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.     

Construction of a permeable reactive barrier in a residential neighborhood

In June 2001, the Massachusetts Department of Environmental Protection (DEP) installed a permeable reactive barrier (PRB) within a roadway in Needham, Massachusetts, to treat a plume of chlorinated solvents migrating toward two public water‐supply wells located in the adjacent town of Wellesley, Massachusetts. The solvents originated from an electronics manufacturer located approximately 2,300 feet upgradient of the roadway and 5,200 feet upgradient of the public supply wells. Chlorinated solvents, primarily trichloroethene (TCE), had migrated past the roadway to within 300 feet of the public supply wells. Two contaminant transport models prepared by the DEP's design contractor and the EPA indicated that the plume would reach the well field if no response actions were taken. To mitigate the future impact to the municipal well field, the DEP decided to install a PRB composed of zero‐valent granular iron across the path of the plume along Central Avenue in Needham. Though several dozen PRBs have been installed at sites worldwide and the technology is no longer considered innovative, the application of the technology in a roadway that receives 17,000 vehicles per day within a residential neighborhood is unique and presented difficulties not typically associated with PRB installations. The Needham PRB was also one of the first zero‐valent iron PRBs installed using the slurry trench method to treat chlorinated compounds. © 2002 Wiley Periodicals, Inc.     

Site characterization to support permeable reactive barrier design

Careful design studies and selection of an effective technique for the installation of permeable reactive barriers (PRBs) are important contributors to the overall success of zero‐valent iron PRBs. This article provides a case study summarizing the successful design and construction of a PRB installed at the former Carswell Air Force Base located in Fort Worth, Texas. Expedited site characterization using a cone penetrometer rig equipped with a mass spectrometer was employed to provide real‐time characterization and lithologic data. These data proved to be invaluable for the design of the PRB and allowed for the development of an accurate preconstruction cost estimate. Field data gained from the expedited water quality and geologic characterization along with aquifer testing and a bench‐scale treatability study provided a comprehensive basis for the design. The biopolymer slurry construction technique provided additional unanticipated benefits to the designed zero‐ valent iron treatment by promoting the development of anaerobic conditions favorable for microbial degradation of trichloroethene. Postconstruction monitoring data are discussed to illustrate the successful performance of the PRB. © 2005 Wiley Periodicals, Inc.     

Design and cost estimation of permeable reactive barriers

Cost-effective use of permeable reactive barriers for groundwater treatment requires properly estimating the amount of reactive material required and choosing the best means of emplacing it. The weight of reactive material per unit cross section of the plume can be estimated from laboratory reaction kinetics data and basic knowledge of the plume and the remediation goals. This parameter has implications regarding the choice of permeable barrier design and emplacement method. The use of tremie tubes, trenching machines, high-pressure jetting, and deep soil mixing may be appropriate for different situations depending on the amount of reactive material required, the dimensions of the plume, and other factors. The specific application considered here is the use of granular iron to treat groundwater contaminated with chlorinated solvents.     

Field performance of a fan‐driven spray evaporator

An emerging evaporation technology uses a powerful axial fan and high‐pressure spray nozzles to propel a fine mist into the atmosphere at high air and water flow rates. Commercial units have been deployed at several locations in North America and worldwide since the mid‐1990s, typically in arid or semiarid climates. A commercial spray evaporator was field tested at the U.S. Department of Energy's Savannah River Site in South Carolina to develop quantitative performance data under relatively humid conditions. A semiempirical correlation was developed from eight tests from March through August 2003. For a spray rate of 250 L/min (66 gpm) and continuous year‐round operation at the Savannah River Site, the predicted average evaporation rate is 48 L/min (13 gpm). © 2006 Washington Savannah River Company     

Re‐evaluation of treatment approach for a site contaminated with Freon‐113 and 1,1,1‐trichloroethane

