Remedial Process Optimization and Ozone Sparging for Petroleum Hydrocarbon‐Impacted Groundwater

A former natural gas processing station is impacted with total petroleum hydrocarbons (TPH) and benzene. Remedial process optimization (RPO) was conducted to evaluate the effectiveness of the historical air sparging/soil vapor extraction (AS/SVE) system and the current groundwater extraction and treatment system. The RPO indicated that both remedial activities offered no further benefit in meeting remediation goals. Instead, an in situ chemical oxidation (ISCO) system was recommended. Ozone was selected, and the results of a bench test indicated that the ozone demand was 8 to 12 mg ozone/mg TPH and that secondary by‐products would include hexavalent chromium and bromate. A capture zone analysis was conducted through groundwater flow modeling (MODFLOW) to ensure containment of the injected oxidant using the existing groundwater extraction system. Results of a pilot study indicated that the optimum frequency of ozone sparging is 60 minutes in order to reach a maximum radius of influence of 20 feet. TPH concentrations within the treatment zone decreased by 97 percent over two months of ozone sparging. Concentrations of hexavalent chromium and bromate increased from nondetect to 44 and 110 mg/L, respectively, during the ozone sparging but attenuated to nondetectable concentrations within three months of system shut down. ©2016 Wiley Periodicals, Inc.     

1,4‐Dioxane Treatment Technologies

The chlorinated solvent stabilizer 1,4‐dioxane (DX) has become an unexpected and recalcitrant groundwater contaminant at many sites across the United States. Chemical characteristics of DX, such as miscibility and low sorption potential, enable it to migrate at least as far as the chlorinated solvent from which it often originates. This mobility and recalcitrance has challenged remediation professionals to redesign existing treatment systems and monitoring networks to accommodate widespread contamination. Furthermore, remediation technologies commonly applied to chlorinated solvent co‐contaminants, such as extraction and air stripping or in situ enhanced reductive dechlorination, are relatively ineffective on DX removal. These difficulties in treatment have required the industry to identify, develop, and demonstrate new and innovative technologies and approaches for both ex situ and in situ treatment of this emerging contaminant. Great strides have been made over the past decade in the development and testing of remediation technologies for removal or destruction of DX in groundwater. This article briefly summarizes the fate and transport characteristics of DX that make it difficult to treat, and presents technologies that have been demonstrated to be applicable to groundwater treatment at the field scale.  ©2016 Wiley Periodicals, Inc.     

A practical approach to steam‐enhanced dual‐phase extraction: A case study

This article presents the results of a pilot test that was conducted to determine the effectiveness of using steam‐enhanced dual‐phase extraction (DPE) at a former industrial site in New York. The pilot test proved that steam‐enhanced DPE was very effective at removing significant contaminant mass from the subsurface in a relatively short time period. Concentrations of volatile organic compounds and semivolatile organic compounds in the vapor stream and groundwater were successfully reduced, in some cases by orders of magnitude. Based on the results of the steam‐enhanced DPE pilot test, the final remedy for the site includes implementing this technology at selected areas as an alternative to DPE alone or other remedial alternatives, such as excavation or groundwater pump and treat. © 2003 Wiley Periodicals, Inc.     

The ART In‐Well Technology test at a chlorinated solvent site in central Iowa

An Accelerated Remediation Technologies (ART) In‐Well Technology pilot test was performed to evaluate the removal of chlorinated volatile organic compounds (VOCs) from groundwater. The ART In‐Well Technology was installed in one well located in the source area where dense nonaqueous‐phase liquid has been identified and VOC concentrations exceed 140,000 μg/L. Monitoring wells at the site were positioned between 10 and 170 feet from the ART test well. Overall, VOC concentrations from samples collected from the groundwater monitoring wells and in the vapors extracted for discharge from the ART treatment well were analyzed over the testing period. Monitoring results showed that concentrations of perchloroethylene were reduced in the closest monitoring well to nondetectable concentrations within 90 days. The cumulative removal of chlorinated VOCs from the ART test well over the six‐month pilot test period exceeded 9,500 pounds based on air monitoring data. The ART technology proved effective and cost‐efficient in reducing contaminant concentrations and removing a large mass of contamination from the subsurface in a short period of time. The radius of influence of the ART technology at the site was estimated to range between 65 and 170 feet. © 2007 Wiley Periodicals, Inc.     

