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.     

Radiological Program of the Los Angeles County Air Pollution Control District

Abstract

One technology Geld tested under the SITE demonstration program was stabilization-solidification. The HAZCON process was one of those tested. It treats hazardous wastes, consisting of both inorganic and organic contaminants, by mixing it with portland cement, water and a proprietary additive called Chloranan in a modified cement mixer to produce a concrete mass. In evaluating the technology during the demonstration, two major criteria were investigated by using existing laboratory tests. These criteria were mobility of the contaminants before and after treatment and the long-term effect on mobility, and durability of the solidified masses. The former criteria was evaluated using various leaching tests, primarily the Toxicity Characteristic Leaching Procedure (TCLP) and permeability. The durability criteria was determined from weathering tests, wet-dry and freezethaw, unconfined compressive strength, microstructural analyses and sampling the prepared blocks from the demonstration twice at 9-month intervals. This paper describes the results of the field sampling performed 9 and 18 months after the initial field demonstration and relates it to the results obtained during the demonstration.

According to the data, little or no change in the chemical and physical properties of the blocks occurred. The technology is capable of immobilizing heavy metals. The organics were not immobilized and the treated material appears quite durable.     

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.     

Waste Reduction Practices at Two Chromated Copper Arsenate Wood-Treating Plants

Abstract

Two chromated copper arsenate (CCA) wood-treating plants were assessed for their waste reduction practices. The objectives of this study were to estimate the amount of hazardous wastes that a well-designed and well-maintained CCA treatment facility would generate and to identify waste reduction opportunities. These practices have been reflected in several areas, including facility designs, process controls, and management practices. The facility designs included enclosed treatment buildings, covered drip pads, a drip pan, an automatic lumber handling system, power rollers, computerized chemical mixing systems, spill containments, and air ventilation systems to minimize mist or droplet emissions from cylinders and work tanks. Management practices have included pretreatment quality control, improved housekeeping, resource recovery and recycling, and operator training.     

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.     

Standards for Air Quality in California

Abstract

During the 1950s and 1960s, hundreds of thousands of underground storage tanks (and above-ground storage tanks) containing petroleum products and hazardous chemicals were installed. Many of these tanks either have been abandoned or have exceeded their useful lives and are leaking, thereby posing a serious threat to the nation’s surface and groundwater supplies, as well as to public health. Cleaning up releases of petroleum hydrocarbons or other organic chemicals in the subsurface environment is a real-world problem,

Biological treatment of hydrocarbon-contaminated soil is considered to be a relatively low-cost and safe technology; however, its potential for effectively treating recalcitrant wastes has not been fully explored. For millions of years, microorganisms such as bacteria, fungi, actinomycete, protozoa, and others have performed the function of recycling organic matter from which new plant life can grow.

This paper examines the biological treatment technology for cleaning up petroleum product-contaminated soils, with special emphasis on microbial enzyme systems for enhancing the rate of biodegradation of petroleum hydrocarbons. Classifications and functions of enzymes, as well as the microbes, in degrading the organic contaminants are discussed. In addition, the weathering effect on biodegradation, types of hydrocarbon degraders, advantages associated with enzyme use, methods of enzyme extraction, and future research needs for development and evaluation of enzyme-assisted bioremediation are examined.     

Recent advances in the application of silica nanostructures for highly improved water treatment: a review

The demand for high-quality safe and clean water supply has revolutionized water treatment technologies and become a most focused subject of environmental science. Water contamination generally marks the presence of numerous toxic and harmful substances. These contaminants such as heavy metals, organic and inorganic pollutants, oil wastes, and chemical dyes are discharged from various industrial effluents and domestic wastes. Among several water treatment technologies, the utilization of silica nanostructures has received considerable attention due to their stability, sustainability, and cost-effective properties. As such, this review outlines the latest innovative approaches for synthesis and application of silica nanostructures in water treatment, apart from exploring the gaps that limit their large-scale industrial application. In addition, future challenges for improved water remediation and water quality technologies are keenly discussed.

