Laboratory validation study of new vapor‐phase‐based approach for groundwater monitoring

Recent improvements in field‐portable analytical equipment allow accurate on‐site measurement of VOCs present in air at concentrations of less than 0.1 parts per million volume (ppmv). The objective of this project is to determine if the use of these instruments for vapor‐phase measurements of headspace in a monitoring well can serve as a reliable and accurate method for monitoring volatile organic compound (VOC) concentrations in groundwater under equilibrium conditions. As part of a comprehensive research project investigating the utility of this proposed monitoring method, the authors have completed a laboratory validation study to identify instruments and sample‐collection methods that will provide accurate measurement of VOC concentrations in groundwater. This laboratory validation study identified two field‐portable instruments (a gas chromatograph and a photoionization detector) with sufficient sensitivity to measure VOCs in groundwater at concentrations below typical monitoring standards (i.e., 1 to 5 μg/L). The accuracy and precision of these field instruments was sufficient to satisfy typical data‐quality objectives for laboratory‐based analysis. In addition, two sample‐collection methods were identified that yield vapor‐phase samples in equilibrium with water: direct headspace sampling and passive diffusion samplers. These sample‐collection methods allow the field instruments (which measure VOC concentrations in vapor‐phase samples) to be used to measure VOC concentrations in water. After further validation of these sample‐collection methods in the field, this monitoring method will provide a simple way to obtain accurate real‐time measurements of VOC concentrations in groundwater using inexpensive field‐portable analytical instruments. © 2009 Wiley Periodicals, Inc.     

Passive soil vapor extraction: A cost effectiveness study

An analysis of the cost effectiveness of passive soil vapor extraction (PSVE) is presented. PSVE, or “barometric pumping,” is an approach to the remediation of volatile organic compounds (VOCs) that seeks to harness and enhance the naturally occurring processes of wind and atmospheric pressure changes to facilitate the release of gas-phase contaminants from the subsurface. The technology background and current status are discussed, niches for the potential applicability of PSVE are identified, and a cost comparison with the conventional treatment method of active soil vapor extraction (ASVE) is examined.     

Using pneumatic fracturing extraction to achieve regulatory compliance and enhance voc removal from low-permeability formations

The New Jersey Department of Environmental Protection and Energy (NJDEPE) has been developing cleanup regulations that focus on remediation, rather than extended delineation, and on integrating regulatory requirements with technological developments. To this end, the NJDEPE, under the regulatory aegis of the Environmental Cleanup and Responsibility Act (ECRA), is monitoring an innovative treatment technology pilot test at a TCE-contaminated ECRA site in Hillsborough, New Jersey. The purpose of the study is to determine the applicability of pneumatic fracturing extraction (PFE) as a source-removal technique for extracting volatile organic compounds (VOCs) trapped informations with low permeability. The technology being pilot tested is pneumatic fracturing extraction, a process for enhancing permeability to promote in-situ removal and treatment of VOCs. The patented process uses high-pressure air injected into an isolated subsurface zone at controlled rates and pressures. At a critical point, the geologic material ruptures, and fractures are created that radiate outward from the fracture location. At the pilot test site, formation air flow was increased from 400 percent to 700 percent. PFE is a key component of the overall remediation strategy at the Hillsborough site. Consistent with proposed NJDEPE regulations, a ground-water pump-and-treat system will be installed for plume migration control. Once the pump-and-treat system has been established and shown to be effective, a more aggressive source removal program will be implemented using PFE. This program will include construction of a vadose zone PFE system and evaluation of the use of pneumatic fracturing to remove saturated zone residual dense nonaqueous phase liquids (DNAPL). Preliminary calculations suggest that if source zone concentrations can be reduced to 10 ppm of TCE, then TCE groundwater concentrations may be reduced to background levels at the property boundary compliance points.     

Expediting remedial designs and assessments

A successful air-based remediation system, now frequently chosen for sites contaminated with VOCs, demands a thorough understanding of the nature and distribution of the VOCs and the soil air permeabilities. Considering likely remediation methods during the site investigation allows collection of all data needed for method selection and design within a single, highly efficient site visit. A case history illustrates how to integrate several data collection and testing activities into a single site visit.     

