Pilot‐scale evaluation using bioaugmentation to enhance PCE dissolution at dover AFB national test site

An Interstate Technology and Regulatory Council (ITRC) forum was recently held that focused on six case studies in which bioremediation of dense nonaqueous‐phase liquids (DNAPLs) was performed; the objective was to demonstrate that there is credible evidence for bioremediation as a viable environmental remediation technology. The first two case studies from the forum have been previously published; this third case study involves a pilot‐scale demonstration that investigated the effects of biological activity on enhancing dissolution of an emplaced tetrachloroethene (PCE) DNAPL source. It used a controlled‐release test cell with PCE as the primary DNAPL in a porous media groundwater system. Both laboratory tests and a field‐scale pilot test demonstrated that bioaugmentation can stimulate complete dechlorination to a nontoxic end product and that the mass flux from a source zone increases when biological dehalorespiration activity is enhanced through nutrient (electron donor) addition and bioaugmentation. All project goals were met. Important achievements include demonstrating the ability to degrade a PCE DNAPL source to ethene and obtaining significant information on the impacts to the microbial populations and corresponding isotope enrichments during biodegradation of a source area. © 2007 Wiley Periodicals, Inc.     

Enhanced reductive dechlorination of PCE in unconsolidated soils

An Interstate Technology and Regulatory Council (ITRC) forum was recently held that focused on six case studies in which bioremediation of dense nonaqueous phase liquids (DNAPLs) was performed. The objective was to demonstrate that there is credible evidence for bioremediation as a viable environmental remediation technology. A discussion of the first case study from the ITRC forum was published in the previous issue of Remediation. This article presents a discussion of the second case study, which involves enhanced reductive dechlorination (ERD) of tetrachloroethene (PCE) in unconsolidated soils—primarily silts and clays with very low permeabilities. The project results indicate that complete reductive dechlorination was achieved and provide encouragement that large amounts of nonaqueous solvent can be brought into the reductive dechlorination treatment process by dissolution and desorption, giving support to the contention that the capacity to attack nonaqueous mass is a prerequisite for any effective treatment of DNAPL source zones. The site geology for this project was relatively unfavorable, and further work is needed to confirm that the ERD technology can economically reach a natural attenuation endpoint for this type of setting. © 2006 Wiley Periodicals, Inc.     

Surfactant-enhanced remediation of DNAPL zones in granular aquifer systems

Dense nonaqueous phase liquids (DNAPLs), in particular chlorinated solvents such as trichloroethene, pose groundwater contamination problems at hazardous waste sites across North America. The mobility of DNAPLs in the subsurface, their low aqueous solubility, and the heterogeneity of typical aquifer systems combine to create conditions that inhibit the rapid remediation of DNAPL sites by traditional pump-and-treat methods. Surfactant-enhanced methods for DNAPL-site remediation accelerate the pace of remediation in granular aquifer systems, e.g., alluvium and outwash. The importance of adequate hydraulic conductivity and aquitard conditions is stressed in the application of surfactant-enhanced aquifer remediation (SEAR).     

Kinetic study of permanganate oxidation of tetrachloroethylene at a high pH under acidic conditions

Since carbon compounds are the main component of dense nonaqueous phase liquids (DNAPLs), the end products of all in situ chemical oxidation (ISCO) will include carbon dioxide. If the production rate of carbon dioxide exceeds the capacity of water to remove the carbon dioxide, degassing will occur. The uncontrolled carbon dioxide gas may change the flow patterns, remobilize the pooled DNAPL, transport DNAPL vapor, and reduce the relative permeability to the aqueous phase. Under high pH buffered conditions, most of the carbon dioxide will be dissolved in water. In this study, potassium permanganate oxidation of tetrachloroethylene (PCE) was conducted using a sodium carbonate buffered solution (1 g/L, pH = 10.6 ± 0.1) at three different temperatures (5, 10, and 20°C) and three potassium permanganate concentrations (0.2, 1, and 5 g/L). Extensive kinetic studies suggest that the overall oxidation is a second‐order reaction and pseudo‐first‐order with respect to PCE and potassium permanganate, respectively. The second‐order rate constant and the activation energy were 0.028 ± 0.001 M^?1s^?1 at 20°C and 43.9 ± 2.85 kJ/M, respectively. This study provides a base for further experimental and field studies on potassium permanganate oxidation of PCE under natural or artificial high pH buffered conditions. © 2004 Wiley Periodicals, Inc.     