This study demonstrates a remedial approach for completing the remediation of an aquifer contaminated with 1,1,2‐trichlorotrifluoroethane (Freon‐113) and 1,1,1‐trichloroethane (TCA). In 1987, approximately 13,000 pounds of Freon‐113 were spilled from a tank at an industrial facility located in the state of New York. The groundwater remediation program consisted of an extraction system coupled with airstripping followed by natural attenuation of residual contaminants. In the first phase, five recovery wells and an airstripping tower were operational from April 1993 to August 1999. During this time period over 10,000 pounds of CFC‐13 and 200 pounds of TCA were removed from the groundwater and the contaminant concentrations decreased by several orders of magnitude. However, the efficiency of the remediation system to recover residual Freon and/or TCA reduced significantly. This was evidenced by: (1) low levels (< 10 ppb) of Freon and TCA captured in the extraction wells and (2) a slight increase of Freon and/or TCA in off‐site monitoring wells. A detailed study was conducted to evaluate the alternative for the second‐phase remediation. Results of a two‐year groundwater monitoring program indicated the contaminant plume to be stable with no significant increase or decrease in contaminant concentrations. Monitored geochemical parameters suggest that biodegradation does not influence the fate and transport of these contaminants, but other mechanisms of natural attenuation (primarily sorption and dilution) appear to control the fate and transport of these contaminants. The contaminants appear to be bound to the soil matrix (silty and clay units) with limited desorption as indicated by the solid phase analyses of contaminant concentrations. Results of fate and transport modeling indicated that contaminant concentrations would not exceed the action levels in the wells that showed a slight increase in contaminant concentrations and in the downgradient wells (sentinel) during the modeled timeframe of 30 years. This feasibility study for natural attenuation led to the termination of the extraction system and a transaction of the property, resulting in a significant financial benefit for the original site owner. © 2003 Wiley Periodicals, Inc.     

ERI evaluation of injectates used at a dry‐cleaning site

A former dry‐cleaning site in Jackson, Tennessee, has undergone remediation to treat dense nonaqueous‐phase liquid (trichloroethene [TCE] and tetrachloroethene [PCE]) contamination in the subsurface. The dry cleaning operation closed in 1977. In 2002, a series of injections were made at the site consisting of corn syrup, vegetable oils, and Simple Green®. In 2004, approximately 200 cubic yards of contaminated soil were excavated, and the bottom of the excavation was covered with sodium lactate. In 2009, the site was characterized using proprietary electrical resistivity imaging (ERI; commercially available as Aestus GeoTrax Surveys^TM). Follow‐up confirmation soil borings targeted anomalies detected via the geophysical work. The results indicate an extremely electrically conductive (less than 1 ohm‐m) vadose zone downgradient from the injection wells, and extremely electrically resistive areas (greater than 10,000 ohm‐m) in the phreatic zone near the injection area. The sample data indicate that the electrically resistive anomalous zones contain moderate to high concentrations of undegraded dry‐cleaning compounds. Electrically conductive anomalous zones are interpreted to be areas of biological activity generated by the amendments injected into the subsurface based on the extreme conductivity values detected, the chemical composition (i.e., PCE degradates are present), and the dominant vadose‐zone location of the conductive zones. © 2012 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.     

Residential vapor‐intrusion evaluation: Long‐duration passive sampling vs. short‐duration active sampling

Sampling indoor air for potential vapor‐intrusion impacts using current standard 24‐hour sample collection methods may not adequately account for temporal variability and detect contamination best represented by long‐term sampling periods. Henry Schuver of the U.S. Environmental Protection Agency Office of Solid Waste stated at the September 2007 Air & Waste Management Association vapor‐intrusion conference that the US EPA may consider recommending longer‐term vapor sampling to achieve more accurate time‐weighted‐average detections. In November 2007, indoor air at four residences was sampled to measure trichloroethene (TCE) concentrations over short‐ and long‐duration intervals. A carefully designed investigation was conducted consisting of triplicate samplers for three different investigatory methods: dedicated 6‐liter Summa canisters (US EPA Method TO‐15), pump/sorbent tubes (US EPA Method TO‐17), and passive diffusion samplers (MDHS 80). The first two methods collected samples simultaneously for a 24‐hour period, and the third method collected samples for two weeks. Data collected using Methods TO‐15 (canisters) and TO‐17 (tubes) provided reliable short‐duration TCE concentrations that agree with prior 24‐hour sampling events in each of the residences; however, the passive diffusion samplers may provide a more representative time‐weighted measurement. The ratio of measured TCE concentrations between the canisters and tubes are consistent with previous results and as much as 28.0 μg/m³ were measured. A comparison of the sampling procedures, and findings of the three methods used in this study will be presented. © 2008 Wiley Periodicals, Inc.     

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.     

Evaluation of natural attenuation at a 1,4‐dioxane‐contaminated site

1,4‐Dioxane entered the environment as a result of historic leaks and spills in the production area at an industrial facility in the southeastern coastal plain. The areal extent of the 1,4‐dioxane plume is several hundred acres and is largely contained on the site. Land use adjacent to the plant property is primarily undeveloped (wetlands or woods) or industrial, with a small area of mixed land use (commercial/residential) to the southwest and north. The surficial aquifer is a relatively simple hydrogeologic system with well‐defined boundaries and is comprised of a 50‐ to 70‐foot‐thick deposit of alluvial/fluvial sand and gravel that overlies an aquitard in excess of 100 feet thick. A groundwater flow model, developed and calibrated using field‐measured data, was used for the fate‐and‐transport modeling of 1,4‐dioxane. The flow‐and‐transport model, combined with the evaluation of other site geochemical data, was used to support the selection of monitored natural attenuation (MNA) as the proposed groundwater remedy for the site. Since the active sources of contamination have been removed and the modeling/field data demonstrated that the plume was stable and not expanding, the proposed MNA approach was accepted and approved by the regulatory agency for implementation in 2004. Subsequent accumulated data confirm that concentrations in the 1,4‐dioxane plume are declining as predicted by the fate‐and‐transport modeling. © 2008 Wiley Periodicals, Inc.     