Application of passive soil gas technology to determine the source and extent of a PCE groundwater plume in an urban environment

In situations where groundwater supplies have been impacted by volatile organic compounds (VOCs), such as tetrachloroethene (PCE), and the source has not been identified, the costs to identify the source and plume migration patterns may be extremely high. The costs for an investigation increase with the number and depth of borings and the number of samples that are collected and analyzed. An environmental investigator and the Arizona Department of Environmental Quality (ADEQ) have successfully utilized passive soil gas (PSG) surveys in Arizona to cost‐effectively investigate VOC impacts to groundwater and identify potential sources of impact. PSG surveys are minimally intrusive, and more samples can be collected for the same cost when compared to active soil gas surveys and conventional soil and groundwater sampling programs. The result is a surficial representation of the contaminant plume and the location of “hot spots,'' which are the potential sources. This provides a better understanding of the nature and extent of the impact and allows for a focused subsurface investigation, which subsequently reduces drilling and sampling costs. © 2008 Wiley Periodicals, Inc.     

Expediting sustainable brownfields redevelopment by applying Triad using the membrane interface probe

Redevelopment and reuse plans are often based upon an expedited delineation and remediation life cycle, since delayed reuse usually has economic consequences. It has also become increasingly important to utilize sustainable practices to achieve investigation and remediation goals. In this article, the Triad approach is used to expedite the delineation of a source area within a municipal landfill to complete the remedial effort prior to construction of an urban civic center. The Triad approach uses the three elements of systematic project planning, dynamic work strategy, and real‐time measurement to expedite site characterization (Interstate Technology and Regulatory Council, 2003). In this article, the Triad sampling strategy consisted of two phases. The first phase included in situ screening of soil and groundwater using the membrane interface probe (MIP), and the second phase included confirmatory sampling via vertical profiles in the soil and groundwater. This study found that, using the MIP in a dynamic sampling strategy, a critical element of the Triad approach, combined with the proper placement of confirmatory samples, significantly reduced overall project cost and will expedite the site redevelopment. The use of the Triad approach also contributed to the integration of green and sustainable practices into the project. © 2010 Wiley Periodicals, Inc.     

Triad case study: Former small arms training range

The U.S. Army Corps of Engineers (US ACE) used the Triad approach to expedite site characterization of contaminated soil at the Former Small Arms Evergreen Infiltration Training Range in Fort Lewis, Washington. The characterization was designed to determine if surface soils contain significant concentrations of metals, with the focus on collecting sufficient data for determining appropriate future actions (i.e., risk analysis or soil remediation). A dynamic sampling and analytical strategy based on rapid field‐based analytical methods was created in order to streamline site activities and save resources while increasing confidence in remediation decisions. Concurrent analysis of soil samples during the demonstration of method applicability (DMA) used both field portable X‐ray fluorescence (FPXRF) and laboratory methodologies to establish a correlation between FPXRF and laboratory data. Immediately following the DMA, contaminated soil from the impact berm was delineated by collecting both FPXRF data and fixed laboratory confirmation samples. The combined data set provided analytical results that allowed for revisions to the conceptual site model for the range and directed additional sample collection activities to more clearly determine the extent and distribution of soil contamination. © 2004 Wiley Periodicals, Inc.     

Sodium Persulfate Oxidation for the Remediation of Chlorinated Solvents (USEPA Superfund Innovative Technology Evaluation Program)

