United States Environmental Protection Agency Research And Development (RD-675) 20R-1001 January 1990 v>EPA Hazardous Substance Research Centers Program Annual Report FY1989 Office of Exploratory Research Printed on Recycled Paper ------- U.S. ENVIRONMENTAL PROTECTION AGENCY OFFICE OF EXPLORATORY RESEARCH ANNUAL REPORT OF THE HAZARDOUS SUBSTANCE RESEARCH CENTERS PROGRAM FY 1989 ------- TABLE OF CONTENTS introduction page l Map: Hazardous Substance Research Centers and Directors page 5 Chapter 1 (Region-Pair 1/2) page 6 Contacts page 6 Budget page 8 Highlights page 10 List of Projects page 13 Project Description page 15 Bibliography page 29 Chapter 2 (Region-Pair 3/5} page 31 Contacts page 31 Budget page 33 Highlights page 37 List of Projects page 39 Project Descriptions page 41 Bibliography page 57 Chapter 3 (Region-Pair 4/6} page 58 Contacts page 58 Budget page 59 Highlights page 60 List of Proj ects page 63 Project Descriptions page 65 Bibliography page 7 6 Chapter 4 (Region-Pair 7/8} page 77 Contacts page 77 Budget page 79 Highlights page 80 List of Projects page 82 Project Descriptions page 83 Bibliography page 103 Chapter 5 (Region-Pair 9/10} page 108 Contacts page 108 Budget page 109 Highlights page ill List of Projects page 116 Project Descriptions page 118 Bibliography page 136 ------- INTRODUCTION The U.S. Environmental Protection Agency (EPA) established the Hazardous Substance Research Center (HSRC) program in response to provisions in the 1986 amendments to the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA, also known as "Superfund") and the Agency's 1988 Appropriation Act. Section 311(d) of the amended Superfund enabled EPA to establish between five and ten university-based HSRCs, whose missions would be to study all aspects of the "manufacture, use, transportation, disposal, and management of hazardous substances and publication and dissemination of the results of such research." The law further instructed that these centers must be distributed "equitably among the regions of the United States", that recipients must dedicate not less than 5% of the center's resources to technology transfer, and that EPA's contribution to the support of these centers could not exceed 80% of the total funding for each center. The law provided a total of $25 million over a five-year period for the support of this program. When EPA received its 1988 Appropriation, that law provided $5 million annually and contained language which further defined the boundaries of the program. This law specified that no more than five centers would be established and that these must be established competitively. The EPA Administrator delegated authority for the management of this program to the Director, Office of Exploratory Research (OER). It is the primary mission of OER to provide support to the academic environmental research community through several vehicles, including a program of investigator-initiated grants and 'competitively selected research centers. This office was, therefore, the logical choice to design and manage the HSRC program. To solve the problem of equitable geographic distribution of the five research centers, it was decided that EPA would establish five geographic subsections of the country, corresponding to two contiguous federal regions. Each of these "region-pairs" would contain one HSRC. The map depicted on page 5 of this report indicates the states contained in each region-pair and the lead institution of the center it contains. Briefly, the geographic partitions are as follows: ------- Region-Pair 1/2. which includes the New England states, New York, New Jersey, and the territories of Puerto Rico and the U.S. Virgin Islands. Region-Pair 3/5. comprised of the Great Lakes states and the mid-Atlantic states of Virginia, West Virginia, Maryland, Pennsylvania, and Delaware. Region-Pair 4/6. which is made up of the Gulf Coast and southern states. Region-Pair 7/8. which contains the states on the eastern side of the Great Basin and the Great Plains. Region-Pair 9/10. which serves the states of the West Coast, plus Idaho, Arizona, Alaska, Hawaii, and Guam. A detailed solicitation for proposals to establish centers in these five region-pairs was prepared and published on March 22, 1988. It appeared first in the Federal Register, then was distributed directly to the more than 3,000 universities across the country which have declared research capabilities. Announcements of the program were published in Science and Environmental Science. and Technology. These announcements generated over 200 requests for copies of the solicitation. Proposers were given a three-month period to respond to the solicitation which, given the scope and depth required, was not very long. Nevertheless, 33 proposals were received from eligible competitors. These proposals were reviewed by five separate panels consisting of between 11 and 17 nationally and internationally recognized experts in hazardous substance research, engineering, and technology transfer. The reviews were comprehensive and multi- tiered, and included two intensive scoring sessions based on proposal contents and, in two cases, site visits to the leading contenders. The final panel recommendations were made to the Agency in October 1989. The five proposers who had been recommended were invited to submit formal applications for federal assistance. All five centers were funded and in place by February 1989. All fiv« of the centers are multi-university consortiums. These center* are: Northeast H>i>rdous Substance Research Center —— The lead institution is the New Jersey Institute of Technology and the Center Director is Dr. Richard Magee. Other consortium partners include the Massachusetts Institute of Technology, Tufts University, Rutgers University, Stevens Institute of Technology, Princeton University, and the University of Medicine and Dentistry of New Jersey. ------- lesearch center — This three-university consortium is headed by Dr. Walter Weber, of the University of Michigan. Michigan State University and Howard University are the partner institutions. Waste Minimiiation and Management Center — North Carolina State University heads this center, in partnership with the University of North Carolina at Chapel Hill and Texas Agricultural and Mechanical University. The Center Director is Dr. Michael Overcash, of North Carolina State University. Hazardous Substance Research Center for Federal Regions 7 St 8 — This large consortium is run by Dr. Larry Erickson, of Kansas State University. The other six participating institutions are Montana State University and the Universities of Iowa, Missouri, Montana, Nebraska, and Utah. Western Region Hazardous Substance Research Center — Stanford University and Oregon State University make up this consortium. Dr. Perry McCarty, of Stanford University, is the Center Director. Each center received an initial grant for a three-year project period. Subject to successful completion of a peer evaluation after two years of operation, the centers can be renewed for another five-year project period, for a total life span, under this program, of eight years. The budget for each center during the first three years of operation is expected to be approximately $4 million, with an expected $1 million per center annually after that. In addition to performing quality innovative research on critical problems associated with hazardous substances, each of these centers is required under the terms of the solicitation to dedicate between 10 and 20% of its total budget to training and technology transfer activities in support of the center's mission. To assist each center director in selecting research topics to pursue and ensure the continued high quality of the center's research, each center is required to establish and maintain a Science Advisory Committee made up of acknowledged experts in relevant disciplines from the federal government, academia, the private sector, and state and local government. This body must convene at least twice annually. A similar group must be established to help the center director plan and manage his training and technology transfer program. The Training and Technology Transfer Advisory Committee, comprised of qualified individuals from EPA, industry, state and local government, private trainers, and others, must meet at least once a year. ------- The five centers have complementary but not overlapping missions. Several mechanisms are in place to assist in the coordination of activities among the centers, including shared advisory committee members, a required annual meeting of center directors, frequent conference calls among center directors, mutual attendance at individual center functions, joint sponsorship of conferences and workshops, and numerous informal coordination mechanisms. In the chapters that follow, the research, training, and technology transfer programs of each center are described in detail. Questions about the activities of plans of individual centers should be directed to the center director, whose names, addresses, and phone numbers appear at the beginning of the chapter for that center. Questions pertaining to the HSRC program in general may be directed to: Karen Morehouse Director, Centers Program Office of Exploratory Research (RD-675) U.S. Environmental Protection Agency 401 M Street, S.W. Washington, D.C. 20460 Phone: 202/382-5750 ------- HRZRRDOUS SUBSTRNCE RESEHHCH CENTERS RND DIRECTORS Or Larry E. Erickson Dept of Chemical Engmeefing DurlandHall Kansas Stale University Manhattan. Kansas 66506 913/532-5564 Dr. Walter J. Weber, Jr DepL ot Civil Engineering 2340 C G Brawn Building University of Michigan Ann Arbor. Miehyan 40109-2125 313/763-2274 Or Richard Magee, Drector Hazardous Substance Management Research Center New Jersey Institute of Technology Newark. New Jersey 07102 201/596-3233 Or Perry L McCarty Center Director Dept. of Crvil Engineering Stanford University Stanford. California 94306 415/723-4131 Dr. Michael R. Overcash Dept of Chemical Engineering North Carohna State University Rateigh, Norti Carolina 27695-7001 91ftT737-2325 ------- Chapter It Northeast Hazardous substance R««aaroh cant«r ------- Center; Participants; Director; Northeast Hazardous Substance Research Center New Jersey Institute of Technology Massachusetts Institute of Technology Princeton University Rutgers University Stevens Institute of Technology Tufts University University of Medicine and Dentistry of New Jersey Richard S. Magee, Director Northeast Hazardous Substance Research Center New Jersey Institute of Technology Newark, New Jersey 07102 Phone: 201/596-3006 FAX: 201/802-1946 THE CENTER AT A GLANCE The Northeast Hazardous Substance Research Center (NHSRC) for Federal Region Pair 1 and 2 was established in February 1989. New Jersey Institute of Technology (NJIT) is the lead institution in a seven-member consortium formed to establish the Center. Consortium members include Massachusetts Institute of Technology, Princeton University, Rutgers University, Stevens Institute of Technology, Tufts University, and the University of Medicine and Dentistry of New Jersey. The Center's administrative headquarters are located in the new Advanced Technology Center building at NJIT. The Center is guided by an 18-member Science Advisory Committee and a 14-member Training and Technology Transfer Advisory Committee. Key personnel currently working for the Center are listed in Table 1. ------- Table it Key Personnel in the NHSRC New Jersey Institute of Technology P.M. Annanente B.C. Baltzis J.W. Bozzelli G. Lewandowski W. Librizzi R. Magee Rutgers University C. Chess M.S. Finstein M. Greenberg P.M. Sandman P.P. Strom Princeton University P.R. Jaffee G. Pinder Massachusetts Institute of Technology J.P. Longwell D. McLaughlin W.A. Peters A.F. Sarofim R.B. Barat G.S. Darivaksi S. Chisolm A. Ducatman J.R. Ehrenfeld J.B. Howard Tufts University B. Cole A. Cortese S. Krimsky D.R. Walt Stevens Institute of Technology K.K. Sirkar Regions 1 and 2 are unique in their combination of age of industrial activity, density of population, economic activity, concentration of chemical and pharmaceutical industries, and rapidly developing high-tech industries. Former waste handling and disposal practices created a large number of sites which have been identified and placed on the National Priorities List. Remediation of these sites is difficult and costly; approximately 75% have groundwater contamination. Treatment, storage, and disposal facility capacity in the region-pair is insufficient. Improved technologies for pre-treatment of industrial wastes are needed. These needs provide the stimulus for the Center's research focus. After soliciting advice from its Science Advisory Committee (SAC), the. Center has decided to focus its initial research efforts on remediation and treatment techniques. At its November 2, 1989 meeting, the) SAC considered 36 proposals of which 11 were continuations and 25 were new topics. The proposals presented ideas in the areas of incineration, groundwater remediation, soil remediation, and treatment. The SAC recommended continued support of all but one ongoing study. The top proposals in each category, as ranked by the SAC, will be initiated. ------- The needs of the region-pair also require increased focus on training and technology transfer as they relate to the Center's research agenda, as well as to the expanding scientific and engineering activities in the hazardous waste management field. The Training and Technology Transfer Advisory Committee (TTAC) has recommended that the Center focus its efforts on activities that advance the state-of-the-art and do not overlap/duplicate ongoing activities, particularly EPA and State on-going training and technology transfer programs. Table 2: Center Budget FUNDING SOURCES FY 1989 FUNDS EPA: Centers Program $2,000,000 Consortium 752,342 Other Government* 78.094 TOTAL $2,830,436 *NJ Commission on Science and Technology CENTER DIRECTOR*8 REPORT Over 100 faculty and staff are currently working on hazardous substance related research within the consortium institutions. The expertise covers chemical, civil, and mechanical engineering; chemistry; environmental biology; hydrology; geology; toxicology; risk assessment; and public policy. The Northeast Hazardous Substance Research Center (NHSRC) was proposed as the nucleus to bring this research effort together and focus on hazardous substance problems of concern in Regions 1 and 2. The Center's initial program focus is intentionally broad, to draw on its large pool of talented researchers. Following a review of Northeast Hazardous Substance Research Center's research needs assessment, the Center's SAC recommended that the Center focus its research efforts in technology development and demonstration, with emphasis on remediation and treatment. Further, these two major research areas encompass a wide range of hazardous substance management problems and Superfund remediation challenges facing the region-pair. The SAC strongly urged the need for in-situ remediation technologies, while recognizing that sites will continue to be remediated using removal/treat technologies. They stressed that researchers should pay special attention to the intermedia efforts, such as impacts on air quality as a result of 8 ------- in-situ extraction or impacts on water quality which may result from in-situ biotreatment of contaminated soils. Hazardous substance treatment technologies that address both treatment of industrial wastes and wastes at contaminated sites were encouraged. These include incineration, separation, stabilization, and biotreatment technologies. Interest and participation from faculty at the consortium schools in the activities of the Center are strong. Thirty-six research proposals, including twenty-five new projects, were submitted for funding consideration in 1990. These proposals were equally distributed among four major research areas: incineration, soil remediation, groundwater remediation, and waste treatment. The SAC reviewed these proposals at its November 2, 1989 meeting and recommended 25 proposals for funding consideration on the basis of scientific merit and relevance to the research needs of the region-pair. Since the budget requests for these proposals exceeded the Center's funding capacity, the SAC further reduced the list to the top 18 proposals. The Director plans to fund these 18 projects which include 10 continuations and 8 new research topics. The major thrusts of the Center include thermal treatment (incineration) and remediation (soil and groundwater). The Center's program for Training and Technology Transfer focuses on development and application of approaches that expand or complement on-going training and technology transfer programs, particularly those of EPA and the states. To the greatest extent possible, such approaches must provide innovative and imaginative concepts that advance the state of the art, meet the defined needs of Regions 1 and 2, and be potentially adaptable for broader use. The TTAC identified three important areas that can have significant impact on the hazardous substance management program: project management, consideration and use of alternative treatment technologies, and pollution prevention. A total of six proposals were submitted for review by the Center's TTAC. These proposals included training initiatives for alternative treatment technologies and risk communication, and technology transfer for emerging waste management technologies, bioremediation and groundwater remediation. The TTAC reviewed these proposals at its November 1, 1989 meeting and recommended funding for five proposals: (1) Overcoming Organizational Barriers to Risk Conunication (continuation), (2) Emerging Waste Management Technologies: A State-of-the-Art Review and Seminar, (3) In-Depth Training in Alternative/Innovative Technology Options for Remedial Actions at Hazardous Waste Sites (this project is a cooperative effort among the Center, New York Sate Center for Hazardous Waste Management-State University of New York at Buffalo, and the New York State Department of Environmental Protection), (4) In-Depth Training in Alternative/Innovative Technology Options for Remedial Actions at Hazardous Waste Sites (this project expands the delivery of the Center/New York State agenda), and (5) Groundwater ------- Contamination Conference. Further, they recommended that a four- page newsletter be published quarterly. The publication can be topic or issue specific and include research summaries or bulletins and a question and answer column. The Center is off to a strong start with an active research program and a comprehensive technology transfer and training program. The Center's two advisory committees have been extremely helpful in assisting Center management in refining its focus and research thrusts. The Director has encountered no difficulty in administering a multi-disciplinary, multi-university program. A solid foundation has been established upon which the Center will build in the years ahead. HIGHLIGHTS TOR 1989 Aquifer Bioremediation Bioremediation of contaminated aquifers is a promising restoration technique. A typical bioreclamation design calls for the introduction of nutrients through wells and circulation of these nutrients through the contaminated zone by pumping one or more wells. Supplementation of the nutrient levels and electron acceptors and recirculation of the water allow the indigenous microbial flora to decompose the contaminants more rapidly than under natural conditions. Nutrients are introduced at point sources, and clogging of soil has often been observed in the vicinity of injection wells due to a large production of biomass in aerobic cases, or the production of biogases in anaerobic cases. Hence, it is difficult to distribute the nutrients uniformly within the contaminated region and achieve biodegradation in regions that are not in the direct vicinity of the wells. Professor Peter Jaffe, Princeton University, has developed a mathematical model for the aerobic case and has verified the model with laboratory data. This model is currently being used to examine strategies for the injection of growth substrates to maximize the zone of biologic activity and minimize plugging of soil. The results will demonstrate an efficient way to inject a carbon source into the subsurface, and should enhance the applica- tion of bioremediation schemes to treat contaminated aquifers. The availability of bioremediation technologies will enable EPA to decontaminate aquifers in a more timely and economic manner. Remote Sensing Groundirater Monitor Groundwater monitoring is essential in several environmental management scenarios including managing the integrity of underground storage tanks and groundwater resources, as well as when performing remedial actions at waste sites. Conventional laboratory techniques suffer from several inherent problems and 10 ------- limitations often associated with alterations to the sample during the sampling procedure. Professor David Walt, Tufts University, has been working to develop a fiber optic sensor that changes its fluorescence characteristics when in contact with volatile organic compounds. It is constructed by fixing a vapor-absorbing polymer to the distal tip of an optical fiber. The layer contains an intimately mixed dye that changes its fluorescence properties in response to organic vapors. Sensors respond to organic vapors between 0.1 and 10,000 ppm. A portable instrument has been constructed and has been tested in conjunction with the fiber sensors. Field test studies at contaminated sites in New Hampshire and Massachusetts are underway. Technology transfer from paper studies, laboratory to field demonstrations, or policy implementation is a critical concern for industry, government agencies, and academia, and is an issue of the highest priority for EPA. The proposed project speaks directly to this issue by accelerating a highly-successful laboratory-based project with a field-based component to provide the essential program development necessary to encourage an early application of the new technology. Incineration of Chlorocarbons Incineration is currently viewed as a practical option for the disposal of chlorinated hydrocarbon (CHC) wastes. However, it has been observed that high CHC loadings in fuels fired in rotary kilns can result in destabilization of these turbulent flames and may increase subsequent products of incomplete combustion (PIC). For CHC incineration to be viable, a detailed understanding of the effects of chlorine on hydrocarbon oxidation in flames is necessary. Mr. R. Barat, Professors A. Sarofim and J. Longwell of the Chemical Engineering Department of MIT, and Professor J. Bozzelli of the Chemical Engineering, Chemistry, and Environmental Science Department of NJIT, examined the destablizing effects of methyl chloride on a fuel lean ethylene/air flame in a toroidal jet stirred combustor (TJSC). The TJSC emulates the highly circulated flame stabilization zone in many large scale burners. It is in this zone vhere CHCs are most likely to affect incinerator performance. A detailed chemical reaction mechanism for fuel lean methyl chloride oxidation has been constructed. Sensitivity analyses of near calculated TJSC blowout offer some fascinating insights into the destablizing effects of chlorine. The chlorine complicates the combustion chemistry in a manner which results in significant flame destabilization. 11 ------- The mechanism is presently being refined. Conditions or additions which will reduce or eliminate the inhibition by chlorine are being explored. Once the full effects of chlorine are understood, the incinerator operations can be altered to minimize the production of PICs when disposing of CHCs. A reduction in PIC emissions supports EPA's risk reduction goal when managing hazardous wastes. Alternative Technologies Hazardous waste management programs for cleaning up inactive disposal sites have evolved away from disposal of contaminated materials in secure landfills to the application of permanent remedies based on the use of alternative technologies. This evolution has resulted from the growing concern regarding protection of groundwater resources, insufficient landfill capacity, and the desire to effect a permanent remedy so that there remains no risk to human health and environment. To implement alternative treatment technologies successfully, EPA Project Managers (RPMs) and State Project Managers (SPMs) must have a strong basic knowledge and understanding of these technologies, including the particular conditions under which such technologies can be effective. They need to be familiar with the status of technology development and the prospects for demonstration of recently developed technologies. EPA RPMs and SPMs need to have a working knowledge of the operational characteristics, constraints and limitations, and residuals management for each applicable technology. For these reasons, it is critical that effective training and technology transfer programs be conducted for EPA and State project managers to provide the depth of knowledge and understanding required to promote and implement appropriate alternative/innovative technologies. The Center maintains close relations with other institutions in the region-pair conducting hazardous substance research programs and educational activities. This has resulted in the establishment of a joint effort between the Center, the New York State Center for Hazardous Waste Management (CHWM) located at the state University of New York at Buffalo, and the New York State Department of Environmental Conservation (DEC). The Center and CHWM will develop and deliver two technical workshops on these topics related to the remediation of inactive hazardous waste disposal sites. These two technology areas are: (1) thermal destruction and (2) treatment of soil and groundwater contaminated with metals. These two areas have been selected on the basis of a needs survey conducted by the Hazardous Waste Remediation Division of the New York State Department of Environmental Conservation, and represent critical areas of concern throughout Regions 1 and 2. These workshops and related instructional materials will be suitable for delivery 12 ------- throughout the region-pair, and it is likely that they will be applicable in other geographic areas as well. Training Activities Successful implementation of a sustained and effective hazardous waste program requires a well-trained cadre of on-scene coordinators/regional project managers (OSC/RPM). EPA has initiated the Superfund Training Institute (SUTI) concept to contribute to the development of staff, by providing basic and advanced training in a number of critical areas that aid EPA in developing experienced and knowledgeable OSC/RPMs, who are being called upon to manage the clean-up of an expanding number of sites with complex administrative, legal, and technical challenges. To assist EPA in this effort, the Center is developing an in- depth advanced training program for Federal and State OSC/RPMs in three critical areas: (1) legal issues, (2) contract administration, and (3) site management. Experts in the areas of focus will use lectures, case studies, and exercises to provide OSC/RPMs with a substantial understanding of the technical concepts, their practical applications, and the available tools that facilitate and enhance their ability to fulfill their responsibilities. The successful completion of this initiative will form the foundation for the establishment of a SUTI to continue the advanced training activity. SUMMARY OF ONGOING PROJECTS Investigators Project Title Groundvater Remediation Jaffe Design of Aerobic and Anaerobic Aquifer Biomanipulation Schemes Armanente/ Treatment of Contaminated Groundwater with LewandowsJci Bioreactors Utilizing a White Rot Fungus Pinder Investigation Into Dissolution of DNAPL in the Subsurface McLaughlin Real-Time Monitoring and Control of Groundwater Contamination Walt Field Based Testing of a New Remote Sensing Groundwater Monitor 13 ------- Finstein/ Optimization of Biological Soil Remediation Storm Howard/ Fundamental Studies of Solids Devolatilization Darivakis/ for Hazardous Waste Destruction Peters Chisolm DNA Characteristics of Indigenous Microbial Communities as Indicator of Mutagenic Hazardous Waste Exposure Incineration Barat/ Effects of Chlorocarbons on Flame Intermit- Sarofim/ tency Stability and Efficiency in a Well Longwell Stirred Reactor Bozzelli Thermal Oxidation Studies on Chloromethane and Chlorobenzene-Detailed Mechanism of Hydrocarbon Flames Doped with Chlorocarbons Waste Treatment Baltzis/ A Dynamic Model of Sequencing Batch Reactors Lewandowski Sirkar Removal and Recovery of Heavy Metals from Waste Water by Hollow Fiber Contained Liquid Membrane Technique Training and Technology Transfer Cortese Promotion of Existing Training/Technology Transfer Courses-EMI Ducatman Research Laboratory Hazards Management Chess Looking Within: Organizational Factors in Risk Sandman Communication Krimsky/ Emerging Paradigms of Risk and Risk Plough Communication and the Policy Implications: A Cultural Synthesis Ehrenfeld Conference on Incineration Modeling Magee/ National Conference on Regional Issues Fischer 14 ------- PROJECT DESCRIPTIONS Qroundvatar Remediation Design of Aerobic and Anaerobic Aquifer Biomanipulation schemes: P.R. Jaffee, Princeton University Goal; The goal of this research is to learn through laboratory experimentation and computer simulations how to operate in-situ bioremediation schemes for the decontamination of aquifers. The main emphasis of the research is on optimizing the injection of growth substrates into the subsurface so as to obtain a uniform region of biostimulation without inducing excessive clogging in the vicinity of the injection well. Rationale; Clogging of soil has often been observed in the vicinity of injection wells due to a large production of biomass in aerobic cases, or the production of biogases, such as nitrogen or methane, in anaerobic cases. Furthermore, because organisms that degrade chlorinated solvents need additional growth substrates, which are used up very rapidly in the vicinity of injection wells, it is not clear how to achieve biodegradation of these solvents in regions that are not in the direct vicinity of the wells. Approach; A mathematical model is being developed that simulates the processes involved in bioremediation schemes, and the model will be verified against a specially designed experimental column study. Status; A mathematical model has been constructed for the aerobic case and has been verified against laboratory data. This model is currently being used to examine strategies for injection growth substrates in order to maximize the zone of biologic activity and minimize plugging of the soil. The simulations will be completed by December 1989. Anaerobic experiments are being conducted in which the degradation of TCE is monitored as a function of the growth substrate. Based on these results, experiments will be designed to study the anaerobic scenario further. Completion of the anaerobic work is expected by December 1991. Treatment of Contaminated Qroundwater with Bioreactors utilizing a Whit* Rot Funguss P.M. Armanente (P.I.) and G. Lewandowski (Co- Pi) , New Jersey Institute of Technology Ooalt The goal of the project is to determine the optimal reactor configuration and the optimal operating conditions required to maximize the degradation activity of the fungus Phanerochaete chrvsosporium against a number of toxic chlorinated aromatic compounds. 