Removal of PCBs from a Contaminated Soil Using CF-Systems® Solvent Extraction Process

ABSTRACT

The U.S. Environmental Protection Agency’s (EPA) Superfund Technical Assistance Response Team (START) in cooperation with EPA’s Superfund Innovative Technology Evaluation (SITE) program evaluated a pilot scale solvent extraction process developed by CF-Systems. This process uses liquefied propane to extract organic contaminants from soils, sludges, and sediments. A pilot-scale evaluation was conducted in Golden, CO at Hazen Research, Inc., using CF-Systems’ trailer-mounted organics extraction unit. Approximately 1,000 pounds of soil, with an average poly-chlorinated biphenyl (PCB) concentration of 260 mg/kg, was obtained from a remote Superfund site. Six 100-pound batches of the contaminated soil were extracted using multiple extraction sequences. Three of the six batch runs were subjected to three extraction sequences each, so that process variability could be evaluated. Results showed that PCB removal efficiencies varied between 91.4 and 99.4%, with the propane-extracted soils retaining low concentrations of PCBs (19.0–1.8 mg/kg). Removal efficiencies of oil and grease (O&G) were found to be 96.0 to 99.6% with propane-extracted soils retaining O&G concentrations from 279 to <20 mg/kg. Overall extraction efficiency was found to be dependant upon the numberof extraction cycles used.     

Thermal Encapsulation of Metals in Superfund Soils

Abstract

Superfund sites frequently contain both heavy metals and organic hazardous waste. If not properly controlled, the metals may be changed to a more leachable form and may also be emitted to the atmosphere via the exhaust stack. This paper documents a batch kiln R&D test program to solve these metal-related problems. It was performed under the U.S. EPA’s SITE (Superfund Innovative Technology Evaluation) Emerging Technology Program. Allis Mineral Systems has developed the Thermal Encapsulation Process. Metals with limits set by EPA’s TCLP (Toxicity Characteristic Leaching Procedure) test and BIF (boiler and industrial furnace) stack emission regulations, such as cadmium, chromium, and lead, are the initial target of this process. This process, while unproven in these areas, may also apply to mixed waste (EPA hazardous waste/low-level radioactive wastes) and may also benefit commercial hazardous waste or Superfund thermal treatment systems. The results of the SITE tests were positive: strong, durable nodules were produced with excellent crush strength and improved resistance to leaching. Feed preparation, particularly control of moisture content, was found to be a key element in initiation of agglomeration. A good correlation was found between decreasing TCLP metals leachate levels and increasing crush strength.     

VOC Recovery through Microwave Regeneration of Adsorbents: Comparative Economic Feasibility Studies

ABSTRACT

Microwave regeneration of adsorbents facilitates the recovery of volatile organic compounds (VOCs) by decoupling the bed heating from the stripping gas. This makes possible the creation of a highly-concentrated regeneration effluent from which the VOCs can be recovered by condensation at near-ambient temperatures. The economic feasibility of two novel microwave-regenerated adsorption systems was evaluated by systematically comparing the capital and operating costs of the proposed systems with 10 conventional VOC control technologies. The microwave systems were found to have similar capital and operating costs to conventional steam regeneration systems and, therefore, may present an attractive alternative for recovering water-miscible solvents. In general, the cost of the microwave subsystem is a relatively small component of the overall system costs, and the microwave power requirements are within the range of commercially available generators, even for large emission streams.     

U.S. EPA SITE demonstration of AWD Technologies' AquaDetox/SVE system.

