [ZVI]) was also used to further degrade the CVOCs, minimizing the generation of 1,1‐DCE and VC, and co‐precipitate temporarily mobilized metals. An in situ aerobic zone was created downgradient of the treatment zone through the injection of oxygen. Remaining CVOC degradation products and temporarily mobilized metals (e.g., iron and manganese) resulting from the geochemically reducing conditions were then allowed to migrate through the aerobic zone. Within the aerobic zone, the lesser chlorinated CVOCs were oxidized and the solubilized metals were precipitated out of solution. The injection of a combination of carbon substrates and ZVI into the groundwater system at the site studied herein resulted in the generation of a geochemically reducing subsurface treatment zone that has lasted for more than 4.5 years. Mass concentrations of total CVOCs were degraded within the treatment zone, with near complete transformation of chlorinated ethenes and a more than 90 percent reduction of CVOC mass concentrations. Production of VC and 1,1‐DCE has been minimized through the combined effects of abiotic and biological processes. CVOC concentrations have declined over time and temporarily mobilized metals are precipitating out of the dissolved phase. Precipitation of the dissolved metals was mitigated using the in situ oxygenation system, also resulting in a return to aerobic conditions in downgradient groundwater. Chloroethane (CA) is the dominant CVOC degradation product within the treatment zone and downgradient of the treatment zone, and it is expected to continue to aerobically degrade over time. CA did not accumulate within and near the aerobic oxygenation zone. The expectations for the remediation system are: (1) the concentrations of CVOCs (primarily in the form of CA) will continue to degrade; (2) total organic carbon concentrations will continue to decline to pre‐remediation levels; and, (3) the groundwater geochemistry will experience an overall trend of transitioning from reducing back to pre‐remediation mildly oxidizing conditions within and downgradient of the treatment zone.     

Managing Excessive Methanogenesis During ERD/ISCR Remedial Action

Excessive production of methane has been observed at some remediation sites following the addition of organic hydrogen donors such as (emulsified) oils/lecithin, sugars, and conventional carbon + zero‐valent iron (ZVI) amendments. This is due to the fact that methanogens are commonly the most ubiquitous indigenous microbes in anoxic aquifer settings, and, under enriched environmental conditions, methanogens replicate every one to two hours (whereas Dehalococcoides spp., e.g., double in 24–48 hr). Hence, methanogens often bloom and dominate the microbial ecosystem following the addition of remedial amendments, thereby liberating large amounts of methane gas. There are at least three important consequences of this response:

1. By utilizing hydrogen, the methanogens compete with dechlorinating microbes, thus making inefficient use of the remedial amendment (just 20 ppm methane in groundwater represents an approximate 30 percent “waste” of added fermentable substrate (i.e., hydrogen donor)—this is a common and tangible detriment);
2. Methanogens can methylate heavy metals and their rapid growth consumes alkalinity, while generating acidity, thereby facilitating multiple potential mechanisms for creating secondary contaminant issues (i.e., arsenic plumes); and
3. Elevated methane concentrations can exceed current and pending regulations of <10 to <28 ppm methane in groundwater and/or 0.5 percent by volume methane in soil gas (e.g., 10 percent of the lower explosive limit) and/or indoor air (methane is flammable between 5 percent and 15 percent by volume) and this will induce migration of contaminant vapors potentially causing indoor air issues.

Considering the recent guidelines for indoor air published by the US Environmental Protection Agency, it is increasingly important to prevent excessive methanogenesis associated with remedial actions. From a regulatory perspective, public safety issues are paramount; from a property re‐use or real estate (brownfield) developers’ perspective, project delays are costly and can jeopardize an entire program. The use of antimethanogenic compounds as inhibitors of protein biosynthesis and the activity of enzyme systems unique to Archaea (i.e., methanogens) during in situ remedial action can improve contaminant removal while offering safer, more efficacious treatment, simply by impeding the methanogenic bacteria's ability to proliferate and out compete desired bacterial communities (e.g., Dehalococcoides spp.). ©2016 Wiley Periodicals, Inc.