Monitored natural attenuation forum: The case for abiotic MNA

The environmental fate and transport of chlorinated volatile organic compounds (VOCs) is controlled by the physical and chemical properties of the compound and the nature of the subsurface media through which the compound is migrating. Several processes (advection, dispersion, diffusion, biodegradation, and abiotic degradation, to name a few) result in a reduction in concentration and/or mass of contaminants in groundwater. Of these processes, biodegradation is often considered the dominant destructive attenuation mechanism for chlorinated VOCs. However, chlorinated VOCs can also degrade through abiotic processes and, in some cases, may be the primary or only destructive process occurring. © 2007 Wiley Periodicals, Inc.     

Electrical Resistance Heating of Volatile Organic Compounds in Sedimentary Rock

Electrical resistance heating (ERH) is a common method of remediation for volatile organic compounds in unconsolidated soils, both above and below the water table. In the past eight years, ERH has been used to successfully treat 10 or more contaminated sedimentary bedrock sites. Sedimentary bedrock treatment has recently expanded to greater depths and into karst limestone environments. This article describes the implementation issues for rock remediation and provides case studies of three sites remediated by ERH in Pennsylvania and Alabama. With proper design, the remediation of sedimentary bedrock can be completed as effectively as the remediation of overburden materials. © 2014 Wiley Periodicals, Inc.     

Electrical resistance heating of volatile organic compounds in Sedimentary rock

Electrical resistance heating (ERH) has become a common method of remediation for volatile organic compounds (VOCs) in unconsolidated soils, both above and below the water table. Recently, use of ERH has expanded to include treatment of contaminated sedimentary bedrock. This article describes the implementation issues for rock remediation and provides case studies of three sites remediated by ERH in Maryland, New Jersey, and Indiana. With proper design, remediation of bedrock can be as effectively completed as remediation of overburden materials. © 2010 Wiley Periodicals, Inc.     

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

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

In Situ Remediation of 1,4‐Dioxane Using Electrical Resistance Heating

Recent regulatory changes need more challenging treatment goals for 1,4‐dioxane. However, significant treatment limitations exist in part due to the high solubility and low Henry's law constant of 1,4‐dioxane. Two case studies are reported with substantial 1,4‐dioxane concentration reductions through in situ thermal remediation via electrical resistance heating (ERH). Concentration reductions greater than 99.8 percent of 1,4‐dioxane have been observed in the field using ERH. Concentrations of 1,4‐dioxane in air and steam extracted by an ERH vapor recovery system have also been evaluated. Laboratory studies were conducted to further understand the mechanisms that enable ERH remediation of 1,4‐dioxane. Vapor liquid equilibrium studies in water and soil were conducted and utilized to develop an ERH treatment cost model for 1,4‐dioxane. Existing field data were correlated to the 1,4‐dioxane treatment cost model. Field observations and laboratory testing indicate steam stripping that occurs through ERH remediation is an effective treatment method for 1,4‐dioxane. ©2015 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.     

Improving public health and environmental protection resulting from Superfund site investigation/remediation

A discussion of some of the deficiencies of Superfund and hazardous chemical site investigation and remediation is presented. Of concern is the adequacy of defining the constituents of concern; stormwater‐runoff monitoring; evaluating excessive bioaccumulation of hazardous chemicals in edible organisms; the extent and degree of groundwater pollution; modeling of pollutant transport in the vadose zone; translocation of subsurface pollutants to surface via plant roots, leaves, and flowers; protection of groundwater quality for nonpriority pollutants that impact aesthetic quality; and deficiencies in the quality of site data reports. Examples of these types of problems are discussed with suggestions on the approach that should be followed to improve the quality of site investigation and remediation. © 2004 Wiley Periodicals, Inc.     