This study has been conducted at the University of Connecticut (UCONN) in connection with the USEPA Superfund Innovative Technology Evaluation (SITE) program to evaluate a chemical oxidation technology (sodium persulfate) developed at UCONN. A protocol to assess the efficacy of oxidation technologies has been used. This protocol, which consists of obtaining data from a treatability study, tested two in-situ chemical oxidation technologies that can be used on soil and groundwater at a site in Vernon, Connecticut. Based on the treatability report results and additional field data collected at the site, the design for the field implementation of the chemical oxidation remediation was completed. The results indicate that both sodium persulfate and potassium permanganate were able to effectively degrade the target VOCs (i.e., PCE, TCE and cis-DCE) in groundwater and soil-groundwater matrices. In the sodium persulfate tests (120 hrs), the extent of destruction of target VOCs was 74% for PCE, 86% for TCE and 84% for cis-DCE by Na₂S₂O₈ alone and 68% for PCE, 76% for TCE, and 69% for cis-DCE by Fe(II)-catalyzed Na₂S₂O₈. The results demonstrate the sodium persulfate's ability to degrade PCE, TCE and cis-DCE. It is expected that given sufficient dose and treatment time, a higher destruction rate of the dissolved phase contamination can be achieved. The data also indicates that the catalytic effect of the iron chelate on persulfate chemistry was much less pronounced in the soil-groundwater matrix. This indicates an interaction between the iron chelate solution and the soil, which may have resulted in a lower availability of the chelated iron for catalysis. The study showed that the remediation of the VOCs-contaminated soil and groundwater by in-situ chemical oxidation using sodium persulfate is feasible at the Roosevelt Mills site. As a result, the USEPA SITE program will evaluate this technology at this site.     

Cost-effective contaminant plume delineation using multilevel drive point samplers

Over the past several years, environmental professionals have sought new and innovative field techniques to allow on-site plume delineation and in-field location of monitoring wells. One technique adopted for site characterization is the multilevel drive point sampler (MLDPS). This technology allows sampling of soil gas and groundwater and measurement of aquifer permeability. MLDPSs offer a cost-effective solution to the high cost of plume delineation by providing in-field data for decisions on monitoring well location and depth. MLDPS technologies can increase the effectiveness of monitoring well installation programs, decrease the cost of site characterization, and accelerate the time between initial site assessment and implementation of a remediation program. MLDPS technologies offer distinct advantages over other field techniques, and a cost comparison is offered. A case study describing application of the MLDPS to the delineation of a TCE-contaminated plume is described.     

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.     

Sustainable soil remediation by refrigerated condensation at sites with “high‐concentration” recalcitrant compounds and NAPL: Two case studies

Remediation of recalcitrant compounds at sites with high concentrations of volatile organic compounds (VOCs) or nonaqueous‐phase liquids (NAPLs) can present significant technical and financial (long‐term) risk for stakeholders. Until recently, however, sustainability has not been included as a significant factor to be considered in the feasibility and risk evaluation for remediation technologies. The authors present a framework for which sustainability can be incorporated into the remediation selection criteria focusing specifically on off‐gas treatment selection for soil vapor extraction (SVE) remediation technology. SVE is generally considered an old and standard approach to in situ remediation of soils at a contaminated site. The focus on off‐gas treatment technology selection in this article allows for more in‐depth analysis of the feasibility evaluation process and how sustainable practices might influence the process. SVE is more commonly employed for recovery of VOCs from soils than other technologies and generally employs granular activated carbon (GAC), catalytic, or thermal oxidation, or an emerging alternative technology known as cryogenic‐compression and condensation combined with regenerative adsorption (C3–Technology). Of particular challenge to the off‐gas treatment selection process is the potential variety of chemical constituents and concentrations changing over time. Guidance is available regarding selection of off‐gas treatment technology (Air Force Center for Environmental Excellence, 1996; U.S. Environmental Protection Agency, 2006). However, there are common shortcomings of off‐gas treatment technology guidance and applications; practitioners have rarely considered sustainability and environmental impact of off‐gas treatment technology selection. This evaluation includes consideration of environmental sustainability in the selection of off‐gas treatment technologies and a region‐specific (Los Angeles, California) cost per pound and time of remediation comparisons between GAC, thermal oxidation, and C3–Technology. © 2008 Wiley Periodicals, Inc.     

