Applications of mulch biowalls—three case studies

Mulch biowalls are proving to be an effective means of generating reducing conditions for the in situ anaerobic reduction of contaminants in groundwater that are amenable to the reduction process. Mulch is an inexpensive and readily available substrate that provides a long‐lasting carbon and electron donor source for the stimulation of the anaerobic reduction process in groundwater. Examples of contaminants that are amenable to the biotic anaerobic reduction process include: chlorinated alkenes and alkanes, explosives, perchlorate, some metals, and petroleum hydrocarbons. The microbial degradation of cellulose fibers (mulch) is arguably the oldest reduction process known and is evident anywhere that plant material, soil, and water are present together. This article presents three case studies discussing three different uses of mulch biowalls to stimulate the anaerobic bioremediation of contaminants in shallow soils and groundwater. © 2009 Wiley Periodicals, Inc.     

Comparing PFAS to other groundwater contaminants: Implications for remediation

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

The effects of in situ chemical oxidation on microbiological processes: A review

The effects of in situ chemical oxidation (ISCO) on biological processes, as reported in the literature, were researched to determine if coupling ISCO with in situ bioremediation could be achieved in field and laboratory experiments. Literature was compiled concerning the effect of ISCO on microbial communities following addition of a chemical oxidant at a range of concentrations designed to treat a variety of subsurface contaminants. The results indicate that although microbial communities may potentially be adversely affected by chemical oxidation in the short term, a rebound of microbial biomass and/or bioremediation activity can be expected. Successfully coupling ISCO with bioremediation in field applications may be a cost‐effective method of achieving risk‐based site remediation goals. © 2006 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.     

In situ treatment of a dilute chlorinated solvent plume in an acidic aerobic aquifer

In situ bioremediation was selected in the Record of Decision (ROD) as the remedial technology for a 29‐acre dilute, acidic and aerobic, chlorinated solvent plume (principally trichloroethylene [TCE] and 1,1‐dichloroethylene) for a Superfund site located in central New Jersey. Implementation of the remedy at full‐scale began in late 2010, using reductive dechlorination and bioaugmentation, and treatment has continued steadily over the last 9 years. The amendments injected include electron donor and alkaline (bicarbonate) buffer solution and, once anaerobic aquifer conditions became established, a bioaugmentation culture. Amendment injections occurred in multilevel injection wells (IWs), to maintain control over the vertical interval of amendment delivery. The areal coverage of the plume has been reduced by 59% based on the 10 µg/L TCE isocontour and the contaminant mass has been reduced by 79% through the 9 years of treatment. Lessons learned from this project include the need for bioaugmentation in the acidic aquifer and an efficient and effective manner of well construction and amendment injection using multiscreen single casing IWs and packer systems. Additional lessons learned include differences in longevity of the electron donor amendment versus the bicarbonate neutralization additive, and the need for varied amendment delivery techniques (IWs, direct injection, horizontal well installation) in selected lower permeable zones to attain treatment.     

Enhanced anaerobic bioremediation of a TCE source at the Tarheel Army Missile Plant using EOS

EOS, or emulsified oil substrate, was used to stimulate anaerobic biodegradation of trichloroethene (TCE) and tetrachloroethene (PCE) at a former Army‐owned manufacturing facility located in the Piedmont area of North Carolina. Previous use of chlorinated solvents at the facility resulted in soil and groundwater impacts. Ten years of active remediation utilizing soil vacuum extraction and air sparging (SVE/AS) were largely ineffective in reducing the TCE/PCE plume. In 2002, the Army authorized preparation of an amended Remedial Action Plan (RAP) to evaluate in situ bioremediation methods to remediate TCE in groundwater. The RAP evaluated eight groundwater remediation technologies and recommended EOS as the preferred bioremediation alternative for the site. Eight wells were drilled within the 100 × 100 feet area believed to be the primary source area for the TCE plume. In a first injection phase, dilute EOS emulsion was injected into half of the wells. Distribution of the carbon substrate through the treatment zone was enhanced by pumping the four wells that were not injected and recirculating the extracted water through the injection wells. The process was repeated in a second phase that reversed the injection/extraction well pairs. Overall, 18,480 pounds of EOS were injected and 163,000 gallons of water were recirculated through the source area. Anaerobic groundwater conditions were observed shortly after injection with a corresponding decrease in both PCE and TCE concentrations. Dissolved oxygen, oxidation‐reduction potential, and sulfate concentrations also decreased after injection, while TCE‐degradation products, ferrous iron, and methane concentrations increased. The reduction in TCE allowed the Army to meet the groundwater remediation goals for the site. Approximately 18 months after injection, eight wells were innoculated with a commercially prepared dechlorinating culture (KB‐1) in an attempt to address lingering cis‐1,2‐dichloroethene (cis‐DCE) and vinyl chloride (VC) that continued to be observed in some wells. Dehalococcoides populations increased slightly post‐bioaugmentation. Both cis‐DCE and VC continue to slowly decrease. © 2007 Wiley Periodicals, Inc.     