15 ------- Rational*: Previous results have shown that this fungus holds great potential for detoxifying aqueous streams contaminated with chlorinated compounds. In spite of the current knowledge on the microbiology of this microorganism, very little information is available for engineers to use in designing, scaling-up, and operating a decontamination system using this fungus. Without this information, the fungus cannot be used in field applications, and feasibility studies cannot be conducted. The project is focused on the determination of such engineering information, and on the modeling of the dynamics of the decontamination process. Approach: The fungal detoxification activity is studied in different types of reactors, such as continuously stirred tank reactors or packed bed columns, under different operating conditions, including critical nutrient concentrations, feed rate of toxic stream to reactor, and temperature, against several toxic compounds of interest to industry. The disappearance of the toxic compound and the appearance of non-toxic products are monitored, and a mathematical model is developed to predict the performance of the reactors as operating conditions are changed. This model can then be used to determine reactor scale-up rules and other relevant engineering information necessary for the implementation of this technology. Status: Experiments are in progress with a model toxic compound (2-chlorophenol). Additional toxic compounds have been selected and experiments with them will begin in the near future. The mathematical model is being developed and tested against the available experimental data. Investigation Into the Dissolution of DNAPL in the Subsurface: G. Finder, Princeton University (now at the University of Vermont) Goal; The goal of this research is to develop a method for removing DNAPL (Dense Non-Aqueous Phase Liquids) from the subsurface so they can be treated in surface facilities. Rationale; It is well known that small amounts of alcohol can significantly modify the solubility of organic solvents, such as TCE, in water. It is also recognized that it is difficult, if not impossible in many instances, to remove organic solvents by attempting to pump them using conventional well technology. Finally, th« oil industry possesses the technology to remove residual oil from reservoirs by displacing and, to a certain degree dissolving, the oil using a secondary fluid. This research combines these concepts to produce a technique that will use oil reservoir hydrodynamic concepts to dissolve and displace DNAPL using injected water containing selected alcohols. 16 ------- Approach: The project will proceed as follows: (1) various alcohols will be evaluated as solvents in the sense described above, (2) of the alcohols tested, the one that appears to be the most effective and environmentally safe will be tested in a laboratory situation involving flow through a soil column, and (3) given successful completion of Step 2, the concept will be tested in the field. At this point, Ciba-Geigy Corporation has indicated an interest in pursuing a field level test of the concept. status: At this time, Step 1 has been successfully completed and work on Step 2 has been initiated. Even at this early stage, it is evident that the concept is probably viable. Real-Time Monitoring and Control of Oroundvater Contamination: D. McLaughlin, Massachusetts Institute of Technology Goal: The overall goal of this project is to develop practical methods for characterizing and controlling contamination at hazardous waste sites when field data are limited. The immediate objective is to test the feasibility of sequential (or real-time) methods of designing field sampling programs at such sites. Rationale: Successful groundwater remediation depends strongly on the ability to describe and predict the spatial distribution of subsurface contaminant plumes. This is a difficult task when field data are limited and soil properties are heterogeneous, as they are in most practical applications. This project is intended to provide new methods of designing monitoring and remediation strategies which explicitly recognize the importance of heterogene ity. Approach; The key to the real-time approach is to combine information gained from field sampling programs with information obtained from physically-based models of contaminant transport. Field samples are used to update model-based estimates of groundwater velocity and contaminant concentration. The updated estimates are, in turn, used to guide subsequent sampling and remediation efforts. Status: During the first year of this project, which is scheduled for completion on February 14, 1990, real-time monitoring concepts were tested at a contaminated coal-tar disposal site. The lessons learned tram this field test can then be used to improve our approach. Field-Based Tasting of a New Remote Sensing aroundvater Monitor: D.R. Walt, Tufts University Goal; This project aims to develop a new fiber optic groundwater contaminant detector as a practical tool for in-situ sensing, and 17 ------- to facilitate an early transfer of this new technology to the solution of environmental problems through the creation of prototype equipment, materials, and testing protocols. The detector is based on a fiber optic sensor that changes its fluorescence properties in contact with volatile organic compounds. Rationale: Groundwater monitoring now plays a pivotal role in the management of underground storage tanks, remedial actions at waste sites, and in the effort to preserve and protect groundwater resources. Current monitoring strategies employing conventional laboratory techniques have several inherent problems and limitations. The sampling procedure may alter the sample being taken, retrieval of results is often slow and costly. In addition, chain-of-custody concerns relative to data documentation are quite expensive. Approach; The sensor operates on the basis of a fluorescence signal enhancement when placed in contact with volatile organic vapors. It is constructed by fixing a vapor-absorbing polymer to the distal tip of an optical fiber. The layer contains an intimately-mixed dye that changes its fluorescence properties in response to organic vapors. Status; Sensors have been prepared and tested in the laboratory. They respond to organic vapors between 0.1 and 10,000 ppm. A portable instrument has been constructed and has been tested in conjunction with the fiber sensors. Field test studies at contaminated sites in New Hampshire and Massachusetts began during Fall 1989. Soil Remediation Optimization of Biological Soil Remediation: M.S. Finstein and P.F. Strom, Cook College, Rutgers University Goal; The goal of this project is to use naturally occurring populations of microorganisms in the on-site detoxification of certain industrially contaminated soils. Candidate soils for biological remediation include those at plants that formerly produced pipeline gas from coal, but were abandoned or decommissioned as coal gas was replaced with natural gas. Approximately 2,000 such sites in North America need soil remediation. Rationale: Most hydrocarbon contaminants, such as those found at coal gas sites, are intrinsically biodegradable under the proper circumstances. When the contaminants persist, it is because of some combination of adverse biological factors. For instance, there may be a lack of inorganic nutrients or of readily metabolized organic substrate. The contaminants may exist in watertight clumps which create an unsuitably dry environment. Other causes may include low temperatures or a lack of compatible 18 ------- organisms. Improved characterization of operative limitations, and development of techniques to relieve them, will aid in the improvement of remediation practices. Approach: Two approaches are being compared. In the first approach, only the inorganic nutrient and physical limitations are relieved. The second approach does these things, plus combines the contaminated soil with readily metabolized bulk organic material, such as wastewater sludge or leaves, thus creating a composting operation, in which the mixture increases in temperature owing to microbial heat generation. Each approach evokes different microbial responses and has different process requirements. The first requires less handling of materials and fewer processing requirements. It relies on the contaminants themselves to support microbial processing, but results in a massive build-up of microbial populations, and encourages in-situ genetic changes, possibly favoring degradative competence. The information gained will help delineate the strengths and limitations of each approach, and their respective practical roles. status; Each approach was previously investigated separately. Apparatus have been fabricated for their comparative evaluation. The comparative study should be completed by January 1991. Fundamental Studies of Solids Devolatilization for Hazardous Waste Destruction: J.B. Howard, 6.S. Darivakis, and W.A. Peters, Massachusetts Institute of Technology Goal; The objective of this project is to contribute to the fundamental understanding of how thermal treatment can destroy hazardous solids without generating adverse by-products. Specific aims are to determine what, and how rapidly, products are formed by thermal decomposition of solids and by further thermal reactions of chemicals evolved by the decomposing solid. Rationale: Initial thermal decomposition of solids and subsequent thermal reactions such as pyrolysis and incomplete oxidation of ambulatory products of that decomposition, are important processes in incineration and in advanced thermal technologies for destruction of solid hazardous wastes such as soils, sludges, and toxic industrial residues. Such reactions can facilitate easy burning of the waste or they may result in hazardous by-products that, if left undestroyed by afterburners or cleanup equipment, might escape the process as toxic emissions. Better understanding of these reactions gives guidance on how to design and operate incinerators, afterburners, and cleanup equipment to achieve desired waste destruction efficiencies without producing adverse emissions. Approach: Yields, compositions, and generation rates of products from the reactions described above are being determined using small scale laboratory apparatus that simulates conditions of practical 19 ------- interest, but does so in such a way that the effects of temperature, treatment time, heating rate, sample dimension, and type of solid can be independently studied. statusi A quantitative study of the rapid thermal decomposition behavior of polyethylene and polystyrene, studied as prototype solid wastes was completed in August 1989. Yields and production rates of two important categories of decomposition products were determined. Future work will identify and measure plastics decomposition products, study rapid thermal decomposition of contaminated soils, and examine thermal reactions of the decomposition products of solids. DNA Characteristics of Indigenous Miorobial Communities as Indicators of Mutagsnio Hazardous Waste Exposure: S.W. Chisolm, Massachusetts Institute of Technology Goal! The ultimate goal of this project is to develop a system for detecting and identifying mutagenic chemicals in the environment by analyzing mutations in the indigenous bacteria. The immediate goal is to determine the naturally occurring DNA sequence variability which would appear as "background" in the proposed test. Rationale; Extensive work with both bacteria and cultured cells have shown that individual mutagenic chemicals induce specific sets of mutations, termed "mutational spectra" that can be used to identify the responsible agents. These prior experiments were performed with uniform, cultured cells. The current investigations will test the feasibility of extending the approach to natural populations of microorganisms. Approach: The general scheme of the proposed work is as follows: (1) select a contaminated watershed in the local area, (2) isolate and identify a bacterial species that is common in the area, (3) pick a highly conserved region of the genome of this species to use as the assay region for mutational spectrum analysis, (4) determine the DNA sequence of this region in the isolate, (5) collect isolates of the same species from a variety of different environments (including pristine ones), and determine the natural variability in the DNA sequence of the gene in question, (6) subject isolates to various known mutagens in the laboratory, and determine the mutational spectra they evoke in the DNA sequence of the gens in question, and (7) go back to a contaminated site to see if the mutational spectra can be detected in samples collected in-situ. This work is being done in collaboration with Dr. William Thilly of MIT's Center for Environmental Health and Sciences. status: The Aberjona watershed near Boston which includes a highly contaminated sits in Woburn, has been chosen as the study area. Several clones of Pseudomonas fluorescens have been isolated from 20 ------- a lake in the watershed for use as the indicator organism. The highly conserved genes for 16s ribosomal RNA have been isolated and sequenced from one of the isolates. Work is progressing on the culturing and sequencing of additional isolates. Incineration The Effects of Chlorocarbons on Flame Intermittency, Stability, and Efficiency in a Well-Stirred Reactor: R.B. Barat, A.F. Sarofim, and J.P. Longwell, Massachusetts Institute of Technology Goal; The goal is to acquire a quantitative understanding of the effect of chlorocarbons on the escape of unburned material from incinerators. Rationale s The presence of chlorocarbons in combustion is known to inhibit ignition in low mixing intensity laboratory flames. The effect of chlorocarbons on highly turbulent combustion is being investigated in the laboratory to develop knowledge and techniques for assessment of the effects in practical systems. The role of chlorine in flame instability and the subsequent increase in products of incomplete combustion needs to be better understood to improve incineration performance. Approach; The toroidal stirred reactor has been specifically developed to provide a well-characterized distributed combustor. Effects of adding chlorocarbons to an ethylene-air mixture are studied using Rayleigh scattering with a sample time of 6.5 x 10 seconds and a sample volume of 200 x 200 x 20 urn3. Unburned material leaving the combustor is determined by chemical analysis of quenched samples leaving the reactor. The effects of chlorine containing fuels on combustion will be interpreted by use of a kinetic model and a mixing model for combustion of the fuels used. Status; Experimental work is underway and has demonstrated the effect of methylchloride on flame intermittency and an increase in unburned material. A chemical kinetic model has been developed with the assistance of Professor J. Bozzelli (NJIT) and is being applied to the interpretation of the results. Thermal Oxidation Studies on Chloromethane and Chlorobenz one- Detailed Iteohanism of Hydrocarbon Flames Doped with Chlorocarbons: J.W. Bozzelli, New Jersey Institute of Technology The objective of this project is to determine how to improve or provide direction toward optimum operation of incinerators used in the oxidation (complete destruction) of chlorinated hydrocarbons. These incineration processes range from refuse recovery to hazardous waste facilities, and are to be optimized for minimum effluent and maximum conversion. 21 ------- Rational*i Chlorocarbon incineration is a complex process and has not been studied thoroughly, but it is a process which can completely destroy chlorinated compounds by converting them into relatively safe basic chemicals — water, CO2, and chloride salts (after the HC1 has been scrubbed) . It is much better to completely destroy waste chemicals than to store them until a future time, when they will again become a problem. Thus, there is a demand for safe and effective incineration of hazardous wastes. Approach: Experiments are being performed in thermal oxidation reaction systems where the physical properties in the reactors, such as temperature, turbulence, and time can be described. Once this is accomplished, the focus shifts to the chemical reactions that are taking place in order to learn and understand the important chemical and mixing processes. The MIT group participates jointly in the project and their aspect is to focus on actual flame studies and turbulence using the NJIT models for the chemistry. The models are based upon fundamental thermochemical principles and Transition State Theory in kinetics. Status: The project has seen the completion of a full set of chlorobenzene thermal oxidation experiments and a reaction mechanism has been developed for this chloroaromatic oxidation. In addition, a complete mechanism has been developed for flame oxidation of chloromethane-ethylene mixtures. A radically new mechanism of chlorine inhibition of flames has resulted from these studies. Experiments are continuing to further verify the mechanistic predictions. Some initial predictions have been made on how to improve effectiveness in Chlorocarbon incineration and these shall be further refined with new experiments. Waste Treatment A Dynamic Model of Sequencing Batch Reactors (SBR): B.C. Baltzis and G. Lewandowski, New Jersey Institute of Technology Goal; The goal of this project is to develop for the first time a dynamic model of a sequencing batch reactor for hazardous waste treatment. The model will employ biochemical reactor analysis, and consider both inhibitory substrates and mixed microbial populations. Rational*! Generally, empiricism cannot be relied on to optimize a hazardous waste treatment process without a great deal of expensively obtained data at a pilot scale or larger. Even with such data, significant deviations in the waste composition, or the microbial population used for treatment, can result in a failed scale-up and a considerable financial loss, unless those factors are previously accounted for by a reliable predictive methodology. Furthermore, diagnostic tools are needed when the system does not perform as promised. A reliable model can also cover otherwise unsuspected system properties, such as the increased efficiency 22 ------- created by drawing down half of the volume in an SBR. For these reasons, it is important to develop a reliable mathematical model that can organize and extrapolate bench and pilot scale data. Considering the importance and complexity of SBRs in hazardous waste treatment applications, significant economic and operational advantages can accrue from a successful modeling effort. Approachi Biodegradation of pollutants in an SBR can be described by a set of unsteady-state equations, and these equations can then be solved numerically. The model focuses on reaction kinetics, and currently does not include a settling phase. Furthermore, it assumes that the kinetic expressions are the same for the fill, react, and draw phases. in order to reduce the number of parameters and generalize the results, the equations are written in a dimensionless form. The model allows us to predict design parameters, and optimize the operating conditions, such that the reactor volume is minimized for a given throughput, and washout of the biomass is prevented. The model will be verified experimentally. Status: Biodegradation of a single compound has been described for cases where the kinetics follow either a Monod model, which depicts an uninhibited substrate, or an Andrews model, which is inhibitory. Problems of optimization have been addressed, and it has been shown that a minimum reactor effluent concentration is achieved when 50% (Honod case), or 40 to 50% (Andrews case), of the reactor contents are drawn down at the end of a cycle. In addition, for inhibitory substrates, the model predicts that under certain conditions steady operation of the unit is impossible unless proper start-up conditions are used. Start-up conditions do not affect operation if the substrate is non-inhibitory. Finally, the model shows that the volume of a fill-and-draw reactor is inherently smaller than that of a continuous flow, well-mixed reactor, for the same throughput. The model has been experimentally verified with a pure culture of Pseudomonas putida. with phenol as the sole carbon source. In all cases, there was excellent agreement between experimental results and theoretical predictions. Future work will examine mixed populations and mixed substrates. Removal and Recovery of Heavy Metal* from Waste Water by Hollow Fiber Contained Liquid Membrane Techniquei K.K. sirkar, Stevens Institute of Technology Qoalt The overall goal of this project is to develop a stable liquid membrane technique by which toxic heavy metals can be simultaneously extracted from an industrial waste stream on one side of the membrane and concentrated in an aqueous solution on the other side of the membrane for recycle. The immediate goal is to study removal and recovery of copper using a liquid ion exchanger containing a membrane placed between two sets of hollow fibers. 23 ------- Rationale; Earlier research results using supported liquid membranes or emulsion liquid membranes suggested that copper removal and simultaneous concentration can be done. However, these liquid membranes were very unstable and, hence, unusable. By containing the liquid membranes between two sets of microporous hollow fibers in a shell, we have recently obtained a very stable liquid membrane. Thus, copper removal and recovery in a stable fashion should be feasible using the hollow fiber contained liquid membrane technique. Approach: The approach consists of the following: (1) build a membrane separation device containing two sets of microporous hydrophobic hollow fibers, (2) study steady-state removal of copper from aqueous solution moving through the lumen of one set of fibers via the liquid membrane and concentrate the copper in the strip solution moving through the lumen of the other set of fibers, and (3) demonstrate long tern stability of the process using one-month- long runs. Such a technique then can be scaled up and efforts made to transfer it to the marketplace. Status; A membrane separation device with two sets of hollow fibers has been built. Transport of copper from an aqueous waste CuSO4 solution to a strongly acidic H,SO4 solution for recycle has been demonstrated. Quantitative modeling and experiments with different liquid membranes to select optimum composition and long term stability studies are expected to be completed by February 1990. Training and Technology Transfer Promotion of Existing Training/Technology Courses—Environmental Management Institute; A.Cortese, Tufts University Goal; The goal of the Environmental Management Institute (EMI) is to provide a curriculum on technology, policy, management, and health topics, as they relate to environmental issues, to a multi- disciplinary audience of environmental professionals. Rationale; Environmental professionals, from government and industry alike, are playing more important roles in the management of environmental resources. These management roles require practical Knowledge and skills available through curriculums based on state-of-the-art technology and research. Approach; EMI is a month-long intensive program. There are 10 courses. Each course is held three nights a week, two hours per night for three-and-a-half weeks. The courses are available on a for-credit or a non-credit basis. The instructors are chosen from industry, government, and academia. 24 ------- status: This year, 110 participants were enrolled, a 40% increase in enrollment form 1989. The EMI Advisory Committee has reviewed 1989's evaluations of courses and speakers and has begun planning for 1990. Brochures listing courses and instructors will be mailed by February 1, 1990. Research Laboratory Hazards Management: A. Ducatman, Massachusetts Institute of Technology Goal: The goal of this training project is to teach laboratory- based participants from a variety of backgrounds what they must know to handle, reduce, and otherwise manage hazardous materials in their laboratory settings. Government, corporate, and institutional research laboratory participants will be invited. The thrust of the seminar will be to integrate laboratory waste management, a relatively new concern, with traditional laboratory concerns about health and safety. Rationale: Both waste disposal and occupational health problems are different in laboratories than in production facilities. Typically, quantities of toxic materials are smaller but their uses are more complex and innovative. Regulations written for production facilities require significant revision before they can be applied to research environments. Approach: Relevant social needs and regulations will be described, and then put in the framework of how to manage waste safely in the unpredictable environment of the laboratory. Special emphasis will be placed upon administrative solutions that create incentives and avoid disincentives for responsible waste management among research personnel. The potential hazards of excessive waste handling and alteration by scientists will be emphasized in order to feature the simplest solutions. Status: The seminar is scheduled for January 31, 1990. Contract agreements for space and audio-visual support are being signed. A mailing list of potential participants is being assembled. Looking Within: Organ!cational Factors in Risk communication: C. Chess, P.M. Sandman, and M. Greenberg, Rutgers University Goal: The goal of this project is to explore how organizational factors affect agency risk communication activities. The report resulting from the project will tentatively identify: (1) organizational factors that may be blocking effective risk communication, (2) organizational factors that may facilitate effective risk communication, and (3) suggestions on how agencies might reduce barriers and encourage effective risk communication. 25 ------- Rational* i Although many agency risk communicators understand what must be done to communicate risk effectively, doing so often remains an elusive goal, in part due to organizational barriers within the agency itself. This project explores the question: "What do we need to do internally within agencies so we can communicate effectively externally?" Approach: Because there has been little research on the subject, an exploratory symposium is being conducted as a first step. The symposium will bring together approximately 20 agency personnel from state and federal levels, with both technical and communication backgrounds, for a day-long roundtable discussion. A few specialists in organizational dynamics will also participate. A brief report, based on an audio tape of the day's discussion, will summarize the issues identified by participants and their recommendations for addressing them. Status; The symposium was held on October 16, 1989. A final report is due in February 1990. Emerging Paradigms of Risk and Risk Communication and the Policy Implications: S. Krimsky, Tufts University Goal; The goal of this project is to conduct a workshop that will: (1) assess the state-of-the-art of research schemata, paradigms, and conceptual frameworks in risk and risk communication studies; (2) address the contributions and limitations of the various theoretical approaches; (3) examine the implications of the research for practitioners; and (4) assess future research directions. Rationale; Risk communication can serve as a bridge between risk assessment and risk management and as a possible means to resolve conflicts between expert and public opinion. The field of risk communication has blossomed in recent years, and while many of the lessons learned have been synthesized into guidelines for risk communication, risk management remains a complex problem and risk communication is no panacea. It is, therefore, an opportune time for academics and practitioners to reflect on the state-of-the-art and share their thoughts. Approacht A two-and-a-half-day workshop will be held from January 10 through January 12. The first day of the workshop will involve 30-50 practitioners from the private and public sectors in the New England region, and will focus on the state-of-the-art in risk theory and communication and the practical implications. The following day-and-a-half will involve approximately 20 academics from Europe and the U.S., and will reflect on and examine the central tenets of the broad range of theoretical perspectives on 26 ------- risk. The workshop will encourage dialogue among experts, and stimulate the production of a set of seminal papers which will be published in the collected volume. The preparation of these papers will be funded separately under an assistance agreement from the EPA (Cooperative Agreement #CR 813481). atatuai Invitations to academics have been sent out. Invitations to practitioners will be sent out when the speakers have been selected and the agenda established. Conference on Incineration Monitoring: J.R. Ehrenfeld, Massachusetts Institute of Technology Goal: The goal is to inform state and local governments, industry, environmental groups, and the general public about the requirements for and capabilities of current hazardous waste incineration operations monitoring systems. Rationale; Better monitoring systems for hazardous and municipal solid waste incinerators have been suggested as a means to enhance public trust and acceptance of incineration facilities. The conference is designed to explore the interface between technology and public decision-making. Approach: The conference is planned as a one-day event, in which two critical reviews of operating parameters and effluent monitoring systems technology, respectively, will be presented. A third session addressing the policy implications will follow. A mini-exhibition of equipment vendors will accompany the technical presentation. Status: Planning is now underway. The conference is scheduled for Spring 1990. National Conference on Regional Issues: R.S. Magee, New Jersey Institute of Technology Goal; The objective of this project is to identify and address key institutional constraints impeding progress toward solving hazardous waste management problems and to define future actions required to remove these constraints. Rationale! The premise is that technology development alone will be insufficient to make the necessary progress in addressing the hazardous substance problems facing the nation and that organizational restrictions and limits must be surmounted or accommodated before significant inroads can be made. 27 ------- Approach: An Engineering Foundation Conference will provide the framework to achieve the project's goal. The conference will deal with the political, economic, insurance, financial, and legal issues surrounding hazardous waste management. The focus will be on institutional or societal barriers to using existing and innovative technologies. Contributors will include legislators, professionals from the insurance and financial industries, hazardous waste management professionals, state and federal environmental regulators, environmental groups, and academia. Topics for sessions will include academia/industry relationships pertaining to technology development, venture capital investment, environmental policy limitations and implementation strategies, technological problems, legal issues, insurance constraints, and the EPA SITE program initiatives. Status: The conference is planned for Summer 1990. SUMMARY OF OUTPUTS IN FY 1989 Refereed Journal Articles Published 2 Articles Submitted or In Press 3 Books and Bound Proceedings 0 Chapters in Books or Proceedings 2 Project Reports 0 Conferences and Workshops Held TOTAL 8 28 ------- BIBLIOGRAPHY Refereed Journal Articles Graham, W. and D. McLaughlin, "Stochastic Analysis of Non- Stationary Subsurface Transport 1. Unconditional Moments", Water Resource Research. 