The Use of Hydrogen Release Compound for the Accelerated Bioremediation of Anaerobically Degradable Contaminants: The Advent of Time-Release Electron Donors

Hydrogen Release Compound (HRC®) is a simple, passive, low-cost, and long-term option for the anaerobic bioremediation of chlorinated hydrocarbons (CHs) via reductive dehalogenation. Applications to the remediation of other compounds, such as MTBE and perchlorate, that are anaerobically degradable by other reductive mechanisms, are in progress. HRC should be viewed as a tool for the acceleration of natural attenuation at sites that would otherwise require high levels of capital investment and operating expense. HRC is a proprietary, food-quality, polylactate ester that, upon being deposited into the subsurface, slowly degrades to lactic acid. Lactic acid is then metabolized to hydrogen, which in turn drives the reductive dechlorination of CHs. This has been demonstrated effectively in the laboratory and in the field. HRC can be manufactured as a moderately flowable, injectable material, or as a thicker, implantable hard gel, to facilitate localized treatment and passive barrier designs. HRC is best utilized for the remediation of dissolved phase plumes and the associated hydrophobically sorbed contaminant. The use of HRC is not appropriate for use on free-phase DNAPL unless the total mass to be remediated is within the scope of economic feasibility in comparison to alternative treatments. Evidence suggests there is competition between reductive dehalogenators and methanogens in which the methanogens compete for the use of hydrogen in the conversion of carbon dioxide to methane. Some researchers believe that a low concentration of hydrogen favors the reductive dehalogenators and starves out the methanogens. The objective, therefore, is to keep hydrogen concentrations low. The time-release feature of HRC, which is based on the hydrolysis rate of lactic acid from the ester and the subsequent lag time to hydrogen conversion, facilitates this objective. HRC, therefore, becomes a passive form of accelerated natural attenuation, in contrast to the more capital-and management-intensive alternatives now available. Laboratory and field results are presented, the latter expanding on the first uses of HRC by various members of the engineering and consulting firm community. © 1999 John Wiley & Sons, Inc.     

Look at groundwater quality to set VOC cleanup levels

In 1981, the Arizona Department of Health Services (ADHS) discovered groundwater contamination by solvents and chromium at the Phoenix Goodyear Airport (PGA), just outside the city of Phoenix. ADHS and the U.S. EPA sampled the site for the next two years, finding that eighteen of their wells were contaminated with trichloroethene (TCE), six exceeding ADHS's action level of five micrograms per liter (μg/l). In 1983, the PGA site was added to the National Priorities List, and, in 1984, EPA began a $3 million remedial investigation, focusing on soils and groundwater. This article discusses how that investigation inspired the authors to develop a stream-lined evaluation method for PGA's volatile organic compounds (VOCs), the process for establishing VOC cleanup levels, and the $26 million of remediation work needed to be done at the site. The heart of this effort is a computer program called VLEACH, loosely standing for VOC-LEACHing, which anticipates the influence of VOCs on PGA's groundwater, even as remediation proceeds.     

Improving public health and environmental protection resulting from Superfund site investigation/remediation

A discussion of some of the deficiencies of Superfund and hazardous chemical site investigation and remediation is presented. Of concern is the adequacy of defining the constituents of concern; stormwater‐runoff monitoring; evaluating excessive bioaccumulation of hazardous chemicals in edible organisms; the extent and degree of groundwater pollution; modeling of pollutant transport in the vadose zone; translocation of subsurface pollutants to surface via plant roots, leaves, and flowers; protection of groundwater quality for nonpriority pollutants that impact aesthetic quality; and deficiencies in the quality of site data reports. Examples of these types of problems are discussed with suggestions on the approach that should be followed to improve the quality of site investigation and remediation. © 2004 Wiley Periodicals, Inc.     

Successful combination of remediation techniques at a former silver factory

A residential area that was formerly part of a silver factory site severely contaminated with chlorinated solvents was remediated using an in situ electro‐bioreclamation technique. Electro‐bioreclamation is a method for heating soil and groundwater combined with soil vapor and low‐yield groundwater extraction and enhanced reductive dechlorination (ERD). During the first two years of remediation in the source area (the intensive phase), a total of 80 kg of volatile organic compounds (VOCs) was removed by heating combined with ERD. After another two years of ERD in the source and plume areas (the attenuation phase), the VOC concentrations were reduced to a level below 100 μg/L in groundwater. Given these satisfying results, electro‐reclamation in combination with ERD turned out to be a successful in situ remediation technique for removing VOCs. © 2006Wiley 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.     

