Radiolytic decomposition of environmental contaminants and site remediation using an electron accelerator

Halogenated and nonhalogenated hydrocarbon contaminants are currently found in natural waterways, groundwater, and soils as a result of spills and careless disposal practices. The development of proper treatment methodologies for the waste streams producing this environmental damage is now a subject of growing concern. A significant number of these waste stream compounds are chemically stable and are thus resistant to environmental degradation. Numerous researchers have investigated the use of ionizing radiation to decompose chlorinated hydrocarbons in diverse matrices and have proposed various free-radical-induced reaction mechanisms. This article is divided into two sections. First, we present data on experimentally measured, radiolytically induced decomposition of hazardous wastes and toxic substances using accelerator-generated bremsstrahlung sources and gamma radiation from cobalt-60. Data are presented on the radiolytically induced reduction in concentration of volatile organic compounds (VOCs) dissolved in water and in air, polychlorinated biphenyls (PCBs) dissolved in oil, high explosives dissolved in groundwater, and chemical weapon surrogates. The results of these studies suggest the potential use of ionizing radiation as a method of hazardous waste treatment. The second section of this article describes the technical aspects of a field-scale radiolytic decomposition site cleanup demonstration using an electron accelerator. A portable, commercially available electron accelerator was set up at the Lawrence Livermore National Laboratory's (LLNL's) Site 300, a Superfund site, where vacuum extraction wells were removing trichloroethylene (TCE) vapor from a ground spill into the unsaturated soil zone. The accelerator was retrofitted into the existing vacuum extraction system such that the extracted TCE-containing vapor passed through the accelerator beam for treatment. The concentration of TCE in the vapor was reduced by an amount dependent on the accelerator beam power. Production of reaction products in the vapor was measured as a function of absorbed dose.     

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.     

Aerobic Cometabolism of Halogenated Aliphatic Hydrocarbons: A Technology Overview

Bioremediation of chlorinated solvents has been moving from an innovative to mainstream technology for environmental applications. Cometablism of chlorinated solvents by monooxygenase has been demonstrated for trichloroethylene (TCE). Cl‐out microbes combine the dehalogenation of PCE with the monooxygenase destruction of TCE to complete the PCE breakdown pathway. Underthe right conditions, cometabolic bioremediation can be cost effective, fast, and complete. Aerobic bioremediation can augment mass transfer technologies such as pump and treat or sparging/vapor extraction to improve their efficiency.     

Potential and Limitations of Microbial Reductive Dechlorination for Bioremediation Applications

Current knowledge and recent advances in the area of microbial reductive dechlorination of polychlorinated organic compounds are summarized. Factors which may limit the efficacy of the dechlorination process for the in situ bioremediation of contaminated soil and sediment systems are identified. Results of recent studies on the anaerobic biotransformation of soil-sorbed chlorinated ethenes and sediment-sorbed chlorinated benzenes are provided to illustrate how low contaminant bioavailability may control the rate and extent of dechlorination in subsurface systems, especially those with long-term contamination. Use of nonionic, polysorbate surfactants as the sole electron donors of a mixed, methanogenic culture supported the microbial sequential reductive dechlorination of either free or sediment-bound hexachlorobenzene (HCB) to primarily 1,3-dichlorobenzene, but did not enhance the bioavailability of sediment-bound HCB as compared to microcosms, which used glucose. Because current knowledge on the interactions of dechlorinating populations with other microbial populations in the presence of alternative terminal electron acceptors (e.g., nitrate, Fe³⁺ , Mn⁴⁺) is limited, such interactions and their effect on the dechlorination process in subsurface systems need to be further explored to improve our understanding of the reductive dechlorination process in complex environmental systems and lead to the development of more efficient in situ bioremediation technologies and strategies.     