25(2), pp. 215-232, 1989. Graham, W. and D. McLaughlin, "Stochastic Analysis of Non- Stationary Subsurface Transport 2. Conditional Moments", Water Resource Research,. 25(11), 1989. Articles Submitted or In Press Barat, R.B., A.F. Sarofim, J.P. Longwell, and J.W. Bozzelli, "Effects of Chlorocarbons on Flame Intermittency and Stability in a Jet-Stirred Combustor", presented at "First International Congress on Toxic Combustion Byproducts: Formation and Control". UCLA, California, August 2-4, 1989. Submitted for publication to Combustion Science and Technology. Darivakis, G.S., J.B. Howard, and W.A. Peters, "Release Rates of Condensables and Total Volatiles From Rapid Devolatilization of Polyethylene and Polystyrene", presented at the "First International Congress on Toxic Combustion Byproducts; Formation and Control", UCLA, California, August 2-4, 1989. Submitted for Peer Review for publication to Combustion Science and Technology. Lewandowski, G.A., P.M. Armanente, and D. Pak, "Reactor Design for Hazardous Waste Treatment Using A White Rot Fungus", Water Research, in press. Chapters in Books and Bound Proceedings Graham, W. and D. McLaughlin, "A Comparison of Numerical Solution Techniques For The Stochastic Analysis of Non- Stationary Transient Subsurface Mass Transport", Proceedings of the 7th International Conference on Computational Methods in Water Resources. Computational Mechanics Publisher. Southampton, UK, 1988. McLaughlin, D., "A Real-Time Approach to Groundwater Monitoring, Prediction and Remediation*1, Proceedings of the ASCE National Conference on Hydraulic Engineering. August 14- 18, 1989, New Orleans, LA, American Society of Civil Engineers, New York, NY, 1989. 29 ------- Project Reports None i conferences and Workshops Held Basu, R. and K.K. Sirkar, "Selection Separations Using Contained Liquid Membranes", at the AIHE Symposium: "Pollution Prevention for the 1990's: A Chemical Engineering Challenge", Washington, DC, December 4-5, 1989. 30 ------- Chapter 2: The Great Lakes and Mid-Atlantic Hazardous Substance Research Center ------- cantart The Great Lakes and Mid-Atlantic Hazardous Substance Research Center participants: Tne University of Michigan Michigan State University Howard University njroetori Walter J. Weber, Jr., Ph.D., P.E. Department of Civil Engineering 181 Engineering Building 1-A College of Engineering The University of Michigan Ann Arbor, Michigan 48109-2125 Phone: 313/763-1464 FAX: 313/764-4292 THE CENTER AT A GLANCE The University of Michigan and Michigan state University combined forces in 1986 to pursue cooperative efforts in fundamental, multidisciplinary, large-scale hazardous substance research. Howard University joined the two Michigan universities in 1988 to develop a proposal to the U.S. Environmental Protection for designation and funding as one of five new regional hazardous substance research centers. The proposal was selected and the three universities were awarded an initial $1 million grant in February 1989 to establish the Great Lakes and Mid-Atlantic Hazardous Substance Research Center for Federal Regions 3 and 5. An additional $1 million was awarded in October of the same year. The Michigan Department of Natural Resources has provided the matching funds. center Personnel The University of Michigan is the lead university in the Center, with Dr. Walter J. Weber, Jr., of Michigan's Department of Civil Engineering, the Center Director, having primary responsibility for its overall research focus and program implementation. Dr. Thomas C. Voice of the Department of Civil and Environmental Engineering at Michigan State University, the Associate Director, coordinates the research at Michigan State University and has principal responsibility for overseeing the training and technology transfer programs. Dr. James H. Johnson, Jr., of the Department of Civil Engineering at Howard University, the Assistant Director, has primary responsibility for coordinating the research and training activities of that Region 3 institution with the two Region 5 institutions in Michigan. The Center brings together a resource of more than 100 faculty and staff with expertise in hazardous substances and environmental engineering and sciences. 31 ------- Table 1: Kay Personnel in the Center university of Michigan Michigan state university W.J. Weber T.c. Voice L.M. Abriola S.A. Boyd J.J. Kukor R.F. Rickey R.H. Olsen J.M. Tiedje T.M. Vogel K. Vigmostad M.C. Berger R. Wallace P.P. Novak M.S. Simmons Howard University J.H. Johnson J.N. Cannon R.C. Chawla M.M. Varma The Center administration interacts closely with two standing advisory groups, the Science Advisory Committee (SAC) and the Training and Technology Transfer Advisory Committee (TrAC). Science and engineering representatives from academic institutions, industry, and state and federal agencies comprise the 14-member SAC. This committee critically reviews the ongoing research programs of the Center, recommends and evaluates new research directions and proposals, and provides general scientific advice and guidance to the Center. The SAC met in May and again in October 1989. The committee as a whole considered presentations from all the investigators at each meeting. At their first meeting, the SAC established three-member Project Oversight Teams for each project to facilitate hands-on participation by SAC members in activities related to their particular interests and expertise. The Center administration engages the SAC in discussions of new areas of research and in identifying those areas that address the needs of the two regions. This process was initiated at the last SAC meeting in October by drafting a new "request for proposals'* outlining areas identified by SAC members as needing research. The T3AC is a 7-member committee composed of representatives of state, federal, and independent training and technology experts. This committee works with the Center administration to structure programs that can effectively use the technical and educational resources of the Center to translate research results into practical application. 32 ------- ffiaaion and Orientation The Center's mission is to provide the philosophical framework, organizational structure, and resources required to foster and support integrated, multidisciplinary, and collaborative research that advances the science and technology of hazardous substance management. The Center promotes integrated university- based research programs focused on common objectives, and fosters joint participation by researchers from different disciplines to ensure a rich resource of approaches and perspectives. Collaboration and interaction with industry, government, other academic institutions, and the general public are key elements of the Center's comprehensive program of research, education, and technology transfer. The Center primarily serves the constituency of Federal Regions 3 and 5; that is Delaware, the District of Columbia, Illinois, Indiana, Maryland, Michigan, Minnesota, Ohio, Pennsylvania, Virginia, West Virginia, and Wisconsin. The heavy industrialization which characterizes these regions is reflected by the fact that about 33 percent of the Nation's regulated hazardous waste generators and 36 percent of the Superfund sites are located here. The most critical hazardous substance issues in these regions involve synthetic organic chemicals and petroleum products. More than 70 percent of all hazardous wastes and most known groundwater contamination problems involve organic compounds such as chlorinated solvents, polychlorinated biphenyls (PCBs), pesticides, and petroleum products. Nearly 10,000 cases of leaking underground storage tanks have been identified in these two regions. The vast majority of these involve petroleum products. Accordingly, Center research emphasizes problems associated with contamination by organic chemicals and addresses such problems by attempting to develop and refine remediation technologies that are effective, environmentally compatible, and that conserve energy and other resources. Funding Sources Initial funding for the Center has been provided by the U.S. Environmental Protection Agency and the Michigan Department of Natural Resources as shown below in Table 2: Table 2: Center Funding FUNDING SOURCES PY 1989 FUNDS Michigan DNR $ 500,000 U.S. EPA 2.000.000 TOTAL $2,500,000 33 ------- CENTER DIRECTOR'S REPORT The research program of the Great Lakes and Mid-Atlantic Hazardous Substance Research Center seeks to develop useable and cost effective control and remediation techniques which are readily adaptable to different site-specific conditions. As noted above, the most serious and extensive hazardous substance problems in Regions 3 and 5 relate to environmental contamination by organic substances. Therefore, projects funded by the Center currently focus on schemes to remediate organic pollutants by integrating bioremediation technologies with complementary chemical and physicochemical technologies in ways that maximize effectiveness and minimize environmental disruption and discord. Strengths of the Center The Center's research program derives its character and strength from a unique combination of two principal features of the Center. The first is the substantial and diverse expertise residing within the three institutions. The second is the structuring of groups of researchers from different disciplines with expertise in related topical areas to work on complementary or interactive projects. Center personnel interact with the SAC and Center faculty to identify and characterize major problems. This is a dynamic and ongoing process. Once a particular problem is characterized, resources from different disciplines — such as fundamental microbiology, process engineering, and system modeling — are brought together to develop a set of techniques to address the problem. The Center uses flexible research groups to bring its considerable expertise to bear most effectively on multifaceted hazardous waste management problems. These groups can be formed and restructured as new research problems emerge and others mature. In this context, the Environmental Protection Agency's Centers Program funding structure enables the Center to do what individual project grants would not. Projects are deliberately designed to establish research groups and to foster multidisciplinary approaches. For example, the Center has drawn together research from microbiology (Olsen and Kukor, Michigan), soil sciences (Tiedje, Michigan State), and environmental engineering (Vogel, Michigan) who work interactively to elucidate fundamental mechanisms and identify appropriate conditions for microbial detoxification and/or destruction of hazardous organic compounds. By way of further example, the effectiveness of employing surface active agents ~ surfactants — for in-sJJtu flushing of residual organic fluids from soils is being investigated from the three different perspectives of enhancing bioavaliability (Chawla 34 ------- and Cannon, Howard), phenoaenological characterization of flow behavior (Wallace, Michigan State) and basic modeling of flow characteristics to permit field predictions of contaminant movement (Abriola, Michigan). These combined efforts facilitate a comprehensive understanding of the dimensions of the problem and of the requirements of research to develop appropriate technologies to address it. The concept of investigator/research-focus groupings allows the Center to be comprehensive in its research approach and flexible and responsive to the needs of those eventually using the research information. It is the intent of the Center management to further strengthen and refine the use of this concept, to foster an even greater and more structured collaboration among researchers, and to promote linkages among groupings. New ways to promote the diversity of scientific interactions and affiliations and to forge multidisciplinary research will be explored. For example, the Center is planning a series of half-day satellite meetings that include all senior faculty researchers and associated research personnel within a specific grouping. This approach will be tested before the end of this program year in a pilot project involving the surfactant group cited above and a small group of other current and potential investigators having related interests and expertise. Research Emphasis There are currently thirteen projects in the Center which address this research focus. Details of the specific projects are provided later in this report. However, these projects may be grouped into three loosely defined topical categories. 1) Microbial degradation phenomena; Four projects emphasize research directed at improving our understanding of specific organisms that have demonstrated the ability to degrade certain classes of organic chemicals, of the reaction pathways involved in degradation, of the interactions among organisms, of the relationships between organisms and their environment, and of methods for selecting or producing organisms with enhanced degradation abilities. Typically, these projects emphasize microbiology, biochemistry, and molecular genetics. 2\ Pollutant properties affecting degradation; Three projects are currently investigating how the physical and chemical properties and the physical environments of waste chemicals affect the ability of organisms to accomplish degradation. These efforts also extend to methods for improving the degradability of target compounds. Current and future projects in this area emphasize environmental chemistry, physics, and engineering. 35 ------- 3) Engineered systems; Six projects target the development of engineered systems designed to carry out degradation of hazardous organic chemicals. These approaches include in situ treatment of environmental contamination, engineered reactors for treatment of hazardous industrial wastes either on-site or at the site of production, and process integrations whereby non-biological and biological processes are integrated into treatment schemes with improved performance. Added Benefits The Center's multidisciplinary approach and successful early efforts have attracted the interest of industrial and regulatory groups confronted by waste management problems that cannot be satisfactorily addressed by current technologies. In response, the Center is expanding its role as a catalyst for establishing related research activities. The Center's approach of flexibly grouping appropriate expertise serves to leverage ongoing research. This, in turn, facilitates pursuit of related projects funded by different organizations, both public and private. Examples of new initiatives involving Center research faculty and staff include a $1.25 million field remediation research program supported jointly by the Michigan Oil and Gas Association and the Michigan Department of Natural Resources, a four-year $6.8 million-hazardous substance basic research program funded by the National Institute of Environmental Health Sciences, and a $250,000 grant from Dow Chemical Company to initiate a hazardous substance post-doctoral research program. New opportunities and initiatives are, in so far as compatible with the interests of the related research, used to draw new faculty and research capabilities into the Center's research activities. Most recently, Center administration and faculty are involved in discussions with the EPA's Office of Underground Storage Tanks (OUST) and Sun Oil to establish multi-investigator research programs targeted to. the particular needs of these organizations. OUST's interests involve improved methods for assessment and remediation activities associated with leaking underground storage tanks. Sun Oil is interested in research on methods for cleaning up soils contaminated with crude oil. In both cases, a group of 36 ------- cross-university faculty is developing an approach which involves investigators from different disciplines working together on a common problem, and in some instances involving a common set of experiments. This approach is modeled after the Centers Program. HIGHLIGHTS FOR 1989 reh Proi acts The Center directly funds fifteen researchers from six departments in the three universities. In addition to the direct interactions resulting from this participation, a large number of secondary interactions have resulted from the linkages the primary Center researchers have to other research projects and programs. The "extended family" of researchers is estimated to include more than 100 faculty and staff at the three universities. Out of this group of faculty and their collective research programs, a number of intensive research efforts involving multiple projects from different funding sources have evolved. These intensive efforts permit the simultaneous attack on a problem from several angles. The exchange of ideas among colleagues, all addressing similar problems with different backgrounds and skills, provides a rich intellectual environment for research. A brief description of some of the key research interactions that have been catalyzed and coordinated by the Center is provided below. In all cases, the Center provides some, but not all, of the funding support for the activities. It should be noted that the areas are not necessarily parallel. Different ways of defining the themes would result in different groupings. o Reductive dechlorination — Drs. Tiedje, Vogel, and Boyd are working on various aspects of the detoxification of certain classes of compounds by reductive dechlorination, that is, removal of toxic chlorine from these compounds. Different classes of compounds — including PCBs, chlorinated aliphatic solvents, chlorophenols, and chlorobenzoate — are being investigated using both specifically isolated groups of organisms and naturally evolving microbial consortia. These efforts are addressing biochemical mechanisms and environmental influences . o Volatile organic compound (VOC) degradation — Drs. Tiedje, Vogel, Boyd, Olsen, Kukor, Hickey, Weber, and Voice are investigating the complete degradation of two classes of VOCs: chlorinated solvents and petroleum-derived contaminants. This work covers a full spectrum of scientific pursuits ranging from basic microbiology, molecular genetics, and biochemistry to the engineering studies necessary to develop treatment systems. These efforts are becoming increasingly intertwined, 37 ------- in a productive sense, as investigators share seed organisms, reactors, and experimental methods to further the overall understanding of VOC degradation. o Development of unique organisms — Drs. Tiedje, Kukor, Olsen, and Vogel are actively involved in developing or isolating organisms with unique biodegradation abilities using approaches ranging from sampling contaminated environments to genetic engineering. This group benefits greatly from the exchange of ideas on experimental approaches. They frequently exchange microbial cultures with each other and with other investigators to enhance overall mutual efforts. o Bioreaetors — Drs. Hickey, Vogel, Weber, Voice, Johnson, and Varma are studying the relationships between reactors, organisms, and degradation activity. Considerable benefit has been derived from the exchange of approaches and experimental designs. These investigators also contribute their expertise to other investigators who need to use reactors but are not expert in reactor engineering. o On-sit« remediation of contaminated groundvater — Virtually all of the Center faculty are involved in some aspect of on- site bioremediation of groundwater. These efforts include biostimulation, introduction of organisms with unique degradation abilities, combined above-ground and in-situ approaches, surfactant mobilization, and forced-air venting. Approaches include laboratory process studies, improved analytical methods development, physical and mathematical modeling, and field studies. This effort has been highly successful in bringing faculty with diverse backgrounds and interests together to attack a problem that involves interfaces between traditional disciplines. Training and Technology Transfer Projects Karen E. Vigmostad came on board in June 1989 to manage the Center's training and technology transfer program. Ms. Vigmostad completed a Master of Science degree in Resource Policy, Economics, and Management at the University of Michigan. She did policy and communication* work for the Michigan Department of Natural Resources b«fore joining the Center. She is working closely with Dr. Voice at Michigan State University, to create a comprehensive publication* package to communicate Center progress and research results. They are also developing a network of key hazardous substance people in the two regions, and facilitating additional multidisciplinary research opportunities for faculty members. The Centers Program structure enables training and technology transfer CT) staff to develop close, cooperative working relationships with individual researchers. Tr staff and 38 ------- researchers are meeting on a one-to-one basis to allow full explanations of current research and to help identify people and organizations that would be interested in particular research findings and applications. For example, Ms. Vigmostad arranged for the collection of PCB-contaminated sediments by Michigan Department of Natural Resources personnel for Drs. Tiedje and Boyd, and performed a preliminary market analysis for a cyanide-destroying enzyme for Dr. Hickey. Research faculty are also participating actively in the T3 effort. Dr. James Johnson of Howard University held a one-week hazardous substance training program for high school teachers in the Washington, DC school system in August 1989. Over 20 science and math teachers from schools around the city spent the week learning about hazardous waste and other environmental issues. They also received pointers on how to guide interested students into environmental careers. Nine Howard University faculty members and representatives from the Environmental Protection Agency and the Chesapeake Bay Foundation gave lectures. Issues of particular interest were Health and Risk Assessment, Challenges for Blacks and Women in Science and Engineering, Career Opportunities in Environmental Engineering and Science, and Programs for Student Involvement at the Environmental Protection Agency. A follow-up meeting with Howard University faculty and workshop participants will be held in 1990, and plans are being made to hold this workshop in other states. Projects in the works include hosting a five-Center national symposium in 1991, publishing a Center brochure and newsletter, assisting states in the two regions to develop and enhance industrial assistance programs, and developing a waste auditing program for the electroplating industry. The five-center national symposium will be an invitational one-week retreat for approximately 100 leading scientists with expertise in on-site remediation. Papers and discussions will be published in a proceedings. SUMMARY O7 ONGOING PROJECTS Investigators Pro^ct Title Microbie.1 Degradation Phenomena Tiedje Isolating Organisms which Dechlorinate Polychlorinated Biphenyls (PCBs) Vogel Investigation of Mechanisms Controlling Rates of Dechlorination of Halogenated Organic Solvents by Methanogens 39 ------- 01sen/ Kuror Vogel Boyd Abriola Wallace Mickey Johnson/ Varma Chawla/ Cannon Voice Weber Simmons Vigmostad Vigmostad Vigmostad Johnson Nowak Engineered Organisms: Development of Microbial Strains with Enhanced Potential for Degradation of Volatile Organic Carbon Compounds (VOCs) Factors Affecting Attachment and Release of Microorganisms to Aquifer Soils Pollutant Properties Affecting Degradation Bioavailability of Aged Residues in Contaminated Soils Modeling Surfactant Mobilization of Entrapped Organic Liquids in Groundwater Systems Modeling Biodegradation in the Presence of Field Complexities Engineered Systems Development of Hazardous Waste Treatment Schemes Using Modular Laboratory-Scale Reactors Detoxification of Hazardous and Substances via In-Vessel Composting Use of Microorganisms and Surfactants for In Situ Detoxification of Hazardous Wastes in Soils Design and Operation of Biological Activated Carbon Adsorption Systems Destruction of Biologically Resistant Organics by Supercritical Water Oxidation Methods of Isolation of Hazardous Substances from Complex Mixtures Training and Technology Transfer Development of State Industrial Assistance Programs Newsletter Five-center Research Symposium Materials and Hazardous Waste Workshop Waste Minimization Information and Training 40 ------- PROJECT DESCRIPTIONS Microbial Degradation Phenomena Isolating Organisms which Dechlorinate Polyohlorinated Biphenyls (PCBs): J.M. Tiedje, Michigan State University Goal: The goal is to isolate a culture of organisms which occur in PCB-contaminated river sediments and which have demonstrated the capacity to dechlorinate PCBs, thus making them less harmful. These organisms may prove to be reliable and inexpensive tools to detoxify PCBs and possibly other chlorinated hydrocarbons. Rationale: Earlier research results suggest that some natural selection for dechlorination occurs and that further selection and stimulation in the laboratory is feasible. If commercialization is possible, the technique would detoxify PCBs and could potentially be developed for use in detoxifying other chlorinated hydrocarbons. Approach; Three approaches will be used. First, dechlorinating organisms will be enriched by incubating them in anaerobic conditions. By so doing, the dechlorinating reaction becomes the only electron acceptor and may perhaps serve as an energy source. This rate of enrichment could be slow, but it is the best means yet known to enrich dechlorinators selectively over other indigenous microorganisms. Second, information learned from microorganisms which dechlorinate other compounds will be used as a clue to recognize unique features that may also occur in PCB dechlorinators. Such features are the unique 16SrRNA sequences, and the presence of CO dehydrogenase. Third, simplified fractions of communities or isolates will be inoculated into sediment communities that don't dechlorinate. The logic is that consortium is needed and this is a way to recognize this missing but unique member. Status; Work on approaches one and three are underway. Some positive results have been seen on the ability to enrich the dechlorinating ability on one of the heavily chlorinated commercial PCB mixtures (Aroclor 1254). Investigation of Mechanisms controlling Rates of Dechlorination of Halogonated Organic Solvents by Methanogens: T.M. Vogel, The University of Michigan Goal: The goal is to determine which microbes are most active in dechlorination of chlorinated solvents, to establish the physiological conditions which give the highest rates of dechlorination, and to elucidate the mechansim of dechlorination. 41 ------- Rational*! Dechlorination of chlorinated organics generally reduces the health hazard they present. Microbial dechlorination shows great promise as a safe, economical technique for cleaning some hazardous waste sites. Previous research illustrates the ability of some anaerobic microbes to dechlorinate hazardous waste compounds, particularly those more highly chlorinated. In many cases, special adapted microbes might not be involved in the dechlorination. If this is accurate, then naturally-occurring microbes might be induced to dechlorinate some hazardous compounds. development of techniques that enhance this process could potentially be valuable in clean-up activities. Approach; The microbial dechlorination process is being investigated at the subcellular level and at the organism level. In the first approach, biochemical studies are underway to determine the role of various electron carriers and their prosthetic groups in reductive dechlorination. The kinetics of dechlorination and the specificity for metal ions are being examined. Most of these metal-organic complexes occur in nature for other reasons than for dechlorination. Examination of the participation of these complexes will also involve microbial systems. In the second approach, isolates known to dechlorinate certain compounds are being tested to further characterize the physiological mechanisms of dechlorination and the range of chlorinated substrates. In addition, different trophic groups enriched from anaerobic habitats will be tested for dechlorinating activity under normal and hyper-reducing conditions. Microbes will be isolated from the most active enrichments and tested in pure culture for their ability to dechlorinate highly chlorinated organics. Status; Initial studies involving metal-organic complexes have begun and have shown some success in dechlorination of chlorinated aliphatic compounds. Mixed culture systems are also currently being studied and isolations from the active dechlorinating cultures are started. Engineered organismss Development of Microbial strains with Enhanced Potential for Degradation of Volatile Organic Compounds (VOCs): R.H. Olsen and J.J. Kukor, The University of Michigan Goal; This project has five goals: (1) to isolate and characterize microbial strains which are able to degrade volatile organic compounds (VOCs) which adhere to soil and/or granular carbon particles, (2) to determine the effect of adhesion on the metabolism of VOCs, (3) to determine the effect of environmental fluctuations on the performance of selected strains, (4) to use genetic technology to extend the substrate range (depth) of selected bacterial strains, and (5) to use generic and modified bioreactors to evaluate the performance of selected bacterial strains. 