Under the Superfund Innovative Technology Evaluation (SITE) Program, a technology developed by AWD Technologies, Inc. was demonstrated in September 1990. This paper presents the major results of the SITE demonstration of AWD Technologies' AquaDetox/SVE treatment system designed for simultaneous on-site treatment of contaminated groundwater and soil-gas. The groundwater and soil at the demonstration site were contaminated with trichloroethylene (TCE) and tetrachloroethylene (PCE). The AWD technology was evaluated on the basis of the removal efficiencies of TCE and PCE from the contaminated groundwater and soil-gas. The conclusions drawn from these evaluations are: (1) the system achieved removal efficiencies as high as 99.99 percent for groundwater and 99.9 percent for soil-gas; (2) the effluent groundwater was in compliance with the regulatory discharge requirements of 5 micrograms/L each for TCE and PCE for all test runs; (3) the demonstrated 1,000 gpm system has an estimated capital cost of $4.3 million and annual operating and maintenance cost of approximately $820,000.     

U.S. EPA SITE Demonstration of AWD Technologies’ AquaDetox/SVE System

Under the Superfund Innovative Technology Evaluation (SITE) Program, a technology developed by AWD Technologies, Inc. was demonstrated in September 1990. This paper presents the major results of the SITE demonstration of AWD Technologies’ AquaDetox®ISVE treatment system designed for simultaneous on-site treatment of contaminated groundwater and soil-gas. The groundwater and soil at the demonstration site were contaminated with trichloroethylene (TCE) and tetrachloroethylene (PCE). The AWD technology was evaluated on the basis of the removal efficiencies of TCE and PCE from the contaminated groundwater and soil-gas. The conclusions drawn from these evaluations are: (1) the system achieved removal efficiencies as high as 99.99percent for groundwater and 99.9 percent for soil-gas; (2) the effluent groundwater was in compliance with the regulatory discharge requirements of 5 fig/L each for TCE and PCE for all test runs; (3) the demonstrated 1,000 gpm system has an estimated capital cost of $4.3 million and annual operating and maintenance cost of approximately $820,000.     

Alternating Current Electrocoagulation for Superfund Site Remediation

Abstract

The Superfund Innovative Technology Evaluation (SITE) Emerging Technology (ET) Program, authorized under the Superfund Amendments and Reauthorization Act (SARA) of 1986, implements the goal of the SITE Program to promote, accelerate the development of, and make commercially available alternative innovative treatment technologies for use at Superfund sites.

Under this program, the technical and economical feasibility of alternating current electrocoagulation (ACE) developed by Electro-Pure Systems, Inc., was evaluated for a two-year period. ACE is an electrochemical technology where highly-charged aluminum polyhydroxide species are introduced into aqueous media for the removal of suspended solids, oil droplets and soluble ionic pollutants. ACE can break stable aqueous colloidal suspensions of up to 10 percent total solids and stable emulsions containing up to 5 percent oil.

Major operating parameters have been defined for different classes of effluents based on experimental results using complex synthetic soil slurries and metals. Test results indicate that ACE produces aqueous and solid separations comparable to those produced by chemical flocculent additions, but with reduced filtration times and sludge volumes. The technology has application where removal of soluble and suspended pollutants from effluents is required, and in the recovery of fine-grained products from process streams. The technology, however, has not yet been demonstrated at full-scale for Superfund site remediation. The principal results of the SITE research program, and results of ACE treatment on some different classes of industrial effluents not part of the SITE Program, are summarized.     

Factors affecting EDTA extraction of lead from lead-contaminated soils

The effects of solution:soil ratio, major cations present in soils, and the ethylenediaminetetraacetic acid (EDTA):lead stoichiometric ratio on the extraction of lead using EDTA were studied for three different Superfund site soils, one rifle range soil, and one artificially lead-contaminated soil. Extraction of lead from the lead-contaminated soils was not affected by a solution:soil ratio as low as 3:1 but instead was dependent on the quantity of EDTA present. Results of the experiments showed that the extraction efficiencies were different for each soil. If sufficiently large amount of EDTA was applied (EDTA-Pb stoichiometric ratio greater than 10), most of the lead were extracted for all soils tested except for a Superfund site soil from a lead mining area. The differences in extraction efficiencies may be due to the major cations present in soils which may compete with lead for active sites on EDTA. For example, iron ions most probably competed strongly with lead for EDTA ligand sites for pH less than 6. In addition, copper and zinc may potentially compete with lead for EDTA ligand sites. Experimental results showed that addition of EDTA to the soil resulted in a very large increase in metals solubility. The total molar concentrations of major cations extracted were as much as 20 times the added molar concentration of EDTA. For some of the soils tested, lead may have been occluded in the iron oxides present in the soil which may affect lead extraction. While major cations present in the soil may be one of the factors affecting lead extraction efficiency, the type of lead species present also play a role.     

