Characterizing soils contaminated with heavy metals: A uranium contamination case study

To stem rising remediation costs for soils contaminated with hazardous metals, increased emphasis is being placed on the development of in-situ and ex-situ treatment technologies. Often, a lack of basic information on the chemical and physical characteristics of the soil and contaminants hampers treatability studies used to design these technologies. This article proposes and demonstrates a characterization program to meet these information needs, employing standard analytical techniques coupled with advanced spectroscopy and microscopy techniques. To support treatments involving physical separation strategies, the program uses standard analytical techniques to characterize the soil and the association of contaminants with different soil fractions (e.g., size and density fractions). Where chemical treatments are required, spectroscopy and microscopy methods are employed to yield quantitative information on the oxidation state and speciation of the contaminant. Examples demonstrate the use of measured soil and contaminant characteristics in the screening of alternative treatment technologies and in the selection of soils for use in treatability studies. Also demonstrated is the use of these characterization tools in the design and optimization of treatment strategies and in support of risk assessment determinations.     

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.     

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.     

Triad case study: Marine Corps Base Camp Pendleton

The U.S. Navy Public Works Center (PWC) Environmental Department, San Diego, California, is home to the Navy West Coast Site Characterization and Analysis Penetrometer System (SCAPS). SCAPS has been extensively used at several Navy sites since 1995 to provide real‐time, high‐density data sets. The U.S. Environmental Protection Agency's Triad approach provided an ideal framework for optimizing the use of the Navy SCAPS during a volatile organic compound (VOC) source investigation at Installation Restoration Site 1114 at Marine Corps Base Camp Pendleton. All three elements of Triad—systematic planning, dynamic work strategy, and use of real‐time measurement tools—were implemented to manage decision uncertainty and expedite the site management process. The investigation was conducted using the Navy SCAPS, outfitted with a cone penetrometer, membrane interface probe, and a direct sampling ion trap mass spectrometry detector, which allowed for real‐ time collection of over 690 feet of continuous lithologic information and VOC concentration data. These data were used collaboratively with 24‐hour turnaround US EPA 8260B VOC groundwater results from temporary direct‐ push wells to support the conclusion of a limited source area. Implementation of the Triad approach for this investigation provided an expedited high‐density data set and a refined conceptual site model (CSM) in real time that resulted in cost savings estimated at $2.5M and reduction of the site characterization and cleanup schedule by approximately three years. This project demonstrates how the US EPA's Triad approach can be applied to streamline the site characterization and cleanup process while appropriately managing decision uncertainty in support of defensible site decisions. © 2004 Wiley Periodicals, Inc.     

Evaluating PFAS cross contamination issues

Avoiding cross contamination from per‐ and polyfluoroalkyl substances (PFAS) that may occur during sampling of environmental media is the key to ensure reliable analytical results during a PFAS sampling program. Due to the ubiquitous nature of PFAS in commonly used sampling materials and personal protective equipment, mitigating the risk of cross contamination is a challenge that requires a conservative approach when planning and executing a PFAS sampling program. This article describes a conservative approach to PFAS sampling and includes a case study that evaluated three insect repellent products to determine their suitability for use during PFAS investigation. The three products were verified to be PFAS‐free for the 17 PFAS included in the analysis and, therefore, these products are suitable for use during PFAS sampling activities without concern for cross contamination.     

