Using an integrated approach for quantifying VOC source areas for site remediation

Locating and quantifying free-phase volatile organic compounds (VOCs) in the subsurface represent one of the more difficult challenges facing hazardous waste site remediation programs. Successful remediation programs require reliable data on the size and extent of potential VOC contamination sources. Improving subsurface quantification of VOCs requires a large number of reliable low-cost samples. Satisfying this objective relies on improved sampling techniques, field analysis of samples, and a modified quality assurance program. This paper describes an integrated approach using conventional split-spoon samplers, microcore sampling, hexane extractions, and a field gas chromatograph with an autosampler as part of a technical demonstration for innovative remediation technologies. Using this approach, it was possible to delineate a subsurface source of free-phase VOCs at a cost of $15 per sample. The distribution of dense nonaqueous phase liquid determined by this sampling approach agreed with the conceptual model for the site.     

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.     

State-of-the-art VOC abatement from soil-venting operations

The development of treatment technologies to limit the discharge of volatile organic compounds (VOCs) into the atmosphere has proceeded apace with the increasing use of soil venting for the remediation of contaminated soil. This article surveys the commonly-used emission control systems that have developed under air pollution control regulations in California. Emphasis is on equipment operating characteristics, typical performance results (destruction efficiencies of VOCs), and operating costs. A recently commercialized process for treating halogen-containing VOCs is described, and some operating and cost data are included.     

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.     

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.     

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.     

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.     

Electrical resistance heating of volatile organic compounds in Sedimentary rock

Electrical resistance heating (ERH) has become a common method of remediation for volatile organic compounds (VOCs) in unconsolidated soils, both above and below the water table. Recently, use of ERH has expanded to include treatment of contaminated sedimentary bedrock. This article describes the implementation issues for rock remediation and provides case studies of three sites remediated by ERH in Maryland, New Jersey, and Indiana. With proper design, remediation of bedrock can be as effectively completed as remediation of overburden materials. © 2010 Wiley Periodicals, Inc.     

Contaminated land clean-up using composted wastes and impacts of VOCs on land

This paper describes experiments that demonstrate the effects and potential for remediation of a former steelworks site in Wales polluted with polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs). Under field conditions, PAH-contaminated soil was composted in-vessel, with or without organic feedstocks, receiving forced aeration for 80 days followed by 4 months maturation. Treatments compared PAH removal in contaminated soil to contaminated soil mixed with three different organic waste mixes after composting and after composts were spread to land. After composting, PAH concentrations declined in all treatments, by up to 38%. Sixteen months after the composts were landspread and vegetation was established, only those containing contaminated soil with organic additions exhibited further PAH removal, by up to 29%. Composting resulted in a decline in the relative concentration of small PAHs, whereas the landspreading-vegetation phase saw a decline in the relative concentration of medium PAHs in two of the three composts exhibiting PAH removal. Under controlled glasshouse conditions, vegetated soil columns of differing depths were exposed to VOCs from beneath. VOC vapour affected both shoot and root growth and soil microbial activity; effects varied with distance from the VOC source. This work demonstrated that on-site remediation of aged PAH-contaminated land can be successfully initiated by in-vessel co-composting followed by land spreading and vegetation, within a practical timeframe.     

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.     

Continuous water‐level monitoring in the assessment of groundwater remediation and refinement of a conceptual site model

An Erratum has been published for this article in Remediation 16(1) 2005, 155–157. Water‐level data collection is a fundamental component of groundwater investigations and remediation. While the locations and depths of monitored wells are important, the frequency of data collection may have a large impact on conclusions made about site hydrogeology. Data‐logging water‐level probes may be programmed to record water levels at frequent intervals, providing site decision makers with abundant, detailed information on the response of an aquifer to both anticipated and unforeseen stresses. In this study, a network of movable probes has provided several years of hourly water‐ level data. The understanding of the site's phytoremediation system has been enhanced by the continuous data, but subsequent insights into an unexpected situation regarding the site's infrastructure have been the most valuable result of the monitoring program. © 2005 Wiley Periodicals, Inc.     

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.     

Advanced site diagnostic tool 3D‐CSIA for in situ remediation

In situ remediation is inherently considered “green remediation.” The mechanisms of destruction by in situ technologies, however, are often unseen and not well understood. Further, physical effects of amendment application affect concentration data in an identical manner as the desired reactive mechanism. These uncertainties have led to the weight‐of‐evidence approach when proving viability: multiple rounds of data collection, bench studies, pilot studies, and so on. Skipping these steps has resulted in many failed in situ applications. Traditional assessment data are often tangential to the desired information (e.g., “Is contaminant being destroyed or just being pushed around and diluted?” and “What is the mechanism of the destruction and can it be monitored directly?”). An advanced site diagnostic tool, “Three‐Dimensional Compound Specific Stable Isotope Analysis” (3D‐CSIA), can assess the viability of in situ technologies by providing definitive data on contaminant destruction that are not concentration‐related. The 3D‐CSIA tool can also locate source zones and apportion remediation cost by identifying plumes of different isotope signatures and fractionation trends. Further, use of the 3D‐CSIA tool allows remediation professionals to evaluate effectiveness of treatment and make better decisions to expedite site closure and minimize costs. This article outlines the fundamentals of advanced site diagnostic tool 3D‐CSIA in detail, and its benefit is highlighted through a series of case studies at chlorinated solvent–contaminated sites. © 2010 Wiley Periodicals, Inc.     