SITE Demonstration of Enhanced In-Situ Bioremediation of Chlorinated and Nonchlorinated Organic Compounds in Fractured Bedrock

A field demonstration of an enhanced in-situ bioremediation technology was conducted between March 1998 and August 1999 at the ITT Industries Night Vision (ITTNV) Division plant in Roanoke, Virginia. The bioremediation process was evaluated for its effectiveness in treating both chlorinated and nonchlorinated volatile organic compounds (VOCs) in groundwater located in fractured bedrock. Chlorinated compounds, such as trichloroethene (TCE), in fractured bedrock pose a challenging remediation problem. Not only are chlorinated compounds resistant to normal biological degradation, but the fractured bedrock presents difficulties to traditional techniques used for recovery of contaminants and for delivery of amendments or reagents for in-situ remediation. The demonstration was conducted under the U.S. Environmental Protection Agency's Superfund Innovative Technology Evaluation (SITE) program. The SITE program was established to promote the development, demonstration, and use of innovative treatment technologies for the cleanup of Superfund and other hazardous waste sites. This article presents selected results of the demonstration and focuses on understanding the data in light of the fractured bedrock formation. © 2002 Wiley Periodicals, Inc.     

Enhanced anaerobic bioremediation in a multicontaminant plume

The potential application of enhanced in situ bioremediation (EISB) for treatment of a plume containing high concentrations of 1,2‐dichloroethane (1,2‐DCA), as well as lower concentrations of other chlorinated ethanes, chlorinated methanes, and chlorinated ethenes was evaluated through the implementation of four field trials. The field trials confirmed that EISB is an effective technology for treating multiple contaminants, with estimated mass removal rates on the order of several kilograms per day and groundwater concentration reductions nearing 100 percent of the initial concentrations. The field trials also demonstrated that engineering controls could be effectively used to overcome potential inhibitions related to high concentrations of 1,2‐DCA. © 2008 Wiley Periodicals, Inc.     

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

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

Practical Perspectives of 1,4‐Dioxane Investigation and Remediation

1,4‐Dioxane (dioxane) is a contaminant of emerging concern that is classified by the U.S. Environmental Protection Agency as a likely human carcinogen. Dioxane has been used as a minor or major ingredient in many applications, and is also generated as an unwanted by‐product of industrial processes associated with the manufacturing of polyethylene, nonionic surfactants, and many consumer products (cosmetics, laundry detergents, shampoos, etc.). Dioxane is also a known stabilizer of chlorinated solvents, particularly 1,1,1‐trichloroethane, and has been commonly found comingled with chlorinated solvent plumes. Dioxane plumes at chlorinated solvent sites can complicate site closure strategies, which to date have not typically focused on dioxane. Aggressive treatment technologies have greatly advanced and are clearly capable of achieving lower parts per billion cleanup criteria using ex situ advanced oxidation processes and sorption media. In situ chemical oxidation has also been demonstrated to effectively remediate dioxane and chlorinated solvents. Other in situ remedies, such as enhanced bioremediation, phytoremediation, and monitored natural attenuation, have been studied; however, their ability to achieve cleanup levels is still somewhat questionable and is limited by co‐occurring contaminants. This article summarizes and provides practical perspectives on dioxane analysis, plume stability relative to other contaminants, and the development of investigation tools and treatment technologies.     

Bioremediation treatability studies of contaminated soils at wood preserving sites

Bioremediation has been used frequently at sites contaminated with organic hazardous chemicals where releases from processing vessels and the mismanagement of reagents and generated waste have contributed to significant impairment of the environment. At wood treater sites, process reagents such as pentachlorophenol (PCP), and creosote have adversely impacted the surrounding soil and groundwater. When PCP has been used at these sites, polychlorinated dibenzo‐p‐dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are typically found. Where creosote has been used as the wood preservative of choice, polynuclear aromatic hydrocarbons (PAHs) are commonly found. Many of these compounds are considered to be persistent, bioaccumulative, and toxic (PBT) and are particularly recalcitrant.     

Remediation of PCB-contaminated sediments: Volatility and solubility considerations

Through volatilization and long distance atmospheric transport, polychlorinated biphenyls (PCBs) have been redistributed throughout the global environment. Over the last 70 years, these compounds have permeated every known environmental niche including the remote polar regions of the globe. In this article, the solubility and volatility of the PCB congeners are reviewed relative to the remedial technologies that are currently in use or under consideration. The following discussion focuses primarily on the management options for PCB-contaminated, subaqueous solids that require removal, dewatering, drying, and other treatment to degrade the target contaminants and/or containment in engineered facilities including constructed islands, upland secure landfills and subaqueous pits. Environmental mobility resulting from natural and engineered processes is discussed in relation to the potential for contributing to the global loading and redistribution of PCBs. Additionally, select emerging technologies and management options are reviewed relative to their potential to produce secondary environmental impacts resulting from the soluble and/or volatile redistribution of PCBs. Based on a lack of long-term experience and the recognition that contaminants will remain unaltered for decades, technologies involving engineered containment structures should be considered temporary remedial measures until cost-competitive, destructive processing of contaminated sediments is feasible.     

