Treatment of Perchlorate‐Contaminated Groundwater Using Highly Selective,Regenerable Ion‐Exchange Technology: A Pilot‐Scale Demonstration

Treatment of perchlorate‐contaminated groundwater using highly selective, regenerable ion‐exchange technology has been recently demonstrated at Edwards Air Force Base, California. At an influent concentration of about 450 μg/l ClO₄^?, the bifunctional anion‐exchange resin bed treated approximately 40,000 empty bed volumes of groundwater before a significant breakthrough of ClO₄^? occurred. The presence of relatively high concentrations of chloride and sulfate in site groundwater did not appear to affect the ability of the bifunctional resin to remove ClO₄^?. The spent resin bed was successfully regenerated using the FeCl₃^?HCl regeneration technique recently developed at the Oak Ridge National Laboratory, and nearly 100 percent of sorbed ClO₄^? was displaced or recovered after elution with as little as about two bed volumes of the regenerant solution. In addition, a new methodology was developed to completely destroy ClO₄^? in the FeCl₃^?HCl solution so that the disposal of perchlorate‐containing hazardous wastes could be eliminated. It is therefore anticipated that these treatment and regeneration technologies may offer an efficient and cost‐effective means to remove ClO₄^? from contaminated groundwater with significantly reduced generation of waste requiring disposal. © 2002 Wiley Periodicals, Inc.     

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.     

Full‐scale in‐situ biobarrier demonstration for containment and treatment of MTBE

The Naval Facilities Engineering Service Center (NFESC), Arizona State University, and Equilon Enterprises LLC are partners in an innovative Environmental Security Technology Certification Program cleanup technology demonstration designed to contain dissolved MTBE groundwater plumes. This full‐scale demonstration is being performed to test the use of an oxygenated biobarrier at Naval Base Ventura County, in Port Hueneme, California. Surprisingly, few cost‐effective in‐situ remedies are known for the cleanup of MTBE‐impacted aquifers, and remediation by engineered in‐situ biodegradation was thought to be an unlikely candidate just a few years ago. This project demonstrates that MTBE‐impacted groundwater can be remediated in‐situ through engineered aerobic biodegradation under natural‐flow conditions. With respect to economics, the installation and operation costs associated with this innovative biobarrier system are at least 50 percent lower than those of a conventional pump and treat system. Furthermore, although it has been suggested that aerobic MTBE biodegradation will not occur in mixed MTBE‐BTEX dissolved plumes, this project demonstrates otherwise. The biobarrier system discussed in this article is the largest of its kind ever implemented, spanning a dissolved MTBE plume that is over 500 feet wide. This biobarrier system has achieved an in‐situ treatment efficiency of greater than 99.9 percent for dissolved MTBE and BTEX concentrations. Perhaps of greater importance is the fact that extensive performance data has been collected, which is being used to generate best‐practice design and cost information for this biobarrier technology. © 2001 John Wiley & Sons, 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.     

Selectivity of Nano Zerovalent Iron in In Situ Chemical Reduction: Challenges and Improvements

Nano zerovalent iron (nZVI) is a promising remediation technology utilizing in situ chemical reduction (ISCR) to clean up contaminated groundwater at hazardous waste sites. The small particle size and large surface area of nZVI result in high reactivity and rapid destruction of contaminants. Over the past 20 years, a great deal of research has advanced the nZVI technology from bench‐scale tests to field‐scale applications. However, to date, the overall number of well‐characterized nZVI field deployments is still small compared to other alternative remedies that are more widely applied. Apart from the relatively high material cost of nZVI and questions regarding possible nanotoxicological side effects, one of the major obstacles to the widespread utilization of nZVI in the field is its short persistence in the environment due to natural reductant demand (NRD). The NRD for nZVI is predominantly due to reduction of water, but other reactions with naturally present oxidants (e.g., oxygen) occur, resulting in situ conditions that are reducing (high in ferrous iron phases and H₂) but with little or no Fe(0). This article reviews the main biogeochemical processes that determine the selectivity and longevity of nZVI, summarizes data from prior (laboratory and field) studies on the longevity of various common types of nZVI, and describes modifications of nZVI that could improve its selectivity and longevity for full‐scale applications of ISCR. © 2016 Wiley Periodicals, Inc.     

In‐Situ Plasma Remediation of Contaminated Soils

Plasma‐torch technology has excellent potential for cost‐effective treatment of contaminated soils and other types of buried waste material. This article describes the evolution and basic features of this technology, with emphasis on the non‐transferred plasma arc torch. In addition, selected results from both laboratory experiments and field demonstrations will show how this technology can successfully destroy hazardous/toxic materials and/or stabilize contaminants in situ so they are no longer a threat to human health and the environment. © 2001 John Wiley & Sons, 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.     