1,4‐Dioxane: Emerging technologies for an emerging contaminant

The synthetic chemical, 1,4‐dioxane, is classified by the U.S. Environmental Protection Agency (EPA) as a probable human carcinogen. Between 2013 and 2015, the EPA detected 1,4‐dioxane in public drinking water supplies in 45 states at concentrations up to 33 µg/L and in groundwater from releases at hazardous waste sites across the United States. Although a Federal maximum contaminant level drinking water standard has not yet been proposed, state‐specific standards and criteria are as low as 0.3 µg/L. 1,4‐Dioxane is a recalcitrant chemical in that applications of conventional treatment technologies have had limited success in reducing concentrations in water to meet current and proposed health‐protective levels. Although mainly used as a stabilizer for the solvent 1,1,1‐trichloroethane, it has been used in other industrial processes and has been detected in a variety of consumer products, such as foods, pharmaceuticals, cosmetics, and detergents. The high aqueous solubility of 1,4‐dioxane coupled with limited solubility of chlorinated solvents typically found in conjunction with 1,4‐dioxane contamination is the primary reason for its treatment challenges. In the last several years, an alternative, cost‐effective technology has been developed that has demonstrated treatment to levels significantly lower than the Federal and state‐specific goals. This article provides a Federal and state‐by‐state summary of 1,4‐dioxane‐specific drinking water and groundwater concentration criteria and qualitative comparison of the effectiveness of conventional treatment technologies compared to the effectiveness of an alternative treatment technology. A case study is also provided to present details regarding the application of an alternative treatment technology at an active groundwater remediation site in California.     

ART in‐well air stripping—An innovative technology succeeds where other technologies have failed

Accelerated Remediation Technologies LLC (ART) developed a proprietary (patent‐pending) effective remediation technology that is based on verified and established concepts. The ART technology combines in‐situ air stripping, air sparging, soil vapor extraction, enhanced bioremediation/oxidation, and Dynamic Subsurface Circulation^TM in an innovative wellhead system. The system is designed to accommodate a 4‐inch well and is cost‐effective when compared with other remediation technologies. The air‐sparging component results in lifting the water table. This lifting of the water in the well causes a net reduction in head at the well location. Vacuum pressure (the vapor‐extraction component) is applied on top of the well point to extract vapor from the subsurface. The negative pressure from the vacuum extraction results in water suction that creates additional water lifting (mounding). A submersible pump is placed at the bottom of the well to recirculate water to the top for downward discharge through a spray head. The water cascades down the interior of the well similar to what occurs in an air‐stripping tower. Enhanced stripping via air sparging near the bottom of the well occurs simultaneously. In essence, the well acts as a subsurface air‐stripping tower. The pumped‐and‐stripped, highly oxygenated water flows down well annulus and over the “mounded” water back in to the aquifer, which creates a circulation zone around the well to further enhance cleanup. The ART technology has been implemented at several sites nationwide, including industrial laundry facilities, manufacturing plants, and service stations, and has achieved significant reductions in contaminant concentrations. Specifically, a concentration of tetrachloroethene (PCE) decreased from 2,700 to 240 μg/l, in 13 days. In less than three months, the concentrations dropped further to 79 μg/l, which is within the range of background levels. Other sites utilizing the technology have exhibited similar reduction trends in complex subsurface environments. © 2002 Wiley Periodicals, Inc.     

