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.     

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.     

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.     

Remediating TCE‐contaminated groundwater in low‐permeability media using hydraulic fracturing to emplace zero‐valent iron/organic carbon amendment

A field pilot test in which hydraulic fracturing was used to emplace granular remediation amendment (a mixture of zero‐valent iron [ZVI] and organic carbon) into fine‐grained sandstone to remediate dissolved trichloroethene (TCE)‐contaminated groundwater was performed at a former intercontinental ballistic missile site in Colorado. Hydraulic fracturing was used to enhance the permeability of the aquifer with concurrent emplacement of amendment that facilitates TCE degradation. Geophysical monitoring and inverse modeling show that the network of amendment‐filled fractures extends throughout the aquifer volume targeted in the pilot test zone. Two years of subsequent groundwater monitoring demonstrate that amendment addition resulted in development of geochemical conditions favorable to both abiotic and biological TCE degradation, that TCE concentrations were substantially reduced (i.e., greater than 90 percent reduction in TCE mass), and that the primary degradation processes are likely abiotic. The pilot‐test data aided in re‐evaluating the conceptual site model and in designing the full‐scale remedy to address a larger portion of the TCE‐contaminated groundwater plume. © 2012 Wiley Periodicals, Inc.     

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

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

Reductive dehalogenation: A subsurface bioremediation process

Introduction and large-scale production of synthetic halogenated organic chemicals over the last fifty years has resulted in a group of contaminants that tend to persist in the environment and resist both biotic and abiotic degradation. The low solubility of these types of contaminants, along with their toxicity and tendency to accumulate in food chains, make them particularly relevant targets for remediation activities. Among the mechanisms that result in dehalogenation of some classes of organic contaminants are stimulation of metabolic sequences through introduction of electron donor and acceptor combinations; addition of nutrients to meet the needs of dehalogenating microorganisms; possible use of engineered microorganisms; and use of enzyme systems capable of catalyzing reductive dehalogenation. The current state of research and development in the area of reductive dehalogenation is discussed along with possible technological application of relevant processes and mechanisms to remediation of soil and groundwater contaminated with chlorinated organics. In addition, an overview of research needs is suggested, which might be of interest for development of in-situ systems to reduce the mass of halogenated organic contaminants in soil and groundwater.     

Abiotic/biotic degradation and mineralization of N‐nitrosodimethylamine in aquifer sediments

The N‐nitrosodimethylamine (NDMA) degradation rate and mineralization rate were measured in two aquifer sediments that received treatments to create oxic, reducing, and sequential reducing/oxic environments. Chemically reduced sediments rapidly abiotically degraded NDMA to nontoxic dimethylamine to parts per trillion levels, then degraded to further products. NDMA was partially mineralized in reduced sediments (6 to 28 percent) at a slow rate (half‐life 3,460 h) by an unknown abiotic/biotic pathway. In contrast, NDMA was mineralized more rapidly (half‐life 342 h) and to a greater extent (30 to 81 percent) in oxic sediments with propane addition, likely by a propane monooxygenase pathway. NDMA mineralization in sequential reduced sediment followed by oxic sediment treatment did result in slightly more rapid mineralization and a greater mineralization extent relative to reduced systems. These increases were minor, so aerobic NDMA mineralization with oxygen and propane addition was the most viable in situ NDMA mineralization strategy. © 2008 Wiley Periodicals, Inc.     

Pilot scale testing composite swellable organosilica nanoscale zero‐valent iron—Iron‐Osorb®—for in situ remediation of trichloroethylene

Iron‐Osorb^® is a solid composite material of swellable organosilica with embedded nanoscale zero‐valent iron that was formulated to extract and dechlorinate solvents in groundwater. The unique feature of the highly porous organosilica is its strong affinity for chlorinated solvents, such as trichloroethylene (TCE), while being impervious to dissolved solids. The swellable matrix is able to release ethane after dechlorination and return to the initial state. Iron‐Osorb^® was determined to be highly effective in reducing TCE concentrations in bench‐scale experiments. The material was tested in a series of three pilot scale tests for in situ remediation of TCE in conjunction with the Ohio Environmental Protection Agency at a site in central Ohio. Results of these tests indicate that TCE levels were reduced for a period of time after injection, then leveled out or bounced back, presumably due to depletion of zero‐valent iron. Use of tracer materials and soil corings indicate that Iron‐Osorb^® traveled distances of at least 20 feet from the injection point during soil augmentation. The material appears to remain in place once the injection fluid is diluted into the surrounding groundwater. Overall, the technology is promising as a remediation method to treat dilute plumes or create diffuse permeable reactive barriers. Keys to future implementation include developing injection mechanisms that optimize soil distribution of the material and making the system long‐lasting to allow for continual treatment of contaminants emanating from the soil matrix. © 2011 Wiley Periodicals, Inc.     