An assessment of hydraulic containment to control vertical DNAPL migration

Because of increased awareness and knowledge about their behavior, dense nonaqueous phase liquids (DNAPLs) are being detected at an increasing frequency at hazardous and solid waste land disposal units. Remedial systems at sites containing DNAPLs need to be designed to address the specific problems presented by DNAPLs. Because of their physical properties, DNAPLs migrate downward and are difficult to remove using conventional recovery methods. Groundwater pumping schemes can be designed to hydraulically contain this vertical migration. The purpose of this article is to present an approach for evaluating the potential to halt the vertical migration of DNAPLs using hydraulic control. Detailed groundwater flow modeling of a group of waste basins indicates that groundwater pumping in low-permeability sands can impose the upward hydraulic gradients required to stop downward DNAPL movement. However, a recovery well system located around the perimeter of the waste basins will not impose the required gradients over a sufficiently large area to effectively contain DNAPLs under the basins because the distribution of vertical gradients that could stop DNAPLs extends only about fifty to sixty feet from the wells. Additional modeling indicates that horizontal recovery wells located directly under the basins can contain the vertical migration of DNAPLs.     

DNAPL Source Depletion: 1. Predicting Rates and Timeframes

Given the relatively rapid rate of dense nonaqueous‐phase liquid (DNAPL) ganglia depletion, source zones are generally dominated by horizontal layers of DNAPL after a release to the saturated zone. Estimating the time required to attain specific source strength reduction targets resulting from partial DNAPL source depletion is challenging due to a lack of available screening models, and because little has been done to synthesize available empirical data. Analytical and semi‐analytical models are used to study general DNAPL pool dissolution dynamics. The half‐life for the decline in DNAPL source strength (i.e., aqueous mass discharge) is demonstrated as proportional to the square root of the pool length, the thickness of the pool, and the solubility for single component DNAPLs. The through‐pool discharge is shown to be potentially significant for thin pools or in upper regions of thicker pools. An empirical analysis is used to evaluate average concentration decline rates for 13 in situ chemical oxidation (ISCO) and 16 enhanced in situ bioremediation (EISB) sites. Mean apparent decline rates, based on the time required to achieve the observed source strength reduction, are calculated for the ISCO and EISB sites (half‐lives of 0.39 year and 0.29 year, respectively). The empirical study sites are shown to have faster decline rates than for a large, complex study site where ISCO was implemented (half‐life of 2.5 years), and for a conceptual pool‐dominated trichloroethene source zone where EISB was simulated (half‐life of 2.5 years). Guidance is provided on using these findings in estimating timeframes for partial DNAPL depletion goals. © 2014 Wiley Periodicals, Inc.     

Rapid Cleanup of Chlorinated Solvent Source Zones: Synergies Between Chemical and Biological Degradation

A chlorinated volatile organic compound (cVOC) source area approximately 25 by 100 ft in a heavily industrialized urban area was characterized with groundwater tetrachloroethene (PCE) concentrations up to 9,180 μg/L. This is approximately 6 percent of PCE's aqueous solubility, indicative of the presence of residual dense, nonaqueous phase liquid. The resulting dissolved‐phase plume migrated off‐site. Biotic and abiotic dechlorination using a combination of a food‐grade organic carbon‐based electron donor and zero‐valent iron suspended in a food‐grade emulsifying agent reduced the source area PCE concentrations by 98 percent within 27 weeks, with minimal downgradient migration of daughter products dichloroethene and vinyl chloride. Combining biological dechlorination with iron‐based chemical dechlorination is synergistic, enhancing treatment aggressiveness, balancing pH, and optimizing degradation of both DNAPL and dissolved‐phase cVOCs. © 2013 Wiley Periodicals, Inc.     