Insights from years of performance that are shaping injection‐based remediation systems

Research and field experience from the past 15 years has allowed remediation professionals to purposefully design injection‐based remediation systems with a high potential for success. Industry professionals can now claim a number of achievements that were unthinkable just a few years ago: (1) we have demonstrated that maximum contaminant levels (MCLs) can be achieved for multiple contaminants; (2) we have successfully targeted dense nonaqueous‐phase liquid (DNAPL) source zones; (3) we have expanded our understanding of injection hydraulics to treat large plumes; and (4) we have collected sufficient data on rates of treatment to be more predictive regarding outcomes. The next decade will continue to evolve the design and execution of these types of systems for application to more complex problems. At this point on the timeline, questions regarding the mechanisms of treatment have largely been addressed, allowing a shift in focus to operational enhancements. Specific operational insights arising from the body of work to date that arguably will continue to shape and influence the design and execution of injection‐based remediation systems include: (1) the fact that delivery does not always equal distribution, (2) treatment optimization requires aquifer tuning, and (3) life‐cycle costs can be reduced with remedy‐optimized investigation. The number of examples that support these concepts and their ramifications to future technology refinement is already increasing, demonstrating how the refinements that can be made around these areas of focus will enhance our ability to effectively tackle larger and more complicated plumes, and do so with maximum efficiency. © 2011 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.     

Pilot‐scale evaluation of in situ cometabolic bioremediation of TCE in groundwater using PHOSter® technology

A study was conducted to evaluate the efficacy of PHOSter® technology for treating groundwater contaminated with trichloroethene (TCE) at Edwards Air Force Base, California. The technology consists of injecting a gaseous mixture of air, methane, and nutrients into groundwater with the objective of stimulating the growth of methanotrophs, a naturally occurring microbial group that is capable of catalyzing the aerobic degradation of chlorinated solvents into nontoxic products. Injection operations were performed at one well for a period of three months. Six monitoring wells were utilized for groundwater and wellhead vapor monitoring and for groundwater and microbial sampling. In the five monitoring wells located within 44 feet of the injection well, the following results were observed: dissolved oxygen concentrations increased to a range between 6 and 8 milligrams per liter (μg/L); the biomass of target microbial groups increased by one to five orders of magnitude; and TCE concentrations decreased by an average of 92 percent, and to below the California primary maximum contaminant level (MCL; 5 micrograms per liter [µg/L]) in the well closest to the injection well. © 2008 Wiley Periodicals, Inc. *

1 This article is a U.S. Government work and, as such, is in the public domain of the United States of America.

     

Complete Degradation of Hexahydro‐1,3,5‐Trinitro‐1,3,5‐Triazine (RDX) by a Co‐Culture of Gordonia sp. KTR9 and Methylobacterium sp. JS178

The presence of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX) in soil and groundwater is a major contamination issue at many military facilities around the world. Gordonia sp. KTR9 metabolizes RDX as a nitrogen source for growth producing 4‐nitro‐2,4‐diazabutanal (NDAB) as a dead‐end product. Methylobacterium sp. strain JS178 degrades NDAB as a sole source of nitrogen for growth. A mixed culture of strains KTR9 and JS178 was able to completely degrade RDX. There was no difference in rate of RDX degradation by KTR9 alone or in co‐culture with JS178. The first‐order degradation coefficients of RDX and NDAB in the co‐culture were 0.08 hr^?1 and 0.002 hr^?1, respectively. In the co‐culture that initially contained RDX plus NDAB, strain JS178 degraded the NDAB that was produced by KTR9 as shown by a decrease in the molar yield of NDAB (from RDX) from 1.0 to –0.11. Co‐cultures of strains KTR9 and JS178 could be used to promote complete degradation of RDX in soils or groundwater. ©2016 Wiley Periodicals, Inc.     