In situ thermal remediation of DNAPL and LNAPL using electrical resistance heating

Electrical resistance heating (ERH) is an in situ treatment for soil and groundwater remediation that can reduce the time to clean up volatile organic compounds (VOCs) from years to months. The technology is now mature enough to provide site owners with both performance and financial certainty in their site‐closure process. The ability of the technology to remediate soil and groundwater impacted by chlorinated solvents and petroleum hydrocarbons regardless of lithology proves to be beneficial over conventional in situ technologies that are dependent on advective flow. These conventional technologies include: soil vapor recovery, air sparging, and pumpand‐treat, or the delivery of fluids to the subsurface such as chemical oxidization and bioremediation. The technology is very tolerant of subsurface heterogeneities and actually performs as well in low‐permeability silts and clay as in higher‐ permeability sands and gravels. ERH is often implemented around and under buildings and public access areas without upsetting normal business operations. ERH may also be combined with other treatment technologies to optimize and enhance their performance. This article describes how the technology was developed, how it works, and provides two case studies where ERH was used to remediate complex lithologies. © 2005 Wiley Periodicals, Inc.     

A Multiple Lines of Evidence Framework to Evaluate Intrinsic Biodegradation of 1,4‐Dioxane

Development of a multiple lines of evidence (MLOE) framework to evaluate the intrinsic biodegradation potential of 1,4‐dioxane is vital to implementing management strategies at groundwater sites impacted by 1,4‐dioxane. A comprehensive MLOE approach was formed to provide significant evidence of natural degradation of 1,4‐dioxane comingled with tetrahydrofuran (THF) within a large, diffuse plume. State‐of‐the art molecular biological analyses and compound‐specific isotope analysis (CSIA) were employed to support more traditional approaches for data analysis (concentration trend analyses, spatial distribution, temporal changes, geochemical biodegradation attenuation indicators, plume mass estimates, and fate and transport modeling). The molecular analyses demonstrated that microorganisms capable of both metabolic and cometabolic degradation of 1,4‐dioxane were present throughout the groundwater plume, whereas the CSIA data provided supporting evidence of biodegradation. 1,4‐Dioxane biomarkers were present and abundant throughout the 1,4‐dioxane plume, and our biomarkers tracked the plume with reasonable accuracy. Evidence also suggests that THF‐driven cometabolic biodegradation as well as catabolic 1,4‐dioxane biodegradation were active at this site. These data supplemented the traditional lines of evidence approaches, which demonstrated that 1,4‐dioxane attenuation was occurring across the groundwater plume and that nondestructive physical processes alone did not account for the observed 1,4‐dioxane attenuation. This MLOE framework combining new and traditional analyses demonstrates that this site has a significant capacity for intrinsic biodegradation of 1,4‐dioxane. ©2016 Wiley Periodicals, Inc.     

Insufficient source area remediation results in the rebound of TCE breakdown products in groundwater

In the early 1990s, a soil removal action was completed at a former disposal pit site located in southern Michigan. This action removed waste oil, cutting oil, and chlorinated solvents from the unsaturated zone. To contain groundwater contaminant migration at the site, a groundwater pump‐and‐treat system comprised of two extraction wells operating at a combined flow of 50 gallons per minute, carbon treatment, and a permitted effluent discharge was designed, installed, and operated for over 10 years. Groundwater monitoring for natural attenuation parameters and contaminant attenuation modeling demonstrated natural attenuation of the contaminant plume was adequate to attain site closure. As a result of incomplete contaminant source removal, a rebound of contaminants above the levels established in the remedial action plan (RAP) has occurred in the years following system shutdown and site closure. Groundwater concentrations have raised concerns regarding potential indoor air quality at adjacent residential properties constructed in the past 9 to 10 years. The only remedial option available in the original RAP is to resume groundwater pump‐and‐treat. To remediate the source area, an alternate remediation strategy using an ozone sparge system was developed. The ozone sparge remediation strategy addresses the residual saturated zone contaminants beneath the former disposal pit and reestablishes site closure requirements without resumption of the pump‐and‐treat system. A pilot study was completed successfully; and the final system design was subsequently approved by the Michigan Department of Environmental Quality. The system was installed and began operations in July 2010. As of the January 2011 monitoring event, the system has shown dramatic improvement in site contaminant concentrations. The system will continue to operate until monitoring results indicate that complete treatment has been obtained. The site will have achieved the RAP objectives when the system has been shut down and meets groundwater residential criteria for four consecutive quarters. © 2011 Wiley Periodicals, Inc.     