42 ------- Rational*; Prior research suggests that noxious contaminants in soils from gasoline spills can be degraded under anoxic conditions (when only small amounts of air is present) in the presence of nutrients associated with the mechanisms by which the microbial cell obtains energy and carbon for growth and reproduction. Analogously, when contaminated groundwater associated with such spills is pumped to carbon filtration units above ground for treatment, these noxious contaminants are removed beyond the granular carbon's capacity to absorb them. It has been postulated that the disappearance of these contaminants may be explained by indigenous microbial species using the contaminants as food. These microbes could be transported to the carbon filtration units where they grow and multiply using the contaminants as food. If the degradation activities by such microorganisms can be optimized — by designing appropriate bioreactors or by adding nutrients to the spill in-situ — then contaminants could be removed at a faster rate and limit further contamination at the spill site. This has the potential for more economical on-site remediation and eliminates the need to remove the soil and transport it to a landfill. Approachi Microorganisms are being isolated from carbon filtration units and sandy soil samples from gasoline-contaminated sites. These microorganisms are being screened for their ability to degrade gasoline components — benzene, toluene, ethylbenzene, and xylene — in the presence of air, as well as under anoxic conditions. From a group of many microbial strains with different physiological characteristics, a few strains which show superior ability to degrade will be selected for more intensive genetic and biochemical characterization. After this, work will be started to manipulate the genetic properties of such strains to enhance their degradative activities towards the target chemicals. Status: Work progresses on the isolation of superior microbial strains. Genetic and physiological characterization of such strains is underway. Factors Affecting Attachment/Release interactions of Microorganisms with Aquifer Solids: T.M. Vogel, The University of Michigan Goaj.; The 9oal of this project is to understand and describe the fate of microorganisms that move through the environment by examining the attachment and detachment phenomena under various nutrient and fluid-flow conditions. Rationale! Microbes are increasingly being used for degradation of hazardous wastes, but the application of such techniques is hampered by poor understanding of factors related to microbial attachment. For the potential detoxification of groundwater contaminants in-situ. it is important to determine factors influencing the movement of native or introduced microbes, excessive attachment may be unfavorable as the microbes might not 43 ------- move into the region where the contaminant resides. Information acquired in these studies will also be useful in understanding and manipulating microbial attachment in bioreactors. In this application, enhanced attachment is desirable to retain a large amount of active biomass, thereby increasing rates of waste degradation. Bioreactors can be used on site for the clean up of hazardous wastes. Approach: The ability of microorganisms to attach to and detach from surfaces is dependent on the microbe, the surface, and environmental conditions, such as pH, nutrient concentrations, and the presence of other microbes. The approach used here is to separate as many of the phenomena as is experimentally possible. First, the attachment of a pure culture fPseudomonas sp.l on different surfaces is examined to study the effect of the surface quality. Charged hydrophilic and hydrophobia surfaces are used in these experiments. Then the propensity of microbes from natural soil populations to attach to one specific surface is being examined under various nutrient regimes. Samples from soil are grown on glass slides and then stained and quantified for morphological type and number. Also, the influence of shear forces on the detachment of microbes is being examined by growing a biofilm in a porous media and subjecting the biofilm to sudden changes in shear stress. Biomass that exits the system is then measured. Statusi Experimental work is underway. Pure culture attachment studies illustrated the favored attachment onto charged surfaces over those that were hydrophobic. Other initial results indicate that morphological groups differ considerably in their ability to attach to glass slides under different nutrient conditions. Pollutant Properties Affecting Degradation Bioavailability of Aged Residues in Contaminated Soils: S.A. Boyd, Michigan State University Goal; The goal is to determine the influence of sorption and desorption processes on the bioavailability and biodegradability of soil- and sediment-bound organic contaminants. Rationale! The working hypothesis is that sorbed (soil-bound) contaminants are unavailable to microbial degraders, that desorption of contaminants into the soil solution phase is a prerequisite for biodegradation, and that the rates of desorption may be sufficiently slow, especially for aged residues, to limit the overall rate of biodegradation. Understanding the bioavailability of contaminants under sorbed and desorbed conditions is essential in determining the appropriateness and limitations of bioremediation strategies. 44 ------- Approach: Two approaches will be taken to evaluate the bioavailability of organic residues in historically contaminated soils and sediments. The first is to measure the rate of release of soil-bound residues into the soil water, and to compare these to those for freshly added chemicals. It is probable that over time contaminants occupy more remote sites in the soil matrix and become increasingly unavailable. Thus, the aged residues may exhibit much slower desorption rates than the fresh residues. These experiments will be complimented by measurements of contaminated concentrations in the soil-solution phase of contaminated field soils. The second type of experiment will compare the rates of biodegradation of aged contaminants to the rates observed immediately after adding the same contaminants to soil, when they are presumable more available. These studies will establish whether limited bioavailability is a major aspect of contaminant behavior in soils that needs to be considered in the implementation of bioremediation strategies. statusi Several field soils with a history of contamination have been identified as possible study soils. Initial experiments have been performed with an agricultural soil that has received simazine (an organic pesticide) additions annually for over 20 years. Sorption/desorption experiments have been conducted on field soils contaminated with pentachlorophenol and polychlorinated biphenyls. Modeling Surfactant Mobilization of Entrapped Organic Liquids in Oroundwater Systems: L.M. Abriola, The University of Michigan Goal: The intent of this project is to develop a mathematical model describing the process of surfactant mobilization and solubilization of non-aqueous phase organic liquids (NAPLs) entrapped within a groundwater system. As a first step, the model will be implemented in a one-dimensional computer simulator capable of analyzing the relative importance of all process variables. Rationale: Surfactant flushing of contaminated soils holds much promise for site remediation and solubilization of NAPLs entrapped in soils. This process has been proposed to reduce residual saturation of entrapped organic liquids by increasing their availability for biodegradation by microorganisms. This model will be a useful tool to develop surfactant selection criteria for field applications. It could also be used to explore the hydraulic parameters affecting the mobilization process, and to predict the success of mobilization for a given system of chemical and surfactant. Earlier petroleum industry research efforts have been successful in modeling the process of enhanced oil recovery using surfactants. Thus, a basic rationale for this project is that with some adaptation the enhanced oil recovery modeling can be used to simulate the process of cleaning up contaminated groundwater systems. 45 ------- Approach! Two distinct but simultaneously occurring mechanisms to remove entrapped organic liquids will be considered: (l) mobilization of organic liquid by immiscible displacement due to reduction of surface tension, and (2) solubilization of the entrapped organic liquid resulting in miscible displacement of the surfactant/water/organic system. The relative importance of these two removal mechanisms will depend on the type and quantity of the surfactant used, and on the resulting equilibrium phase relationship. The physical model can be described as follows. A contaminated zone is initially assumed to exist in a saturated region of the aquifer. Then a surfactant solution is flushed through the system. As the surfactant solution (an aqueous phase) reaches the contaminated zone, the entrapped organic blobs are simultaneously mobilized and solubilized. One or two flowing phases (the aqueous and oleic phases) will then develop depending on the type of surfactant used and on the equilibrium phase relationship between the surfactant, water, and organic. A compositional mathematical model will be developed to simulate the recovery of the entrapped organic liquids as a function of several process variables. Functional forms of the parameters used in the model will be obtained from a literature review of previous experiments and from collaboration with other Center investigators at Michigan State University. Status: The literature review and mathematical model development are complete. Implementation of the one-dimensional mathematical model in a computer program is underway. Model construction, mathematical verification, and sensitivity analysis is expected to extend over the next year of the project. Modeling Biodegradation in the Presence of Field Complexities: R.B. Wallace, Michigan State University Goal; The goal is to develop a physical laboratory model with which to study the mobilization of residual organic non-aqueous phase liquids (NAPLs) when adding surfactants and the subsequent biodegradation of the organics in the subsurface area near the water table. Rationale: Earlier research has demonstrated the value of studying the transport of contaminants in the field as well as with small one-dimensional laboratory models. The expense and difficulty of obtaining permission to create spills suitable for study have hampered field experiments, and one-dimensional models oversimplify hydrogeologic environments. Using large physical models to study the process of contaminated spills remediation with surfactants offers a manageable alternative to field experiments. It also permits a realistic representation of the hydrogeologic 46 ------- environments than do one-dimensional models. Developing large model experiments focused on remediation of benzene, toluene, and xylene (BTX) contamination near the water table targets study of a zone that often contains large quantities of trapped petroleum products, such as these components of gasoline. Establishing a sufficiently complex flow situation will allow the assessment of the significance of preferential flow paths and other hydrologic complexities. Data from a well-documented experiment will be useful in evaluating how well mathematical models can predict which conditions are most like those encountered in the field. Approachi A model aquifer was built as a two meter by one meter by 15 centimeter tank made of glass, stainless steel, and teflon. The objective is to learn how to run and measure conditions during a remediation experiment in the model aquifer. The preliminary experimental scenario is as follows: (1) create the model aquifer with known structural complexity (heterogeneity) representative of the field, (2) produce a well-documented spill, (3) subject the aquifer and contaminant to well-characterized hydrologic conditions (vertical water flux, one or more water table oscillations), (4) remove easily mobilized NAPL with a primary recovery method that depends on NAPL flow to a recovery well, (5) apply a surfactant to mobilize residuals, (6) measure total BTX efflux from the model over time, and (7) measure microbial and BTX distribution within the aquifer prior to introducing the surfactant and at the end of the experiment. Initially, experiments will be conducted in smaller models to replicate studies reported by the Texas Research Institute. These tests will be used to develop test protocols, including measurement methods and sampling procedures. Status: The large tank has been designed and experiments in small tanks are underway. Engineered Systems Development of Hazardous Wast* Treatment Schemes Using Modular Laboratory-Seal* Reactors: R.F. Mickey, Michigan State University and Michigan Biotechnology Institute Goalt This project has two goals: (1) to develop a set of versatile modular reactors that can be used to evaluate and compare the capabilities of isolated organisms and consortia to perform the desired biodegradation reactions in engineered reactors, and (2) to monitor these reactors intensively to develop a database to assist in development of improved process monitoring and control strategies. Rationale: There are four principal elements in the development of effective, reliable biotechnology for treating hazardous wastes. These are: (1) isolating organisms with the desired capabilities, 47 ------- (2) improving understanding and optimization of the enzymatic processes, (3) "housing" the organisms in reactor systems that best exploit the capabilities of the organisms, and (4) developing process monitoring and control strategies that assure reliable performance and help overcome any user confidence hurdles that may impede application of bio-processes. Approacht Sets of one- and two-inch diameter reactors of varying heights were constructed. Because of the versatility of these reactors most process configurations such as suspended growth reactors, biological fluidized beds, sequencing batch reactors, etc., can be comparatively evaluated for "housing" isolates and consortia of organisms that display desired biodegradative capabilities. The reactors are designed to allow easy measurement of gas, liquid, and solid phases to permit quantification of the fate of the toxic materials (biodegradation, volatilization, and partitioning to the solid phase). The gaseous headspace is designed to enable continuous monitoring for both major and trace gases via an online computer-controlled data acquisition system available at Michigan Biotechnology Institute. These reactors will be monitored at steady state and under dynamic conditions to allow system response to be identified, and improved process monitoring and control strategies to be developed. Status; Design and construction of the modular reactors is complete and initial testing is getting underway. Detoxification of Hazardous Substances Via In-Vessel Composting: J.H. Johnson, Jr., and M.M. Varma, Howard University Goal; The goal is to quantify and determine optimum conditions for the detoxification of wastewater sludges and soils containing trace amounts of polycyclic aromatic hydrocarbons (PAHs) via in-vessel composting. Rationale; Single contaminant pure and mixed culture studies have indicated that the microbial biodegradation of PAHs with up to five rings is possible. An evaluation of the biodegradation of PAHs in mixed cultures in the presence of other substrates has not been conducted and is necessary for the development of workable bioremediation strategies for soils and sludges. Approach! Two approaches are being investigated to determine the optimum conditions for biodegradation of multicontaminant systems containing two or more PAHs. First, 36 batch-type reactors were used. Some of the reactors served as controls to determine the stability of PAHs studied under experimental conditions. The reactors were placed in a water bath and the temperature of the bath was increased 5 degrees Celsius per day up to 60 degrees celsius. Samples were withdrawn every other day up to the 21st day, when the experiment was ended. 48 ------- The second approach uses a laboratory-scale continuous composter. The composting mass will be contaminated using 14 Carbon-labeled PAHs. The compost mass will be monitored for quality of effluent gas, pH, temperature, porosity, and moisture content. status: Three batch-type reactor experiments have been conducted using pyrene and anthracene as contaminants. Reductions of 59 and 46 percent were achieved for pyrene and anthracene, respectively, after 21 days. In the next 12-month period, additional binary component studies as well as single component studies will be conducted using the previously described batch procedure. In addition, experiments will be conducted with a continuous laboratory-scale composter contaminated with 14 Carbon-labeled PAHs. Use of Microorganisms and Surfactants for In-situ Detoxification of Hazardous Wastes in Soils: R.C. Chawla and J.N. Cannon, Howard University Goal; The goal of this project is to develop a process using surfactants and microorganisms for jjj-situ cleanup of soils contaminated with hazardous wastes. Rationale: Properly formulated surfactants under controlled laboratory conditions have been shown to be effective in solubilizing organic contaminants bound to soils. Additionally, selected cultures of microorganisms can detoxify hazardous compounds in the liquid phase. Surfactant washing alone is only a dissolution process, while biodegradation works better when the contaminants are in the liquid phase and not bound to soil. Therefore, a combination of these processes — when applied in a single step or sequentially — could provide an in-situ technique with the advantages of both. Approach: A series of batch and column studies with a selected hazardous material, such as trichloroethylene (TCE), will be designed and carried out. The studies will determine: (1) the adsorption/desorption rates and limits in TCE/soil/surfactant systems, (2) the biodegradation limits and rates using selected cultures of microorganisms that have been acclimated to TCE, (3) the biod«gradation rates and limits in surfactant/microorganism systems for both single (combined) and sequential applications, (4) the optimum contacting schemes and operating parameters to enhance biodegradation, and (5) the thermodynamic and kinetic parameters for development of general design and site application criteria. Status: Adsorption/desorption studies are underway. Experiments are being designed for biodegradation studies and are expected to be underway by January 1990. Preliminary assessments of optimum schemes and parameters will be based on the results of the biodegradation studies. 49 ------- Design and Operation of Biological Activated carbon Adsorption Systems: T.C. Voice, Michigan State University Goal: The goal is to demonstrate that biological activated carbon (BAG) adsorption systems are superior to systems using either adsorption or biodegradation alone for the treatment of certain hazardous and industrial wastes. Within this framework, research will focus on demonstrating the advantages of such systems, identifying the mechanisms and the interactions among mechanisms which are responsible for performance advantages, and relating the results to design and operational practices. Rationale: Activated carbon systems are very effective for removing a wide range of organic chemical contaminants from aqueous wastes. The removed materials are simply concentrated on the carbon particles. As a result, the carbon becomes exhausted and disposal or treatment of the spent carbon is required. Biological treatment systems can be designed to produce complete degradation of many organic chemicals such that no further treatment is required and the systems may continue to operate indefinitely. One of the primary disadvantages of these systems is their sensitivity to variations in the characteristics of the waste stream being treated. BAG systems should perform better than either of these others since biodegradation will reduce the pollutant load to the carbon, thereby extending its life. BAG systems should also perform as better biodegradation systems since adsorption by the carbon should dampen changes in the waste stream that will tend to destabilize the system and provide "back-up" removal capability when the biological system is upset. Approach; Bench-scale laboratory systems have been designed to simulate full-scale systems using granular activated carbon (GAG) without biodegradation, GAG with biodegradation (BAG), and biodegradation by a fixed-film (non-activated carbon) on a poorly adsorbing surface. These systems will be subjected to different types of "shock-loads" or changes in the characteristics of the waste stream being treated. Parallel to this effort will be studies designed to develop methods for investigating the removal mechanisms operative in the columns. These techniques will then be studied to understand why each system responds as it does to the various shock-loads. In later years, we will use these results to determine optimal design and operational conditions for BAG columns. status: Bench-scale systems have been designed and built and are being tested to determine their baseline operating characteristics. Preliminary shock-load studies indicate that BAG systems are significantly more stable than non-activated carbon systems and continue to operate long after GAG systems are exhausted. We are currently trying to stress the BAG systems to the point of failure 50 ------- to determine appropriate test limits. A test has been developed to measure the amount of biological material in the systems "non- destructively," without disturbing their operation. The measurement technique will allow us to isolate the effects resulting from the amount of biological material from other mechanisms that affect system performance. The technique is currently being compared to traditional methods in which the system is analyzed destructively (that is, by disturbing the operation of the system). Destruction of Biologically Resistant Organic* by Supercritical Water oxidation: W.J. Weber, Jr., The University of Michigan floal t The goal is to explore and develop the use of supercritical water oxidation (SCWO) as a means for destroying biologically resistant hazardous organic substances, such as PCBs and higher molecular weight polycyclic aromatic hydrocarbons (PAHs), in the concentrates and residues of more traditional biological and physicochemical remediation processes. Rationale: Supercritical fluids exhibit properties of both liquids and gases. Water becomes a supercritical fluid at temperatures above 374 degrees Celsius and at pressures above 218 atmospheres. The oxidation of organics in water at these conditions is potentially a more rapid, yet more controllable process than more traditional incineration techniques. Moreover, because the SCWO process occurs in a closed system, an essentially complete destruction is possible without release of harmful intermediate products to the environment. Approach; The first phase of the research uses a completely mixed batch reactor (CMBR) system designed to handle viscous organics and solids as well as more ordinary organic solutions. These experiments involve the injection of small amounts of organics into a supercritical mixture of oxygen and water, then monitoring the oxidation of the organic compounds. Analyses are to include characterization of intermediate products, mechanisms, and reaction kinetics. Status: Design criteria and specifications for a 1.8 liter CMBR system constructed of Hastelloy C-276 to accommodate the extreme conditions (heat, pressure, corrosion) of SCWO reactions have been completed and construction initiated. The formal experimental program is scheduled to begin in December 1989. Methods of Isolation of Hazardous Substances from complex Mixtures: M.S. Simmons, The University of Michigan Goal: The goal is to establish conditions for extractions of bound organics from soils and other materials using supercritical fluid extraction techniques. 51 ------- Rational*i Most methods for extracting hazardous organics from complex mixtures are not only tedious, but also inefficient. Extractions using a supercritical fluid which possesses good solvating power as well as diffusivity offer potential means to isolate bound organics from different matrices associated with hazardous wastes. One of the drawbacks against using this technique is the lack of knowledge and experience of its performance compared to the conventional methods of extraction already approved as test methods. This study focuses on the comparison of the extraction efficiency and selectivity for selected organics using both conventional and supercritical fluid extraction techniques. Approach; Mixtures of selected chemicals representing a wide range of polarity are being used. Selection criteria are based on how frequently the chemicals are found in hazardous waste samples, commercial availability of pure samples, and availability of existing methods for their analysis. Recovery of these chemicals in different matrices such as soils, activated carbon, clays, plastic materials, etc., will be studied by varying the conditions of the supercritical fluid extraction. Recovery from these matrices will be related in terms of the solvating ability of the supercritical fluid at different temperatures and pressures for extraction. Statust Mixtures of chemicals have been selected and conditions for their analyses established. Several samples have been spiked with the standard mixtures and split for both conventional and supercritical methods of extraction. Training and Technology Transfer Development of State Industrial Assistance Programs: K.E. Vigmostad, Michigan State University Goal: The goal is to assess the current situation of state programs for industrial assistance to small and medium-sized hazardous substances companies in Region 3 and 5 states. Rationale: All states have small to medium-sized industries that can benefit from state assistance programs designed to improve industrial management of hazardous substances. Industries often need help to understand state and federal hazardous substance laws and regulations. They also can gain from improved plant processes, and other industry-specific guidance. Regulatory and enforcement costs are believed to decrease when this type of state assistance is provided. Of the eleven states and the District of Columbia in Regions 3 and 5, only five states have an industrial assistance program. This project will provide assistance to help establish such programs as needed. 52 ------- Approachx State industrial assistance comes in many forms such as telephone consulting services, centralized information referral, industry-specific written materials, in-plant audits, applied research, and grants for innovative waste management practices. Some states — North Carolina, Minnesota, and California — have programs which are considered to be very successful. The factors that make them successful will be studied by looking at how they are structured, what steps were taken to set them up, and their successes and failures. The information will be used to determine if there are any elements that might be incorporated into Region 3 and 5 state programs. Each Region 3 and 5 state will be visited to explore individual state needs and visit their facilities first hand. Every effort will be made to avoid duplication and to develop referral services to existing clearinghouses and information sources. Information needs will be evaluated and a final report with recommendations will be written and presented to the Region 3 and 5 states at a forum such as the National Waste Reduction Roundtable. gtatuai Initial telephone contacts have been made. Brochures, fact sheets, project reports, enabling legislation and other information are being collected and will be assessed. The feasibility of a simple computerized data base to serve as a referral tool about the capabilities and personnel in the state programs is being explored. A Spring 1990 tour of each state is being planned. Completion of a final report is expected in 1990. Newsletter: K.E. Vigmostad, Michigan State University Qoalt The goal is to develop an extensive list of people interested in the research findings of Center researchers, and to produce a newsletter to communicate our research activities and progress to these individuals. Rationale; A newsletter is a useful tool to communicate information to a given audience on a specified topic. Despite many excellent newsletters available on a full range of topics, there is a need to produce a newsletter which communicates highlights of selected research conducted under the auspices of the Center. In this way, research findings as well as discussions of potential or actual applications of the research will reach those most interested. Approachi Rather than trying to be all things to all people, the Center's newsletter will focus on informing a select audience about critical research and research findings involving Center researchers. No attempt will be made to announce meetings or events of other organizations which would duplicate the efforts of other newsletters. The Center's newsletter will also serve as an information referral service, rather than primary source, steering people to existing sources of information. It will be written for 53 ------- an audience with some understanding of hazardous substance issues and research. It will communicate highly technical information in an easy-to-understand way. Center staff will refine the format and content of the newsletter over time as needed. status; Many different newsletters have been collected and analyzed for the effectiveness of their format and content. An initial format has been designed to meet the needs of the Center. A mailing list of people interested in hazardous substance research is being compiled. Arrangements for producing and distributing the newsletter are being made. The first issue is scheduled to be ready by early 1991. The newsletter will be an ongoing semi-annual Center publication. Research Symposium: K.E. Vigmostad, Michigan State University Goal; The goal is to summarize and disseminate the latest research information about on-site remediation at a national or international, invitational research symposium involving all five regional EPA centers. Published proceedings on the research findings and summary conclusions will be finalized and distributed six to nine months after the symposium. Rationalei Research symposia are often designed to share information among researchers from the same discipline who are engaged in related research on a specified topic. Seldom is there any attempt to critically examine the state-of-the-knowledge on a single topic by presenting and discussing current research findings with peers in many disciplines in order to reach consensus conclusions about the overall findings. Involving all five EPA Centers together will result in a comprehensive approach and will help build bridges among researchers across the nation. On-site remediation is a critical topic with many people in industry and government eager for information and guidance about research and application on this subject. Approach: The five center directors will select co-conveners to oversee participant selection for a few focal areas. Having two conveners for each focal area will spread the work load as well as help stimulate ideas. The co-conveners will be responsible for developing a list of not more than 100 people to invite to present papers and otherwise participate. Participants will take part in a one-weak intensive symposium in a retreat-like setting. Participants will present prepared papers that have been distributed in advance. The conclusions reached at the symposium will be recorded and a draft version will be ready by the end of the week for participants to take home. Co-conveners will monitor the publishing of the complete proceedings which will include the conclusions reached at the symposium. 54 ------- gtatua: The Kellogg Biological Station, located on Gull Lake in southwestern Michigan, has been reserved for the week of June 9- 14, 1991. One-hundred people can be comfortably accommodated for the week. Initial exploration with the other center directors is underway, and focal area possibilities are being discussed. Conference coordinators have been contacted and a conference planning budget has been drafted. Completion is expected in 1991. Materials and Hazardous Waste Workshop: J.H. Johnson, Howard University goal: The goal of this project is to orient science and mathematics teachers to environmental issues, career opportunities, and challenges in the field. The teachers are expected to share this information with students in junior and senior high schools and eventually to develop teaching modules and/or class projects which can be incorporated into future environmental programs. Rationale: Teachers and counselors are the cornerstones of the education of future scientists and engineers. By training this target group, it is expected that their students will obtain a more profound awareness of environmental issues and become more interested in pursuing careers in environmental science, mathematics, and engineering. Approach: Twenty participants from the Washington, DC school system were selected to attend a five-day workshop. Hazardous waste issues were defined, described, and discussed by participants. Lectures, discussions, and interactive sessions were given by nine Howard University faculty members and representatives from the US Environmental Protection Agency and the Chesapeake Bay Foundation. The topics included Hazardous Waste, Health/Risk Assessment, and Interactive Outreach Programs and Environmental Careers. Status: The workshop was held August 1989. As a follow-up, Howard University faculty will meet with the teachers and counselors again in 1990. At that meeting the teachers and counselors will present environmental issue teaching modules and class projects that can be used for future programs. Based on an evaluation of the workshop, a refined version will be presented in another urban center in Region 3 and 5 during the next funding period and possibly made available for national distribution. Completion is expected in 1991. 