Effects of cosolvency in the fate and transport of PCBs in soil

Under the purview of EPA's Remedial Engineering Management (REM III) Superfund contract, a CERCLA RI/FS was performed at the Pinettes Salvage Yard site located in Washburn, Maine (EPA Region I). The purpose of the RI/FS was to fully characterize the nature, extent, and fate and transport of PCB contamination resulting from an alleged surface spill of transformer dielectric fluid containing Arochlor 1260 (a polychlorinated biphenyl) and various volatile and semivolatile organic constituents. The RI/FS was performed subsequent to both an immediate removal action (IRA) and a deletion remedial investigation (DRI) performed by EPA contractors. Results of both efforts indicated that the site was unsuitable for deletion from the National Priorities List (NPL) because the site soils contained elevated levels of PCBs. This article presents a case history of the extensive field investigations performed to characterize the contaminant source and evaluate the fate and transport of PCBs in site soils. These investigations included on-site mobile laboratory gas chromatograph (GC) analytical techniques for PCBs and targeted volatile and semivolatile organic compounds; confirmatory Contact Laboratory Program (CLP) laboratory analyses of soils, sediments, surface water, and groundwater samples; statistical analyses and correlation of field mobile laboratory GC data with CLP laboratory analytical results; and an evaluation of the potential effects of cosolvency in the fate and transport of PCBs in subsurface soils.     

Assessment of sampling and chemical analysis of source-separated organic household waste

The quality of the waste sampling procedure and chemical analysis was evaluated in a research program on characterization of organic waste obtained after disc screening of source-separated organic household waste. The sampling procedures focused on a truckload of waste and involved several steps of subsampling including shredding, mixing, blending, high-speed-blending, drying and milling prior to analysis of the organic waste with respect to ash content, crude fibers, crude fat, crude protein, sugar, starch, enzyme-digestible organic matter, P, N, C, H, S and calorific value. The statistical evaluation of the procedures involved 10 samples of the same truckload of waste obtained by splitting the sample at each level in the procedure according to a staggered, incomplete nested statistical design. Furthermore, one sample was analysed six times over a period of approximately one year. The statistical evaluation showed that no single step in the sampling procedure contributed with excessive variance and that the variance caused by the sampling procedure was approximately the same as the variance in the chemical analysis observed over a year. The variance varied with the analytical parameter but for most parameters the uncertainty was satisfactorily low (of the order of 3-10% expressed as the relative standard deviation, which is considered to be satisfactory for waste characterization).     

Results of a field study—Sampling with ISOCS and SAM 935 at the Savannah River Site

This article focuses on the results of a delineation of radioactive contaminants using expedited field characterization equipment at the Department of Energy's Savannah River Site in South Carolina. The objective of the study was to delineate a potential contamination area in the TNX Inner Swamp using cost‐effective field sampling equipment that would give results in a timely manner. The expedited field characterization equipment used was the In Situ Object Counting System (ISOCS) and the Model 935 Surveillance and Measurement System (SAM 935). The study involved an area of approximately 200 acres with 89 surveyed locations. Originally, the contaminant of concern was thorium‐232 because of the health risk to future on‐site workers. As the fieldwork progressed, there were no exceedances in thorium‐232 activities; however, there was one slight exceedance of uranium‐238. The delineation was established from using the ISOCS and SAM 935 sampling equipment in addition to soil sampling from the 0‐ to 1‐foot interval. There was a strong correlation in the analytical data from both the ISOCS and SAM 935 measurements. Thus, this type of sampling characterization is beneficial for determining the extent of contamination at hazardous waste sites. © 2006 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.     

Using uncertainty analysis to reduce costs at a pump-and-treat site

The former Nebraska Ordnance Plant site in east-central Nebraska was included on the National Priorities List because of explosives and trichloroethene contamination. The preferred groundwater remedy includes hydraulic containment of the contaminated groundwater and focused extraction of the more highly contaminated groundwater as components of the remedial action. The purpose of hydraulic containment is to stop the spread of contamination, while the more aggressive focused extraction will be used to speed up the remediation and reduce total cleanup costs. This case study illustrates how straightforward groundwater models were combined with uncertainty analysis to select a precise definition of the focused extraction areas. The purpose of the analysis was to reduce ultimate remediation costs, given the significant uncertainty associated with the estimated remediation times. The selected definition provides a basis for more sophisticated groundwater modeling, the goal of which was to locate extraction wells and define their flow rates. The batch flushing model provided the governing equations, and Monte Carlo analysis was used for the uncertainty analysis. All of the analysis was performed on a personal computer using commercially available software.     