Creosote DNAPL Recovery‐Well Design for Mass Removal

Sites with dense nonaqueous‐phase liquid (DNAPL) contamination present significant remediation challenges in terms of technical practicability and cost. Remedial approaches to DNAPL sites often follow a management approach rather than removal or eradication approaches, particularly due to the uncertainties associated with the benefits of partial source mass removal, as complete source removal is unlikely. Mass‐removal technologies should be evaluated for all DNAPL sites, although implementation of recovery technologies will be limited to a few sites based upon site‐specific factors. Sitewide remedial strategies that employ source reduction, where applicable, and incorporate associated risk‐reduction technologies, including monitored natural attenuation, are advised. Creosote DNAPL sites are particularly challenging, as they are predominantly composed of low‐solubility polycyclic aromatic hydrocarbons that form long‐term continuing sources. Additionally, the physical properties of creosote DNAPL, including high viscosity and relatively low density, result in significant migration potential and considerable dissolved‐phase groundwater impacts. An innovative creosote DNAPL source recovery well design was developed to achieve separate‐phase removal of pooled creosote DNAPL. The design presented herein employs modified circulation‐well technology to mobilize DNAPL to the engineered recovery well, where it is gravity‐settled into a sump to permit separate‐phase mass removal of the emplaced DNAPL source without groundwater production or treatment. A discharge mass flux protocol was developed to verify dissolved‐phase plume stability and the benefit of the source mass removal. © 2013 Wiley Periodicals, Inc.     

Mobility control: How injected surfactants and biostimulants may be forced into low‐permeability units

Recovering dense nonaqueous‐phase liquid (DNAPL) remains one of the most difficult problems facing the remediation industry. Still, the most common method of recovering DNAPL is to physically remove the contaminants using common technologies such as total fluids recovery pumps, vacuum systems, and “pump‐and‐treat.” Increased DNAPL removal can be attained using surfactants to mobilize and/or solubilize the pollutants. However, very little is understood of the methods developed by petroleum engineers beginning in the 1960s to overcome by‐passed, low‐permeability zones in heterogeneous oil reservoirs. By injecting or causing the formation of viscous fluids in the subsurface, petroleum engineers caused increased in‐situ pressures that forced fluid flow into low permeability units as well as the higher permeability thief zones. Polymer flooding involves injecting a viscous aqueous polymer solution into the contaminated aquifer. Foam flooding involves injecting surfactant to decontaminate the high‐permeability zones and then periodic pulses of air to cause a temporary viscous foam to form in the high‐permeable zones after all DNAPL is removed. Later surfactant pulses are directed by the foam into unswept low‐permeable units. These methods have been applied to DNAPL removal using surfactants but they can also be applied to the injection of bio‐amendments into low‐permeability zones still requiring continued remediation. Here we discuss the principles of mobility control as practiced in an alluvial aquifer contaminated with chlorinated solvent and coal tar DNAPLs as well as some field results. © 2003 Wiley Periodicals, Inc.     

Coupling surfactants/cosolvents with oxidants for enhanced DNAPL removal: A review

Surfactants and cosolvents are useful for enhancing the apparent solubility of dense nonaqueous‐phase liquid (DNAPL) compounds during surfactant‐enhanced aquifer remediation (SEAR). In situ chemical oxidation (ISCO) with permanganate, persulfate, and catalyzed hydrogen peroxide has proven to be a cost‐effective and viable remediation technology for the treatment of a wide range of organic contaminants. Coupling compatible remedial technologies either concurrently or sequentially in a treatment train is an emerging concept for more effective cleanup of DNAPL‐contaminated sites. Surfactants are effective for DNAPL mass removal but not useful for dissolved plume treatment. ISCO is effective for plume control and treatment but can be less effective in areas where large masses of DNAPL are present. Therefore, coupling SEAR with ISCO is a logical next step for source‐zone treatment. This article provides a critical review of peer‐reviewed scientific literature, nonreviewed professional journals, and conference proceedings where surfactants/cosolvents and oxidants have been utilized, either concurrently or sequentially, for DNAPL mass removal. © 2010 Wiley Periodicals, Inc.     