Enhancing Reductive Dechlorination With Nutrient Addition

Enhanced reductive bioremediation (ERB) of halogenated organics has become widely accepted and implemented to reduce risks to human health and the environment posed by these compounds. The family of chlorinated ethenes (e.g., trichloroethene) is among the most common contaminants treated using ERB techniques. The number of microbial species able to fully dechlorinate ethenes is small, and many times their population numbers are low. As a result, many ERB practitioners have turned to the injection of designer bacteria within treatment zones as a means to accelerate the process. Otherwise, many remediation projects encounter “cis‐stall,'' or the accumulation of the cis‐1,2‐dichloroethene and vinyl chloride intermediates. This article discusses three unique case studies where the addition of a balanced macro‐ and micro‐nutrient source substantially accelerated the chlorinated ethene ERB process, independent of the electron‐donor substrate applied. © 2013 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.     

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.     

Full‐scale bioremediation of a dilute 50‐acre plume

Enhanced anaerobic dechlorination is being conducted to remediate a 50‐acre groundwater area impacted with chlorinated volatile organic compounds (CVOCs). The plume, which is over 3,000 feet (ft) long, initially contained tetrachloroethene and breakdown products at concentrations of 2 to 3 milligrams per liter. The site's high groundwater flow velocity (greater than 1,000 ft per year) was incorporated into the design to help with amendment distribution. Bioaugmentation was conducted using a mixed culture containing Dehalococcoides ethenogenes. There is evidence that it has migrated to distances exceeding 600 ft. The major benefit of the high groundwater flow velocity is greater areal coverage by the remediation system, but the downside is the difficulty in delivering sufficient donor to create the required anaerobic conditions. Overall performance has been excellent with total CVOC reductions and conversion to ethene of 98 percent within a 25‐acre area downgradient of the treatment transect that has operated the longest. © 2011 Wiley Periodicals, Inc.     

Microbially Mediated In Situ Desorption Accelerates Remediation of Large Gasoline Product Plume

Remediation of a large separate‐phase hydrocarbon product and associated dissolved‐phase gasoline plume was accelerated by coupling multiphase extraction with in situ microbial stimulation. At the beginning of remediation activities, the separate‐phase hydrocarbon plume extended an estimated seven acres with product thickness measuring up to 2.1 feet thick. Within 18 months after beginning extraction, reduction of gasoline constituents in groundwater became asymptotic and measureable product disappeared from the upgradient source area. At that time, the remediation team initiated a program of limited in situ anaerobic bioremediation with the goal of stimulating production of natural surfactants from native microbes to release petroleum from the soil matrix. Groundwater concentrations of gasoline constituents increased gradually over the next three years, improving recovery without biofouling the pump‐and‐treat infrastructure. Using this approach, the groundwater component of the remedy was completed in less than five years, substantially less than the 10 years to 15 years predicted by modeling. This strategy demonstrated a more sustainable approach to remediation, reducing electrical usage by an estimated 800 megawatt hours, reducing infrastructure requirements, and preserving an estimated 150 million gallons of groundwater for this arid agricultural area. © 2014 Wiley Periodicals, Inc.     