Rapid full‐scale bioremediation of perchlorate in soil at a large brownfields site

The former Bermite site north of Los Angeles, California, was used to manufacture various explosives and related products containing energetic compounds, including perchlorate. Remediation of perchlorate in site soil and groundwater is being conducted to meet regulatory requirements and allow planned redevelopment activities to proceed. The general approach to perchlorate remediation of shallow soil at the site includes excavation of affected soils followed by ex situ bioremediation. Glycerin was chosen for use as an electron donor because of its stability, safety, low cost, and regulatory acceptance. However, full‐scale bioremediation operation with glycerin initially resulted in inconsistent results despite consistent perchlorate biodegradation observed in treatability study microcosms. To eliminate the inconsistency and optimize the biotreatment process, additional studies were performed in the field on parallel tracks to determine crucial factor(s) that influenced inconsistent breakdown of perchlorate in site soils. Total Kjeldahl nitrogen (TKN) was determined to be a significant factor limiting perchlorate biodegradation. The addition of di‐ammonium phosphate (DAP) resulted in the consistent and complete perchlorate removal, generally within two weeks of incubation with a median destruction rate of about 200 μg/kg/day. Soil processing rates were gradually increased over the year, and, by the summer, approximately 2,000 to 2,500 tons of soil were being processed per day with a total of approximately 160,000 tons processed by the end of July. The total unit treatment cost for the process is about approximately $35/ton. The glycerin‐DAP process is playing a major role in the remediation of this 1,000‐acre former industrial site. © 2008 Wiley Periodicals, Inc.     

Combined thermal and zero‐valent iron In Situ soil mixing remediation technology

Thermal remediation of contaminated soils and groundwater by injection of hot air and steam using large‐diameter auger in situ soil mixing effectively remediates volatile and semivolatile organic compounds. This technology removes large amounts of contamination during the early treatment stages, but extended treatment times are needed to achieve high removal percentages. Combining thermal treatment with another technology that can be injected and mixed into the soil, and that continues to operate after removal of the drilling equipment, improves removal efficiency, and reduces cost. Using field‐determined pseudo first‐order removal rates, the cost of the combined remediation of chlorinated volatile organic compounds (CVOCs) by thermal treatment followed by reductive dechlorination by iron powder has been estimated as 57 percent of the cost of thermal treatment alone. This analysis was applied to a case‐study remediation of 48,455 cubic yards, which confirmed the cost estimate of the combined approach and showed over 99.8 percent removal of trichloroethene and other chlorinated VOCs. © 2010 Wiley Periodicals, Inc.     

Potential for bioremediation of the perchlorate‐contaminated sediments in the Las Vegas Wash area,Henderson, Nevada

This study investigates the potential for perchlorate biodegradation in the sediments of the Las Vegas Wash area in Henderson, Nevada. The continuous transport of perchlorate from a contaminated seepage to the Las Vegas Wash, Lake Mead, and the Colorado River has resulted in considerable deposition of perchlorate along the sediments of the Las Vegas Wash. The contaminated sediments act as a distributed source of perchlorate, making efforts to stop the flow of perchlorate to the Colorado River very challenging. In this study, perchlorate‐ reducing bacteria were enumerated and microcosm tests were performed to investigate the role of indigenous microorganisms and the limitations to natural perchlorate biodegradation in the contaminated sediments. The results of microcosm tests revealed that, despite the high number of perchloratereducing bacteria present, natural perchlorate in the area appears to be limited by (1) high salinity levels, the presence of nitrate, and the low perchlorate concentrations present in the sediments and (2) an insufficient carbon source. However, the potential for in situ bioremediation of the sediments along the Wash area is considered to be high due to the presence of significant numbers of perchlorate‐ reducing bacteria and to the ease in which an additional carbon source could be provided to sustain nitrate and perchlorate biodegradation. The economics of this process are expected to be very favorable; however, detailed cost estimates, pilot‐scale testing, and permit applications are required before this concept can be applied. © 2005 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.     