Hydrogen Release Compound: A Cost‐Effective Alternative to PCE Remediation at Dry Cleaning Facilities

Tetrachloroethylene, also known as perchloroethylene or PCE, is one of the most difficult to treat chlorinated solvents when present in groundwater. Unfortunately, this elusive and recalcitrant compound is also the most commonly used dry cleaning solvent. As a result, releases of PCE at dry cleaning sites are somewhat common. Regenesis Bioremediation Products, of San Clemente, California, has developed Hydrogen Release Compound (HRC), which has been successfully used to promote bioremediation of PCE in groundwater. This product is directly injected into contaminated groundwater to speed up the natural attenuation of PCE through an anaerobic, natural process known as reductive dechlorination. A key benefit of HRC is its ability to slowly release hydrogen over extended periods of time. Reductive dechlorination relies on a steady source and readily available supply of electron donors as part of the degradation process. Hydrogen is one of the best electron donors available, and thus, the application of HRC significantly enhances the rate of PCE degradation. For dry cleaners, this technology can substantially reduce major design, capital, and operating costs, allowing the implementation of a low‐impact application and remediation solution. This article discusses the use of the HRC to remediate PCE contamination and presents the results of two specific HRC‐treated dry cleaner sites. © 2002 Wiley Periodicals, Inc.     

Remediation of a Former Dry Cleaner Using Nanoscale Zero Valent Iron

Nanoscale zero valent iron (nZVI) was evaluated in a laboratory treatability study and subsequently injected as an interim measure to treat source area groundwater impacts beneath a former dry cleaner located in Chapel Hill, North Carolina (the site). Dry cleaning operations resulted in releases of tetrachloroethene (PCE) that impacted site soil at concentrations up to 2,700 mg/kg and shallow groundwater at concentrations up to 41 mg/L. To achieve a design loading rate of 0.001 kg of iron per kilogram of aquifer material, approximately 725 kg of NanoFe? (PARS Environmental) was injected over a two‐week period into a saprolite and partially weather rock aquifer. Strong reducing conditions were established with oxidation–reduction potential (ORP) values below –728 mV. pH levels remained greater than 8 standard units for a period of 12 months. Injections resulted in near elimination of PCE within one month. cis‐1,2‐Dichloroethene accumulated at high concentrations (greater than 65 mg/L) for 12 months. MAROS software (Version 2.2; AFCEE, 2006 ) was used to calculate mass reduction of PCE and total ethenes at 96 percent and 58 percent, respectively, compared to baseline conditions. Detections of acetylene confirmed the presence of the beta‐elimination pathway. Detections of ethene confirmed complete dechlorination of PCE. Based on hydrogen gas generation, iron reactivity lasted 15 months. © 2013 Wiley Periodicals, Inc.     

Partitioning tracer tests as a remediation metric: Case study at naval amphibious base little creek,Virginia Beach,Virginia

The partitioning tracer test (PTT) is a characterization tool that can be used to quantify the porespace saturation (S_N) and spatial distribution of dense nonaqueous phase liquids (DNAPLs) in the subsurface. Because the method essentially eliminates data interpolation errors by directly measuring a relatively large subsurface volume, it offers significant promise as a remediation metric for DNAPL‐zone remediation efforts. This article presents, in detail, the design and results of field PTTs conducted before and after a DNAPL‐zone treatment at the Naval Amphibious Base Little Creek, Virginia Beach, Virginia. The results from different tracers yield a relatively large range in S_N estimates, indicating notable uncertainty and presenting significant challenges for meaningful interpretation. Several potential interpretation methods are presented, resulting in an estimated DNAPL removal range of 15 to 109 L. While this range is large, it is consistent with the DNAPL removal (～30 L) determined from analysis of effluent concentration measurements collected during the remediation efforts. At this site, the initial and final S_N values are low, and the relatively inconsistent performance of the various tracers indicates that these levels are near the lower practical quantification limit for these PTTs; however, the effective lower quantification limit for these tests is unknown. Generally, an understanding of lower quantification limits is particularly important for interpretation of post‐remediation PTTs because S_N values are likely to be low (due to remediation efforts) and the S_N estimated from the PTT may be used to predict long‐term dissolved plume behavior and assess associated environmental risk. Partitioning tracer test quantification limits are test‐specific, as they are dependent on a variety of factors including analytical uncertainty, tracer breakthrough characteristics, and tracer data integration techniques. The results of this case study indicate that methods for estimating lower quantification limits for field PTTs require further development. © 2004 Wiley Periodicals, Inc.     