Field‐scale evaluation of a biobarrier for the treatment of a trichloroethene plume

In the 1960s, trichloroethene (TCE) was used at what is now designated as Installation Restoration Program Site 32 Cluster at Vandenberg Air Force Base to flush missile engines prior to launch and perhaps for other degreasing activities, resulting in releases of TCE to groundwater. The TCE plume extends approximately 1 kilometer from the previous launch facilities beyond the southwestern end of the site. To limit further migration of TCE and chlorinated degradation by‐products, an in situ, permeable, reactive bioremediation barrier (biobarrier) was designed as a cost‐effective treatment technology to address the TCE plume emanating from the source area. The biobarrier treatment would involve injecting carbon‐based substrate and microbes to achieve reductive dechlorination of volatile organic compounds, such as TCE. Under reducing conditions and in the presence of certain dechlorinating microorganisms, TCE degrades to nontoxic ethene in groundwater. To support the design of the full‐scale biobarrier, a pilot test was conducted to evaluate site conditions and collect pertinent design data. The pilot test results indicated possible substrate delivery difficulties and a smaller radius of influence than had been estimated, which would be used to determine the final biobarrier well spacing. Based on these results, the full‐scale biobarrier design was modified. In January 2010, the biobarrier was implemented at the toe of the source area by adding a fermentable substrate and a dechlorinating microbial culture to the subsurface via an injection well array that spanned the width of the TCE plume. After the injections, the groundwater pH in the injection wells continued to decrease to a level that could be detrimental to the population of Dehalococcoides in the SDC‐9^TM culture. In addition, 7 months postinjection, the injection wells could not be sampled due to fouling. Cleaning was required to restore their functions. Bioassay and polymerase chain reaction analyses were conducted, as well as titration tests, to assess the need for biobarrier amendments in response to the fouling issues and low pH. Additionally, slug tests were performed on three wells to evaluate possible localized differences in hydraulic conductivity within the biobarrier. Based on the test results, the biobarrier was amended with sodium carbonate and inoculated a second time with SDC‐9^TM. The aquifer pH was restored, and reductive dechlorination resumed in the treatment zone, evidenced by the reduction in TCE and the increase in degradation products, including ethene. © 2011 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.     

A method to compare groundwater cleanup technologies

DuPont has developed a method to compare, on a consistent economic basis, in situ remediation technologies. The methodology employs a template site with a perchloroethylene plume 1000 ft long by 400 ft wide, and incorporates various aquifer thicknesses and depths. Variables considered in the methodology include duration of the remediation; estimated engineering and flow/transport modeling costs; equipment costs; and operation, maintenance, and monitoring costs. In this article, substrate-enhanced anaerobic bioremediation, intrinsic bioremediation, in situ permeable reactive barriers, and pump-and-treat systems are evalutated. Cost metrics include present cost, cost per pound of contaminant removed, and cost per 1000 gals treated, using a discounted cash-flow analysis. Costs of the remedial alternatives increase starting from intrinsic bioremediation, to substrate-enhanced anaerobic bioremediation, to a biological substrate-enhanced anaerobic barrier, to in situ permeable reactive barriers, to pump-and-treat systems with air stripping and carbon adsorption.     

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.     

A universal design approach for in situ bioremediation developed from multiple project sites

This article describes a design approach that has been developed for bioremediation of chlorinated volatile organic compound–impacted groundwater that is based upon experience gained during the past 17 years. The projects described in the article generally involve large‐scale enhanced anaerobic dechlorination (EAD) and combined aerobic/anaerobic bioremediation techniques. Our design approach is based on three primary objectives: (1) selecting and distributing the proper additives (including bioaugmentation) within the targeted treatment zone; (2) maintaining a neutral pH (and adding alkalinity when needed); and (3) sustaining the desired conditions for a sufficient period of time for the bioremediation process to be fully completed. This design approach can be applied to both anaerobic and aerobic bioremediation systems. Site‐specific conditions of hydraulic permeability, groundwater velocity, contaminant type and concentrations, and regulatory constraints will dictate the best remedial approach and design parameters for in situ bioremediation at each site. The biggest challenges to implementing anaerobic bioremediation processes are generally the selection and delivery of a suitable electron donor and the proper distribution of the donor throughout the targeted treatment zone. For aerobic bioremediation processes, complete distribution of adequate concentrations of a suitable electron acceptor, typically oxygen or oxygen‐yielding compounds such as hydrogen peroxide, is critical. These design approaches were developed based on understanding the biological processes involved and the mechanics of groundwater flow. They have evolved based on actual applications and results from numerous sites. An EAD treatment system, based on our current design approach, typically uses alcohol as a substrate, employs groundwater recirculation to distribute additives, and has an operational period of two to four years. An aerobic in situ treatment system based on our current design approach typically uses pure oxygen or hydrogen peroxide as an electron acceptor, may involve enhancements to groundwater flow for better distribution, and generally has an operational period of one to four years. These design concepts and specific project examples are presented for 17 sites. © 2012 Wiley Periodicals, Inc.     