Laser-induced fluorescence and fast gas chromatography/mass spectrometry with subsurface thermal extraction of organics: Field analytical technologies for expediting site characterization and cleanup

This article describes new field-based technologies that support the Dynamic Workplan/Adaptive Sampling and Analysis Program employed to better characterize hazardous waste sites at lower cost. A laser-induced fluorescence (LIF) probe was designed and field-tested with a cone penetrometer (CP) for investigating petroleum contaminants present at under-ground tank farms. The LIF produced real-time quantitative data for naphthalene and semiquantitative results for total petroleum hydrocarbons and diesel range organics. Two different projects are described employing fast gas chromatography/mass spectrometry (GC/MS) in the field. A 70-foot heated transfer line and probe were used in combination with a cone penetrometer to thermally extract (TE) subsurface soil-bound semivolatile organics. In the second project, soil samples were collected by a Geoprobe^TM and brought to the surface for analysis. The direct measurement TECP data produced semiquantitative results while the more conventional means of collecting and analyzing samples produced risk analysis quality data in the field. A new set of mass spectrometry algorithms provided the technology breakthrough for identifying and quantifying a wide range of Environmental-Protection-Agency-listed target compounds in the presence of high levels of matrix (petroleum) interferents under fast, 7 min/sample, GC conditions.     

Legal and technical defensibility of data and the Triad approach

The Triad approach was developed primarily to limit decision uncertainty during cleanups at hazardous waste sites. The fundamental principles of the Triad approach include development of a site characterization model and use of emerging technologies, which can provide data at a higher density than could be affordably collected using traditional data collection methodologies, to refine the model in essentially real time. New data formats are used collaboratively with data in traditional formats to iteratively pin down the relative concentration, nature, and extent of contaminants, thus minimizing decision uncertainties. This article examines the potential admissibility as evidence in legal proceedings of data collected by technologies designed to improve the density of information that are commonly used during the course of Triad‐type projects. The article explains that such criteria may vary depending on the purpose for which the evidence is to be used (e.g., as direct evidence to prove site conditions or as support for the testimony of an expert witness) and the court in which the legal proceeding would take place (e.g., federal court or state court). Admissibility in federal courts of data both as direct evidence and as support for expert witness testimony is covered. © 2005 Wiley Periodicals, Inc.     

Triad case study: Rattlesnake Creek

The U.S. Army Corps of Engineers (US ACE) is responsible for conducting the cleanup of radiological contaminated properties as part of the Formerly Utilized Sites Remedial Action Program. One property is the Rattlesnake Creek (RSC) portion of the Ashland sites. The RSC stream sediments are contaminated with thorium‐230, radium‐226, and uranium. The US ACE is closing RSC using protocols contained within the Multi‐Agency Radiation Survey and Site Investigation Manual (MARSSIM). At RSC, the US ACE developed site‐specific derived concentration guideline level (DCGL) cleanup requirements consistent with the MARSSIM guidance. Because of uncertainty about the distribution of contamination within the creek, the US ACE used the Triad approach to collect data and design remedial actions. Systematic planning helped target the areas of concern, develop a conceptual site model, and identify data gaps to be addressed before remediation plans were finalized. Preremediation sampling and analysis plans were designed to be explicitly consistent with final status survey requirements, allowing data sets to support both excavation planning needs and closure requirements in areas where contamination was not encountered above DCGL standards. Judicious use of real‐ time technologies such as X‐ray fluorescence and gamma walkover surveys minimized expensive off‐ site alpha spectrometry analyses, and at the same time provided the ability to respond to unexpected field conditions. © 2004 Wiley Periodicals, Inc.     