Best Available Treatment Technologies Applied to Groundwater Circulation Wells

Groundwater circulation wells (GCWs) are a quasi‐in‐situ method for remediating groundwater in areas where remediation techniques that limit the water available for municipal, domestic, industrial, or agricultural purposes are inappropriate. The inherently resource‐conservative nature of groundwater circulation wells is also philosophically appealing in today's culture, which is supportive of green technologies. Groundwater circulation wells involve the circulation of groundwater through a dual‐screen well, with treatment occurring between the screens. The wells are specifically designed so that one well screen draws in groundwater and the second returns the groundwater after it has been treated within the well. Historically, the treatment has been performed with specialized equipment proprietary to GCW vendors. Two full‐scale pilot systems at a formerly used Defense Superfund site in Nebraska used best available technologies for treatment components. A multiple‐tray, low‐profile air stripper typically used for pump‐and‐treat remediation systems was successfully adapted for the GCW pilot system located in a trichloroethylene (TCE) hot spot. An ultraviolet water disinfection system was successfully adapted for the GCW pilot system located in a hot spot contaminated with the explosive compound hexhydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX). The pilot systems showed that GCW technology is competitive with a previously considered pump‐and‐treat alternative for focused extraction, and the regulatory community was supportive of additional GCW applications. A remedial design for the site includes 12 more GCW systems to complete focused remediation requirements. © 2002 Wiley Periodicals, Inc.     

In Situ Remediation of 1,4‐Dioxane Using Electrical Resistance Heating

Recent regulatory changes need more challenging treatment goals for 1,4‐dioxane. However, significant treatment limitations exist in part due to the high solubility and low Henry's law constant of 1,4‐dioxane. Two case studies are reported with substantial 1,4‐dioxane concentration reductions through in situ thermal remediation via electrical resistance heating (ERH). Concentration reductions greater than 99.8 percent of 1,4‐dioxane have been observed in the field using ERH. Concentrations of 1,4‐dioxane in air and steam extracted by an ERH vapor recovery system have also been evaluated. Laboratory studies were conducted to further understand the mechanisms that enable ERH remediation of 1,4‐dioxane. Vapor liquid equilibrium studies in water and soil were conducted and utilized to develop an ERH treatment cost model for 1,4‐dioxane. Existing field data were correlated to the 1,4‐dioxane treatment cost model. Field observations and laboratory testing indicate steam stripping that occurs through ERH remediation is an effective treatment method for 1,4‐dioxane. ©2015 Wiley Periodicals, Inc.     

Treatment technologies for 1,4‐Dioxane: Fundamentals and field applications

1,4‐Dioxane is a synthetic industrial chemical frequently found at contaminated sites where 1,1,1‐trichloroethane was used for degreasing. It is a probable human carcinogen and has been found in groundwater at sites throughout the United States. The physical and chemical properties and behavior of 1,4‐dioxane create challenges for its characterization and treatment. It is highly mobile and has not been shown to readily biodegrade in the environment. In December 2006, the U.S. Environmental Protection Agency's Office of Superfund Remediation and Technology Innovation (OSRTI) prepared a report titled “Treatment Technologies for 1,4‐Dioxane: Fundamentals and Field Applications.” The report provides information about the chemistry of dioxane, cleanup goals, analytical methods, available treatment technologies, and site‐specific treatment performance data. The information may be useful to project managers, technology providers, consulting engineers, and members of academia faced with addressing dioxane at cleanup sites or in drinking water supplies. This article provides a synopsis of the US EPA report, which is available at http://cluin.org/542R06009 . © 2007 Wiley Periodicals, Inc.     