Field and laboratory evaluation of the treatment of DNAPL source zones using emulsified zero‐valent iron

Emulsified zero‐valent iron (EZVI) is a surfactant‐stabilized, biodegradable emulsion that forms droplets consisting of a liquid‐oil membrane surrounding zero‐valent iron (ZVI) particles in water. This article summarizes the results obtained during the first field‐scale deployment of EZVI at NASA's Launch Complex 34 (LC34) located on Cape Canaveral Air Force Station, Florida, in August 2002 and presents the results of recent follow‐on laboratory tests evaluating the mechanisms, which contribute to the performance of the technology. The field‐scale demonstration evaluated the performance of EZVI containing nanoscale zero‐valent iron (NZVI) when applied to dense, nonaqueous phase liquid (DNAPL) trichloroethylene (TCE) in the saturated zone. Results of the field demonstration indicate substantial reductions in TCE soil concentrations (greater than 80 percent) at all but two soil boring locations and significant reductions in TCE groundwater concentrations (e.g., 60 percent to 100 percent) at all depths targeted with EZVI. Laboratory tests conducted in 2005 suggest that both NZVI particles and EZVI containing NZVI can provide significant reductions in TCE mass when used to treat TCE DNAPL in small test reactors. However, EZVI was able to reduce TCE concentrations to lower levels than were obtained with NZVI alone, likely as a result of the combined impact of sequestration of the TCE into the oil phase and degradation of the TCE with the NZVI. © 2006 Wiley Periodicals, Inc.     

ERD of Residual TCE DNAPL Achieving Nondetect from a Single Injection of Food‐Grade Waste

Residual dense nonaqueous phase liquid (DNAPL) composed of trichloroethene (TCE) was identified in a deeper interval of an overburden groundwater system at a manufacturing facility located in northern New England. Site hydrostratigraphy is characterized by two laterally continuous and transmissive zones consisting of fully‐saturated fine sand with silt and clay. The primary DNAPL source was identified as a former dry well with secondary contributions from a proximal aboveground TCE storage tank. A single additive‐injection mobilization in 2001 utilizing a food‐grade injectate formulated with waste dairy product and inactive yeast enhanced residual TCE DNAPL destruction in situ by stimulating biotic reductive dechlorination. The baseline TCE concentration was detected up to 97,400 μg/L in the deeper interval of the overburden groundwater system, and enhanced reductive dechlorination (ERD) achieved >99 percent reduction in TCE concentrations in groundwater over nine years with no evidence of sustained rebound. TCE concentrations have remained nondetect below 2.0 μg/L for the last five consecutive sampling rounds between 2013 and 2015. ERD utilizing a food‐grade injectate is a green remediation technology that has destroyed residual DNAPL at the site and achieved similar results at other residual DNAPL sites during both pilot‐ and full‐scale applications. ©2016 Wiley Periodicals, Inc.     

Chemical oxidation of tetrachloroethene in a fractured saprolite/bedrock aquifer

Two chemical oxidizers, Fenton's Reagent (FR) and sodium permanganate (NaMnO₄), were used to remediate groundwater contaminated by tetrachloroethene (PCE) in a fractured saprolite and bedrock aquifer in Rockville, Maryland. Initial PCE concentrations ranged from 11 to 25,000 μg/L, averaging 8,684 μg/L in March 2000. A total of 28,256 pounds of hydrogen peroxide (as 35 percent solution) and iron catalyst were injected during the FR treatment program. The FR failed to achieve the desired clean‐up goal, after which 11,114 pounds of NaMnO₄ (as 40 percent solution) were diluted to a 20 percent solution and injected into the aquifer. An additional 855 pounds of dilute NaMnO₄ was later injected, which ultimately reduced the original PCE mass by an estimated 95 percent through November 2001. © 2003 Wiley Periodicals, Inc.     

Enhanced anaerobic bioremediation in a DNAPL residual source zone: Test Area North case study

An Interstate Technology and Regulatory Council (ITRC) forum was recently held that focused on case studies in which bioremediation of dense nonaqueous‐phase liquids (DNAPLs) was performed. This first case study, the Test Area North (TAN) site of the Idaho National Engineering and Environmental Laboratory, involves a trichloroethene (TCE) residual source area in a deep, fractured basalt aquifer that has been undergoing enhanced bioremediation since January 1999. Complete dechlorination from TCE to ethene was documented within nine months of operation, and sodium lactate injections were shown to enhance TCE mass transfer from the residual source. Since that time, optimization of injection strategies has maintained efficient dechlorination while demonstrating accelerated cleanup at a lower cost by changing to a whey powder amendment that solubilizes DNAPL. © 2006 Wiley Periodicals, Inc.     