Effectiveness of Capture Zones Generated by Intermittent Pumping of a PV‐Powered Pump‐and‐Treat System Without Energy Storage

A common technology to remediate and/or contain contaminated groundwater is pump‐and‐treat remediation (P&T). Traditionally, P&T systems have been designed to operate continuously to achieve steady‐state capture zones, for which large amounts of energy are required. Green and sustainable remediation (GSR) is emerging as a viable method to minimize the adverse effects of remediation on the environment. One of the challenges associated with photovoltaic‐ (PV‐) powered P&T systems is the assessment of their performance given the intermittent nature of the power availability. This article characterizes the hydraulic containment effectiveness of a PV‐powered P&T system without energy storage using data collected at two different remediation sites, a Dry‐Cleaning Environmental Response Trust Fund site in Rolla, Missouri, and the Former Nebraska Ordnance Plant near Mead, Nebraska. Additionally, a method to estimate the effectiveness of the hydraulic containment as a function of the total volume of groundwater expected to be extracted is being proposed. Two transient and a continuously pumped capture zones were modeled using Visual MODFLOW^® 2012.1 along with MODPATH and compared. The study shows that smaller capture zones will be generated from intermittent pumping when compared to continuous pumping. © 2013 Wiley Periodicals, Inc.     

Modified Fenton's processes for effective in‐situ chemical oxidation—Laboratory and field evaluation

Fenton's reagent in its conventional form, although effective for contaminant treatment, is impractical from an in‐situ field application perspective due to low pH requirements (i.e., pH 3‐4), and limited reagent mobility when introduced into the subsurface. Modified Fenton's processes that use chelated‐iron catalysts and stabilized hydrogen peroxide have been developed with the goal of promoting effective in‐situ field application under native pH conditions (i.e., pH 5‐7), while extending the longevity of hydrogen peroxide. Laboratory experiments conducted in soil columns packed with organic soil to compare modified Fenton's catalysts with conventional catalysts (acidified iron [II]) indicated superior mobility and sorption characteristics for modified Fenton's catalysts. Furthermore, the acidic pH of a conventional catalyst was buffered to the native soil range, leading to increased iron precipitation/adsorption following permeation through the soil column. The chelates present within the modified Fenton's catalyst showed greater affinity toward iron compared with the native soil and, hence, minimized iron loss through adsorption during the permeation process even at pH 5‐7. Field effectiveness of the modified Fenton's process was demonstrated at a former dry‐cleaning facility located in northeast Florida. Preliminary laboratory‐scale experiments were conducted on soil‐slurry and groundwater samples to test the process efficacy for remediation of chlorinated solvents. Based on successful experimental results that indicated a 94 percent (soil slurry) to 99 percent (groundwater) reduction of cis‐1,2‐DCE, PCE, and TCE, a field‐scale treatment program was initiated utilizing a plurality of dual‐zone direct push injection points installed in a grid fashion throughout the site. Results of treatment indicated a 72 percent reduction in total chlorinated contamination detected in the site groundwater following the first injection event; the reduction increased to 90 percent following the second injection event. © 2002 Wiley Periodicals Inc.     

Web‐based automated remediation performance monitoring and visualization of contaminant mass flux and discharge

Environmental monitoring, data processing, and reporting methods are expensive, labor‐ and resource‐intensive, time‐consuming, and often inaccurate. An innovative project management platform was developed for integrating environmental monitoring sensors, telemetry, geographical information systems, models, and geostatistical algorithms for automatically generating contour maps and time‐stamped renderings of sensor attributes and multivariate analyses. More specifically, algorithms converting sensor‐derived head and solute concentration values allow for automated monitoring of mass flux and discharge to evaluate groundwater remediation system performance and contaminant discharges from aquifers to surface‐water receptors. Life‐cycle costs and carbon footprints were reduced due to the elimination of energy and labor expenditures associated with transportation, data collection, laboratory efforts, report generation, and information dissemination. A brief summary of two demonstrations of this sensor‐based water resources management application is presented. © 2011 Wiley Periodicals, Inc.     

Steady‐state field‐scale gas permeability estimation and pore‐gas velocity calculation in a domain open to the atmosphere

Field‐scale estimation of gas permeability and subsequent computation of pore‐gas velocity profiles are critical elements of sound soil venting design. It has been our experience, however, in U.S. Environmental Protection Agency's (EPA's) technical assistance program, provided by the Office of Research and Development in support EPA regional offices, that many venting practitioners are unaware of equations and data interpretation methods appropriate for gas permeability estimation and pore‐gas velocity computation. To ameliorate this situation, we use data collected at a U.S. Coast Guard Station in Traverse City, Michigan, to demonstrate gets permeability estimation and pore‐gas velocity calculation for steady‐state, axisymmetric, two‐dimensional gas flow in a domain open to the atmosphere. For gas permeability estimation, we use random guesses constrained with decreasing intervals of radial and vertical permeabilityand analysis of root mean square errors to ensure attainment of a global versus local minimum. We demonstrate confidence in permeability estimation by providing plots of observed versus simulated pressure response. Finally, we illustrate how plots of pore‐gas velocity as a function of distance and flow rate can be helpful in venting design.