55 ------- waste Minimisation and Training: P.P. Nowak, The University of Michigan Goal; The goal is to develop information and training materials that will help soil and hazardous waste generators reduce the amount of waste they generate. This will be done by creating technology transfer materials designed directly to focus on this problem. Both industry and government representatives will be involved as advisors on this project. Rationale; Both EPA and industry representatives have acknowledged the need to develop information and training in this area since Congress mandated a 25 percent reduction in wastes generated by 1992. Education, training, and information transfer appear to be most important current tools for making an immediate sizable impact on the problem. Approach; The project managers have previously developed a series of EPA-funded training projects that use written materials and video to bring organized information to professionals in the field. The same approach is planned for this project. The value of this system is that it can be used by individuals in widely separated locations. It is developed from the experience of working with involved professionals and guided by their insights to create practical solutions that will work. Status: An outline of the basic points of this program has been developed. Currently, industry officials are being contacted to see if they would be interested in supporting the project with both advisory help and financial support. Additional support is being provided through EPA's Office of Solid Waste. Project planning should be completed in 1989. The final project is expected in 1991. SUMMARY OF OUTPUTS IN FY 1989 Refereed Journal Articles 0 Articles Submitted or In Press 0 Books and Bound Proceedings 0 Chapters in Books or Proceedings 1 Project Reports 1 Conferences and Workshops Held 4 TOTAL 6 56 ------- BIBLIOGRAPHY Chapters in Books and Bound Proceedings Kukor, J.J. and R.H. Olsen, "Diversity of Toluene Degradation Following Long-term Exposure to BTEX In-Situ." Biotechnology and Biodearadation. Kamely, D., A. Chakrabarty, and G. Omenn (eds.)r Gulf Publishing Co., Houston, TX (in press). Project Reports Johnson, J.H., Jr., "Teacher Notebook for the Materials and Hazardous Waste Workshop," Howard University, Washington, DC, August 1989. Conferences and Workshops Anaerobic Dechlorination of PCBs — General Electric-sponsored workshop, Tiedje, J.M., June 1989 (by invitation). American Society of Civil Engineers 1990 Conference "Biodegradation and Stabilization of Sludges Containing PAHs" — J.H. Johnson, Jr. and M.M. Varma, Washington, DC, July 9- 11, 1990 (abstract submitted) Biotechnology and Biodegradation Workshop — "Diversity of Toluene Degradation Following Long-term Exposure to BTEX In- Situ." — J.J. Kukor and R.H. Olsen, Portugal, 1989 (by invitation). Soil Science and Society of American 1989 Annual Meeting — "Bioremediation of Contaminated Soils" — J.M. Tiedje, October 1989 (by invitation). 57 ------- Chapter 3 Waste Minimisation and Management Hazardous Substance Research Center ------- Center: Waste Minimization and Management Center Participants: North Carolina State University The University of North Carolina, Chapel Hill Texas A&M University, Galveston and College Station Director: Michael Overcash Department of Chemical Engineering Box 7905 North Carolina State University Raleigh, North Carolina 27695-7905 Phone: 919/737-2325 FAX: 919/737-3465 THE CENTER AT A GLANCE Following a competitive selection process, in February 1989 a hazardous substance research center was awarded to a three- university consortium headed by North Carolina State University. The University of North Carolina at Chapel Hill and two campuses of Texas A&M University (College Station and Galveston) are partners in the consortium. According to EPA guidelines, the broad mission of the Center is to perform innovative research and technology transfer activities on topics of concern to the States in Federal Regions 4 and 6 and to the Nation at large. Within that context, the specific mission of the Center is three-fold: o to develop practical means for industry to eliminate the use and generation of hazardous substances; o to treat those wastes that cannot be eliminated; and o to provide secure containment for treatment residues. The role of the partner institutions in the Center is dictated by the skills aix that each school has to offer. Under the direction of Dr. Kirk Brown, Texas A&M University has taken the lead in research on solids and long-term containment. Dr. William Glaze heads the research team at the University of North Carolina which is investigating treatment and discharge of pollutants to the air and aquatic environments. Waste minimization and transporta- tion research efforts are spearheaded by the researchers at North Carolina State University. 58 ------- The Center offers a creative research staff from numerous disciplines including engineers committed to industrial productivity improvements, environmental scientists, and researchers from several basic sciences. These individuals work together to devise inventive solutions to critical hazardous substance management problems. This teamwork extends to collaborative, multidisciplinary studies, based on the philosophy that a major benefit of the center approach to research is the opportunity to put talented minds from diverse backgrounds to work solving key problems. A list of key individuals currently associated with the Center appears below as Table 1. Table it Key Personnel in the Center North Carolina state University Dr. Michael R. Overcash Dr. Richard M. Felder Dr. Ruben G. Carbonell Dr. Peter K. Kilpatrick Dr. H. Henry Lamb Dr. P.K. Lim Dr. Edward P. Stahel Dr. Dale A. Denny Dr. Cliff M. Kaufman Dr. Thomas W. Joyce Dr. Josef S. Gratzl Dr. John R. Stone Dr. John Sutton Dr. Thomas W. Stephenson University of North Carolina at Chapel Hill Dr. Bill Glaze Dr. Fran DiGiano Dr. Rich Kamens Dr. Debbie Amaral Dr. Judy Charles Dr. Don Francisco Texas A&M University Dr. Kirk Brown Dr. C.S. Giam Dr. R. Lytton A core of funding is provided by EPA. Important additional support is received from the states of North Carolina and Texas. A synopsis of center funding is given below in Table 2. Table 2: Funding FUNDING SOURCES EPA: Centers Program Other Government TOTAL FY 1989 FUNDS $2,000,000 898.464 $2,898,464 59 ------- CENTER DIRECTOR'S REPORT Managing waste of any kind has become an increasingly complex process requiring a hierarchy of decision-making and technologies, including minimization of wastes at the source, treatment or detoxification of wastes, and containment of residues. Although the Center conducts research at each level of the hierarchy, its major goal is to prevent chemical losses and reduce waste generation by industry. The focus on waste reduction evolved in North Carolina a decade ago as a centrally identified collection of technologies for improving waste management. As a result, the Center has benefited from a historical perspective as well as a multi-university commitment. A critical job for the Center is to identify the leading edge of research needs to advance the technologies used at each level of the hierarchy, particularly with respect to waste minimization. This is a difficult and evolving task. Although the Center's emphasis has been on issues in Regions 4 and 6, the Center's contributions to waste reduction can be expected to be of significant value across the Nation. Because of that, the Center is committed to achieving and maintaining continuing cooperation among the HSRCs and other organizations engaged in related work. When it comes to waste minimization, most large corporations actively employ any effective technology known to them. The Center, therefore, is concentrating its efforts on identifying the difficult processes and chemicals for which waste reduction alternatives are not available or cost-effective. Another priority within the Center is to perform innovative research on treatment techniques and long term containment of wastes. The Center's contributions in these areas should significantly enhance the Nation's progress in detoxifying and containing waste. HIGHLIGHTS FOR 1989 Although the Center has been operating for less than one year, some significant results have already been generated. Some of these are summarized below. Public disclosure of fugitive emissions of listed chemicals from industrial sites is required under Superfund. Reliable emission data are scarce and hard to interpret. Much of the emissions estimation data come from refineries, which do not accurately represent emissions from other .industries. For instance, refineries do not characteristically emit methylene chloride or chlorofluorocarbons (CFCs). Polyurethane manufacturing plants, on the other hand, produce significant quantities of 60 ------- fugitive methylene chloride and CPCs. The Center is conducting projects which seek to understand the reason for these unintentional emissions and to devise ways to recover these compounds. Preliminary analysis has determined that fugitive loss from mechanical design flaws, such as leaking valves, may be significant. Similarly, laboratory investigations of polyurethane foam have established the dynamics of emissions and, hence, have provided a starting point for developing recovery strategies. Many manufacturing processes require a high degree of cleanliness on the surface of the manufactured article. Such a need for purity frequently results in the generation of significant quantities of hazardous wastes. This is true, for instance, in the production of integrated circuits and optical storage media. With an ultimate goal of developing alternative surface cleaning techniques which employ fewer hazardous substances, the Center has undertaken research to understand the mechanisms of particle deposition from solvents and the adhesion forces which are responsible for particle attachment. Early results show that glass particles and polystyrene latex spheres, which have little or no affinity for a silicon wafer surface with a thin native oxide film can, nevertheless, be deposited on the wafer, as it is removed from the solution through the air-water interface. The number of particles deposited is directly proportional to the bulk particle concentration. When the wafer is completely immersed, the number of particles adsorbed to the wafer does not increase with time because of the low particle fluxes in the aqueous phase. If the aqueous film containing the particles is allowed to dry, the adhesion forces increase considerably. Even this discovery greatly increases our understanding of the complex processes involved in microchip manufacture. As a first step in developing better cleaning methods, investigators are simultaneously pursuing research to determine whether efficient gas-phase processes, such as ultraviolet/ozone cleaning, may supplant conventional solvent- based techniques, thus eliminating a major portion of the objectionable waste generated by the microelectronics industry. The Center is developing an expert system to help locate disposal sites and plan transportation routes for hazardous wastes. The Federal Highway Guidelines for Transporting Hazardous Materials provides the basis for the system which analyzes route characteristics, accident probabilities, property value, and population exposure for route and site access alternatives. The project will provide an easy-to-use systematic method for identifying safe route and disposal site access alternatives. Future application of the routing and planning method will help provide needed accuracy to truck manifests which currently depend on the "honor system". 61 ------- Effluent biomonitoring of wastewater is fast becoming the cornerstone of policy for state regulatory agencies as they issue new National Pollution Discharge Elimination Permit System (NPDES) permits for control of toxic pollutants. While EPA is developing a protocol for toxicity reduction evaluations, experience is lacking and the knowledge base for relating chemical structure to toxicity is limited. The goal of one Center project is to develop a systematic approach to toxicity identification that can be easily adopted by major classes of industry in EPA Regions IV and VI, with the eventual goal of providing recommendations on chemical replacement or treatment. A list of 13 industrial effluents in Tennessee, North Carolina, and South Carolina that exhibit aquatic toxicity and that contain specific chemicals of concern to human health was developed by screening available data sources in Region IV. From this list, textile and organic chemicals manufacturing plants have been targeted for closer examination as candidates for laboratory research on fractionation schemes to identify specific sources of toxicity that may be applicable industry-wide. For atmospheric emissions, the Center effort on treatment has focused on developing a framework to decide among alternative technologies. This is a potentially important tool for industry and government to enhance decision-making rather than to avoid the selection of one alternative over another. Currently, the Center is examining the disposal of flame-retardants. Waste products containing flame-retardant materials such as polybrominated biphenyls (PBBs) must be disposed of cautiously: the PBBs are themselves hazardous and, if deposited in landfills or treated chemically, may end up in the water table or degrade into more toxic compounds. When such materials are incinerated, they can generate toxic by-products, such as polybrominated dibenzo-p-dioxin or furans. The fate of these compounds in the atmosphere is currently unknown. However, preliminary work suggests that they may be fully photodegradable. Should this prove to be the case, incineration may present a clearly better treatment alternative than other chemical or physical options. Past waste disposal practices have caused contamination of landfills by hazardous compounds which cannot be removed from the landfill, but which must be contained, to avoid leakage into the groundwater or runoff onto public or private lands. Landfill containment has proven to be difficult enough that the Center has made a commitment to investigate effective methods for securing these sites. The initial focus of the Center's effort is on the study of multiple liners in hazardous waste containment facilities. Preliminary data show that the addition of cement (3% by weight) to clay soils used for landfill liners will reduce the hydraulic conductivity by one order of magnitude below that of the unamended soil. Additions of 3%, 7%, and 9% hydrated lime appear to increase the hydraulic conductivity of compacted clay soils. This research 62 ------- brings us closer to the eventual goal of minimizing the possibility that present waste disposal activities will require future remediation. In a separate research project, the technique of in-situ bioremediation of contaminated vadose zone soils is being studied. This effort will advance our ability to reclaim subsurface soils which otherwise serve as continued sources for migration. This research will develop a scientific basis on which others may base the design of future field installations for in-situ degradation of hazardous organic compounds in the vadose zone. The preliminary study has been conducted using undisturbed soil cores taken from the vadose zone of an area contaminated with diesel fuel and gasoline from leaking underground storage tanks. The results indicate that the microbial activity and consequent degradation of the pollutant chemicals can be increased through the addition of oxygen and heat. Analysis of the concentrations present in the residual soil after treatment will provide estimates of the degradation rates which can potentially be achieved in the field. Several technology transfer and training activities have been undertaken. A university-level course entitled Waste Minimization - Legal. Technical, and Human Factors, is being developed. This appears to be one of the first universities offering to incorporate at the level of a full course to advanced undergraduates and graduate students the concepts of waste minimization. In addition, eleven continuing education courses on hazardous waste management and technology have been offered in conjunction with the Center. These have been in Texas, Pennsylvania, and North Carolina. A primary Center goal is the actual demonstration of waste minimization technology in industrial plants. A current emphasis is given to identifying hydrofluoric acid users to complete a reuse loop with generators of such materials from semiconductor manufacturing. In order to transfer environmental research at an even larger scale, the Center is sponsoring a conference called Environmental Research in the Sunbelt. SUMMARY 07 ONGOING PROJECTS Investigator* Pro-tect Title Waste Minimization Lamb Surface Cleaning in Microelectronics Fabrication Lim Minimization and Recovery of Volatile Organic Losses 63 ------- Felder Trace Hazardous Substance Reduction in Chemical Manufacturing Overcash Multi-Industry Waste Reduction Model Denny Analysis of North Carolina Super fund listed Air Emissions for Waste Reduction Potential Transportation Stone Optimal Routing Strategies for the Truck Transport of Hazardous Materials Treatment t Management DiGiano Aquatic Toxicity Mechanisms of Compounds in Industrial Wastewater Discharges Kamens A Methodology for Analyzing Hazardous Waste Materials from Incineration & Other Treatment Alternatives run ant i Clean-u Brown Effectiveness of Multiple Liner Systems for Hazardous Waste Containment Facilities Giam In-Situ Bioremediation of Hazardous Substances in the Vadose Zone Training and Technology Transfer Denny Waste Minimization-Legal Technical, and Human Factors Denny Hydrofluoric Acid Reuse Kaufman Research Conference 64 ------- PROJECT DESCRIPTIONS Wast* Minimilation surface Cleaning in Microelectronics Fabricationt Alternatives to Aqueous (RCA) Solutions and CFCst R. Carbonell and H. Lamb, North Carolina State University Goal; The objectives of this project are to: (1) elucidate the mechanisms of particle deposition from solvents onto silicon wafers during microelectronics fabrication, and (2) devise alternatives for removing particles and organic films from wafers that do not involve corrosive aqueous solutions (as in conventional RCA cleans) or chlorofluorocarbons. Rationale: The microelectronics industry has stringent requirements for surface cleaning of silicon wafers. During the manufacturing process, particles are deposited from bulk solution and when the wafer passes through the gas/liquid interface. Electrostatic, van der Waals, and capillary forces affect particle deposition and the strength of particle adhesion on surfaces. Understanding of the deposition mechanisms and knowledge of the strengths of adhesion of particles on wafers should lead to rational selection and use of alternative solvents and surfactant- based cleaning systems. UV/ozone cleaning has been demonstrated to remove organic contamination from silicon wafers, producing CO2 and H2O. To facilitate acceptance of this technology by the microelectronics industry, the detailed surface chemistry of UV/ozone cleaning, which has a critical impact on wafer viability in subsequent processing, needs to be assessed by in-situ spectroscopic characterization. Approach: Micron- and submicron-size particles of glass, polystyrene, metals, ceramics, and silicon are deposited on silicon wafer surfaces from the aqueous phase. The number of adherent particles is measured using a laser wafer scanner, as a function of suspended particle concentration, immersion time, and the number of passes through the gas/liquid interface. The relative strengths of adhesion are measured using a megasonics unit that allows variation of the power and time of exposure. A gas-phase wafer cleaning station with additional capabilities for in-situ surface analysis by multiple internal reflection infrared spectroscopy and for deposition of thin Si and SiO2 films is being constructed. Initial studies will focus on the kinetics for removal of adsorbed organic films and of concomitant oxide growth during UV/ozone surface cleaning. Factors to be considered are ozone concentration, radiation intensity, substrate temperature, and surface chemical structure of the adsorbate film. 65 ------- Statusx The investigation of particle deposition and removal is underway and results are forthcoming. The equipment for the gas- phase cleaning with in-situ surface characterization has been received. Construction of the apparatus is underway and experimentation should begin by 1/90. Minimization and Recovery of Volatile Organic Losses: P. Lim and C. Kaufman, North Carolina State University Goal: For two separate projects underway, the goals are to: (1) identify and study the principal loss mechanisms by which fugitive emissions of volatile substances occur from valves, flanges, pressure relief devices, drains, and the seals of compressors, pumps, and agitators, and (2) quantify the volatization dynamics of blowing agent loss and to examine innovative means to maintain safe worker conditions and current soft polyurethane product formulations while simultaneously recovering the auxiliary blowing agent. The goal is to increase the ambient concentration of auxiliary blowing agents to the level where recovery/recycle is economically feasible. Subsequently, air emissions of either ozone-depleting CFCs or of a volatile organic (methylene chloride) would be minimized. Rationale: The Comprehensive Environmental Response, Compensation, and Liability Act (a.k.a. "Superfund") mandates the public disclosure of fugitive emissions of listed chemicals from industrial sites. Reliable emission data -are scarce and hard to interpret, and estimates of chemical emissions based on refinery emission factors are considered to be excessive. The study seeks to rectify the present lack of fundamental understanding of the emissions mechanisms, so that, ultimately, sensible and effective control measures may be developed which would reduce volatile emissions that are of concern under Superfund regulations. A second diffuse atmospheric emission occurs in manufacturing open- cell polyurethane foam. Polyurethane foam density is currently reduced by the use of chlorofluorocarbons or methylene chloride as auxiliary blowing agents which are promptly emitted in the manufacturing process. The recovery of an auxiliary blowing agent is a complex issue coupled directly with another manufacturing requirement, the maintenance of safe plant working conditions in the presence of small quantities of isocyanates. Approach i The first step is a theoretical study and model development of fugitive organics. Next, an experimental study will be performed to verify, extend, or modify these models. For the polyurethane foam research, a series of experiments have been completed using laboratory prepared foams with representative formulations to determine overall weight loss, auxiliary blowing agent weight loss, and foam temperature profiles versus time. 66 ------- These data allow a basic understanding of the timing and sequence of events in the laboratory foam reactions, comparison with analogous plant experiments, and development of possible strategies for recovery/reuse of the auxiliary blowing agent. status: The results of the model analyses suggest that for the so- called "non-leakers", which are defined by EPA as leak sources with concentration levels below 10,000 ppm, capillarity is the principal mechanism governing the emissions of condensible vapors from valves, flanges, drains, and pressure relief devices. Five dimensionless groups composed of the properties of the capillary flow fluid, pore dimensions and surface characteristics, and temperature have been identified. A sorption-diffusion model and a hydrodynamic lubrication model are being developed, respectively, for the emission of non-condensible vapors from valves and flanges and for volatile emissions from the seals of rotating equipment. An apparatus consisting of an emission chamber and a gas chromatograph is near completion for testing the capillarity model. In the next year, a coalition of foam manufacturers, chemical suppliers, and relevant machinery manufacturers, as appropriate, will be formed to develop the necessary design modifications for tunnel retrofit/isolation and collection of tunnel and post-tunnel emissions on one foam line. The goal for this demonstration project at one plant would be to accomplish the following tasks to determine costs versus benefits: - determine foam quality with recycled auxiliary blowing agent, - determine worker exposure levels to TDI (and methylene chloride), - serially vary operating parameters to quantify an appropriate range of design variables and costs, - quantify any changes in productivity and yields, and - quantify collection efficiencies for all emissions from the tunnel area. Trace Hazardous Substance Reduction in Chemical Manufacturing: R. Felder, C. Chen, J. Gratzl, T. Joyce, P. Lodrini, North Carolina State University Goal* This is actually two projects in one. Task Number 1 has two objective*. They are to: (1) evaluate processes that minimize the production of toxic effluents in bleach plants, and (2) recommend alternate bleach sequences that do not favor the production of such compounds. Task Number 2 seeks to formulate a procedure for selecting hazardous chemical substances amenable to waste minimization solutions, catalog chemical processes that give rise to these solutions, and identify possible process modifications or alternative processes that could lower or eliminate the occurrence of these constituents in wastes. 67 ------- Rational** Part of the Center's mission is to demonstrate the utility of a broad variety of approaches to waste minimization. Tha two activities described herein represent completely different approaches. The pulp bleaching study focuses on determining the formation chemistry of a specific class of pollutants in a particular process. The benzene effort is a component of a broad literature survey intended to identify candidate processes that might serve as targets for subsequent focused research studies. ADDroachi For Task Number 1, Kraft pulp (Kappa 32.6) is prepared from loblolly pine. The pulp is bleached (3% - active alkali). The leachate and the black liquor (BL) are extracted with ether at pH 8. The unbleached pulp is also extracted with ether followed by acetone. The extracts are then analyzed by gas chromatography- mass spectroscopy. Benzene has been chosen as the substance to be studied in Task Number 2. A great deal is known about benzene emission rates and alternative pathways exist for a number of the products that utilize benzene as a feed material. The production of ethylbenzene has been chosen as a first production process. Three alternative processes have been developed for producing ethylbenzene: the A1C13 process, the Alkar process, and the Mobil/Badger process. As much technical data as possible will be collected on benzene emissions in these three processes. A primary data source will be the "benzene docket", a large collection of information about gaseous benzene emissions compiled by the Environmental Protection Agency and kept on file at the Office of Air Quality Planning and Standards in Durham, North Carolina. Other needed data — primarily having to do with process technology and condensed phase emissions — will be identified, and preliminary efforts to locate sources of these data will be undertaken. 8tatus» In Task Number 1, the first phase (isolation and characterization of monomeric phenols in the BL and pulp) is completed. The BL contains considerable amounts of vanillin and acetoguaiacone. GC-MS studies further indicate that both these compounds are absorbed on the pulp. These compounds could be the possible precursors for chlorophenols during bleaching in addition to some high-molecular mass compounds from the pulp in the residual lignin. The second phase (bleaching and kinetic studies)are being initiated. In Task Number 2, contacts have been established with the EPA office in Durham, and arrangements have been made to access the benzene docket. Multi-Industry Waste Reduction Model: M. Over cash, North Carolina State University Goal: The purpose of this project is to develop and use a computer-based framework to assess the overall reduction of waste to determine if particular changes at individual facilities actually lead to net waste reduction. 68 ------- Rationale! Industrial manufacturing is a complex phenomenon, involving a wide range of inputs and products. The field of waste minimization is complex and necessitates a far-reaching view of potential consequences: too often improvements are made in one medium, but at the cost of off-setting decrements in another. The result is not minimization of waste, but relocation. Approacht In the first phase of this study, data are being collected from available sources to couple energy use or savings with increases or decreases in pollutant emissions to the air and water are being considered. This analysis will include thermal and radioactive wastes, as well as listed pollutants. Case studies will be conducted in the second phase, in which data are available to track the wastes produced at all stages of the raw materials and the influence, if any, on product use. These will better describe the mass and thermodynamic information from which the computer frame can be started. Statust The collection of reports and data are underway. Analysis of North Carolina Super fund-listed Air Emissions for Waste Reduction Potentials D. Denny, North Carolina State University Goali The work product from the analysis will be a book containing a technical description of waste reduction technologies in place at North Carolina industrial plants and other sites with similar manufacturing processes. Opportunities for technology transfer, cost information, and research needs for difficult-to-control emissions will be included. Rationale: Staff at the North Carolina Pollution Prevention Pays Program (PPP) provide waste reduction assistance to North Carolina companies. An organized record of installed waste reduction technologies and recommended opportunities for technology transfer would greatly enhance PPP staff productivity. Identification of research needs will be useful to the Center program. Approachi The 1988 and 1989 SARA emissions data base were obtained from the North Carolina Environmental Defense Fund. Software to manipulate the data base has been obtained and installed. A draft workbook format has been completed and will be submitted to PPP for review and approval. Status t Completion of the workbook is planned for June 30, 1990. 