Use of a low‐cost substrate in a continuous recirculation process to stimulate plumewide anaerobic dechlorination of chlorinated solvents

Over the past 20 years, significant time and money have been spent on better understanding and successfully applying bioremediation in the field. The results of these efforts provide a deeper un‐derstanding of aerobic and anaerobic microbial processes, the microbial species and environ‐mental conditions that are desirable for specific degradation pathways, and the limitations that may prevent full‐scale bioremediation from being successfully applied in heterogeneous subsur‐face environments. Numerous substrates have been identified as effective electron donors to stimulate anaerobic dechlorination of chlorinated ethenes, but methods of delivering these sub‐strates for in situ bioremediation (direct‐push injections, slug injections, high‐pressure injections, fracture wells, etc.) have yet to overcome the main limitation of achieving contact between these substrates and the contaminants. Therefore, although it is important (from a full‐scale remedia‐tion standpoint) to select an appropriate, low‐cost substrate that can be supplied in sufficient quantity to promote remediation of a large source area and its associated plume, it is equally im‐portant to ensure that the substrate can be delivered throughout the impacted plume zone. Failure to achieve substrate delivery and contact within the chlorinated solvent plume usually re‐sults in wasted money and limited remediation benefit. Bioremediation is a contact technology that cannot be effectively implemented on a large scale unless a method for rapidly delivering the low‐cost substrate across the entire source and plume areas is utilized. Unfortunately, many cur‐rent substrate delivery methods are not achieving sitewide distribution or treatment of the sorbed contaminant mass that exists in the organic fraction of a soil matrix. The following discussion sum‐marizes substrate delivery using an aggressive groundwater recirculation approach that can achieve plumewide contact between the contaminants and substrate, thus accelerating dechlori‐nation rates and shortening the overall remediation time frame. © 2006 Wiley Periodicals, Inc.     

Recovery and Microbial Remediation of Organic Wood Preservatives in Groundwater at a Former Wood Treating Plant

Well-recovery networks coupled to immobilized microbe bioreactors (IMBRs) were installed at a 172-acre former wood preserving facility for the bioremediation of organic wood preservatives present in site groundwater. Free-phase creosote from the hardpan and soluble preservative fractions contained in subsurface groundwater were pumped separately to different holding tanks. Trace creosote fractions contained in the subsurface groundwater were further gravity separated in the holding tank. Immobilized microbial isolates evaluated in earlier laboratory and field pilot tests were established into two 40, 000-liter bioreactors for the biodegradation of all targeted consitituents. Microbial growth, dissolved oxygen, pH, nutrients, flow rate, and temperature were monitored in this in situ/ex situ bioremediation system. The process was used to remove the polycyclic aromatic hydrocarbon (PAH) and phenolic components of creosote and pentachlorophenol from contaminated groundwater. Data generated during the past 2 1/2 years indicate that 26 target compounds consistently are reduced to levels acceptable for discharge. Currently operating in Baldwin, Florida, this full-scale prototype is remediating the former wood preserving facility and is being used as a model system for the design and construction of new bioreactor systems needed at similar industrial sites in the United States and abroad.     

Remediation of persistent organic pollutants (POPs) in two different soils

Persistent organic pollutants (POPs) are a set of chemicals that are toxic, persist in the environment for long periods of time, and biomagnify as they move up through the food chain. The most widely used method of POP destruction is incineration, which is expensive and could result in undesirable by‐products. An alternative bioremediation technology, which is cheaper and environ‐mentally friendly, was tested during this experiment. Two different soil types containing high and low organic matter (OM) were spiked with 100 mg/kg each of pyrene and Aroclor 1248 and planted with three different species of grasses. The objective of the study was to determine residue recovery levels (availability) and potential effectiveness of these plant species for the remediation of POPs. The results showed that recovery levels were highly dependent on the soil organic matter content—very low in all treatments with the high OM content soil compared to recoveries in the low OM soil. This indicates that availability, and, hence, biodegradability of the contaminants is dependent on the organic matter content of the soil. Moreover, the degree of availability was also significantly different for the two classes of chemicals. The polyaromatic hydrocarbon (PAH) recovery (availability) was extremely low in the high organic matter content soil compared to that of the polychlorinated biphenyls (PCBs). In both soil types, all of the plant species treatments showed significantly greater PCB biodegradation compared to the unplanted controls. Planting did not have any significant effect on the transformation of the PAHs in both soil types; however, planting with switchgrass was the best remedial option for both soil types contaminated with PCB. © 2005 Wiley Periodicals, Inc.     