Developing Life‐Cycle Environmental Response Costs for Leaking Underground Storage Systems at Service Station Sites

Leaking underground storage tank systems at service stations have resulted in tens of thousands of petroleum releases and associated groundwater chemical plumes often extending hundreds of feet off‐site. Technical and engineering approaches to assess and clean up releases from underground tanks, product lines, and dispensers using technologies such as soil vapor extraction, air sparging, biostimulation, and monitored natural attenuation are well understood and widely published throughout the literature. This article summarizes life‐cycle environmental response costs typically encountered using site‐specific cost estimation or metric‐based cost categories considering the overall complexity of site conditions: (1) simple sites where response actions require smaller scale assessments and/or remediation and have limited or no off‐site impacts; (2) average sites where response actions require larger scale assessments and/or remediation typical of petroleum releases; (3) complex sites where response actions require greater on‐site and/or off‐site remediation efforts; and (4) mega sites where petroleum plumes have impacted public or private water supplies or where petroleum vapors have migrated into occupied buildings. Associated cleanup cost estimates rely upon appropriate combinations of individual work elements and the duration of operation, maintenance, and monitoring activities. These cost estimates can be offset by state reimbursement funds, coverage in purchase agreements, and insurance policies. A case study involving a large service station site portfolio illustrates the range of site complexity and life‐cycle environmental response costs. © 2014 Wiley Periodicals, Inc.     

A study of treatment options to remediate explosives and perchlorate in soils and groundwater at Camp Edwards,Massachusetts

The Army National Guard initiated an Innovative Technology Evaluation (ITE) Program in March 2000 to study potential remedial technologies for the cleanup of explosives‐contaminated soil and groundwater at the Camp Edwards site on the Massachusetts Military Reservation. The soil technologies chosen for the ITE program were: soil washing, chemical oxidation, chemical reduction, thermal desorption/destruction (LTTD), bioslurry, composting, and solid phase bioremediation. The technologies were evaluated based on their ability to treat both washed and untreated soil. A major factor considered was the ability to degrade explosives, such as RDX, found in particulate form in the soils. The heterogeneous nature of explosives in soils dictates that the preferred technology must be able to treat explosives in all forms, including the particulate form. Groundwater remediation technologies considered include: in situ cometabolic reduction, two forms of in situ chemical oxidation, Fenton‐like oxidation and potassium permanganate. This article presents the results of each of the remedial technologies evaluated and discusses which technologies met the established ITE performance goals. © 2003 Wiley Periodicals, Inc.     

Ex situ treatment of MTBE‐containing groundwater by a UV peroxide system

This article describes the design, implementation, and operating results for an ex situ ultraviolet/hydrogen peroxide (UVP) system to treat methyl tert‐butyl ether (MTBE) in extracted groundwater. The UVP modification was designed to reduce the operation and maintenance costs of an existing groundwater pump‐and‐treat treatment system that relied on air stripping and carbon adsorption. The UVP system is relatively inexpensive and can easily be scaled to cope with different groundwater extraction rates up to 80 gpm by adding UV lamps in series or in parallel at the higher groundwater extraction rates. The MTBE concentration in the effluent from the UVP system to the carbon vessels decreased from an average of 590 μg/L to approximately 2 μg/L on average over 33 months of operation of the UVP. Incorporation of this UVP modification as a second‐stage treatment to the groundwater pump‐and‐treat/soil vapor extraction system, after the air stripper and prior to the carbon vessels, significantly increased the usable life of the carbon (from two months previously to about two years after installation) and completely resolved the issue of frequent MTBE breakthroughs of the carbon that had plagued the remediation system since its inception. © 2006 Wiley Periodicals, Inc.     

UV peroxidation with air stripping for optimized removal of VOCs from groundwater

No one remedial technology is best suited to treat every groundwater contaminant plume. This article describes how pilot testing and analytical evaluation targeted selection of two treatment technologies, UV peroxidation and air stripping, to be used in series to create a synergistic, cost-effective pump-and-treat system for the removal of VOCs from groundwater. Pilot plant size equipment was employed to treat the VOC-contaminated groundwater in order to obtain site-specific reaction rates and to develop full-scale design parameters. It was found that by using the two treatment technologies in combination, the influent concentration of 2,000 ppb total VOCs could be reduced to less than 1 ppb, thus meeting drinking water standards.     