Evaluation of white‐rot fungi for the remediation of creosote‐contaminated soil

Application of fungal‐based bioaugmentation was evaluated for the remediation of creosote‐contaminated soil at a wood‐preserving site in West Virginia. Soil at the site contained creosote‐range polycyclic aromatic hydrocarbons (PAHs) at concentrations in some areas that exceed industrial risk‐based levels. Two white‐rot fungi (Pleurotus ostreatus and Irpex lacteus) were evaluated for remediation effectiveness in a two‐month bench‐scale treatability test. Both fungi produced similar results, with up to 67.3 percent degradation of total PAHs in 56 days. Pilot‐scale testing was performed at the site using Pleurotus ostreatus grown on two local substrate mixtures. During the 276‐day field trial, total PAHs were degraded by up to 93.2 percent, with all individual PAHs except one achieving industrial risk‐based concentrations. It was recommended that fungal‐based remediation be applied to all contaminated soil at the site. © 2002 Wiley Periodicals, Inc.     

New advancements for in situ treatment using electrical resistance heating

Electrical resistance heating (ERH) is proving to be an effective technology to rapidly heat the subsurface and, in doing so, removing volatile organic compounds. Practitioners of this technology have observed that other processes (biodegradation, abiotic degradation, hydrolysis, and possibly others) occur to break down the chemicals of concern, and remediation is not solely accomplished through vaporization. Few sites treated using ERH have been monitored during and after treatment to identify and evaluate the processes occurring and assess the contribution of these other biological and chemical processes in the remediation effort so that they may be incorporated in the remediation design. At Fort Lewis, Washington, a landfill has been undergoing ERH treatment in three phases, where chlorinated volatile organic compounds represent the primary chemicals of concern in soil and groundwater. Other chemicals of concern include petroleum products, oils, and lubricants. The Fort Lewis remediation projects provided an opportunity to observe the reactions occurring in the subsurface during ERH and fine‐tune the study with each phase of operation. This study is still under way. However, the data gathered to date, which focuses on biodegradation, provides insights into the processes that have been observed. For the Fort Lewis site, biotic and abiotic degradation processes have been observed throughout the range of operating temperatures. At the lower temperature ranges (up to 70°C), biological processes appear to predominate. Above 70°C, abiotic processes become much more active. The goal of this work is to eventually optimize the use of these intrinsic processes in ERH remediation to reduce energy requirements and costs. © 2007 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.     

An evaluation of permeable reactive barrier projects in California

Permeable reactive barriers made of zero‐valent iron (ZVI PRBs) have become a prominent remediation technology in addressing groundwater contamination by chlorinated solvents. Many ZVI PRBs have been installed across the United States, some as research projects, some at the pilot scale, and many at full scale. As a passive and in situ remediation technology, ZVI PRBs have many attractive features and advantages over other approaches to groundwater remediation. Ten ZVI PRBs installed in California were evaluated for their performance. Of those ten, three are discussed in greater detail to illustrate the complexities that arise when quantifying the performance of ZVI PRBs, and to provide comment on the national debate concerning the downgradient effects of source‐zone removal or treatment on plumes of contaminated groundwater. © 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.     

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

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

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

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

Evaluation of algal phytoremediation of light extractable petroleum hydrocarbons in subarctic climates

The presence of an organic mat in a hydrocarbon‐impacted creek in Whitehorse, Yukon Territory, Canada was examined for contributions to in situ remediation of petroleum‐contaminated water. This article investigates the role of algae, found in the organic mat, in the remediation of light extractable petroleum hydrocarbons (LEPHs) at the site and in the laboratory. During the study, LEPH concentrations were reduced by 16.8 percent in the presence of algae alone (algal solution) and 30.4 percent in the combined organic mat solution containing microbial consortia. The study results indicate that algal species at the site did not directly phytoremediate hydrocarbons. Rather, they were part of the total biological degradation taking place. © 2009 Wiley Periodicals, Inc.     