石化废水挥发性有机物逸散量的估算方法

总结了实测法、物料衡算法、模型法、排放系数法、工程估算法等国内外石化废水挥发性有机物(VOCs)逸散量估算方法的主要特点及适用范围。应用排放系数法和实测法估算国内某石化厂废水收集处理系统VOCs逸散量为354.26 t/a。根据估算方法的实际应用研究,建议物料衡算法中废水油相VOCs逸散可结合油相敞口面积和油相性质,提供废水油相的排放系数;应用Water 9软件估算含油膜废水设施逸散量时,应单独估算油膜VOCs逸散量;建议排放系数法中废水收集系统排水口、检查井未密闭VOCs排放系数均确定为0.032 kg/h(每个逸散源),废水处理系统油水分离器、气浮装置按进水中石油类浓度的大小,分别提供VOCs排放系数。     

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.     

Assessment of in situ thermal treatment for chlorinated organic source zones

The East Gate Disposal Yard (EGDY) at Fort Lewis is the source of a large trichloroethene (TCE) plume at this military installation. Source reduction using thermal treatment was applied using electrical resistance heating. A total of about 5,800 kg of TCE‐equivalent volatile organic compounds (VOCs; TCE and dichloroethene) was extracted during thermal treatment of the three zones selected for source reduction. Pretreatment groundwater TCE concentrations were measured up to 100 ppm. Posttreatment groundwater TCE concentrations within the treatment zones averaged less than 100 ppb. Posttreatment soil TCE concentrations decreased by over 96 percent compared to pretreatment soil concentrations. The overall contaminant flux from EGDY was reduced by an estimated 60 to 90 percent by the source reduction effort. The traditional and new techniques for site characterization and remediation performance monitoring applied at EGDY provide insight for installing, operating, monitoring, and assessing thermal treatment. © 2009 Wiley Periodicals, Inc.     

Before‐after control‐impact paired modeling of groundwater bentazon treatment at a phytoremediation site

A Before‐ After Control‐ Impact Paired (BACIP) model was used to evaluate the effectiveness of phytoremediation treatment on reduction of bentazon concentrations in shallow groundwater at a study site in Louisiana. Two different statistical approaches were made to evaluate the impact to this test site from the remediation program through time. Data were evaluated by Bayesian analysis of variance test methods. Data sets were unique in that the control data used for impact evaluation, as compared to before and after data, were compiled from groundwater upgradient monitoring wells existing prior to remediation. The statistical model supports the hypothesis that the phytoremediation program has positively impacted groundwater at the study site. © 2006 Wiley Periodicals, Inc.     

SITE Demonstration of Enhanced In-Situ Bioremediation of Chlorinated and Nonchlorinated Organic Compounds in Fractured Bedrock

A field demonstration of an enhanced in-situ bioremediation technology was conducted between March 1998 and August 1999 at the ITT Industries Night Vision (ITTNV) Division plant in Roanoke, Virginia. The bioremediation process was evaluated for its effectiveness in treating both chlorinated and nonchlorinated volatile organic compounds (VOCs) in groundwater located in fractured bedrock. Chlorinated compounds, such as trichloroethene (TCE), in fractured bedrock pose a challenging remediation problem. Not only are chlorinated compounds resistant to normal biological degradation, but the fractured bedrock presents difficulties to traditional techniques used for recovery of contaminants and for delivery of amendments or reagents for in-situ remediation. The demonstration was conducted under the U.S. Environmental Protection Agency's Superfund Innovative Technology Evaluation (SITE) program. The SITE program was established to promote the development, demonstration, and use of innovative treatment technologies for the cleanup of Superfund and other hazardous waste sites. This article presents selected results of the demonstration and focuses on understanding the data in light of the fractured bedrock formation. © 2002 Wiley Periodicals, Inc.     

Application of the operating window concept to remediation‐option selection

An Erratum has been published for this article in Remediation 14(4) 2004, 141. The selection of remediation options for the management of unacceptable risks at contaminated sites is hindered by insufficient information on their performance under different site conditions. Therefore, there is a need to define “operating windows” for individual remediation options to summarize their performance under a variety of site conditions. The concept of the “operating window” has been applied as both a performance optimization tool and decision support tool in a number of different industries. Remediation‐option operating windows could be used as decision support tools during the “options appraisal” stage of the Model Procedures (CLR 11), proposed by the Environment Agency (EA) for England and Wales, to enhance the identification of “feasible remediation options” for “relevant pollutant linkages.” The development of remediation‐option operating windows involves: 1) the determination of relationships between site conditions (“critical variables”) and option performance parameters (e.g., contaminant degradation or removal rates) and 2) the identification of upper‐ and lower‐limit values (“operational limits”) for these variables that define the ranges of site conditions over which option performance is likely to be sufficient (the “operating window”) and insufficient (the “operating wall”) for managing risk. Some research has used case study data to determine relationships between critical variables and subsurface natural attenuation (NA) process rates. Despite the various challenges associated with the approach, these studies suggest that available case study data can be used to develop operating windows for monitored natural attenuation (MNA) and, indeed, other remediation options. It is envisaged that the development of remediation‐option operating windows will encourage the application of more innovative remediation options as opposed to excavation and disposal to landfill and/or on‐site containment, which remain the most commonly employed options in many countries. © 2004 Wiley Periodicals, Inc.     

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.