Iron‐mediated abiotic degradation of RDX in a contaminated aquifer

The influence of aqueous‐ and mineral‐phase iron on royal demolition explosive (RDX) destruction has been previously investigated in theoretical settings and bench‐scale tests by various practitioners. The feasible use of in situ redox manipulation to create reactive Fe(II) is contingent upon the aquifer containing enough iron oxides and iron‐bearing clay minerals for the treated zone to remain effective. The following is a summary of a bench‐scale assessment of this relationship using aquifer material from an ongoing groundwater remediation effort at the Iowa Army Ammunition Plant (IAAP). A bench‐scale study was designed to determine the relative contributions of the biotic and iron‐mediated abiotic degradation processes to the net decrease in RDX observed at the site using saturated aquifer samples collected from within the RDX plume. Sterilized samples with a sufficient stoichiometric excess of both soluble and mineral‐phase iron reduced concentrations of RDX in both the soil and water fractions to the same extent as the samples containing native biota. These results indicate that in situ, abiotic degradation of RDX is feasible in areas unsuitable to biotic degradation processes, yielding an additional alternative for in situ RDX remediation. © 2012 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.     

Passive soil vapor extraction: A cost effectiveness study

An analysis of the cost effectiveness of passive soil vapor extraction (PSVE) is presented. PSVE, or “barometric pumping,” is an approach to the remediation of volatile organic compounds (VOCs) that seeks to harness and enhance the naturally occurring processes of wind and atmospheric pressure changes to facilitate the release of gas-phase contaminants from the subsurface. The technology background and current status are discussed, niches for the potential applicability of PSVE are identified, and a cost comparison with the conventional treatment method of active soil vapor extraction (ASVE) is examined.     

Management Systems Approach to Building Vapor Intrusion: A Facility Manager's Guide

Vapor intrusion (VI) has the potential to affect over 100,000 developed and undeveloped sites in the United States. Vapor intrusion occurs when the migration of volatile chemicals from the subsurface enters overlying buildings. A myriad of adverse health effects have been documented based on the inhalation of volatile chemicals from VI. At a time when most state and federal agencies have yet to set firm standards, the burden of responsibility is often placed on the facility manager to decide how to protect building occupants from volatile organic compounds potentially seeping into buildings. This article outlines a detailed step‐by‐step process for facility managers on how to begin a VI assessment and, when warranted, establish a site‐specific vapor intrusion management system for building occupant protection. This document should be used concurrently with current federal and state guidelines as it pertains to VI. © 2014 Wiley Periodicals, Inc.     

Utilization of nanoscale zero‐valent iron for source remediation—A case study

A pilot‐scale study was performed using a palladium‐catalyzed and polymer‐coated nanoscale zero‐valent iron (ZVI) particle suspension at the Naval Air Station in Jacksonville, Florida. A total of 300 pounds of nanoscale ZVI particle suspension was injected via a gravity feed and recirculated through a source area containing chlorinated volatile organic compounds (VOCs). The recirculation created favorable mixing and distribution of the iron suspension and enhanced the mass transfer of sorbed and nonaqueous constituents into the aqueous phase, where the contaminants could be reduced. Between 65 and 99 percent aqueous‐phase VOC concentration reduction occurred, due to abiotic degradation, within five weeks of the injection. The rapid abiotic degradation processes then yielded to slower biological degradation as subsequent decreases in ‐elimination parameters were observed—yet favorable redox conditions were maintained as a result of the ZVI treatment. Post‐treatment analyses revealed cumulative reduction of soil contaminant concentrations between 8 and 92 percent. Aqueous‐phase VOC concentrations in wells side gradient and downgradient of the source were reduced up to 99 percent and were near or below applicable regulatory criteria. These reductions, coupled with the generation of innocuous by‐products, indicate that nanoscale ZVI effectively degraded contamination and reduced the mass flux from the source, a critical metric identified for source treatment. A summary of this project was recently presented at the US EPA Workshop on Nanotechnology for Site Remediation in Washington, D.C., on October 21–22, 2005. This case study supplied evidence that nanoscale zero valent iron, an emerging remediation technology, has been implemented successfully in the field. More information about this workshop and this presentation can be found at www.frtr.gov/nano/index.htm. © 2006 Wiley Periodicals, Inc.     