Incorporating Bioavailability Considerations Into the Evaluation of Contaminated Sediment Sites

In March 2011, the Interstate Technology & Regulatory Council (ITRC) Contaminated Sediments Team published a web‐based Technical and Regulatory Guidance on the concepts, processes, and uses of bioavailability in a risk decision‐making framework at a contaminated sediment site. Bioavailability processes, as defined by the National Research Council (NRC; 2003), are the “individual physical, chemical, and biological interactions that determine the exposure of plants and animals to chemicals associated with soils and sediments.” Bioavailability assessment tools aid in the assessment of human and ecological exposure and development of site‐specific remedial objectives. The guidance provides information on the processes that may affect contaminant bioavailability within sediments to understand exposure within ecological and human receptors; supports the development of conceptual site models (CSMs); and describes available tools (biological, chemical, and physical) and models that are used to measure and characterize the fate and transport and potential bioavailability of contaminants. Case studies, referenced throughout the document, demonstrate the practical application of bioavailability measures. The guidance will describe the proper application of traditional and emerging sediment remediation technologies to support the selection of a remedy that is protective of human health and the environment. © 2013 Wiley Periodicals, Inc.     

Facilitating brownfields transactions using Triad and environmental insurance

A significant hindrance to reuse of brownfields properties is the risk associated with redevelopment,specifically the uncertainty associated with environmental cleanup. This article explores an approach tomanaging environmental risk through a combination of risk quantification, environmental insurance, and theTriad Approach to site sampling and data interpretation. The expected costs of environmental liabilities areestimated using the Marsh Peer ReviewSM risk quantification process that employs statistical techniques andhighly experienced technical staff. The outputs of the process indicate premiums and attachment points forinsurance products, but they also point to “critical uncertainties” that drive the insurancepremiums. Insurance premiums are often linked to site delineation deficiencies, such as the magnitude ofimpacted soil or the size of a groundwater plume. The Triad Approach is an integrated site characterizationprocess developed by the Environmental Protection Agency that combines systematic planning, dynamic or adaptivefield decision making and field analytical methods (FAMs). The real‐time data produced by FAMsallow for in‐field resolution of uncertainty about sample location, which in turn provides morerepresentative delineation of contaminant distribution. The trade‐off of using slightly less accuratebut substantially lower cost FAMs is an increase in sampling frequency or density, thereby reducing the risk ofincomplete detection or delineation while yielding a “data set” that is more powerful than fewerindividual data points analyzed through traditional methods. Employing the Triad Approach to analyze the“critical uncertainties” identified in the Peer Review Process can impact insurance premiums andallow for better terms of coverage. The combination of using the Triad Approach and environmental insuranceproducts can lead to more predictable and profitable Brownfield transactions. © 2003 Wiley Peridicals,Inc.     

Evaluation of soil-washing process for “unwashable” clays and silts from the palmerton zinc site

The Palmerton Zinc Site is a Superfund site in Palmerton, Pennsylvania. Its former mineral processing operations have contaminated nearby wells and soils with zinc and cadmium. Preliminary analysis of soil and dust sampling conducted in May 1991 has revealed that the dust poses a potential threat to human health. Based on the results of a previous study, which showed a high percentage of silt and clay in soils from Palmerton residential properties, it was concluded that soil washing is not likely to be a viable method to treat the soil and dust contamination in Palmerton. However, since the completion of this study, a soil-washing process for “unwashable” clays and silts has been developed. A residential soil sample from Palmerton, which had low concentrations of arsenic, cadmium, and lead, and a somewhat high concentration of zinc, was washed in a bench-scale version of this process. The results showed that the new soil-washing process for “unwashable” clays and silts may be a viable method to treat the soil and dust contamination in Palmerton, depending on the soil quality criteria concentrations selected for site cleanup.     