A conceptual study on the bio-wall technology: Feasibility and process design

In-situ bioremediation is a process by which contaminants in subsurface environments are biologically eliminated or mineralized; however, it is often difficult to implement. Microbes sparsely distributed in deep soils are incapable of degrading a chemical rapidly; furthermore, fine-pore structures of soils tend to retard the penetration and propagation of these microbes and hinder oxygen transfer. The latter is particularly detrimental to the aerobic growth of microbes, which is often essential for bioremediation. Measures intended to promote bioremediation, such as the addition of surfactants for enhancing dissolution and the application of genetically engineered microbes for accelerating the biodegradation of contaminants, are almost impossible to adopt. This is attributable to the fact that various facets of the bioremediation process (e.g., the distribution of dissolved contaminants, nutrients, and oxygen, and the concentration of microbes) cannot be readily manipulated. This article proposes a novel technology, namely, bio-wall. This technology resorts to an in-situ constructed medium with porosity and organic content greater than those of the original soil for promoting the adsorption and retention of microbes and the biodegradation of contaminants. Moreover, oxygen and nutrients are supplied to the bio-wall to facilitate microbialgrowth. The results of conceptual design study and simulation have revealed that the technology is indeed feasible and, under certain environmental conditions, cost-effective. Particularly noteworthy is the fact that bio-wall can prevent contaminant migration through the enhancement of the biodegradation rate and reduction of the plume-distance, both by several orders of magnitude.     

Formation of persistent chlorinated aromatic compounds in simulated and real fly ash from iron ore sintering

Effects of carbon concentration and Cu additive in simulated fly ash (SFA) and real fly ash (RFA) on the formation of polychlorinated dibenzofurans (PCDFs), polychlorinated dibenzo-p-dioxins (PCDDs), chlorobenzenes, and polychlorinated biphenyls which were all regarded as persistent chlorinated aromatics in iron ore sintering were investigated. In the annealing process of SFA with various carbon contents, the yield of chlorinated aromatics and the I-TEQ obtained their maximum at 10 wt% carbon content. Active carbon in SFA acted as the carbon source as well as an adsorbent which led to higher production of PCDD/F in solid phase at 10 wt% carbon content. The increase of carbon content will be beneficial on the formation of 2,3,7,8-Chloro-substituted PCDF compared with 2,3,7,8-Chloro-substituted PCDD. In addition, the CuCl₂·2H₂O was a much more powerful catalyst in the formation of chlorinated aromatic compounds compared with elementary Cu, since it served as both a catalyst and a chlorine donor. However, the RFA behaved similarly with SFA with elementary Cu in the formation of chlorinated aromatic compounds. The effect of carbon content and copper additives on formation of 2,3,7,8-chloro-substituted congeners displayed similar characteristics with the tetra- to octa-PCDD/F isomers and even the total PCDD/Fs.     

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.     

Successful ISCR‐enhanced bioremediation of a TCE DNAPL source utilizing EHC® and KB‐1®

Remediation of chlorinated solvent DNAPL sites often meets with mixed results. This can be attributed to the diametrically opposed nature of the impacts, where the disparate dissolved‐phase plume is more manageable than the localized, high‐concentration source area. A wide range of technologies are available for downgradient plume management, but the relative mass of contaminants in a DNAPL source area generally requires treatment for such technologies to be effective over the long term. In many cases, the characteristics of DNAPL source zones (e.g., depth, soil heterogeneity, structural limitations) limit the available options. The following describes the successful full‐scale implementation of in situ chemical reduction (ISCR) enhanced bioremediation of a TCE DNAPL source zone. In this demonstration, concentrations of TCE were rapidly reduced to below the maximum contaminant level (MCL) in less than six months following implementation. The results described herein suggest that ISCR‐enhanced bioremediation is a viable remedial alternative for chlorinated solvent source zones. © 2010 Wiley Periodicals, Inc.