The use of zero‐valent iron injection to remediate groundwater: Results of a pilot test at the Marshall Space Flight Center

In situ treatability studies are being conducted to evaluate various in situ technologies to manage groundwater contamination at the NASA Marshall Space Flight Center in Huntsville, Alabama. The focus of these studies is to evaluate remediation options for contaminated (mostly aerobic) groundwater occurring within the basal portion of a clayey residuum called the rubble zone. The tension‐saturated media and unsaturated media lying above the rubble zone are also being treated where they make up a significant component of the contaminant mass. An in situ chemical reduction field pilot test was implemented (following bench‐scale tests) during July and August 2000. The test involved the injection of zero‐valent iron powder in slurry form, using the Ferox^SM process patented by ARS Technologies, Inc. The pilot test focused on trichloroethene (TCE)‐contaminated groundwater within the rubble zone. Maximum pre‐injection concentrations of about 72,800 micrograms per liter (μg/l) were observed and no secondary sources are believed to exist beneath the area. The potential presence of unexploded ordnance forced an implementation strategy where source area injections were completed, as feasible, followed by overlapping injections in a down gradient alignment to create a permeable reactive zone for groundwater migration. Eight post‐injection rounds of groundwater performance monitoring were completed. The results are encouraging, in terms of predicted responses and decreasing trends in contaminant levels. © 2003 Wiley Periodicals, Inc.     

Remediating TCE‐contaminated groundwater in low‐permeability media using hydraulic fracturing to emplace zero‐valent iron/organic carbon amendment

A field pilot test in which hydraulic fracturing was used to emplace granular remediation amendment (a mixture of zero‐valent iron [ZVI] and organic carbon) into fine‐grained sandstone to remediate dissolved trichloroethene (TCE)‐contaminated groundwater was performed at a former intercontinental ballistic missile site in Colorado. Hydraulic fracturing was used to enhance the permeability of the aquifer with concurrent emplacement of amendment that facilitates TCE degradation. Geophysical monitoring and inverse modeling show that the network of amendment‐filled fractures extends throughout the aquifer volume targeted in the pilot test zone. Two years of subsequent groundwater monitoring demonstrate that amendment addition resulted in development of geochemical conditions favorable to both abiotic and biological TCE degradation, that TCE concentrations were substantially reduced (i.e., greater than 90 percent reduction in TCE mass), and that the primary degradation processes are likely abiotic. The pilot‐test data aided in re‐evaluating the conceptual site model and in designing the full‐scale remedy to address a larger portion of the TCE‐contaminated groundwater plume. © 2012 Wiley Periodicals, Inc.     

Combining Ion‐exchange (IX) technology and biological reduction for perchlorate removal

Ion‐exchange (IX) resin is perhaps the most promising technology to remove the contaminant perchlorate (ClO₄^?) from waters. However, ion exchange is only a separation technology that transfers the perchlorate from waters to the waste solutions used to regenerate the resins. The waste solutions contain high perchlorate concentrations, and treatment technologies for these regenerant solutions are needed. In this article, we review the latest knowledge on perchlorate removal by ion‐exchange resins; propose three systems that combine ion‐exchange resins (for perchlorate removal) and biological reduction for treating the waste solutions resulting from resin regeneration; and discuss the challenges and research needed to fully develop the proposed technology. © 2002 Wiley Periodicals, Inc.     

The Hidden Potential of Mass‐based Treatment: A Method for Preventing Rebound

A major challenge for in situ treatment is rebound. Rebound is the return of contaminant concentrations to near original levels following treatment, and frequently occurs because much of the residual nonaqueous phase liquid (NAPL) trapped within the soil capillaries or rock fractures remains unreachable by conventional in situ treatment. Fine‐textured strata have an especially strong capacity to absorb and retain contaminants. Through matrix diffusion, the contaminants dissolve back into groundwater and return with concentrations that can approach pretreatment levels. The residual NAPL then serves as a continuing source of contamination that may persist for decades or longer. A 0.73‐acre (0.3‐hectare) site in New York City housed a manufacturer of roofing materials for approximately 60 years. Coal tar served as waterproofing material in the manufacturing process and releases left behind residual NAPL in soils. An estimated 47,000 pounds (21,360 kg) of residual coal tar NAPL contaminated soils and groundwater. The soils contained strata composed of sands, silty sands, and silty clay. A single treatment using the RemMetrik^® process and Pressure Pulse Technology^® (PPT) targeted the contaminant mass and delivered alkaline‐activated sodium persulfate to the NAPL at the pore‐scale level via in situ treatment. Posttreatment soil sampling demonstrated contaminant mass reductions over 90 percent. Reductions in posttreatment median groundwater concentrations ranged from 49 percent for toluene to 92 percent for xylenes. Benzene decreased by 87 percent, ethylbenzene by 90 percent, naphthalene by 80 percent, and total BTEX by 91 percent. Mass flux analysis three years following treatment shows sustained reductions in BTEX and naphthalene, and no rebound. ©2015 Wiley Periodicals, Inc.     