69 ------- Transportation Highway Routing strategies for Safely Transporting Hazardous Substances: J. Stone, North Carolina State University Goal; The goal of this project is to develop an expert system which is capable of aiding planners for hazardous waste routes and for access to disposal sites. Rationale! Current research elsewhere indicates that documented guidelines for transporting hazardous waste have been effective in reducing highway accidents and spills. Furthermore, expert systems within the broader field of artificial intelligence have provided frameworks for solving data-intensive, heuristically defined routing and other problems. The premise is that various rules-of- thumb and documented guidelines may be efficiently incorporated into easy-to-use computer programs based on artificial intelligence methodologies. Approach; An expandable approach to developing a route planning tool will be followed. Initially, Federal Highway Administration Guidelines will form the basis of an expert system using software called "EXSYS" to rank route alternatives. A top-level command file controls the flow of the system with a customized menu which includes options for entering route information, route analysis and selection, and reporc generation. The route information option interfaces with a series of spreadsheets used to determine route characteristics, accident probabilities, property value, and population exposure for individual route alternatives. The route analysis and selection option ranks the routes according to estimated risk, and the results will be displayed by a customized report generator in EXSYS. Provisions have been made for future extensions to the expert system so that a geographic information system can provide route and other characteristics. There is also the flexibility to incorporate network route optimization algorithms. Status: The EXSYS framework has been designed and linked with Lotus spreadsheets which perform the calculations from the FHWA Guidelines. A working prototype expert system is expected in the summer of 1990. Treatment ft Management Aquatic Toxicity Mechanisms of Compounds in Industrial Wastewater Discharges: F. DiGiano, J. Charles, D. Amaral, D. Francisco, University of North Carolina - Chapel Hill Goal: The immediate goal of this project is to cooperate with a direct industrial discharger in a study of fractionation schemes 70 ------- aimed at identifying the specific chemical source(s) of effluent toxicity. The ultimate goal is to develop and test a laboratory protocol that can be adopted by various classes of industry important to Regions IV and VI to solve their aquatic toxicity problem. Rationale: The fractionation schemes developed so far by EPA focus on identifying non-polar agents using one specific, fractionating column material: CIS Solid Phase Extraction Column. However, this may not even separate compounds like phenol that are moderately non-polar. In addition, polar compounds, such as dyes used in the textile industry, may contribute to aquatic toxicity and will not be identified. Another concern is the complexity of the EPA protocol which links aquatic toxicity testing with high- pressure liquid chromatography (HPLC) and mass spectrometry (MS). The need exists, therefore, for exploration of other solid phase extraction procedures aimed at more polar compounds and for practical ways to combine sophisticated HPLC/MS analyses with biomonitoring. Ultimately, aquatic toxicity information for specific industries should be a key element of pollution minimization plans. Approacht A listing of industries whose discharges may cause aquatic toxicity and that discharge organic chemicals of possible human health concern has been generated for North Carolina, South Carolina, and Tennessee (this will be repeated later for other Region IV states and then for Region VI states). General classes of organic chemicals in use will be developed using available data from NPDES permits and effluent guideline documents. Initially, one industry representative of an important class will be selected for investigation of fractionation procedures; others will be added later. Various solid phase extraction options will be tested, as will subsequent analytical approaches for specific identification of those chemicals causing acute toxicity to Ceriodaphnia. Chronic toxicity aspects are in the long-range plans. Protocols will be developed for industry-wide use. Status: An industry is soon to be selected for initial testing. Over the next 2.5 years (March 1992), four to six representative industries should be tested. Strategy for Analysing Hazardous Wast* incineration and other Treatment Technologies: R. Kamens, D. Amaral, J. Charles, University of North Carolina - Chapel Hill Goal: The objective of this project is to provide a framework model for analyzing sets of alternatives for the treatment of different types of hazardous materials. In this study, we will compare, as a model situation, the thermal treatment of flame retardant materials such as polybrominated biphenyls (PBBs) with other physical or chemical disposal alternatives. 71 ------- Rationale: Upon incineration of discarded materials which contain flame retardant chemicals, toxic polybrominated dibenzo-p-dioxins and furans (generally referred to as PBDDs & PBDFs) can be generated. Little is known about the atmospheric stability of PBDDs and PBDFs although very preliminary work suggests that some of these PBDDs may photodegrade . Should this be the case, incineration may be a more attractive disposal alternative than landfill ing or chemical treatment. Using these compounds as test cases we can develop a model to provide information which would help one decide between discarding materials containing fire retardants in a land fill (knowing all the costs, risks, and societal concerns associated with this option) versus incineration, with all the costs, risks, and societal concerns. Approach: The potential treatment alternatives for discarded materials which contain fire-retardant materials will be investigated. Potential health and environmental impacts will be combined with potential costs to provide an integrated analysis of each relevant alternative of treatment and disposal. To provide information on the stability of potentially toxic materials from the incineration of fire retardants we will burn these materials in a high temperature ignition vessel and add them directly to existing 25m outdoor transparent Teflon film chambers. This will permit us to age brominated dioxins in a captured air parcel under realistic outdoor conditions and assess the overall stability or reactivity. status; Work on the framework model has already begun. An ignition vessel has been developed and used to generate chamber samples of brominated dioxins and furans. Atmospheric stability experiments are planned for the 1989 fall months. "inent t clean~up Effectiveness of Multiple Liner Systems for Hazardous Waste Containment Facilities: K. Brown, R. Lytton, C. Giam, Texas A&M University Goal; The immediate goal of this project is to evaluate the potential use of stabilizing agents and additives for clay to enhance the ability to withstand chemical attack and to retard the migration of organic contaminants. Future goals include: (1) evaluation of ventilation systems to extract the volatile constituents from the leachate collection and leak detection systems, and (2) development of a mathematical model to describe the transport of organic contaminants through a composite liner system. Rationale; Many of the wastes resulting from RCRA waste treatment and cleanup of Super fund sites which need to be disposed in landfills still contain small quantities of hazardous constituents 72 ------- which could drain from the waste, adversely impact the integrity of landfill liners, and migrate through them to the groundwater. Recent data by Haxo indicate that certain organic contaminants, even when occurring in dilute solutions, will solubilize in and migrate through the plastics utilized for lining landfills. More secure waste containment may be possible through improvements in liner technology. These include addition of stabilizing agents to prevent chemical attack, the addition of polymeric chemicals to clay to increase the sorption capacity, and the use of ventilation systems to remove volatile organic vapors before penetrating liners. Approacht The effects of several stabilizing agents on the hydraulic conductivity of compacted clay soils will be evaluated through a laboratory study employing fixed wall permeameters and three soils of differing mineralogies. Specially constructed diffusion test chambers similar to those used by Haxo will be made and employed to measure the diffusion constants of various organics through several thicknesses of high-density polyethylene (HOPE). A mathematical model to describe the movement of chemicals through a multicomponent state-of-the-art landfill liner will be assembled and calibrated using the laboratory data. This will then provide a means to design an optimum liner needed for long-term waste containment. statusi The laboratory testing of amendments (lime and cement) is nearing completion. The diffusion test chambers have been fabricated and diffusion measurements will begin in October 1989. Preliminary work on assembling the model has begun and calibration should be completed in the forthcoming year. The project will be completed in February 1991. In-Bitu Bioremediation of Hazardous Substances in the Vadose Zone: C. Giam and K. Brown, Texas A&M University Goal: The goal of this project is to develop and calibrate a mathematical model to describe the in-situ biodegradation rate of hazardous organics in vadose zone subsoils under given soil, moisture, fertility, temperature, and oxygen conditions. Rationale: Microorganisms indigenous to soils are capable of degrading momt organic contaminants if the environment can be adjusted to enhance the activity. Possible soil environmental parameters to be adjusted may include: temperature, oxygen, moisture, and fertility. A mathematical model based on scientific principles is needed so that large-scale field systems can be properly designed and operated for optimum efficiency and productivity. Approach: This study is being conducted using a three-level approach. First, a mathematical model is being developed to 73 ------- describe the in-situ biodegradation rate of hazardous organics in vadose zone subsoils under given soil, moisture, fertility, temperature, and oxygen conditions. The second level will involve laboratory measurements of biodegradation rates needed to calibrate the model. In the third level, field experiments will be conducted to document the effectiveness of the optimum treatments as predicted from the level 1 and 2 studies. Statuat Preliminary work on assembling the model (level 1) has begun and calibration using laboratory data (level 2) should be completed in the forthcoming year. Field experiments and final model adjustments will be completed by February 1991. Training and Technology Transfer waste Minimisation - Legal/ Technical, and Human Factors: D. Denny, North Carolina State University Goal; The goal is to provide the necessary background for engineering students to design, sell, and implement a waste reduction program in an industrial environment. Rationale: Current engineering educational curricula emphasize the techniques and controls necessary to manufacture profitable products. Most major companies are now committed to manufacturing those products in a socially responsible manner. The waste reduction course is consistent with this attitude and supplements the rest of the engineering curriculum. Approach: An advisory committee was formed, consisting of representatives from academia, state government, federal government, state industry, national industry, and environmental groups. A course outline has been prepared and sent to the advisory committee for comment. The first module of the course material is in preparation. The course has been scheduled for the spring semester in the Chemical Engineering Department at North Carolina State University as a pilot. Status; Course material preparation and review is scheduled to be completed by the end of calendar year 1989. Hydrofluoric Acid Reuse: D. Denny, North Carolina State University Goal: Th« goal is to identify users of spent hydrofluoric acid from the electronics industry. Rationale: Electronics component manufacturers use hydrofluoric acid for etching and cleaning purposes. The spent acid must be dis disposed of as a hazardous waste. Research has shown the spent acid can be used to treat steel and aluminum. Finding a user for the spent acid would reduce the amount of hazardous waste generated. 74 ------- Approach: A feasibility study will be designed, simultaneously, interested companies which generate hydrofluoric acid will be recruited to assist in locating users. statusi A feasibility study is planned for completion by the end of February 1990. Two of the three companies that supplied material for the research no longer have a need to find a user for the spent acid. The third is interested in the project and plans to participate. One other spent acid generator has been identified as has a potential user for the spent acids. Research Conference: C. Kaufman, North Carolina State University Goal: The goal is to transfer environmental research information from Sunbelt university and government laboratories to regional industries. Rationale: There is a very large amount of relatively unkown, steadily developing environmental research underway at universities and research institution. It is important for industry and government personnel to better understand these efforts since few resources exist to duplicate this research. Thus, a regional research conference and compendium were selected to bridge this information transfer need. Approach: A series of invited plenary lectures on current environmental legislative activities and selected research topics will be complimented with an extensive poster session. Additionally, a comprehensive compendium of all regional environmental research will be appropriately indexed and published. Status: A two-day regional conference, The First Annual Exposition: Environmental Research In The Sunbelt — 1989, was held in Raleigh, North Carolina on November 14 and 15, 1989. To ensure complete coverage of Regions 4 and 6, state coordinators facilitated the dissemination of conference materials and the collection of research abstracts for publication. SUMMARY OF OUTPUTS IN FY 1989 Refereed Journal Articles 1 Articles Subaitted or In Press 0 Books and Bound Proceedings 0 Chapters in Books and Proceedings 0 Project Reports 0 Conference or Workshops Held • 0 Presentations _2— TOTAL 3 75 ------- BIBLIOGRAPHY Refereed Journal Articles Brown, K. W. and J. C. Thomas 1989. "Variability of Hydraulic Conductivity with Depth within a Lift of Compacted Clay Soil," Agronomy Abstract, p. 32. Presentations D. Amaral, J. Charles, R. Kamens. "Strategy for Analyzing Hazardous Waste Incineration of Fire Retardant Materials," presented to the Brominated Flame Retardant Industry Panel, Research Triangle Park, NC, August 31, 1989. D. Amaral. "Incinerator Risk Management for Polybrominated Flame Retardants," presented at the Society for Risk Analysis, San Francisco, November 1, 1989. 76 ------- Chapter 4 Hazardous Substanc* Research C«nt«r for R«gion Pair 7/8 ------- center: Hazardous Substance Research Center for U.S. EPA Regions 7 and 8 Participant** Kansas state University Montana State University University of Iowa University of Missouri University of Montana University of Nebraska University of Utah Directori Larry E. Erickson Department of Chemical Engineering Durland Hall Kansas State University Manhattan, Kansas 66506-5102 Phone: 913/532-5584 FAX: 913/532-7810 THE CENTER AT A GLANCE Kansas State University (KSU) leads the seven institution consortium comprising the Hazardous Substance Research Center for Federal Regions 7 and 8. The other universities are Montana State University, and the Universities of Iowa, Missouri, Montana, Nebraska, and Utah. All of these states are located in Region-Pair 7/8, as are Colorado, Wyoming, and the Dakotas. The Center was established in February 1989 to conduct research pertaining to the identification, treatment, and reduction of hazardous substances resulting from agriculture, forestry/ mining, mineral processing, and other activities of local interest. The Center is headed by Dr. Larry E. Erickson, Professor of Chemical Engineering at KSU. Dr. Erickson is responsible for coordinating all of the Center's activities. He is assisted primarily by Dr. Richard Hayter, of KSU's Engineering Cooperative Extension Service, who oversees the conduct of the Center's training and technology transfer program. The Center benefits from guidance supplied by a 15 person Science Advisory Committee which meets twice a year and a 24 person Training and Technology Transfer Advisory Committee which meets annually. Researchers from several specialties are interacting in the Center, bringing a diversity of perspectives to address the complex problems associated with hazardous substances. Table 1 provides a list of key personnel from each participating institution. 77 ------- Table it Kansas State Univ. B.R. Biles L. Erickson L.T. Fan L.A. Glasgow R.B. Hayter J.R. Schlup w.P. Wa1awender University of Missouri Bajpai Banerj i Clevenger Harbourt Hinderberger R.K. S.K. T.E. C.O. E.J. S. Kapila T.J. O'Keefe D.S. Viswanath J.L. Watson A.F. Yanders University of Montana No researchers this round Key Personnel in the center Montana state W.G. Characklis F.D. Culver A.B. Cunningham W.L. Jones R.S. Hunter University of Iowa D.T. Gibson B.C. Kross G.F. Parkin J.L. Schnoor University of Nebraska M.W. Gilliland G.B. Keefer W.E. Kelly University of Utah S. Ghosh Region-Pair 7/8 has a curious diversity of interests, resulting from the grouping of mineral-rich states, such as Colorado and Utah, with the states of the great plains and chaparral, whose economic foundations rest on agriculture and animal husbandry. The Center has defined its original mission in terms of these wide-ranging activities and has undertaken research in the following areas, listed in order of their current priority within the region-pair: 1. Studies of soil and water contamination by heavy metals such as cadmium, chromium, copper, lead, and zinc associated with mining wastes and other industrial activities. 2. Research on groundwater contamination from a variety of souro«*. Wood preservatives including pentachlorophenol and creosote, polynuclear aromatic hydrocarbons, carbon tetrachloride, trichloroethylene, vinyl chloride, and other chlorinated aliphatic hydrocarbons, polychlorinated biphenyls (PCBs), and dioxin have been identified as priority substances contaminating groundwater. Numerous pesticides have been identified to be hazardous substances; the fate and transport of pesticides are of particular interest because of the agricultural orientation of Regions 7 and 8. A general need exists for research to develop treatment technologies to clean up contaminated soil. 78 ------- 3. Development of incineration, biodegradation, and immobili- zation technology. Research is needed for rendering wastes nonhazardous before they are returned to the environment. 4. Development of simplified and inexpensive methods for analyzing contaminated soil. 5. Hazardous waste minimization. This is a desirable long term goal. 6. Research on hazardous substance release to the atmosphere at waste sites. 7. Determination of the safe concentration levels of hazardous substances in soils and in water. The diversity of the region-pair's interests and the large geographic area represented are further reflected in the training and technology transfer program currently being supported by the Center. Much of the Center's efforts are dedicated to the support of activities which can reach large audiences with a minimum of resources. For instance, the Center is collecting audio and video training materials relating to hazardous substances and making these materials available for loan, three issues of the newsletter "HazTech Transfer" have been disseminated throughout the region- pair, an information clearinghouse has been established, and general public education efforts are underway. These activities, augmented by some carefully selected special audience functions, appear to provide the most effective means of disseminating necessary technical information across this large and varied area. The Center's base support comes from EPA. However, the participating schools have all made substantial contributions as well. It is hoped that private industry and other public sector organizations will find the center concept attractive and will contribute funds in the future. The Center's first-year funding is summarized in Table 2. Table 2i Center Budget FDMDIMQ SOURCES PY 1989 FUNDS SPA: Centers Program $2,000,000 Private Sector 10,000 Consortium 1.530.068 TOTAL $3,540,068 79 ------- CENTER DIRECTOR'S REPORT The establishment of the Center has provided a focal point for hazardous substances research, training, and technology transfer in Federal Regions 7 and 8. A long term goal is to serve the needs of the 10-state area using as many of the available resources within the region-pair as possible. Through personal visits, the newsletter, telephone calls, and direct mailings, efforts have been made to emphasize inclusiveness and the idea of "working together for a better environment." Visits have been made to all of the consortium universities, several other universities, the EPA regional offices, other State and Federal offices, and a variety of professional gatherings and conferences have been sponsored and atended. The research and technology transfer projects currently underway were selected prior to the award of the center, based on our understanding of the priorities within the region-pair, plus the particular strengths brought to the Center by the participating universities. As the Center grows, it can be assumed that its priorities will change. The advisory committees will be most valuable in guiding the Center in selecting research and technology transfer areas to pursue. One other aim for the Center is to use the resources provided by the EPA-supported Hazardous Substance Research Center to solicit support for academic environmental research from other Federal agencies, states, and private industry. The Center has the potential to be a powerful magnet for attracting such support. HIGHLIGHTS FOR 1989 Stabilization and Solidification of Wastes One of the research projects in support of mining, mineral processing, and heavy metal wastes is an experimental study of stabilization/solidification of hazardous wastes. Statistically designed experiments are being carried out on arsenic-containing wastes and baghouse dust from a steel plant. There is a critical need for such work because it is possibly the only feasible technique for treating heavy metals. These wastes are being immobilized using appropriate pozzolanic materials, such as fly ash and Portland cement, and solidification-aiding reagents. An important objective of this research is to identify conditions that reduce the leaching rate of the hazardous substances to an acceptable level. The process must be economically feasible, also. This technology has advanced to the point that it may be employed in field applications following successful laboratory studies to identify the optimal conditions for immobilization of the waste. The investigators presented a paper on their research at the 1989 Conference on Hazardous Waste Research held at Kansas State University. 80 ------- An enzymatic ozonation process to render hazardous substances nonhazardous has been investigated and shown to have considerable potential as a water treatment method for rural water supplies that are contaminated with low levels of pesticides. Cost effective methods to treat rural water supplies are extremely important in Regions 7 and 8 because many farm families depend on their own wells for their drinking water and for agricultural uses. The results presented in the master's thesis of Lee Hunter Odell indicate that the extent of oxidation is dependent upon the concentration of ozone and the contact time between the ozone and the pesticide. The process appears to eliminate the functional groups on pesticides such as atrizine and alachlor. The concentration of the active pesticide can be reduced to values below the health advisory level. A granular activated carbon bed may be used to adsorb refractory organic compounds which remain after the ozonation. These results are beneficial to those designing and operating ozonation water treatment processes. Training and Technology Transfer The University of Missouri has developed and presented its three-day training course "Introduction to Hazardous Substance Management." The course, which is designed for individuals responsible for hazardous waste management programs, was attended by a near capacity audience of approximately 60 participants. Those who participated offered highly favorable written evaluations at the end of the course. The course is being offered in Sioux Falls, South Dakota in November; Lincoln, Nebraska in December; Denver, Colorado in January; Kansas City, Kansas in February; and Helena, Montana in March, 1990. The course assists employers and employees in meeting Resouce Conservation and Recovery Act (RCRA) and Occupational Safety and Health Administration (OSHA) training requirements. The two-day Conference on Hazardous Waste Research was held May 23 and 24, 1989. More than 90 papers were presented by researchers from academia, industry, and government, and over 200 representatives attended. The proceedings of the conference are being published. The conference was appreciated by all of the attendees as a valuable opportunity for the exchange of information. The newsletter, "HazTech Transfer", is distributed without charge to appropriate professionals in Regions 7 and 8, and it has been well received. Three issues have been published. The newsletter is useful because professionals from several different disciplines are involved in hazardous substance research, technology, and management and there is no professional 81 ------- organization which reaches all of these individuals. The newsletter is also circulated to EPA's four other hazardous substance research centers, and others as appropriate. Investigator Research Fan Clevenger Keefer Ghosh Parkin Erickson Banerj i Characklis Yanders Schnoor Glasgow Walawender Viswanath SUMMARY OF ONGOING PROJECTS Title Experimental Study of stabilization/ Solidification of Hazardous Substances Reclamation of Metal- and Mining-Contaminated Superfund Sites Using Sewage/Fly Ash Amendments Metal Recovery and Reuse Using an Integrated Vermiculite Ion Exchange-Acid Recovery System Removal of Heavy Metals from Hazardous Wastes by Protein Complexation for Their Ultimate Recovery and Reuse Feasibility of In-Situ Anaerobic Bioreclamation of Mixtures of Toxic Chemicals Development Technology of In-.Situ Biodegradation Migration and Biodegradation Pentachlorophenol in Soil Environment of Microbial Processes in Groundwater Formations Time Dependent Movement of Dioxin and Related Compounds in Soil Modeling Dissolved Oxygen, Nitrate, and Pesticide Contamination in the Subsurface Environment Vadose Zone Decontamination by Air Injection Thermochemical Treatment of Hazardous Wastes Development, Characterization, and Evaluation of Adsorbent Materials for Waste Streams 82 ------- Fan Computer-Aided Design and Control of Systems for Treatment of Hazardous Waste and Minimization of Waste Products Hunter Computer Method to Estimate Safe Level Water Quality Concentrations for Organic Chemicals Kross Removal of Nitrogenous Pesticides from Rural Well Water Supplies by Enzymatic Ozonation Process O'Keefe Characterization and Treatment of Hazardous Materials from Metal/Mineral Processing Wastes Schlup Adsorption of Hazardous Substances onto Soil Constituents Training and Technology Transfer Harbourt Introduction to Hazardous Substance Management Gilliland Hazardous Waste Management in Rural States Hayter Audio and Video Training Hayter Newsletter Hayter Electronic Bulletin Board Hayter Seminar Program Hayter HSRC Contribution Repository and Information Clearinghouse Hayter Conferences Hayter Public Education Biles Technology Data Base RESEARCH PROJECT DESCRIPTIONS Experimental Study of Stabilisation/Solidification of Hazardous Wastes: L.T. Fan, Kansas State University Goal: The objectives of this research are to determine experimentally the feasibility and suitability of solidification/stabilization for typical and prevailing hazardous wastes and to establish extensive knowledge and data bases necessary for optimal treatment of such wastes. 83 ------- Rational*; For many heavy metals and mine tailings, stabilization/ solidification is the only economically feasible management alternative. A better understanding of the immobilization of hazardous substances in soils is imporant for commercial products and waste management. Various factors affect the immobilizing mechanism of stabilization/solidification of hazardous wastes. These include the type and amount of pozzolanic materials and solidification-aiding reagents, and the characteristics of the wastes. To identify environmentally acceptable and economically feasible stabilization/solidification techniques for treating organic and inorganic hazardous wastes generated in EPA Regions 7 and 8, it is necessary to carry out a series of statistically designed experiments for each of these wastes. Approachi Statistically designed experiments are being conducted for three diverse types of wastes. The leachability and compressive strength of the solidified samples are being measured. Status: Experimental work has been completed on three specific studies, a low-level radioactive liquid waste, an arsenic containing waste, and a baghouse dust waste from a steel plant. Manuscripts describing the results are being prepared for two of the studies. The results from the third study have been presented and are to be published in the Proceedings of the Conference on Hazardous Waste Research. Reclamation of Metal and Mining Contaminated Superfund sites Using Sewage Sludge/Fly Ash Amendment: T.E. Clevenger and E.J. Hinderberger, University of Missouri (Columbia and Environmental Trace Substances Research Center) Goal: The goal of this project is to investigate the utility of sewage sludge/fly ash mixtures in the reclamation of a metal contaminated Superfund site. Rationale: Through the use of a mixture of sludge and fly ash, one can increase the organic content of the soil. As a result, plant cover can be established, the pH is increased, and the mobility and availability of the metals is controlled. Approach! An abandoned lead tailings pile in Desloge, MO, has been selected for the study site. Different ratios of sewage sludge and fly ash will be tested with different herbaceous species. Total metal analysis and speciation methods are being used to evaluate the potential for mobilization of the metals. Sewage sludge and fly ash amendments are being evaluated as cover materials in column studies. 