     

1992 Update of U.S. EPA’s Superfund Innovative Technology Evaluation (SITE) Emerging Technology Program

The Superfund Innovative Technology Evaluation (SITE) Emerging Technology Program (ETP) has encouraged and financially supported further development of bench- and pilot-scale testing and evaluation of innovative technologies suitable for use at hazardous waste sites for five years. The ETP was established under the Superfund Amendments and Reauthorization Act (SARA) of 1986. The ETP complies with the goal of the SITE Program to promote, accelerate and make commercially available the development ofalternative /innovative treatment technologies for use at Superfund sites.

Technologies are submitted to the ETP through yearly solicitations for Preproposals. Following a technical review, chosen applicants are asked to submit a detailed project proposal and a cooperative agreement application that requires Developer I EPA cost sharing. EPA co-funds selected Developers for one to two years. Second-year funding requires documentation of significant progress during the first year. Facilities, equipment, data collection, performance and development are monitored throughout the project. The U. S. Department of Energy (DOE) and the U. S. Air Force (USAF) are participants in the ETP. DOE has co-funded ETP projects since 1990 and the USAF since 1991.

A primary goal of the ETP is to move developed technologies to the field-demonstration stage. Therefore, a developer may be considered for participation in the SITE Demonstration Program provided performance in the ETP indicates the technology is field-ready for demonstration and evaluation.

Six technology categories: biological, chemical, materials handling, physical, solidification/ stabilization and thermal, are presently in the ETP.

Technologies of primary interest to EPA are those that can treat complex mixtures of hazardous organic and inorganic contaminants and provide improved solids handling and/orpretreatment.

An account of the background and progress of the ETP’s first five years is presented in this paper. Technologies currently in the ETP, including those selected from the fifth (EOS) solicitation, are noted, and developers, along with EPA Project Managers, are listed.     

Stabilization of Heavy Metal Containing Hazardous Wastes with Byproducts from Advanced Clean Coal Technology Systems

ABSTRACT

The purpose of this investigation was to evaluate the success of residues from advanced Clean Coal Technology (CCT) systems as stabilization agents for heavy metal containing hazardous wastes. In the context examined here, stabilization refers to techniques that reduce the toxicity of a waste by converting the hazardous constituents to a less soluble, mobile, or toxic form.¹ Three advanced CCT byproducts were used: coal waste-fired circulating fluidized bed combustor residue, pressurized fluidized bed combustor residue, and spray drier residue. Seven metal-laden hazardous wastes were treated: three contaminated soils, two air pollution control dusts, wastewater treatment plant sludge, and sandblast waste. Each of the seven hazardous wastes was treated with each of the three CCT byproducts at dosages of 10, 30, and 50% by weight (byproduct:waste). The treatment effectiveness of each mixture was evaluated by the Toxicity Characteristic Leaching Procedure. Of the 63 mixtures evaluated, 21 produced non-hazardous residues. Treatment effectiveness can likely be attributed to mechanisms such as precipitation and encapsulation due to the formation of hydrated calcium silicates and calcium sulfo-alu-minates. Results indicate that these residues have potential beneficial uses to the hazardous waste treatment community, possibly substituting for costly treatment chemicals.     

Automated Economic Analysis Model For Hazardous Waste Minimization

Abstract

The U.S. Army has established a policy of achieving a 50 percent reduction in hazardous waste generation by the end of 1992. To assist the Army in reaching this goal, the Environmental Division of the U.S. Army Construction Engineering Research Laboratory (USACERL) designed the Economic Analysis Model for Hazardous Waste Minimization (EAHWM). The EAHWM was designed to allow the user to evaluate the life cycle costs for various techniques used in hazardous waste minimization and to compare them to the life cycle costs of current operating practices. The program was developed in C language on an IBM compatible PC and is consistent with other pertinent models for performing economic analyses. The potential hierarchical minimization categories used in EAHWM Include source reduction, recovery and/or reuse, and treatment. Although treatment is no longer an acceptable minimization option, its use is widespread and has therefore been addressed in the model. The model allows for economic analysis for minimization of the Army’s six most important hazardous waste streams. These include, solvents, paint stripping wastes, metal plating wastes, industrial waste-sludges, used oils, and batteries and battery electrolytes. The EAHWM also includes a general application which can be used to calculate and compare the life cycle costs for minimization alternatives of any waste stream, hazardous or non-hazardous. The EAHWM has been fully tested and implemented in more than 60 Army installations in the United States.     