New advancements for in situ treatment using electrical resistance heating

Electrical resistance heating (ERH) is proving to be an effective technology to rapidly heat the subsurface and, in doing so, removing volatile organic compounds. Practitioners of this technology have observed that other processes (biodegradation, abiotic degradation, hydrolysis, and possibly others) occur to break down the chemicals of concern, and remediation is not solely accomplished through vaporization. Few sites treated using ERH have been monitored during and after treatment to identify and evaluate the processes occurring and assess the contribution of these other biological and chemical processes in the remediation effort so that they may be incorporated in the remediation design. At Fort Lewis, Washington, a landfill has been undergoing ERH treatment in three phases, where chlorinated volatile organic compounds represent the primary chemicals of concern in soil and groundwater. Other chemicals of concern include petroleum products, oils, and lubricants. The Fort Lewis remediation projects provided an opportunity to observe the reactions occurring in the subsurface during ERH and fine‐tune the study with each phase of operation. This study is still under way. However, the data gathered to date, which focuses on biodegradation, provides insights into the processes that have been observed. For the Fort Lewis site, biotic and abiotic degradation processes have been observed throughout the range of operating temperatures. At the lower temperature ranges (up to 70°C), biological processes appear to predominate. Above 70°C, abiotic processes become much more active. The goal of this work is to eventually optimize the use of these intrinsic processes in ERH remediation to reduce energy requirements and costs. © 2007 Wiley Periodicals, Inc.     

Examining the economics of remediation by fluid injection with vacuum extraction

Enhanced methods of in-situ remediation based on patented technology involving fluid injection with vacuum extraction have been used successfully at the Sand Creek Superfund Site in Commerce City, Colorado. Approximately 177,000 pounds of volatile organic compounds (VOCs) were removed from the subsurface in six months, two months ahead of schedule. Remediation goals were achieved on this thermally enhanced soil vapor extraction project by using vertical and horizontal wells interchangeably in vacuum or pressure service for vapor extraction, dual vacuum extraction, heated vapor reinjection, and air sparging. Although VOCs consisted of mixed chlorinated and petroleum hydrocarbons, the petroleum hydrocarbons, some in the form of nonaqueous phase liquids, had not been fully characterized. This article examines the evolution of the remedial design from that conceptualized in the Record of Decision (ROD) of the U.S. EPA, presents the rationale for the selection of alternative system components, and provides a cost analysis of the selected remedial technology, with comparisons to that of alternatives considered for use at Sand Creek.     

Breakthrough in 2D‐CSIA Technology for 1,4‐Dioxane

A dual isotope technology based on compound‐specific stable isotope analysis of carbon and hydrogen (2D‐CSIA) was recently developed to help identify sources and monitor in situ degradation of the contaminant 1,4‐dioxane (1,4‐D) in groundwater. Site investigation and optimized remediation have been the focus of thousands of CSIA applications completed for volatile organic contaminants (VOCs) worldwide. CSIA for the water miscible 1,4‐D, however, has been technically challenging. The most commercially available sample preparation settings “Purge and Trap” for VOC could not efficiently extract 1,4‐D out of water for a reliable CSIA measurement, especially when the concentration is below 100 μg/L. Such a high reporting limit has prevented CSIA from being used for effective site investigation and remediation monitoring at most 1,4‐D contaminated sites, where 1,4‐D is often present at very low ppb levels. This article outlines the recent breakthrough in 2D‐CSIA technology for 1,4‐D in water, reported down to ～1 μg/L for carbon, and ～10 μg/L to 20 μg/L for hydrogen using solid‐phase extraction based on EPA Method 522, and its benefit is highlighted through a case study at a 1,4‐D contaminated site. ©2016 Wiley Periodicals, Inc.