Closing the mass balance at chlorinated solvent sites: Sources and attenuation processes

Using detailed mass balance and simple analytical models, a spreadsheet‐based application (BioBalance) was developed to equip decision makers with a predictive tool that can provide a semiquantitative projection of source‐zone concentrations and provide insight into the long‐term behavior of the associated chlorinated solvent plume. The various models were linked in a toolkit in order to predict the composite impacts of alternative source‐zone remediation technologies and downgradient attenuation processes. Key outputs of BioBalance include estimates of maximum plume size, the time frame for plume stabilization, and an assessment of the sustainability of anaerobic natural attenuation processes. The toolkit also provides spatial and temporal projections of integrated contaminant flux and plume centerline concentrations. Results from model runs of the toolkit indicate that, for sites trying to meet traditional, “final” remedial objectives (e.g., two to three orders of magnitude reduction in concentration with restoration to potable limits), “dispersive” mechanisms (e.g., heterogeneous flow and matrix diffusion) can extend remedial time frames and limit the benefits of source remediation in reducing plume sizes. In these cases, the removal of source mass does not result in a corresponding reduction in the time frame for source remediation or plume stabilization. However, this should not discourage practitioners from implementing source‐depletion technologies, since results from the toolkit demonstrate a variety of measurable benefits of source remediation. Model runs suggest that alternative, “intermediate” performance metrics can improve and clarify source remediation objectives and better monitor and evaluate effectiveness. Suggested intermediate performance metrics include reduction in overall concentrations or mass within the plume, reduction of flux moving within a plume, and reduction in the potential for risk to a receptor or migration of a target concentration of contaminant beyond a site boundary. This article describes the development of two key modules of the toolkit as well as illustrates the value of using intermediate performance metrics to evaluate the performance of a source‐remediation technology. © 2010 Wiley Periodicals, Inc.     

Centrifugal Bioreactors and Their Application in Remediation

A new approach to the maintenance of large microbial populations for bioremediation purposes has been developed in which a centrifugal bioreactor is used to immobilize microbial populations at extremely high density. The cells are ordered into a three‐dimensional array through which wastewater or groundwater volumes may be flowed, unimpeded by frits or screens. The process methodology is independent of the type, shape, or viability of the individual cells immobilized and, thus, may be adapted to many different bioremediation needs. The utilization of this new process has been explored for three different types of remediation: the removal of heavy metals from wastewater, the aerobic degradation of methyl‐tert‐butyl ether (MTBE), and the anaerobic reduction of nitrate to nitrogen gas. This article discusses the use of centrifugal bioreactors and their application in remediation. © 2001 John Wiley & Sons, Inc.     

Historical analysis of monitored natural attenuation: A survey of 191 chlorinated solvent sites and 45 solvent plumes

A survey of experts in the application of natural attenuation was conducted to better understand how monitored natural attenuation (MNA) is being applied at chlorinated solvent sites. Thirty‐four remediation professionals provided general information for 191 sites where MNA was evaluated, and site‐specific data for 45 chlorinated solvent plumes being remediated by MNA. Respondents indicated that MNA was precluded as a remedy at only 23 percent of all sites where evaluated as a remedial option. Leading factors excluding MNA as a remedial approach were the presence of an expanding plume and an unreasonably long estimated remediation time frame. MNA is being used as the sole remedy at about 30 percent of the sites, and 33 percent are implementing MNA in conjunction with source zone remediation. The remaining sites are implementing MNA with plume remediation (13 percent), source containment (9 percent), or some other strategy (16 percent). © 2004 Wiley Periodicals, Inc.