An alternative supercritical fluid extraction system for aqueous matrices and its application in pesticides residue analysis

Supercritical fluid extraction (SFE) is a rapid and convenient method for the isolation of organic compounds from environmental samples. This paper describes a supercritical carbon dioxide (CO2) extraction system that uses a newly designed extraction cell to recover organic compounds from an aqueous matrix. Analysis of the extracts by gas chromatography-electron capture detector (GC-ECD) indicated that the herbicide trifluralin (2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline) could be quantitatively extracted by using the SFE system proposed with small amounts of sample. The percentage of recovery obtained with the SFE system described was twice as high as the result obtained using a conventional solid-phase extraction technique. Extraction by SFE was completed in a short period of time using a simple and low-cost home-made system that did not require the use of organic solvents.     

Control Technologies for Remediation of Contaminated Soil and Waste Deposits at Superf und Lead Battery Recycling Sites

This paper primarily addresses remediation of contaminated soils and waste deposits at defunct lead-acid battery recycling sites (LBRS) via immobilization and separation processes. A defunct LBRS is a facility at which battery breaking, secondary lead smelting, or both operations were performed for the primary purpose of reclaiming lead from spent lead-acid batteries. Metallic lead and lead compounds are generally the principal contaminants of concern in soils and waste deposits (i.e., buried, piled, landfilled waste) at these sites. Other metals (e.g., cadmium, copper, arsenic, antimony, and selenium) are often present at LBRS, but usually at much lower concentrations than lead and often present below hazardous concentrations. This article is primarily based on experience gained from: (1) Superfund site investigation, removal, and remedial actions, and (2) development and demonstration of control technologies under the Superfund Innovative Technology Evaluation (SITE) Program. The primary remedial options for lead contaminated soils and waste deposits include: (1) no action, (2) off-site disposal, (3) containment, (4) immobilization, (5) separation with resource recovery, and (6) separation without resource recovery. In spite of the toxicity of lead at low concentrations, the relative immobility of lead and site-specific risk assessments can still result in the selection of no action or containment remedies. Solidification/stabilization of lead-contaminated soils has been implemented at three Superfund sites and is the selected remedy at several others. Separation technologies (e.g., screening, extraction) are attractive because, if successful, they actually remove the contaminant from the environmental media. Separation technologies also offer the possibility that a valuable product (e.g., lead, plastic, energy) can be recovered, but careful consideration of economic and technical factors are required. Compared to the implementation of containment and solidification I stabilization remedies, separation technologies tend to be relatively novel, complex, and costly.     

Evaporative mass transfer behavior of a complex immiscible liquid

A series of laboratory experiments was conducted with a multiple-component immiscible liquid, collected from the Picillo Farm Superfund Site in Rhode Island, to examine liquid-vapor mass-transfer behavior. The immiscible liquid, which comprises solvents, oils, pesticides, PCBs, paint sludges, explosives, and other compounds, was characterized using gas chromatography and gas chromatography/mass spectrometry to determine mole fractions of selected constituents. Batch experiments were conducted to evaluate equilibrium phase-partitioning behavior. Two sets of air-stripping column studies were conducted to examine the mass-transfer dynamics of five selected target compounds present in the immiscible-liquid mixture. One set of column experiments was designed to represent a system with free-phase immiscible liquid present; the other was designed to represent a system with a residual phase of immiscible liquid. Initial elution behavior of all target components generally appeared to be ideal for both systems, as the initial vapor-phase concentrations were similar to vapor-phase concentrations measured for the batch experiment and those estimated using Raoult's law (incorporating the immiscible-liquid composition data). Later-stage removal of 1,2-dichlorobenzene appeared to be rate limited for the columns containing free-phase immiscible liquid and no porous medium. Conversely, evaporative mass transfer appeared to be ideal throughout the experiment conducted with immiscible liquid distributed relatively uniformly as a residual phase within a sandy porous medium.     