Measurement of Ozone Levels by Ship Along the Eastern Shore of Lake Michigan

The U.S. Environmental Protection Agency (EPA), in cooperation with the Toronto Harbour Commissioners (THC), conducted a Superfund Innovative Technology Evaluation (SITE) demonstration of the THC Soil Recycle Treatment Train. The treatment train consists of three technologies operated in sequence: a soil wash process, a metals removal process, and a biological treatment process. The THC conducted an extensive demonstration of the treatment train at a 55 tons per day pilot plant in order to evaluate an approach for remediation of industrial/commercial sites that are situated in the Toronto Port Industrial District (PID). Three soils were processed during the THC demonstration. The EPA SITE demonstration project examined, in detail, soil processing from one of the sites being evaluated as part of the overall THC project. Contaminants included organic compounds and heavy metals. It has been estimated by THC that as much as 2,200,000 tons of soil from locations within the PID may require some form of treatment due to heavy metal and/or organic contamination that resulted from various industrial processing operations. The objective of the SITE demonstration was to evaluate the technical effectiveness of the process in relation to THC’s target criteria.

Gravel and sand that met the THC target criteria for medium to fine soil suitable for industrial/commercial sites was produced. The fine soil from the biological treatment process did not meet the target level of 2.4 ppm for benzo(a)pyrene. However, there was a significant reduction in polynuclear aromatic hydrocarbon (PAH) compounds. The metals removal process achieved reductions of greater than seventy percent for copper, lead, nickel, and zinc.     

A Modular Approach to A Microcomputer Monitoring System

Abstract

Under a cooperative agreement with the U.S. Environmental Protection Agency's (USEPA) Superfund Innovative Technology Evaluation (SITE) Emerging Technology Program, COGNIS, Inc. conducted bench-scale studies on the COGNIS TERRAMET® Lead Extraction Process. The process leaches, or extracts, lead from contaminated soil and consists of a lead leaching stage followed by recovery of the dissolved lead from the leachant. Prior to treatment, the soil is characterized, the type and extent of lead contamination is identified, and the soil is pretreated by physical separation methods to facilitate the extraction process. The physical pretreatment, for example, may include particle size separation to allow separate leaching of the sand and fines fractions and removal of larger lead particles by density separation techniques. As part of the SITE Program, COGNIS investigated seven different lead-contaminated soil samples in small bench-scale batch studies and three soils in larger bench-scale continuous-treatment studies. This bench-scale work led to the design, construction, and operation of a full-scale treatment plant by COGNIS at the Twin Cities Army Ammunition Plant (TCAAP), New Brighton, MN where lead and seven other heavy metals were extracted and recovered from over 20,000 tons of treated soil to meet cleanup criteria.     

Incineration at Bayou Bonfouca Remediation Project

The Bayou Bonfouca hazardous waste site is located in Slidell, Louisiana, approximately 96 kilometers (60 miles) northeast of New Orleans. This site is ranked number 1,006 on the National Priorities List of Superfund sites. The U.S. Environmental Protection Agency (EPA) conducted a remedial investigation in 1986 and determined the primary potential exposure sources to be groundwater, surface waste piles, and contaminated sediment in Bayou Bonfouca. Based on the results of investigations, EPA and the Louisiana Department of Environmental Quality chose a remedy that involves dredging contaminated sediment from the bayou, excavating contaminated waste piles and soil, and incinerating the solid wastes in a transportable incinerator. The site remedy, which included incineration, was specified in the Record of Decision signed in March 1987.