Surfactant‐Oxidant Co‐Application for Soil and Groundwater Remediation

In situ chemical oxidation (ISCO) typically delivers oxidant solutions into the subsurface for contaminant destruction. Contaminants available to the oxidants, however, are limited by the mass transfer of hydrophobic contaminants into the aqueous phase. ISCO treatments therefore often leave sites with temporarily clean groundwater which is subject to contaminant rebound when sorbed and free phase contaminants leach back into the aqueous phase. Surfactant Enhanced In situ Chemical Oxidation (S‐ISCO^®) uses a combined oxidant‐surfactant solution to provide optimized contaminant delivery to the oxidants for destruction via desorption and emulsification of the contaminants by the surfactants. This article provides an overview of S‐ISCO technology, followed by an implementation case study at a coal tar contaminated site in Queens, New York. Included are data points from the site which demonstrate how S‐ISCO delivers desorbed contaminants without uncontrolled contaminant mobilization, as desorbed and emulsified contaminants are immediately available to the simultaneously injected oxidant for reaction. ©2016 Wiley Periodicals, Inc.     

In Situ treatment of PFAS‐impacted groundwater using colloidal activated Carbon

Poly‐ and perfluoroalkyl substances (PFASs) have been identified by many regulatory agencies as contaminants of concern within the environment. In recent years, regulatory authorities have established a number of health‐based regulatory and evaluation criteria with groundwater PFAS concentrations typically being less than 50 nanograms per liter (ng/L). Subsurface studies suggest that PFAS compounds are recalcitrant and widespread in the environment. Traditionally, impacted groundwater is extracted and treated on the surface using media such as activated carbon and exchange resins. These treatment technologies are generally expensive, inefficient, and can take decades to reach treatment objectives. The application of in situ remedial technologies is common for a wide variety of contaminants of concern such as petroleum hydrocarbons and volatile organic compounds; however, for PFASs, the technology is currently emerging. This study involved the application of colloidal activated carbon at a site in Canada where the PFASs perfluorooctanoate (PFOA) and perfluorooctane sulfonic acid (PFOS) were detected in groundwater at concentrations up to 3,260 ng/L and 1,450 ng/L, respectively. The shallow silty‐sand aquifer was anaerobic with an average linear groundwater velocity of approximately 2.6 meters per day. The colloidal activated carbon was applied using direct‐push technology and PFOA and PFOS concentrations below 30 ng/L were subsequently measured in groundwater samples over an 18‐month period. With the exception of perfluoroundecanoic acid, which was detected at 20 ng/L and perfluorooctanesulfonate which was detected at 40 ng/L after 18 months, all PFASs were below their respective method detection limits in all postinjection samples. Colloidal activated carbon was successfully distributed within the target zone of the impacted aquifer with the activated carbon being measured in cores up to 5 meters from the injection point. This case study suggests that colloidal activated carbon can be successfully applied to address low to moderate concentrations of PFASs within similar shallow anaerobic aquifers.     

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.     

The horizontal reactive media treatment well (HRX Well®) for passive in situ remediation: Design,implementation, and sustainability considerations

A new in situ remediation concept termed a Horizontal Reactive Media Treatment Well (HRX Well^®) is presented that utilizes a horizontal well filled with reactive media to passively treat contaminated groundwater in situ. The approach involves the use of a large‐diameter directionally drilled horizontal well filled with solid reactive media installed parallel to the direction of groundwater flow. The engineered contrast in hydraulic conductivity between the high in‐well reactive media and the ambient aquifer hydraulic conductivity results in the passive capture, treatment, and discharge back to the aquifer of proportionally large volumes of groundwater. Capture and treatment widths of up to tens of feet can be achieved for many aquifer settings, and reductions in downgradient concentrations and contaminant mass flux are nearly immediate. Many different types of solid‐phase reactive treatment media are already available (zero valent iron, granular activated carbon, biodegradable particulate organic matter, slow‐release oxidants, ion exchange resins, zeolite, apatite, etc.). Therefore, this concept could be used to address a wide range of contaminants. Laboratory and pilot‐scale test results and numerical flow and transport model simulations are presented that validate the concept. The HRX Well can access contaminants not accessible by conventional vertical drilling and requires no aboveground treatment or footprint and requires limited ongoing maintenance. A focused feasibility evaluation and alternatives analysis highlights the potential cost and sustainability advantages of the HRX Well compared to groundwater extraction and treatment systems or funnel and gate permeable reactive barrier technologies for long‐term plume treatment. This paper also presents considerations for design and implementation for a planned upcoming field installation.