Making Cleanup Decisions at Hazardous Waste Sites: The Clean Sites Approach

This paper provides a summary of the results of an 18-month study conducted by Clean Sites, Inc. of Alexandria, Virginia. The study was designed to take a critical look at the way remedies are selected for abandoned hazardous waste sites that are cleaned up under the authority of the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA or Superfund) and to develop recommendations for improving that process. The recommendations were released in an October 1990 report entitled “Improving Remedy Selection: An Explicit and Interactive Process for the Superfund Program.” Through a cooperative agreement with the U.S. Environmental Protection Agency, Clean Sites is working to test these recommendations. At two actual Superfund sites, Clean Sites will assist EPA in performing the remedy selection in accordance with the process Clean Sites has developed.     

Making cleanup decisions at hazardous waste sites: the clean sites approach.

This paper provides a summary of the results of an 18-month study conducted by Clean Sites, Inc. of Alexandria, Virginia. The study was designed to take a critical look at the way remedies are selected for abandoned hazardous waste sites that are cleaned up under the authority of the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA or Superfund) and to develop recommendations for improving that process. The recommendations were released in an October 1990 report entitled "Improving Remedy Selection: An Explicit and Interactive Process for the Superfund Program." Through a cooperative agreement with the U.S. Environmental Protection Agency, Clean Sites is working to test these recommendations. At two actual Superfund sites, Clean Sites will assist EPA in performing the remedy selection in accordance with the process Clean Sites has developed.     

Demonstration of In Situ Steam and Hot-Air Stripping Technology

Between September 5 and October 5,1989 a field demonstration of the NovaTerra, Inc. Detoxifier [formerly called Toxic Treatment (USA)] was performed by the U.S. EPA under the Superfund Innovative Technology Evaluation (SITE) program. The NovaTerra Detoxifier process injects steam and hot air directly into the ground to vaporize and strip volatile and semivolatile organics. Two augers loosen and homogenize the soil during the stripping process. The steam, hot air and organics are carried to the soil surface and collected for treatment.

The field demonstration was performed at the GATX Annex Terminal located at the Port of Los Angeles, San Pedro, California. Approximately 17 percent of the 5.2 acre site is contaminated with chlorinated solvents, plasticizers, coatings, adhesives and paint additives, and other miscellaneous chemicals from aboveground storage tanks and transfer operations to railroad cars.

The objectives of this SITE Demonstration were to determine the in situ soil concentrations before and after treatment, quantify process stream emissions (fugitive and sidestreams), determine process operating conditions, and determine if vertical migration of contaminants is occurring. Results from the SITE demonstration showed that a substantial amount of the VOCs were removed, about half the SVOCs were removed, there was very little fugitive air emissions from the operation, and what little downward migration occured (if any) was inconsequential.     

SITE Demonstration of Slurry-Phase Biodegradation of PAH Contaminated Soil

This paper summarizes a joint Superfund Innovative Technology Evaluation (SITE) project on slurry-phase biodegradation and a project to collect information for the data base on Best Demonstrated Available Technologies (BOAT). In this 12-week study, a creosote contaminated soil from the Burlington Northern Superfund site in Brainerd, Minnesota was used to evaluate the effectiveness of the bioslurry reactors. During the demonstration, five 64-liter stainless steel bioreactors, equipped with agitation, aeration and temperature controls were used. The pilot scale study employed a 30 percent slurry, an inoculum of indigenous polynuclear aromatic hydrocarbon (PAH) degraders, and inorganic nutrients.