The use of enhanced bioremediation at the Savannah River Site to remediate pesticides and PCBs

Enhanced bioremediation is quickly developing into an economical and viable technology for the remediation of contaminated soils. Until recently, chlorinated organic compounds have proven difficult to bioremediate. Environmentally recalcitrant compounds, such as polychlorinated biphenyls (PCBs) and persistent organic pesticides (POPs) such as dichlorodiphenyl trichloroethane (DDT) have shown to be especially arduous to bioremediate. Recent advances in field‐scale bioremedial applications have indicated that biodegradation of these compounds may be possible. Engineers and scientists at the Savannah River Site (SRS), a major DOE installation near Aiken, South Carolina, are using enhanced bioremediation to remediate soils contaminated with pesticides (DDT and its metabolites, heptachlor epoxide, dieldrin, and endrin) and PCBs. This article reviews the ongoing remediation occurring at the Chemicals, Metals, and Pesticides (CMP) Pits using windrow turners to facilitate microbial degradation of certain pesticides and PCBs. © 2003 Wiley Periodicals, Inc.     

Geochemical evaluation of metals in groundwater at long‐term monitoring sites and active remediation sites

At many sites, long‐term monitoring (LTM) programs include metals as chemicals of concern, although they may not be site‐related contaminants and their detected concentrations may be natural. At other sites, active remediation of organic contaminants in groundwater results in changes to local geochemical conditions that affect metal concentrations. Metals should be carefully considered at both types of sites, even if they are not primary contaminants of concern. Geochemical evaluation can be performed at LTM sites to determine if the monitored metals reflect naturally high background and, hence, can be removed from the analytical program. Geochemical evaluation can also be performed pre‐ and post‐treatment at active remediation sites to document the effects of organics remediation on metals and identify the processes controlling metal concentrations. Examples from both types of sites are presented in this article. © 2008 Wiley Periodicals, Inc.     

Assessment of in situ thermal treatment for chlorinated organic source zones

The East Gate Disposal Yard (EGDY) at Fort Lewis is the source of a large trichloroethene (TCE) plume at this military installation. Source reduction using thermal treatment was applied using electrical resistance heating. A total of about 5,800 kg of TCE‐equivalent volatile organic compounds (VOCs; TCE and dichloroethene) was extracted during thermal treatment of the three zones selected for source reduction. Pretreatment groundwater TCE concentrations were measured up to 100 ppm. Posttreatment groundwater TCE concentrations within the treatment zones averaged less than 100 ppb. Posttreatment soil TCE concentrations decreased by over 96 percent compared to pretreatment soil concentrations. The overall contaminant flux from EGDY was reduced by an estimated 60 to 90 percent by the source reduction effort. The traditional and new techniques for site characterization and remediation performance monitoring applied at EGDY provide insight for installing, operating, monitoring, and assessing thermal treatment. © 2009 Wiley Periodicals, Inc.     

Let biodegradation promote in-situ soil venting

Although vapor extraction systems (VES) certainly help remediate volatile hydrocarbons (e.g., gasoline in unsaturated soils), recent studies have found that much of the related hydrocarbon removal is due to aerobic biodegradation, not simple volatilization. In many cases, more than 50 percent of the hydrocarbon removal by these systems is due to biodegradation. By emphasizing biodegradation and minimizing volatilization, the costs of system operation can be reduced, especially for off-gas treatment. Maximizing biodegradation also supports more efficient site remediation because not only are the volatile hydrocarbons cleaned up, but the less volatile contaminants are also cleaned up—by biodegradation. More complete site cleanups are possible through bioventing, especially when cleanup criteria are related to total petroleum hydrocarbons. This article explores the major environmental conditions that influence biodegradation, analyzes several bioventing case histories, and calculates biodegradation's remedial costs.     

Fungal Degradation of Poly(Butylene Adipate-Co-Terephthalate) in Soil and in Compost

The present work mainly dedicated to fungal degradation of poly(butylene adipate-co-terephthalate) [PBAT], to enclose the role of fungi in a real process of biodegradation, the degree of degradation, and to understand the kinetics of PBAT biodegradation. Respirometer tests were realized in soil at 30 °C, and in compost at 30 and 58 °C. Results have shown that temperature is one of the essential parameters governing the fungal degradation of PBAT. Moreover, the final rates of PBAT biodegradation in an inoculated compost with fungi and in a real compost were found comparable, which means that the selected fungi were efficient as much as a mixture of bacteria and fungi. The curves of PBAT biodegradation were modeled by Hill sigmoid. Fungal degradation was completed by investigating the physical and the chemical properties of the polymer during the process of degradation using several analytical methods such as matrix assisted laser desorption ionization-time of fly spectroscopy, size exclusion chromatography, and differential scanning calorimetry. These experiments led to a better understanding of the various stages of fungal degradation of PBAT: hydrolysis as well as mineralization. Furthermore, the analysis of metabolizing products was investigated also.     