Screening Technology Trains for DNAPL Remediation

The Department of Energy (DOE) is conducting a Comprehensive Environmental Response, Compensation and Liability Act (CERCLA) mandated Remedial Investigation/Feasibility Study for a site contaminated with Dense Non-Aqueous Phase Liquid (DNAPL) pollutants. Three key efforts were a hydrogeological modeling approach, the generation of feasible sequences of technologies, and the screening of alternative technologies. This research uses a decision analysis process to provide a quantitative assessment of the candidate technologies. Decision analysis modeling was used to gain insight into each sequence of technologies. Sensitivity analysis was also conducted to assess the impact of key assumptions. The results provided the DOE with an objective and traceable rationale for screening and reducing all of the potential technology combinations to 58 technology combinations and a method for identifying the top scoring combinations. The approach has wide applicability to similar CERCLA remediation efforts.     

Successful unsaturated zone treatment of PCE with sodium permanganate

In situ chemical oxidation (ISCO) with permanganate has been widely used for soil and groundwater treatment in the saturated zone. Due to the challenges associated with achieving effective distribution and retention in the unsaturated zone, there is a great interest in developing alternative injection technologies that increase the success of vadose‐zone treatment. The subject site is an active dry cleaner located in Topeka, Kansas. A relatively small area of residual contamination adjacent to the active facility building has been identified as the source of a large sitewide groundwater contamination plume with off‐site receptors. The Kansas Department of Health and Environment (KDHE) currently manages site remedial efforts and chose to pilot‐test ISCO with permanganate for the reduction of perchloroethene (PCE) soil concentrations within the source area. KDHE subsequently contracted Burns & McDonnell to design and implement an ISCO pilot test. A treatability study was performed by Carus Corporation to determine permanganate‐soil‐oxidant‐demand (PSOD) and the required oxidant dosing for the site. The pilot‐test design included an ISCO injection approach that consisted of injecting aqueous sodium permanganate using direct‐push technology with a sealed borehole. During the pilot test, approximately 12,500 pounds of sodium permanganate were injected at a concentration of approximately 3 percent (by weight) using the methods described above. Confirmation soil sampling conducted after the injection event indicated PCE reductions ranging from approximately 79 to more than 99 percent. A follow‐up treatment, consisting of the injection of an additional 6,200 pounds of sodium permanganate, was implemented to address residual soil impacts remaining in the soil source zone. Confirmation soil sampling conducted after the treatment indicated a PCE reduction of greater than 90 percent at the most heavily impacted sample location and additional reductions in four of the six samples collected. © 2009 Wiley Periodicals, Inc.     

Reductive dechlorination of a chlorinated solvent plume in Houston,Texas

Chlorinated solvents such as tetrachloroethene (perchloroethene, PCE) and trichloroethene (TCE) have been extensively used in various industrial applications for many years. Because neither are typically consumed through their various uses, they are often released to the environment through industrial application or disposal. Once released, PCE and TCE tend to migrate downward into groundwater, where they persist. In the current case study, cheese whey was used as a groundwater amendment to facilitate the reductive dechlorination of a chlorinated solvent plume underlying an auto dealer/repair shop in Harris County, Texas. From September 2010 to January 2014, over 32,000 gallons of cheese whey were injected into the subsurface resulting in a marked reduction in oxidation–reduction potential (ORP) and nitrate concentrations, coupled with an increase in ferrous iron concentrations. Statistical trend analyses indicate the primary contaminants, PCE and TCE, as well as the daughter product cis‐1,2‐dichloroethene (cDCE), all exhibited a positive response, as evidenced by statistically decreasing trends, and/or reversal in concentration trends, subsequent to cheese whey injections. Maximum concentrations of PCE and TCE in key test wells decreased by as much as 98.97 percent and 99.17 percent, respectively. In addition, the bacterial genus Dehalococcoides, capable of complete reduction of PCE to non‐toxic ethene, was found to be more abundant in the treatment area, as compared to background concentrations. Because cheese whey is a by‐product of the cheese making process, the cost of the product is essentially limited to transport. This study demonstrates cheese whey to be an effective groundwater amendment at a cost which is orders of magnitude lower than popular industry alternatives.