Total PAH degradation averaged 93.4 ± 3.2 percent over all five operating reactors in the 12 weeks with 97.4 percent degradation of the 2- and 3-ring PAHs and 90 percent degradation of the 4- to 6-ring PAHs. A study of the air emissions, both semivolatile compounds such as naphthalene, anthracene, and phenanthrene and volatile compounds such as toluene, xylene, and benzene, from the units showed that the greatest amount of emissions occurred during the loading of the reactors and during the first few days of operation. Therefore, it may not be cost-effective to require elaborate emissions controls unless there are significant quantities of volatile compounds present in the soil or water to be treated in a bioslurry reactor system.     

The Use of Electrokinetics for Hazardous Waste Site Remediation

The Superfund Innovative Technology Evaluation (SITE) program was authorized as part of the 1986 amendments to the Superfund legislation. It represents a joint effort between U.S. EPA’s Office of Research and Development and Office of Solid Waste and Emergency Response. The program is designed to assist and encourage the development of waste treatment technologies that would contribute to more solutions to our hazardous waste problems.

Recently, EPA, through the SITE program, issued a work assignment to assess the “stateof- the-art” of electroklnetically enhanced contaminant removal from soils. Prior research efforts, both laboratory and field, have demonstrated that electroosmosis has the potential to be effective In facilitating the removal of certain types of hazardous wastes from soils. Particularly encouraging results have been achieved with inorganics in fine-grained soils where more traditional removal alternatives are less effective.

Although the results of various studies suggest that electrokinetics is a promising technology, further testing Is needed at both the laboratory and field levels to fully develop this technology for site remediation. A conceptual test program Is presented based on best available data which incorporates system design and operating parameters used in previous applications of this technology In the use of electrokinetics treatment as a remediation technique at hazardous waste sites.     

Microtox testing of pentachlorophenol in soil extracts and quantification by capillary electrochromatography (CEC)--a rapid screening approach for contaminated land

An approach to rapid soil testing which involved the use of simple solvent extraction methods was developed. The analytes of interest were priority pollutants of low water solubility which could not be readily removed from the soil using water. Direct toxicity testing of the soil samples by Microtox showed a high background toxicity which prevented realistic toxicity data from being obtained for the contaminants present. A range of different extraction solutions was used in an attempt to extract the contaminants while eliminating the matrix effects of the soil. It was necessary that the solvents selected for extraction of the soil samples were not of significant toxicity, as this could potentially mask the toxic effects of any compounds extracted from the soil. The extraction efficiencies of solvent systems were evaluated using pentachlorophenol (PCP) as a model compound of known toxicity in the Microtox assay. A rapid and cost-effective method was developed in order to determine the amount of PCP recovered from the soil by the extraction solvents employed. This method consisted of a solid phase extraction (SPE) step followed by quantification using capillary electrochromatography (CEC). Recoveries were greater when a higher proportion of organic solvent (methanol) was used in the extraction process, and lowest when water was used. An extraction based on water could provide information on the potential for leaching of contaminants from the soil into nearby water bodies in an environmental setting. An organic solvent extraction method could indicate how much toxicity soil-dependent organisms might be exposed to through ingestion. Extraction based on 50% (v/v) methanol in water was considered to be the most suitable overall extraction solution for soil screening, given that this permitted extraction of the water-insoluble compound PCP at a level which was clearly toxic in the Microtox assay while also retaining the capability to extract water-soluble contaminants.     