Modeling remediation time using natural attenuation at a dry‐cleaner site

Contaminants from dry‐cleaning sites, primarily tetrachloroethene (PCE), trichloroethene (TCE), cis‐dichloroethene (cis‐DCE), and vinyl chloride (VC), have become a major concern because of the limited funds and regulatory programs to address them. Thus, natural attenuation and its effectiveness for these sites needs to be evaluated as it might provide a less costly alternative to other remediation methods. In this research, data from a site in Texas were analyzed and modeled using the Biochlor analytical model to evaluate remediation times using natural attenuation. It was determined that while biodegradation and source decay were occurring at the site, the resulting attenuation rates were not adequate to achieve cleanup in a reasonable time frame without additional source remediation or control strategies. Cleanup times exceeded 100 years for all constituents at the site boundary and 800 years at the source for PCE, assuming cleanup levels of 0.005 mg/L for PCE and TCE and 0.07 mg/L and 0.002 mg/L for cis‐DCE and VC, respectively. © 2005 Wiley Periodicals, Inc.     

In situ remediation of MTBE utilizing ozone

There has been a great deal of focus on methyl tertiary butyl ether (MTBE) over the past few years by local, state, and federal government, industry, public stakeholders, the environmental services market, and educational institutions. This focus is, in large part, the result of the widespread detection of MTBE in groundwater and surface waters across the United States. The presence of MTBE in groundwater has been attributed primarily to the release from underground storage tank (UST) systems at gasoline service stations. MTBE's physical and chemical properties are different than other constituents of gasoline that have traditionally been cause for concern [benzene, toluene, ethylbenzene, and xylenes (BTEX)]. This difference in properties is why MTBE migrates differently in the subsurface environment and exhibits different constraints relative to mitigation and remediation of MTBE once it has been released to subsurface soils and groundwater. Resource Control Corporation (RCC) has accomplished the remediation of MTBE from subsurface soil and groundwater at multiple sites using ozone. RCC has successfully applied ozone at several sites with different lithologies, geochemistry, and concentrations of constituents of concern. This article presents results from several projects utilizing in situ chemical oxidation with ozone. On these projects MTBE concentrations in groundwater were reduced to remedial objectives usually sooner than anticipated. © 2002 Wiley Periodicals, Inc.     

Perfluoroalkyl and polyfluoroalkyl substances thermal desorption evaluation

Per‐ and polyfluoroalkyl substances (PFAS) are highly resistant to biotic and abiotic degradation and can withstand very high temperatures before breaking down. The storage of PFAS‐impacted water and sediments in a holding pond or stockpiled investigation or remedial action‐derived waste is occurring on an increasing number of sites. The most common PFAS water treatment options include granular‐activated carbon and resins and the most common soil treatment options have been primarily limited to excavation, offsite incineration, and, in some cases, soil stabilization. An increasing number of states across the United States are establishing part per trillion PFAS guidance levels for drinking water. Removing PFAS from soils removes PFAS source impacts to groundwater. In this study, volatilization of PFAS from soil treated using in situ thermal heating is evaluated as a treatment method to achieve a high degree of PFAS removal from soils. The evaluation of temperatures needed to achieve removal is described. To minimize vapor treatment required for PFAS thermal remediation, a scrubber was incorporated into the treatment train to transfer PFAS to the liquid phase in a concentrated, low‐volume solution. Vapor‐liquid equilibrium behavior and the extent of PFAS volatilization from impacted soil over a range of temperatures were evaluated. Results showed that heating soil to 350°C and 400°C reduces PFAS soil concentrations by 99.91% and 99.998%, respectively. It was also confirmed that sulfonate‐based PFAS generally required higher temperatures for volatilization to occur than carboxylate‐based PFAS.