Low intervention soil remediation approaches

Traditional bioremediation approaches have been used to treat petroleum source contamination in readily accessible soils and sludges. Contamination under existing structures is a greater challenge. Options to deal with this problem have usually been in the extreme (i.e., to dismantle the facility and excavate to an acceptable regulated residual, or to pump and treat for an inordinately long period of time). The excavated material must be further remediated and cleanfill must be added to close the excavation. If site assessments were too conservative or incomplete, new contamination adulterating fill soils may result in additional excavation at some later date. Innovative, cost-efficient technologies must be developed to remove preexisting wastes under structures and to reduce future remediation episodes. An innovative soil bioremediation treatment method was developed and evaluated in petroleum hydrocarbon contaminated (PHC) soils at compressor stations of a natural gas pipeline running through Louisiana. The in-situ protocol was developed for remediating significant acreage subjected to contamination by petroleum-based lubricants and other PHC products resulting from a chronic leakage of lubricating oil used to maintain the pipeline itself. Initial total petroleum hydrocarbon (TPH) measurements revealed values of up to 12,000 mg/kg soil dry weight. The aim of the remediation project was to reduce TPH concentration in the contaminated soils to a level of <200 mg/kg soil dry weight, a level negotiated to be acceptable to state and federal regulators. After monitoring the system for 122 days, all sites showed greater than 99-percent reduction in TPH concentration.     

Soil contamination by halogenated polycyclic aromatic hydrocarbons from open burning of e-waste in Agbogbloshie (Accra,Ghana)

Detailed composition of chlorinated and brominated polycyclic aromatic hydrocarbons (Cl-PAHs and Br-PAHs) generated during informal recycling of e-waste and their toxic relevance are still poorly understood. This study investigated the occurrence of Cl-PAHs and Br-PAHs in surface soil samples from the Agbogbloshie e-waste recycling site (Accra, Ghana) using quantitative gas chromatography–mass spectrometry (GC–MS) and comprehensive two-dimensional GC–time-of-flight mass spectrometry (GC × GC–ToFMS) profiling. The results of GC–MS analysis showed elevated concentrations in open e-waste burning areas (160–220 and 19–46 ng/g dry weight for Cl- and Br-PAHs, respectively) with substantial contribution from unidentified compounds (respectively, more than 36 and 70%, based on the total areas of potential peaks). Cl- and Br-PAHs from e-waste burning had a distinctive composition dominated by ring–ring compounds. Several homologue groups not monitored with GC–MS were found using GC × GC–ToFMS: PAHs with up to 5Cl or 3Br, mixed halogenated PAHs and chlorinated methylPAHs. The dioxin-like toxic equivalents of the identified Cl-/Br-PAHs in soils, estimated from their in vitro AhR agonist potencies relative to 2,3,7,8-tetrachlorodibenzo-p-dioxin, were much lower than the range reported for chlorinated and brominated dioxins. However, the toxicity of the unidentified halogenated PAHs remained unclear.     

In situ Remediation of Metals Comes of Age

Since the early 1970s, technologies for remediating organic contamination in soils and groundwater have evolved through three stages with primary emphasis on (1) gross removal processes, (2) active in situ treatment, and (3) risk-based closure and natural attentuation. Technologies for treating metals contamination are evolving through similar stages. In the late 1990s, metals remediation has arrived at the second stage in which a wide range of in situ technologies are available either to extract metals directly from the subsurface or to render them immobile and harmless. In situ geochemical fixation is an example of a commercial technology capable of addressing a wide range of metals contamination sites. Four case histories demonstrate the versatility of this approach. Other promising technologies for treating metals contamination are also emerging. These include geokinetics, biocatalytic precipitation processes, phytoremediation, and artificial wetlands. As our knowledge continues to grow, the most elegant solutions to metals contamination will rely more and more heavily on the soil's natural capacity to stabilize and immobilize metals over time.     

Improved direct push technologies: Quicker and cheaper on-site methods for sampling and monitoring

Cost-effective remedial action is dependent on clear identification of site conditions and accurate delineation of contamination. Many site cleanups have been hampered by complex subsurface conditions. Standard drilling and monitoring well installations have proven to be costly and time-consuming. Improved direct push technologies, however, are being developed to perform quicker and less expensive on-site sampling and testing. This article describes the benefits of improved direct push technologies.