Sustainable Remediation Considerations for Treatment of 1,4‐Dioxane in Groundwater

1,4‐Dioxane remediation is challenging due to its physiochemical properties and low target treatment levels. As such, applications of traditional remediation technologies have proven ineffective. There are a number of promising remediation technologies that could potentially be scaled for successful application to groundwater restoration. Sustainable remediation is an important consideration in the evaluation of remediation technologies. It is critically important to consider sustainability when new technologies are being applied or new contaminants are being treated with traditional technologies. There are a number of social, economic, and environmental drivers that should be considered when implementing 1,4‐dioxane treatment technologies. This includes evaluating sustainability externalities by considering the cradle‐to‐grave impacts of the chemicals, energy, processes, transportation, and materials used in groundwater treatment. It is not possible to rate technologies as more or less sustainable because each application is context specific. However, by including sustainability thinking into technology evaluations and implementation plans, decisions makers can be more informed and the results of remediation are likely to be more effective and beneficial. There are a number sustainable remediation frameworks, guidance documents, footprint assessment tools, life cycle assessment tools, and best management practices that can be utilized for these purposes. This paper includes an overview describing the importance of sustainability in technology selection, identifies sustainability impacts related to technologies that can be used to treat 1,4‐dioxane, provides an approximating approach to assess sustainability impacts, and summarizes potential sustainability impacts related to promising treatment technologies. ©2016 Wiley Periodicals, Inc.     

The treatment of contaminated water at remedial wood preserving sites

Contaminated groundwater and surface water have posed a great challenge in restoring wood preserving sites to beneficial use. Often contaminated groundwater plumes extend far beyond the legal property limits, adversely impacting drinking water supplies and crop lands. To contain, treat, and/or remediate these valuable resources is an important part of restoring these impacted sites. Various options are available for remediating the groundwater and other affected media at these sites. Frequently, pump and treat technologies have been used that can provide well‐head treatment at installed extraction wells. This approach has shown to be costly and excessively time consuming. Some of the technologies used for pump and treat are granular activated carbon (GAC), biotreatment, and chemical oxidation. Other approaches use in‐situ treatment applications that include enhanced bioremediation, monitored natural attenuation (biotic and abiotic), and chemical reduction/fixation. Ultimately, it may only be feasible, economically or practicably, to use hydraulic containment systems. Depending upon site‐specific conditions, these treatment approaches can be used in various combinations to offer the best remedial action. A comparison of water treatment system costs extrapolated from the treatability studies performed on contaminated groundwater from the McCormick/Baxter Superfund site in Stockton, California, yielded operation and maintenance costs of $1.19/1,000 gal. for carbon treatment and $7.53/1,000 gal. for ultraviolet (UV) peroxidation, respectively.     

Sustainable wind‐driven bioventing at a petroleum hydrocarbon–impacted site

Bioventing—the injection of air into the vadose zone to increase microbial activity—is a commonly used, proven technology for remediating volatile organic compounds present in the vadose zone. Passive systems driven by wind or solar power are both more cost‐effective and sustainable than conventional systems. Such a passive system is being applied successfully to remediate a site impacted with total petroleum hydrocarbons (TPH) and benzene, toluene, ethylbenzene, and xylenes (BTEX) in soil. Bioventing technology was approved by the regulatory agency as an interim remedial action to remove chemicals of concern (COCs) in the vadose zone. A bioventing pilot study was conducted to evaluate the effectiveness of COC removal and collect parameters for full‐scale design and implementation. To evaluate the potential to use wind‐driven bioventing technology, two mobile weather stations were installed at the site and monitored for one month for a wind speed study. Based on the pilot‐test data and wind speed research, 12‐inch diameter funnel/vane 360‐degree wind collectors were designed as passive wind‐driven air‐injection devices and connected to existing monitoring wells. The measured air velocity ranged from 20 to 110 feet per minute during the start‐up and the first three months of operation and maintenance. Monitoring indicated a 20 percent oxygen delivery and greater than 90 percent reduction in COC concentrations, demonstrating a successful sustainable remediation with no power requirement and minimal operation and maintenance. © 2012 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.