Of the total 142,000 megagrams (Mg) (157,000 tons) of waste to be incinerated, approximately 119,000 Mg (132,000 tons) consist of hazardous sediment from the bayou; 22,600 Mg (25,000 tons) consist of lightly contaminated soils and waste piles, cellulosic materials, and other miscellaneous wastes on the ground. The solid wastes are primarily low heat content sediment and soils and cellulosic materials with polyaromatic hydrocarbon (PAH) concentrations from milligrams per kilogram (parts per million) levels up to two percent. The dredged bayou sediment will be dewatered in six, 115-cubiometer (150-cubic-yard) plate and frame filter presses before processing in the incinerator. A rotary-kiln-based single train incinerator is deployed at Bayou Bonfouca to process the solid waste feed.

On-site pilot studies indicated that the PAHs in groundwater could be removed by on-site pumping, treatment, and discharge of treated effluent to the bayou. The groundwater treatment plant went on-stream in June 1991. Treatment involves oil/water separation, filtration, carbon bed adsorption, and aeration.

IT Corporation-OH Materials, a joint venture, was awarded a contract in May 1991 and a notice to proceed in February 1992 to remediate and restore the Bayou Bonfouca site. The remediation project includes air quality monitoring and controls, site preparation, dredging and excavation, bayou bank stabilization and monitoring, equipment mobilization and erection, the trial burn, incineration, demobilization, and site closure. The project completed a successful trial burn in November 1993, and the commercial operation began in December 1993. The expected duration of the project is 40 months from mobilization to site closure.     

Public Policy impacts on the Generation and Disposal of Hazardous Waste in New York State

A number of policies adopted by the federal government and the states have been designed to promote waste reduction or influence the choice of waste disposal technologies employed by generators of hazardous waste. Graphic analysis of smoothed time series data for hazardous wastes manifested in New York State for the period between June 1982 and February 1987 suggests that some of these policies have had the intended effects.

Significant shifts in manifested waste volumes are evident that coincide with the following policy interventions: (1) increased state waste-end tax rates; (2) state and federal landfill bans; (3) federal restrictions on burning hazardous wastes and waste oils for energy recovery; and (4) changes in the federal regulatory definition of hazardous waste. Other changes in waste generation and management appear to be attributable to such factors as state and regional economic conditions and changes in instate treatment and disposal facility capacity. Analysis of the management of specific waste types supports evidence from the graphic analysis that waste generators changed from land disposal to “higher” waste handling technologies in response to several policy interventions.     

Qualitative and quantitative assessment of waste generation in a refrigerator-manufacturing plant based on a waste tree and mass balance

In this study, wastes originating at each production station during refrigerator manufacturing were identified and classified based on a waste tree. A mass balance study revealed a total waste production factor of 0.046 kg/kg of a product of which 75.3%, 23.9%, and 0.8% were non-hazardous wastes (NHWs), packaging wastes (PWs), and hazardous wastes (HWs), respectively. Wastes produced during refrigerator manufacturing were grouped under 35 different waste codes. Waste codes that contributed more than 5% by weight were 15 02 02 (contaminated absorbent material), 15 01 10 (contaminated packaging), 16 02 13 (electronic cards), 07 02 14 (polyol) and 08 05 01 (isocyanates), 19 08 13 (treatment sludge), 16 02 15 (capacitors), and 13 01 13 (hydraulic oil) for HWs, 12 01 01 (ferrous metal), and 16 02 16 (components) for NHWs, and, finally, 15 01 03 (wooden), 15 01 01 (paper&cardboard), and 15 01 02 (plastic) for PWs over 5 years. Scrap costs were used as a surrogate to determine production stages that generated high amounts of metal and plastic wastes. Logarithmically, increasing and decreasing trends were observed for PWs and NHWs over the study period, respectively. HW amounts did not exhibit a statistically significant trend. Twenty-eight BATs (best available techniques) were identified that could be applied in refrigerator manufacturing for waste minimization and management. Among those, 8 of them were proposed for further improvement for waste management in the facility.