Treatment of an explosives plume in groundwater using an organic mulch biowall

A field demonstration of a mulch permeable reactive barrier (PRB), or “biowall,” as an in situ treatment technology for explosives in groundwater is summarized. Organic mulch consists of insoluble carbon biopolymers that are enzymatically hydrolyzed during decomposition to release aqueous total organic carbon (TOC). The released TOC is then available for microorganisms to use as an electron donor to transform electrophilic contaminants via reductive pathways. A 100‐foot‐long and 2‐foot‐thick mulch biowall was installed at the Pueblo Chemical Army Depot in Colorado to treat a shallow groundwater plume containing hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX). To discourage groundwater flow bypassing around and under the biowall in this highly permeable formation, a hydraulic control was installed and the PRB was keyed into the bedrock. Technology performance was monitored using a monitoring well network to establish the development and extent of the downgradient treatment zone. Performance objectives of the field demonstration were: (1) greater than 90 percent removal of RDX across the PRB and the treatment zone; (2) an RDX concentration of less than 0.55 μg/L in the treatment zone; and (3) cumulative toxic intermediate concentration (nitroso intermediates of RDX, MNX, DNX, and TNX) of less than 20 percent of the upgradient RDX concentration. All performance objectives were met within seven months after installation once the system reached a pseudo‐steady state. By this point, a sustained reducing/treatment zone had been created downgradient of the mulch PRB that showed greater than 93 percent RDX removal, RDX concentrations less than 0.55 μg/L, and no accumulation of toxic intermediates. The mulch biowall implemented during this demonstration was successful at meeting performance objectives while addressing the majority of potential concerns of the technology. © 2009 Wiley Periodicals, Inc.     

Remedial options for chlorinated volatile organics in a partially anaerobic aquifer

A laboratory study was conducted for the selection of appropriate remedial technologies for a partially anaerobic aquifer contaminated with chlorinated volatile organics (VOCs). Evaluation of in situ bioremediation demonstrated that the addition of electron donors to anaerobic microcosms enhanced biological reductive dechlorination of tetrachloroethene (PCE), trichloroethene (TCE), and 1,1,1‐trichloroethane (1,1,1‐TCA) with half‐lives of 20, 22, and 41 days, respectively. Nearly complete reductions of PCE, TCE, 1,1,1‐TCA, and the derivative cis‐dichloroethene were accompanied by a corresponding increase in chloride concentrations. Accumulation of vinyl chloride, ethene, and ethane was not observed; however, elevated levels of ¹⁴CO₂ (from ¹⁴C‐TCE spiked) were recovered, indicating the occurrence of anaerobic oxidation. In contrast, very little degradation of 1,2‐dichloropropane (1,2‐DCP) and 1,1‐dichlorethane (1,1‐DCA) was observed in the anaerobic microcosms, but nutrient addition enhanced their degradation in the aerobic biotic microcosms. The aerobic degradation half‐lives for 1,2‐DCP and 1,1‐DCA were 63 and 56 days, respectively. Evaluation of in situ chemical oxidation (ISCO) demonstrated that chelate‐modified Fenton's reagent was effective in degrading aqueous‐phase PCE, TCE, 1,1,1‐TCA, 1,2‐DCP, etc.; however, this approach had minimal effects on solid‐phase contaminants. The observed oxidant demand was 16 g‐H₂O₂/L‐groundwater. The oxidation reaction rates were not highly sensitive to the molar ratio of H₂O₂:Fe²⁺:citrate. A ratio of 60:1:1 resulted in slightly faster removal of chemicals of concern (COCs) than those of 12:1:1 and 300:1:1. This treatment resulted in increases in dissolved metals (Ca, Cr, Mg, K, and Mn) and a minor increase of vinyl chloride. Treatment with zero‐valent iron (ZVI) resulted in complete dechlorination of PCE, and TCE to ethene and ethane. ZVI treatment reduced 1,1,1‐TCA only to 1,1‐DCA and chloroethane (CA) but had little effect on reducing the levels of 1,2‐DCP, 1,1‐DCA, and CA. The longevity test showed that one gram of 325‐mesh iron powder was exhausted in reaction with > 22 mL of groundwater. The short life of ZVI may be a barrier to implementation. The ZVI surface reaction rates (k_sa) were 1.2 × 10^?2 Lm^?2h^?1, 2 × 10^?3 Lm^?2h^?1, and 1.2 × 10^?3 Lm^?2h^?1 for 1,1,1‐TCA, TCE, and PCE, respectively. Based upon the results of this study, in situ bioremediation appeared to be more suitable than ISCO and ZVI for effectively treating the groundwater contamination at the site. © 2004 Wiley Periodicals, Inc.     

Injecting remediation compounds—How you inject is equally as important as what you inject

The injection of remediation compounds has rapidly become a widely accepted approach for addressing contaminated sites. One of the most fundamental questions surrounding the use of in situ remediation has been “What compound are you injecting at your site?” With the advances in the industry's understanding and acceptance of the in situ remediation process remediation professionals are now asking a follow‐up question that has become equally important to the success of a project: “How are you injecting a compound at your site?” This article discusses advances in field applications for in situ remediation and injecting remediation compounds. © 2003 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.