84 ------- Preliminary experimental work indicates that the predominant forms of lead in the tailings are oxide and sulfide. Thirty-six columns have been constructed and the column studies have begun. Metal Recovery and Reuse Using an Integrated Vermioulite Ion Exchange-Acid Recovery Bysteas G.B. Keefer, University of Nebraska-Lincoln The goal of this research is to evaluate and optimize a system for zinc recovery and reuse from plating wastewaters or contaminated groundwater. Rationale i The metal plating process currently creates large quantities of metal -contaminated waste (pickle liquor) . This wastewater is commonly treated by neutralization resulting in the production of metal laden waste sludges. The proposed research would evaluate a system for metal recovery for reuse in the plating process while producing a nonhazardous liquid waste stream and a spent vermiculite which could also be disposed as a nonhazardous material. Approach i A system which uses a multiple countercurrent vermiculite ion exchange column treatment scheme is being developed to treat zine plating wastewaters or zinc contaminated groundwaters . Three columns are used in series, with the pH of the influent wastewater to each being adjusted progressively higher to aid in the zinc removal process. In addition, as the columns become expended on the front end of the system, they have been exposed to the lowest system pH. This pH adjustment scheme, therefore, aids in both the metal removal process and in the acid recovery of the zinc by minimizing the acid requirement. Once the columns are exhausted, they are acid leached for zinc recovery. Status i The results of a series of batch experiments show that the exchange capacity increases as the pH is increased. Confined fixed bed ion exchange columns gave better results than columns which were allowed to expand under normal flow conditions. A paper was presented at the Nebraska APWA/NWPCA/AWWA Conference, November 9, 1989. Removal of Heavy Metals from Hazardous wastes by Protein Complexities for Their Ultimate Recovery and Reuses S.Ghosh, University of Utah goal i The objectives of the research are to develop a basic understanding of the mechanism, kinetics, and parametric dependence of complexation of heavy metals with microbial protein, and ultimately to develop an innovative continuous-flow process to remove these potentially hazardous elements from aqueous wastes for subsequent recovery and reuse. 85 ------- Rationale; It is well known that many strains of bacteria, yeast, and mold are resistant to high concentrations of heavy metals which could be removed from the aqueous environment by extracellular or intracellular uptake. The metals may bind by interacting with the anionic sites at the hydrophilic surface of the outer membrane of a microbial cell. Extracellular uptake is effected by physical entrapment by the polysaccharide matrix outside of the cell wall, adsorption, ion exchange, chelation, and complexation by ligand formation. Metals also form complexes with small intracellular globular proteins, the syntheses of which are induced by the metals themselves. Protein complexation could account for the uptake of up to several milligrams of metal per gram of dry cell mass and the organisms may be tolerant to heavy metals concentrations of up to 100 g/1. Should the process prove feasible, it would provide an economical and natural way to remove and reuse toxic heavy metals. Approach; In the initial phase of the research, experimental work is being conducted to study the effects of metal and protein concentrations, growth phases, culture temperature and pH, and electrode potential on the kinetics and efficiencies of intracellular and extracellular uptake of metals. Mutual inhibition or stimulation of the uptake of some metals by the antagonistic and synergistic actions of others will be studied. Both aerobic and anaerobic cultures will be investigated. In the second phase of the project, a continuous-flow process scheme involving a bioreactor harboring a protein filter (biotrap) and a metal extractor will be developed to demonstrate the concept of cyclical uptake, concentration and recovery of heavy metals. The optimum bioreactor and extractor designs and operating conditions will be delineated by conducting bench-scale runs. status: A review of the literature was conducted. Aerobic and anaerobic chemostats have been designed, fabricated, and installed. Three metal uptake runs have been conducted using aerobic batch reactors. Feasibility of In-8itu Anaerobic Bioreclamation of Mixtures of Toxic Cheaicalss G.F. Parkin and D.T. Gibson, University of Iowa Goal: The goal of this research is to assess the impact of mixtures of toxic chemicals on the biotransformation of individual organics, with toxic organic concentrations in the range of 1 to 100 mg/liter. The feasibility of using genetically engineered bacteria to degrade selected organics in a laboratory activated sludge system is being investigated. Rationale: Recent research has shown that chlorinated aliphatic compounds, such as trichloroethylene and carbon tetrachloride are degraded under anaerobic conditions. Such conditions are likely to exist at a wide variety of Superfund sites. At the present time, very little is known about the biodegradation of mixtures of 86 ------- these and related compounds in the concentration ranges likely to be found at or near Superfund sites (1-100 mg/1) . In order to assess the feasibility of using bioreclamation techniques, information concerning the anaerobic biotransformation of mixtures of these compounds is required. Such information will be useful in determining the potential for using anaerobic biological processes for remediating contaminated soils and groundwaters . Approach: Anaerobic biofilm reactors with glass beads or gravel are being used to investigate the biodegradation of chloroform, methylene chloride, and 1,1,1-trichloroethane alone and in combination. Acetate is provided as a carbon and energy source. status x Several experiments have been completed. The results indicate that biodegradation processes are dependent upon the mix of chemical compounds which are present. For example, methylene chloride was degraded more completely when fed in combination with chloroform and 1,1,1-trichloroethane with acetate as a carbon and energy source compared to experiments in which methylene chloride and acetate were fed together. Development of In-Situ Biodegradation Technology: L.E. Erickson and L.T. Fan, Kansas State University Goal : The goal of this research is to conduct an investigation of in-situ biodegradation both through experimentation and through model-based simulation. Rationale: In-situ bioremediation has many potential applications. However, a better understanding of the technology is desirable for many field applications. Laboratory experiments and a model-based simulation are being used to generate new knowledge. The development of methods for supplying oxygen and maintaining optimal water activity for aerobic biodegradation in the vadose zone are of particular interest. Approach: Microcosm studies are being conducted with various levels of soil moisture to study the effects of soil moisture and oxygen transfer limitation on biodegradation rate. Soil columns will be investigated with air supplied to the vadose zone of the column. Mathematical models of bioremediation in the three-phase environment of the vadose zone are being formulated. status: Modeling and simulation of in-sitU bioremediation in the saturated zone was conducted by Jianchu Wu under the principal investigator's guidance. The results show that the rate of biodegradation may be limited not only by insufficient oxygen supply, but also by transport resistance to the contaminant (substrate) desorption. The simulation of the operation involving recycle of unreacted contaminants indicates that biodegradation takes place mainly in the upper zone of the bed. Additional research is in progress. 87 ------- Migration and Biodegradation of Pentachlorophenol in Soil Environments S.K. Banerji and R.K. Bajpai, University of Missouri- Columbia Goals; The objectives are to determine the migration rate of pentachlorophenol (PCP) and other additives used in wood preservation and to evaluate the feasibility of above-ground and in-situ biodegradation of PCP containing leachate under laboratory and field conditions. Rationale: Wood preservatives are used extensively in Regions 7 and 8. Research on the migration and biodegradation of pentachlorophenol will be useful in developing plans to clean sites which have been affected by wood preservative wastes containing pentachlorophenol. Approach; Laboratory studies will be conducted to determine the migration of PCP formulations used in wood preservation. The amount of vaporization and photodegradation of the components will also be evaluated. Later, lysimeter field studies will be conducted to verify the laboratory results. Status; The experimental work is underway. Microbial Processes in Groundvater Formations: W.G. Characklis, A.B. Cunningham, and W.L. Jones, Montana State University Goal; The goal of the research is to improve the rate and efficiency of in-situ microbial degradation of subsurface contaminants through an improved understanding of processes which govern transport, attachment, growth, and activity of microorganisms in porous media. Rationale; Subsurface biofilm growth is complicated by the nature of fluid and nutrient transport which, in a porous medium, occurs along tortuous flow paths of various dimension and geometry. The wide distribution of pore velocities introduces considerable variation in the microbial processes of desorption, attachment, and detachment. An understanding of cause and effect relationships which influence these and other biofilm processes is essential in order to describe net subsurface biofilm accumulation. Accumulation of biofilm in porous media is of fundamental importance because it governs the potential for: (1) in-situ biodegradation of groundwater contaminants and (2) subsurface biofouling, such as, reduction of permeability due to biomass plugging of pore space—both of which are crucial considerations in the design of subsurface biodegradation systems. 88 ------- ApproachI The project will be carried out through a carefully designed program of laboratory experimentation. Microbial transport and activity will be investigated in media containing pentachlorophenol. Image analysis will be used to monitor microbial processes including transport rates, adsorption/ desorption, growth, and filtration. Status: The results show that the accumulation of biofilm follows an "S" shaped progression with time and ultimately reaches a quasi- stable maximum thickness. The presence of extensive biofilm accumulation in porous media results in decreased porosity and permeability and an increased hydrodynamic dispersion coefficient. A variety of microorganisms are capable of growth on penta- chlorophenol; however, a significant lag phase may precede subsequent good removal rates. Two papers are included in the Proceedings of the Conference on Hazardous Waste Research. Tim* Dependent Movement of Dioxin and Related Compounds in Soil: A.F. Yanders and S. Kapila, University of Missouri Environmental Trace Substances Research Center Goal: The objective is to study the rate of migration of loss of 2,3,7,8 tetrachlorodibenzo-p-dioxin (TCDD) in soil at a contaminated site. Rationale! This study will establish parameters for the rate of migration and loss of TCDD and similar compounds in soil which will be important in determining the most appropriate cleanup procedures to be used at the various sites in Missouri and comparable situations elsewhere. Approach; The degree of translocation and loss of TCDD in contaminated soil will be determined at Times Beach, MO, the state's most extensively contaminated site, by measuring the concentration profiles of TCDD in experimental plots and soil columns located at the experimental site and in the laboratory. Status: The results indicate that there has been practically no volatilization/photolysis loss of TCDD from experimental plots at Times Beach. Experiments are underway to delineate the role of co- contaminant* on partition behavior. The results obtained so far indicate that apparent solubilization at the contaminated sites can be attributed to the colloidal suspensions of the co-contaminants. Modeling Dissolved Oxygen, Nitrate and Pesticide Contamination in the Subsurface Environment: J.L. Schnoor and G.F. Parkin, University of Iowa Goal: There are three objectives: (1) to develop better mathematical model formulations for the fate and transport of pesticides in the unsaturated zone and saturated groundwater, (2) 89 ------- to perform field and laboratory experiments on the fate and transport of alachlor and atrazine to test model formulations, and (3) to assess the effects of best management practices. Rationalei Both models and field studies are necessary to improve our ability to estimate toxic organic concentrations in groundwater using different agricultural management practices. Better kinetic formulations that can be used in models are to be developed in this work. These will be used to assess the effects of best management practices on the fate and transport of pesticides. Approach: Experiments are being conducted at an instrumented field plot site. Three types of sites will be examined, one barren ground, one planted with corn, and one covered with poplar trees. The quantitative mass balance is based on measurements in the plants, soil, and groundwater. The data will be used to test the model formulations. Statusi The results of the first field season show that alachlor is more mobile than atrazine; it showed greater runoff rates and percolation to the groundwater, but it also disappeared at a more rapid rate than atrazine. Atrazine was tightly bound to the soil, especially in the small plot planted in popular trees. Vadose Zone Decontamination by Air Injection: L.A. Glasgow, Kansas State University Qoalt The goal of this research is to provide a preliminary design protocol that can be employed when air stripping is contemplated as a remedial measure. Rationale: The efficiency of and coverage provided by air injection/venting have not been reliably characterized. It is necessary to develop design methods that can be used to employ air injection/venting processes efficiently and economically to remove volatile contaminants. Approach: A simple computer code is being developed that can be used to calculate gas flow patterns obtained with various venting arrangement*. Numerical simulation is being used to investigate the effect* of injection and withdrawal well placements. statust Thai initial numerical results show that in cases where withdrawal/suction is applied only at the surface, the effective treatment area is confined to a small region (a three meter radius) in the vicinity of the injection well. Preliminary calculations indicate properly located withdrawal wells can maintain high rates of mass transfer over larger areas. 90 ------- Tnermochemioal Treatment of Hazardous Wastest w.p. Walawender and L.T. Fan, Kansas stats Univsrsity 2211» Ths goals ars to obtain experimental performance data with a bench-scale incinerator for ths thsnnal destruction of hazardous substances and to develop models for the design and operation of hazardous substance incineration systems. Rationalei This research is designed to provide extensive information on the influence of operating conditions on the performance of hazardous waste incinerators. The results should provide a basis for development of models for the design and effective operation of hazardous waste incineration systems. Approachi A bench-scale incinerator has been designed and constructed for the investigation. Experiments are being conducted with model chlorinated compounds. status: The results of preliminary experiments using carbon tetrachloride with hexane as liquid carrier show that effective destruction was achieved with chlorine loadings up to 33% with low excess air. Operating temperatures were typically around 2000°F under near stoichiometric conditions. Development, Characterization, and Evaluation of Adsorbent Materials for Treatment of Waste 8treamst D.S. Viswanath, S. Kapila, and T.E. Clevenger, University of Missouri (Columbia and Environmental Trace Substances Research Center) Qoali The objectives of the project are to investigate the use of adsorbent materials, such as surface modified resin and covalently bonded sulfurated siloxanes, for effective removal of extremely toxic substances from waste streams and to study the effective regeneration (desorption) of adsorbents with supercritical fluid extraction. Rationale! Adsorption is commonly used for the removal of hazardous organic* from waste streams. Adsorbents that can be regenerated using supercritical fluids may provide significant cost and efficiency advantages. The methods may also have analytical chemistry applications. Approacht Experiments have been carried out to determine the efficacy of desorption/regeneration of bonded alkyl siloxane adsorbents with supercritical carbon dioxide. Substances desorbed using supercritical carbon dioxide have been analyzed chromatographically. Sensitivities below parts per trillion can be measured with this method. statust The experiments were started in March 1989. Covalently bonded sulfoxide stationary phase adsorbents have been prepared. The experiments on the regeneration of carbon-based adsorbents are underway. 91 ------- Computer-Aided Design and Control of Systems for Treatment of Hazardous Waste and Minimization of Waste Production: L.T. Fan, Kansas State University Goal: The goal is to develop intelligent computer-based process design and control tools for creating optimal systems for the treatment of hazardous wastes and the minimization of waste production. Rationale: Improvements in process design and control methods which incorporate waste minimization as an integral part of the synthesis process are needed to achieve pollution prevention and waste reduction objectives. This study will yield a set of rudimentary heuristics for design and operation of hazardous waste treatment systems and process plants with minimal waste production. Approach: A significant portion of the research effort will be directed towards the identification of the important characteristics of process systems for treating hazardous wastes and the minimization of waste production. Specifically, the investigation will focus on the various processing schemes, design guidelines, safety regulations, and economic aspects of waste treatment and disposal. The integration of process design and control in the synthesis of processes is part of the investigation. Status: Three specific studies are in progress. These include the synthesis of mass exchanger networks, the application of neural networks to hazardous waste processing, and the application of an artificial intelligence approach to the design of a process with a high degree of structural controllability. Papers were presented at the 3rd Oklahoma Symposium on Artificial Intelligence in Tulsa and at the 1989 Annual Meeting of the American Institute of Chemical Engineers in San Francisco. Computer Method to Estimate Safe Level Water Quality Concentrations for Organic Chemicals: R.S. Hunter and F.D. Culver, Montana State University Goals: The objective is to design and implement a microcomputer prototype system capable of estimating advisory concentrations and water quality criteria for organic chemicals. Rationalei EPA has established ambient National Water Quality Criteria for only about 73 toxic organic chemicals. Meanwhile, thousands of other chemicals, mostly organic chemicals, have no established criteria or safe level estimates. 92 ------- Approacht Two concentration levels are necessary to estimate Water Quality Criteria for a chemical: the criterion Maximum Concentration (CMC) and the Criterion Continuous Concentration (CCC). The QSAR System, developed by the U.S. EPA and Montana State University, is being enhanced to give approximations or estimates for CMC and CCC for organic chemicals. The QSAR system contains EPA's AQUIRE database compilation of 60,000 aquatic toxicity test results for 2,800 organic chemicals. A modified QSAR system using these test results, guided by EPA guidelines and methods, would estimate CMC and CCC values for the chemical. The proposed system, besides providing values, would summarize those tests and arrive at CMC and CCC estimates. Status: The necessary software is being developed. The basic requirements to estimate ambient aquatic life advisory concentrations have been identified. Removal of Nitrogenous Pesticides from Rural Well-Water Supplies by Enzymatic Ozonation Process: B.C. Kross, University of Iowa Goal: The goal of this study is to determine the mechanisms by which nitrogenous pesticides are removed from well water using an enzymatic ozonation process. Rationale; This research will contribute needed information for the development of a point-of-use water treatment system to remove pesticides from well water. The need for inexpensive, effective point-of-use water treatment systems for rural water supplies is critical. Rural residents with shallow wells who have herbicide contamination problems are most likely to use this technology. Approach: A pilot-scale enzymatic ozonation process will be built and tested. Whenever possible, commercially available components such as the ozone generator, filters, and reaction chambers will be used in the process. Status: Results of preliminary work indicate that ozonation in association with the hydrogen peroxide radical renders atrazine and alachlor more hydrophilic and eliminates the functional groups for the two pesticides. The Characterization and Treatment of Hazardous Materials from Metal/Mineral Processing Wastes: T.J. O'Keefe and J.L. Watson, University of Missouri-Rolla Goal: The objective of the research is to develop processing procedures to treat waste oxides generated by the mining and metals industry. 93 ------- Rational*: A major problem associated with physical and chemical processing operations involving metals and minerals is the treatment of waste streams. This research is directed toward developing a generic approach to the treatment of hazardous waste products from the mineral industry. Approach: The slag generated by a Missouri lead smelter (Doe Run Company) has been selected for investigation. This slag will be processed in a small furnace to obtain a non-hazardous residue and an oxide fume containing zinc, cadmium, and lead. The oxide fume will be used as a feed to an electrolytic plant. Characterization and processing feasibility tests are being conducted. Status: The experimental research is underway. A small furnace run on the slag was made. The results were quite successful. It may be possible to process the oxide fume economically in an existing metal processing facility. Adsorption of Hazardous Substances onto Soil Constituents: J.R. Schlup, Kansas State University Goal: The objective of the research is to investigate adsorbate- adsorbent interactions between inorganic solids representative of soil constituents and hazardous organic compounds. Rationale: Very little information is available on adsorbate- adsorbent interactions involving hazardous organic compounds and soil constituents; however, such knowledge is essential for modeling and design of remediation processes. Approach; Fourier transform infrared photoacoustic spectroscopy is being used as the detection scheme for the adsorbed species. The phenanthrene/silica system has been studied to test the ability of the instrument to observe polynuclear aromatic compounds adsorbed onto solids. The adsorption of naphthalene onto alumina is being investigated. Status: The results show that photoacoustic spectroscopy can provide Fourier transform infrared spectra of polynuclear aromatic hydrocarbons adsorbed onto model soil constituents. Adsorption isotherms are being obtained for polynuclear aromatic compounds adsorbed onto several soil constituents. Training and Technology Transfer Introduction to Hazardous Substance Management: C.O. Harbourt, University of Missouri-Columbia Goal: The goal is to provide the knowledge necessary for participants to properly store, treat, and dispose of hazardous materials produced or used by regulated facilities under 40 CRF 94 ------- Parts 264 and 265. In addition, the participants receive training which can be applied toward the requirements of RCRA and OSHA for employers and employees engaged in operations involving hazardous materials. RfrtJpnalf« Regulated industries need continuing education to satisfy state and federal requirements in the management of hazardous materials with the ultimate goal of reducing or eliminating both short and long term negative effects on the environment. This training is needed by a broad range of professionals including engineers, chemists, managers of affected facilities, public officials, owners and operators of hazardous waste facilities, generators, and transporters. The course was the result of the promulgation of requirements for training in response to regulations regarding hazardous materials. Approach: The course evolved over eight years from a five-day annual institute presented by the University of Missouri-Columbia Engineering Extension. The training is provided over a three day period in a classroom setting using a variety of instructional media, and experts on each facet of the program. The faculty include a core group of professors and staff from the university who are active in hazardous waste management research and applications as well as specialists drawn from the geographic area of each training site who are experts on local requirements and technology which affect the regulated community in the area. Status: The first session was conducted on the University of Missouri-Columbia campus. Fifty-seven individuals participated in the workshop. The second site was in Sioux Falls, South Dakota, where ten individuals attended. Although small in number, the South Dakota participants included an excellent mist of individuals who will have a positive impact on the proper management of hazardous substance. They included consulting engineers, state regulated facility managers, and university engineering faculty. Future site include Lincoln, NE; Denver, CO; Kansas City. KS; and Helena, MT. Hazardous Wast* Management in Rural States: M.w. Gilliland and W.E. Kelly, University of Nebraska-Lincoln Goal: The objective is to provide sufficient knowledge to participants to assure that hazardous materials unique to the rural areas of the great plains and mountain states are properly managed. Rationale: Many of the hazardous substances encountered by the rural areas of the midwest include wastes from agriculture and mining industries. The individuals who handle the materials may not have sufficient technical knowledge to manage hazardous wastes properly. In addition, they represent a geographically dispersed 95 ------- population. This program provides the needed information in a delivery format to meet their needs and to assure proper disposal and management of the hazardous substance. Approach! The delivery mechanism will use video tapes and will expand on the experience of the University of Nebraska at Lincoln in developing and delivering live, two-way interactive TV for hazardous waste management for professionals. Three video tapes are presently under development. The content of the training materials was developed after communication with the rural states to determine their specific needs and topics that should be included to meet those needs. It was determined that three video tapes could best respond to the needs identified. The first tape deals with a basic understanding of hazardous materials and is entitled "Hazardous Waste: What It Is, Why We Have It, and Who is Regulated." The second deals with hazardous materials in rural areas and is entitled "What are the Sources of Hazardous Waste in Rural Areas, and What are the Management Problems in these Areas?" The third deals with problems associated with use and disposal and is entitled "What are the Impacts of Improper Use and Disposal of Hazardous Waste." Consideration is being given to development of a fourth tape on hazardous waste management strategies. status: Contacts have been made with states having needs unique to the rural areas for program content and delivery opportunities. These states have provided an individual to serve on a review team as the tapes are developed to assure that they meet the needs of each state. The information received plus that which presently exists at the University of Nebraska at Lincoln formed the basis for scripts for the tapes. The three scripts are presently out for review. Production of the tapes will soon be underway. The first three tapes when completed will be distributed to the states in the two regions for use through their individual delivery networks such as those of state environmental agencies, extension services and trade organizations. Audio and Video Training: R.B. Hayter, Kansas State University Goalsi The goal is to provide information needed by those developing new technology in the minimization, management, and disposal of hazardous materials and those generating the materials in a format that is timely, accessible given the geographic distribution of those involved, and effective in transferring new information. Rationalet The effective transfer of new technology is inhibited by the distances and time of travel previously required in traditional on-site delivery formats. Although print media will continue to serve a critical role in technology transfer, experience has demonstrated that electronic delivery is an 96 ------- effactive tool in transferring information. Video and audio programming can include simple teleconferencing between researchers to discuss research results, capturing presentations before live audiences, transmitting live satellite presentations with interactive audio, or entire non-credit courses. Opportunities for inexpensive training occur when materials developed at other locations are made available at reasonable cost. This project allows the Center to take advantage of these opportunities. Industry and government use video tapes extensively for training. Approacht Audio and video materials are being produced and collected from a variety of sources and made available through the Center and the Kansas State University library. For example, approximately 20 people participated in the live teleconference "Ask the Experts: 2nd Annual Hazardous Materials Teleconference" which originated at Oklahoma State University; others have watched the video tape. The Training and Technology Transfer Advisory Committee will assist in identifying special needs for technology transfer that could be delivered electronically. Where cost can be justified, Kansas state University or another participating school will use their satellite transmissin capabilities for video conferencing. Uplinking from the great plains states has the advantage that a single transmissin is all that is required for reception throghout North America. In addition to training specifically designed for electronic delivery, opportunities for taping other programs will regularly be reviewed. This may be a single lecture or an entire conference. Selection will be based on needs identified by the advisory committee or judgment of the Center Director as the cost to produce these tapes is quite economical. The availability of the tapes will be promoted through the Center's newsletter and will be maintained on file in the Center's special collection in the KSU library. statust The collection of audio and video materials includes video tapes from a hazardous waste minimization short course, training for automotive maintenance hazardous waste managers, and a modeling study of organic vapor releases and site remediation. Materials are being made available through the Kansas State University library. Audio conferencing has already successfully been used to communicate between both the Science Advisory Committee and the Training and Technology Transfer Advisor Committee. This low cost method of inetant communication between members of the committees proved effective and economical. Some of the tapes will be used during the coming term for students both on campus and remote from the university. A tape produced in Iowa was given to the Center for cataloging and distribution, and various other tapes have been recored and preserved. These acquisitions are too recent for extensive demand. However, their availability has been announced in the Center's newsletter, and the materials are being used. 97 ------- Newsletters R.B. Hayter, Kansas State University Goal: The objective is to provide useful information to hazardous substance professionals who are involved in research, management, and technology transfer. Rationalet No single professional society serves all those working with hazardous substances. The newsletter provides a mechanism for the Center to communicate useful information within the region- pair. Approacht A newsletter, HazTech Transfer, is published quarterly and distributed without charge to professionals in Regions 7 and 8. It is distributed to professionals who are actively involved in the development of new technology or who have need for applying that technology. Included in the distribution of approximately 3000 are state and federal regulatory agencies, researchers and educators, generators of hazardous materials, and consultants. HazTecfr Transfer contains announcements of training opportunities, descriptions of research, calendars of meetings and other events, and accomplishments of the Center. In addition, the newsletter lists recent acquisitions of the Center's special library collection, calls for proposals, and announcements of major events sponsored by the Center such as the annual research conference. status: Three issues have been published; April, July, and October. To date, information has been contributed by Missouri, Iowa, Montana, Nebraska, and Kansas. Electronic Bulletin Board: R.B. Hayter, Kansas State University Goal; The goal is to make important information on conferences, short courses, and other Center activities available through an electronic bulletin board. Rational*; The electronic bulletin board provides a mechanism for inexpensive communication between two individuals or all the Center's associates. It is typically less costly to post information that need not be interactive as in a traditional phone communication, and by virtue of its accessibility by all the associate* of the Center it is less costly than FAX. Much information that was once transmitted by letter or memorandum will now be posted on the board electronically. This expedites the delivery of the information and at a substantial cost savings, particularly if the information is to be sent to multiple recipients. 