An alternative supercritical fluid extraction system for aqueous matrices and its application in pesticides residue analysis

Abstract

Supercritical fluid extraction (SFE) is a rapid and convenient method for the isolation of organic compounds from environmental samples. This paper describes a supercritical carbon dioxide (CO₂) extraction system that uses a newly designed extraction cell to recover organic compounds from an aqueous matrix. Analysis of the extracts by gas chromatography‐electron capture detector (GC‐ECD) indicated that the herbicide trifluralin (2,6‐dinitro‐N,N‐dipropyl‐4‐trifluoromethylaniline) could be quantitatively extracted by using the SFE system proposed with small amounts of sample. The percentage of recovery obtained with the SFE system described was twice as high as the result obtained using a conventional solid‐phase extraction technique. Extraction by SFE was completed in a short period of time using a simple and low‐cost home‐made system that did not require the use of organic solvents.     

Biomonitoring for metal contamination near two Superfund sites in Woburn, Massachusetts, using phytochelatins

Characterizing the spatial extent of groundwater metal contamination traditionally requires installing sampling wells, an expensive and time-consuming process in urban areas. Moreover, extrapolating biotic effects from metal concentrations alone is problematic, making ecological risk assessment difficult. Our study is the first to examine the use of phytochelatin measurements in tree leaves for delimiting biological metal stress in shallow, metal-contaminated groundwater systems. Three tree species (Rhamnus frangula, Acer platanoides, and Betula populifolia) growing above the shallow groundwater aquifer of the Aberjona River watershed in Woburn, Massachusetts, display a pattern of phytochelatin production consistent with known sources of metal contamination and groundwater flow direction near the Industri-Plex Superfund site. Results also suggest the existence of a second area of contaminated groundwater and elevated metal stress near the Wells G&H Superfund site downstream, in agreement with a recent EPA ecological risk assessment. Possible contamination pathways at this site are discussed.     

A review of the Texas,USA San Jacinto Superfund site and the deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans in the San Jacinto River and Houston Ship Channel

The San Jacinto River (SJR) waste pits that lie just under the 1–10 overpass in eastern Harris County east of Houston, Texas, USA, were created in the 1960s as dumping grounds for paper mill waste. The deposition of this waste led to accumulation of highly toxic polychlorinated dibenzo-p-dioxins and dibenzofurans (PCCDDs/PCDFs) over the course of several decades. After abandonment, the waste material eventually became submerged under the waters of the SJR, resulting in widespread environmental contamination that currently constitutes a significant health concern for eastern Harris County communities. The original waste pits were rediscovered in 2005, and the San Jacinto waste site is now a designated EPA superfund site. The objective of this review then is to discuss the history and current state of containment around the San Jacinto waste pits and analyze spatial and temporal trends in the PCDD/PCDF deposition through the SJR system from the data available. We will discuss the current exposure and health risks represented by the Superfund site and the SJR system itself, as well as the discovery of liver, kidney, brain (glioma), and retinoblastoma cancer clusters in eastern Harris County across multiple census tracts that border the Superfund site. We will also cover the two primary management options, containment versus removal of the waste from the Superfund and provide recommendations for increased monitoring of existing concentrations of polychlorinated waste in the SJR and its nearby associated communities.     

Sequential Extraction Versus Comprehensive Characterization of Heavy Metal Species in Brownfield Soils

The applicability of sequential extraction as a means to determine species of heavy-metals was examined by a study on soil samples from two Superfund sites: the National Lead Company site in Pedricktown, NJ, and the Roebling Steel, Inc., site in Florence, NJ. Data from a standard sequential extraction procedure were compared to those from a comprehensive study that combined optical- and scanning-electron microscopy, X-ray diffraction, and chemical analyses. The study shows that larger particles of contaminants, encapsulated contaminants, and/or man-made materials such as slags, coke, metals, and plastics are subject to incasement, non-selectivity, and redistribution in the sequential extraction process. The results indicate that standard sequential extraction procedures that were developed for characterizing species of contaminants in river sediments may be unsuitable for stand-alone determinative evaluations of contaminant species in industrial-site materials. However, if employed as part of a comprehensive, site-specific characterization study, sequential extraction could be a very useful tool.