     

Organic compound emissions from a landfarm used for oil and gas solid waste disposal

Solid or sludgy hydrocarbon waste is a by-product of oil and gas exploration and production. One commonly used method of disposing of this waste is landfarming. Landfarming involves spreading hydrocarbon waste on soils, tilling it into the soil, and allowing it to biodegrade. We used a dynamic flux chamber to measure fluxes of methane, a suite of 54 nonmethane hydrocarbons, and light alcohols from an active and a remediated landfarm in eastern Utah. Fluxes from the remediated landfarm were not different from a polytetrafluoroethylene (PTFE) sheet or from undisturbed soils in the region. Fluxes of methane, total nonmethane hydrocarbons, and alcohols from the landfarm in active use were 1.41 (0.37, 4.19) (mean and 95% confidence limits), 197.90 (114.72, 370.46), and 4.17 (0.03, 15.89) mg m^?2 hr^?1, respectively. Hydrocarbon fluxes were dominated by alkanes, especially those with six or more carbons. A 2-ha landfarm with fluxes of the magnitude we observed in this study would emit 95.3 (54.3, 179.7) kg day^?1 of total hydrocarbons, including 11.2 (4.3, 33.9) kg day^?1 of BTEX (benzene, toluene, ethylbenzene, and xylenes).

Implications: Solid and sludgy hydrocarbon waste from the oil and gas industry is often disposed of by landfarming, in which wastes are tilled into soil and allowed to decompose. We show that a land farm in Utah emitted a variety of organic compounds into the atmosphere, including hazardous air pollutants and compounds that form ozone. We calculate that a 2-ha landfarm facility would emit 95.0 ± 66.0 kg day^?1 of total hydrocarbons, including 11.1 ± 1.5 kg day^?1 of BTEX (benzene, toluene, ethylbenzene, and xylenes).     

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.     

Detection Limits for Hazardous and Radioactive Elements in Airborne Aerosols Using Inductively Coupled Air Plasma – Atomic Emission Spectrometry

Abstract

This research presents investigations into the use of inductively coupled air plasma – atomic emission spectrometry (air-plasma ICPAES) to determine the presence of inorganic contaminants in airborne aerosols. Limits of detection (LOD) in the ppm to ppb range for 19 hazardous metals and radionuclides were determined for aerosols of solutions nebulized into the air plasma. For many elements, the determined LOD surpass the threshold limit values established by the American Conference of Governmental Industrial Hygienists by one to three orders of magnitude. The potential of air-plasma ICPAES for continuous on-line monitoring of airborne contaminants is discussed.     

Conversion of chromium-containing solid wastes into value-added products through a plasma-assisted aluminothermic process

Chromium-containing solid wastes have been generated by chemical and leather/tanning industries, and the management and proper disposal of the same wastes have been challenging tasks. A significant fraction of these wastes contains chromium compounds with chromium present in the hexavalent (Cr⁺⁶) form, which is hazardous to human beings, animals, and ecosystems. Since these wastes are discarded largely without proper treatments, soil and groundwater get contaminated and they can cause several health issues to human beings. Conventional methods developed to convert hazardous Cr⁶⁺ to Cr³⁺/Cr metal either generate secondary toxic wastes and unwanted by-products and/or are time-consuming processes. In this work, a plasma-assisted aluminothermic process is developed to convert the toxic waste into non-toxic products. The waste was mixed with aluminium powder and subjected to transferred arc plasma treatment in a controlled air atmosphere. Chemical analysis and Cr leachability studies of the waste material prior to plasma treatment have shown that it is highly toxic. Analysis of the products obtained from the plasma treatment showed that Cr and Fe present in the waste could be recovered as a metallic mixture as well as oxide slag, which were found to be non-toxic. Easy separation of the metallic fraction and the slag from the treated product is one of the merits of this process. Besides converting chromium-containing toxic waste to non-toxic materials, the process is rapid and recovers the metals from the waste completely.