98 ------- Approachx The calendar of events and other important information will be made available electronically. Opportunities to use existing electronic bulletin boards are being investigated. One option is to use the OSWER technology transfer electronic bulletin board. Status: There has been a delay in activating the bulletin board. The original intent was to use the Kansas State University "Sunflower Dispatch" which is used by the Cooperative Extension Service. However, access ports were limited. As a result, other boards presently available through EPA as well as other sources are being investigated. HSRC Contribution Repository and Information Clearinghouse: R.B. Hayter, Kansas State University Goal: The goal is to collect and make available technical information produced by the Center and others. Users of the repository will primarily be Center associates, generators in the ten state region, state and federal regulatory agencies, and others needing the technical information. In addition, the repository will be available to those outside the immediate sphere of the Center who have need of information on hazardous substances. Rationalet An important aspect of a successful research program is the dissemination of the results of the research. It is critical that there be a convenient, single source of information generated by the Center and others for effective use of the information. As technology is being developed by a large number of individuals, access to that information would be hindered if those needing it were required to individually request information from each laboratory or agency. In addition, it is important that this information be safely archived for future reference. Approach: The Kansas State University library is the repository for technical reports, theses, dissertations, and other publications produced as a result of Center funding. The library will make these materials available to all interested parties through interlibrary loan. The library is developing a hazardous substance collection of literature in support of the research and technology transfer activities of the Center. In addition to the information produced by the Center, the library has agreements with EPA's Center for Environmental Research Information as well as other agencies and research centers to insure receipt of appropriate documents on a timely basis. Through the generation of a master bibliography and computer searching capabilities, the library provides members of the Center consortium with subject specific access to all items added to the collection. Materials are available through interlibrary loan to all interested parties. 99 ------- Status: This project is underway. Several members of the library staff are assisting with this project. In addition to the materials which the library has acquired on Superfund, RCRA Treatment processes, waste minimization, analytical methods, risk analysis, etc., the Center has provided seven videos, proceedings of conferences on hazardous waste research sponsored by the Center, and other research reports and papers. Conferences: R.B. Hayter, Kansas State University Goal: The goal is to hold an annual conference on hazardous substance research and to encourage and support other related conferences in the region-pair to provide opportunities for individuals from the public and private sectors to share technical information regarding the management of hazardous substances. Rationale; Conferences provide excellent opportunities for the exchange of informtion. Professional societies that organize technical conferences should have the support of the Center as this is an effective method for holding conferences. There are many advantages to working with professional societies to make their conferences stronger technically, more cost effective, and better attended. Approach; The Center is working with professional societies to have several conferences each year. The Center plans to host an annual conference each May. The conferences are normally open to all who wish to register unless there are space limitations. Some serve the needs of one or two states while others are national conferences. Each conference has a specific purpose which helps the Center meet its technology transfer goals. Status; A conference on hazardous waste research was held May 23- 24, 1989. The Center co-sponsored a waste minimization training event on April 24-25, 1989, in conduction with a conference organized by the St. Louis Section of the American Institute of Chemical Engineers. The Center is a co-sponsor of the cluster of conferences to be held February 20-22, 1990, being organized by the National Water Well Association/Association of Ground Water Scientists and Engineers. Public Education: R.B. Hayter, Kansas State University Goal: Th« objective is to provide printed, video, and audio materials on hazardous substances in support of the education of the public to elevate their consciousness and understanding of hazardous substances so that they can better manage that which they use or produce, and to give them the information they need in making decisions dealing with waste minimization. 100 ------- Rational*i Public education in hazardous substance management is needed for public participation in decision making and waste minimization. A better educated public will have a positive impact on hazardous substance management. Approach* Locally prepared and purchased printed materials and video materials from a variety of sources are being made available to the public through the Kansas State University library. Center staff provide public education programs on Center activities and hazardous substance management in response to requests as time permits. Printed materials on Center activities are prepared for publication in newspapers and magazines. Print and electronic news media are used to increase awareness by the public regarding their role in hazardous waste management. Media releases describe sources of technical information available to the public, including limited consumer information from the Center and the Center repository. In addition, certain releases contain technical information of benefit to the lay public in proper management of their hazardous wastes. status; Some video materials are available for loan through the Kansas State University library. Center staff have made presentations to groups, participated in radio and TV programs, and interviews with journalists. Several news releases have been prepared and released for publication. Technology Data Base: B.R. Biles, Kansas State University Goal: The goal is to develop a data base of professional expertise in hazardous substance research for the region-pair. Rationale; Information on the expertise of hazardous substance professionals in the consortium universities of the region-pair will be helpful to the Center, government, and industr. Approach; An electronic data base will be -prepared through interviews with hazardous substance professionals. Software has been developed by Kansas State University for this specific purpose. It is presently being used to catalogue expertise within the state supported universities so that sources of expertise are readily available to researchers as well as industry. The information has the potential to be guarded so that those seeking the information may work through a central system to maintain a certain degree of privacy. 101 ------- The Center will use this technique to electronically catalogue sources of expertise within the two regions. Access to the data base will be available on disc (or possibly by modem) to Center participants and appropriate agencies. Availability beyond that will be determined by the Center's advisory committee. statust This project is scheduled to start in year 2. SUMMARY 0? OUTPUTS ZN FY 1989 Refereed Journal Articles Published 0 Articles Submitted or In Press 13 Books and Bound Proceedings 1 Chapters in Books or Proceedings 0 Projects Reports 20 Conferences and Workshops Held 4 TOTAL 38 102 ------- BIBLIOGRAPHY Articles submitted or In Press Berry, N. and J. Schlup, "initial FT-IR studies of the Adsorption of Polycyclic Aromatic Hydrocarbons onto Soil Constituents," Proceedings off the Conference on Hazardous Waste Research. Erickson L.E. (ed.), Kansas State University, Manhattan, Kansas, 1989. Chou, S.T. and L.T. Fan, "Stabilization/Solidification of Low- Level Radioactive Liquid from a BWR Nuclear Power Plant with Pozzolan-Based Fixation Process," Proceedings of the Conference on Hazardous Waste Research. Erickson, L.E, (ed.), Kansas State University, Manhattan, Kansas, 1989. Cunningham, A.B., F. Abedeen, W.G. Characklis, and E.M. Bouwer, "Influence of Microbial Transport on the In-Situ Bioremediation of Organic Groundwater Contaminants," Proceedings of the Conference on Hazardous Waste Research. Erickson, E.E. (ed.), Kansas State University, Manhattan, Kansas, 1989. Dhawan, S., L.E. Erickson, L.T. Fan, P. Tuitemwong, and R. Mahadevaiah, "Microcosm Techniques for Investigating the Biodegradation Potential of Light-Non Aqueous Phase Liquids and Dense-Non Aqueous Phase Liquids," Proceedings of the Conference on Hazardous Waste Research. Erickson, L.E. (ed.), Kansas State University, Manhattan, Kansas, 1989. Gilliland, M.W., W.E. Kelly, and 0. Lokke, "Hazardous Waste Management in Rural Communities in EPA Regions 7 and 8," Proceedings of the Conference on Hazardous Waste Research. Erickson, L.E. (ed.), Kansas State University, Manhattan, Kansas, 1989. Glasgow, L.A., "Some Engineering Considerations in the Venting of Vadose Zone Soils," Proceedings of the Conference on Hazardous Waate Research. Erickson L.E. (ed.), Kansas State University, Manhattan, Kansas, 1989. Huang, Y.L., Y.W. Huang, and L.T. Fan, "An Artificial Approach to the Synthesis of a Mass Exchanger Network for Hazardous Waste Minimization and Treatment,1* Proceedings of the Conference on Hazardous Waste Research. Erickson L.E. (ed.), Kansas State University, Manhattan, Kansas, 1989. Huang, Y.W., L.T. Fan, and W.w. Olson, "Potential Application of Neural Networks to Hazardous Waste Processing," Proceedings of the Conference on Hazardous Waslpe Research. Erickson L.E. (ed.), Kansas State University, Manhattan, Kansas, 1989. 103 ------- Jones, W.L., K.B. Bucklin, A.K. Camper, and P. Stoodley, "Optimization of In Situ Biodegradability of Subsurface Soil Contaminants," Proceedings of the Conference on Hazardous Waste Research. Erickson, L.E. (ed.), Kansas State University, Manhattan, Kansas, 1989. Seybert, R.A., W.P. Waiavender, and L.T. Fan, "Preliminary Evaluation of Carbon Tetrachloride Destruction in the KSU Bench-Scale Incinerator," Proceedings of the Conference or\ Hazardous Waste Research. Erickson L.E. (ed.), Kansas State University, Manhattan, Kansas, 1989. Wu, J.C., L.T. Fan, and L.E. Erickson, "Modeling and Simulation of Bioremediation of Contaminated Soil," Environmental Progress, submitted 1989. Wu, J.C., L.T. Fan, and L.E. Erickson, "Three-Point Backward Finite Difference Method for Solving a System of Mixed Hyperbolic-Parabolic Partial Differential Equations," Computers and Chemical Engineering, submitted 1989. Wu, J.C., L.T. Fan, and L.E. Erickson, "Modeling and Simulation of Bioremediation of Contaminated Soil: A Case Study with Recycle of Nutrient Solution," Proceedings of the Conference on Hazardous Waste Research. Erickson, L.E. (ed.), Kansas State University, Manhattan, Kansas, 1989. Books and Bound Proceedings Erickson. L.E. (ed.), Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, May 23-24, 1989. Project Reports Banerji, S.K. and R.K. Bajpai, "Migration and Biodegradation of Pentachlorophenol in Soil Environment, "Technical Progress Report, Hazardous Substance Research Center for U.S. Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 29, 1989. Clev«ng«r, T.E. and E.J. Hinderberger, "Reclamation of Metal and Mining Contaminated Superfund Sites Using Sewage Sludg«/Fly Ash Amendments, "Technical Progress Report, Hazardous Substance Research Center for U.S. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 27, 1989. 104 ------- Cunninhgam, A.B., W.B. Characklis, and W.L. Jones, "Influence of Microbial Transport Processes on In-Situ Biodegradation of Groundwater Contaminants, "Technical Progress Report, Hazardous Substance Research Center for U.S. Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 15, 1989. Erickson, L.E. and L.T. Fan, "Development of In-Situ Biodegradation Technology, "Technical Progress Report, Hazardous Substance Research Center for U.S. Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 29, 1989. Fan, L.T., "Experimental Study of Stabilization/Solidification of Hazardous Wastes," Technical Progress Report, Hazardous Substance Research Center for U.S. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 29, 1989. Fan, L.T., "Computer-Aided Design and Control of Systems for Treatment of Hazardous Waste and Minimization of Waste Production," Technical Progress Report, Hazardous Substance Research Center for U.S. Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 29, 1989. Ghosh, S., S. Bupp, and L. DeBirk, "Removal of Heavy Metals from Hazardous Wastes by Protein Complexation for Their Ultimate Recovery and Reuse, "Technical Progress Report, Hazardous Substance Research Center for U.S. Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1989. Gilliland, M.W. and W.E. Kelly, "Hazardous Waste Management in Rural Communities in EPA Regions 7 and 8," Progress Report, Hazardous Substance Research Center for U.S. Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1989. Glasgow, L.A., "Vadose Zone Decontamination by Air Injection," Technical Progress Report, Hazardous Substance Research Center for U.S. Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 29, 1989. Harbourt, C.O., "Introduction to Hazardous Waste Management," Progress Report, Hazardous Substance Research Center for U.S. Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1989. 105 ------- Hunter, R.S. and F.D. Culver, "Computer Method to Estimate Safe Level Water Quality Concentrations for Organic Chemicals," Technical Progress Report, Hazardous Substance Research Center for U.S. Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 20, 1989. Keefer, G.B. and G.J. Theis, "Metal Recovery and Reuse Using an Integrated Vermiculite Ion Exchange-Acid Recovery System," Technical Progress Report, Hazardous Substance Research Center for U.S. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30,1989. Kross, B.C., "Removal of Nitrogenous Pesticides from Rural Well Water Supplies by Enzymatic Ozonation Process, "Technical Progress Report, Hazardous Substance Research Center for U.S. Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1989. O'Keefe, T.J., J.W. Watson, L. Chia, and Z. Wang, "The Characterization and Treatment of Hazardous Materials from Metal/Mineral Processing Wastes," Technical Progress Report, Hazardous Substance Research Center for U.S. Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1989. Parkin, G.F. and D.T. Gibson, "Feasibility of In-Situ Anaerobic Bioreclamation of Mixtures of Toxic Chemicals, "Technical Progress Report, Hazardous Substance Research Center for U.S. Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1989. Schlup, J.R., "Adsorption of Hazardous Substances onto Soil Constituents," Technical Progress Report, Hazardous Substance Research Center for U.S. Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1989. Schnoor, J.L. and G.F. Parkin, "Modeling Dissolved Oxygen, Nitrate, and Pesticide Contamination in the Subsurface Environment, "Technical Progress Report, Hazardous Substance Research Center for U.S. Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1989. Visvanath, D.S., K. Shubhender, T.E. Clevenger, and R.K. Puri, "Development, Characterization and Evaluation of Regenerable Adsorbent Material for Treatment of Waste Streams," Technical Progress Report, Hazardous Substance Research Center for U.S. Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1989. 106 ------- Walawender, W.P. and L.T. Fan, "Thermochemical Treatment of Hazardous Wastes," Technical Progress Report, Hazardous Substance Research Center for U.S. Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 29. 1989. Yanders, A.P., K. Shubhender, and R. Puri, "Time Dependent Movement of Dioxin and Related Compounds in Soil, "Technical Progress Report, Hazardous Substance Research Center for U.S. Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1989. Conferences and Workshops Held Two-day Workshop — "Waste Minimization Workshop," St. Louis, MO, April 24-25, 1989. One-day Teleconference — "Ask the Experts: 2nd Annual Hazardous Materials and Waste Management Update," Manhattan, KS, May 10, 1989 (provided by Oklahoma State University). Two-day Conference — "Conference on Hazardous Waste Research," Manhattan, KS, May 23-24, 1989. Three-day Training Course — "Introduction to Hazardous Waste Management," Columbia, MO, August 7-9, 1989. 107 ------- Chapter 5 Western Region Hazardous Substance Research Center ------- Center: Western Region Hazardous Substance Research Center Participants: Stanford University Oregon State University center Director; Perry L. Mccarty Department of Civil Engineering Stanford University Stanford, CA 94305-4020 Phone: 415/723-4131 FAX: 415/723-5599 THE CENTER AT A GLANCE The Western Region Hazardous Substance Research Center (WRHSRC) is a cooperative activity between Stanford University and Oregon State University that was established in February 1989 to address critical hazardous substance problems in EPA Regions 9 and 10. These regions include the states of Alaska, Arizona, California, Hawaii, Idaho, Nevada, Oregon, Washington, and Guam. The objectives of the Center are: 1. To promote through fundamental and applied research the development of alternative and advanced physical, chemical, and biological processes for treatment of hazardous substances in the surface and subsurface environments. 2. To disseminate the results of research to the industrial and regulatory communities, to foster exchange of information with these communities, and to promote a better understanding of the scientific capability to detect, assess, and mitigate risks associated with all aspects of hazardous substance usage and disposal. The research and training activities of the Center fqcus on the major hazardous substance problems in EPA Regions 9 and 10, including chlorinated and non-chlorinated solvents, petroleum products, pesticides, and toxic inorganic ions including heavy metals. Environmental problems from these substances, which often occur in mixtures, result largely from the production of electronic equipment, chemicals, forestry products, and food, as well as mining and military activities, all of which are important in the region-pair. Table 1 below lists key center personnel. 108 ------- Table It Key Personnel in the Center Stanford University Oregon state University D.L. Freyberg J.D. Istok D. Grbic-Galic P.O. Nelson S.M. Gorelick K.J. Williamson P.K. Kitanidis S.L. Woods J.O. Leckie P.L. Mccarty D.W. North M. Reinhard P.V. Roberts The Center receives its base financial support from the U.S. Environmental Protection Agency, but also is supported through grants, contracts, and gifts from other federal agencies, states, municipalities, and industry. A summary of the Center's funds is shown in Table 2: Table 2: Center Budget FUNDING SOURCES FY 1989 FUNDS EPA: Centers Program $2,000,000 Other Government 130,000 Consortium 346,093 Private Sector 186.467 TOTAL * $2,662,560 CENTER DIRECTOR*8 REPORT The Western Region Hazardous Substance Research Center is focusing its activities on the development of alternative and advanced processes for treatment of hazardous substances in the surface and subsurface environment. Two specific goals relating to subsurface contamination are: (1) development of a greater understanding of processes governing the movement and fate of contaminants in groundwater, and (2) development and evaluation of schemes for groundwater clean-up. Contamination of groundwater by hazardous substances is one of the major environmental problems facing the western region and the nation as a whole. The team of researchers assembled in the Center have a long history of research on groundwater problems, so this is a logical topic for the Center to address. In addition, this focus complements the missions of 109 ------- other research centers that address hazardous substance problems, both within Regions 9 and 10 and in other parts of the country. By concentrating on a carefully selected few of the several environmental problems of significance, the center increases its chances of solving important, but complex, problems. This focus also accommodates a multidisciplinary approach to problem-solving, which is vital to the successful resolution of the complex physical, chemical, biological, and geological problems caused by subsurface contamination by hazardous substances. In addition to research on subsurface contamination, the Center is developing new treatment systems that are capable of removing, concentrating, and in some cases, destroying hazardous substances. Such processes are urgently needed to treat hazardous substance-containing waste streams from industries and municipalities. The center's studies on groundwater are helping to define new processes that are potentially applicable in surface treatment systems as well. For example, studies on groundwater processes have lead to the finding that there are naturally occurring microorganisms which can destroy man-made organic chemicals that were previously believed to persist in the natural environment. often these microorganisms grow slowly, or degrade the compounds fortuitously by co-metabolism while consuming other organic materials for food. Efforts are being made to capture this natural ability in engineered systems so that the reaction rates can be greatly increased and the overall process can be better controlled. The development of such advanced treatment systems requires new engineering concepts and increased knowledge about the physical, chemical, and biological processes involved. Again, a team approach is essential to address the various difficult issues inherent in complex technology development. The Center initially supported 14 research projects, six to address subsurface contamination, four to focus on above-ground treatment systems, and four to research basic mechanisms of hazardous substance removal and transformation that are applicable both in above-ground and subsurface treatment systems. Since its inception, five additional projects have been added to the Center's activities. Industries have found the interdisciplinary activity fostered by the Center to be beneficial to the solution of their environmental problems and have consequently contributed funds to support projects conducted by the Center. The U.S. Department of the Navy has also agreed to sponsor a Center project. This is anticipated to be a strongly positive aspect of the Center's program. In addition to research, the Center has fostered training and technology transfer initiatives. Kenneth Williamson, head of the Center's training and technology program, led an effort to determine the training and technology transfer needs throughout the region-pair, through discussions with state and federal regulatory 110 ------- agencies and from input by the Center's Training and Technology Advisory Committee. Several needs emerged: (1) development of a university-based continuing education hazardous substance training program, (2) establishment of an annual hazardous substance conference in the Northwest region, similar to programs presently in operation in California, and (3) a series of seminars to present results of research that has direct application in the field. In response to these needs, two short courses on hazardous substance chemistry and management were given in Oregon, and an advanced workshop was held on chemical transformations in groundwater and biological approaches to in-situ remediation. HIGHLIGHTS FOR 1989 Groundwater contamination continues to be one of the country's most pressing environmental problems. Contamination has resulted from a variety of past activities including seepage from waste storage lagoons and dumps, accidental spills, and leaking underground storage tanks. While preventive measures are now being taken to reduce the incidence of such contamination, the country is faced with the consequences of poor waste practices in the past. Indeed, the majority of designated and potential Superfund sites have groundwater contamination as the major health concern. A major emphasis of the Center's activities is to obtain greater knowledge of natural biological processes, both to obtain a better understanding of how hazardous chemicals move in the natural environment and to take advantage of the natural processes in engineered systems for contaminant control. Biological degradation is particularly attractive as it has the potential for ridding the environment of harmful chemicals, rather than simply moving them from one location to another. To apply biological treatment at contaminated sites, knowledge of interrelated chemical, physical, and geological phenomena is required and research by an interdisciplinary team is essential. There are two particularly exciting research areas that have stemmed from past studies at the Center and elsewhere, and are highlighted here. One is the use of methanotrophic bacteria for in-situ biodegradation of chlorinated solvents. The other is research on the natural degradation of aromatic hydrocarbons in the absence of oxygen. In-8itu Biodagradation of Chlorinated Solvents Among the most prevalent groundwater contaminants are chlorinated organic solvents, such as trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA), gasoline and other petroleum hydrocarbons including benzene, toluene, and xylene (BTX), and a broad group of homocyclic and heterocyclic aromatic compounds that are associated with preserving wood. The latter include polynuclear aromatic hydrocarbons (PAH) and pentachlorophenol 111 ------- (PCP). In the past, it was thought that most of these compounds were not degraded by natural biological processes under the environmental conditions existent in soils and groundwaters. In recent years, however, research by the Center faculty and others has clearly demonstrated that TCE and TCA can slowly disappear in groundwater, as a result of both biological and chemical processes that occur in the absence of oxygen (anaerobic processes). The transformations usually result in the formation of other less-chlorinated products, such as vinyl chloride, dichloroethylene (DCE), 1,1-dichloroethane (1,1-DCA), or 1,1-dichloroethylene (1,1-DCE) and acetic acid. In some instances, complete mineralization to harmless end products is possible but often the final step occurs so slowly that it is difficult to make use of it in an engineered system. EPA researchers John T. Wilson and Barbara Wilson reported in 1985 that when oxygen and natural gas were added to soil, TCE degradation occurred. They showed that the effect resulted from growth of bacteria that consume methane and oxygen in order to derive energy for growth (methanotrophic bacteria). Fortuitously, the enzyme (MMO) used by these organisms to oxidize methane, also initiates the oxidation of TCE by the process of co-metabolism. Subsequently, the TCE intermediate formed is chemically hydrolyzed and the products are converted by other bacteria to harmless end products. As used in this sense, co-metabolism is a process in which the chlorinated compound is incidentally degraded by an enzyme produced by the bacteria to oxidize its primary energy source, in this case methane. Since the organism gains no advantage by degrading the chlorinated compound, the process cannot work unless an energy source is provided. The reaction kinetics are complicated because the co-metabolized compound competes with the primary energy source for this key enzyme. Before it is possible to take commercial advantage of the abilities of these methanotropic organisms, it is necessary to develop a complete understanding of the chemical, biological, and physical processes which occur, and the limitations involved. Toward that end, Center faculty have just completed a four-year laboratory and field study to evaluate the potential for this complex process at the Moffett Naval Air Station in Mountain View, California. In addition to advancing our understanding of the process of co-metabolism, the study sought to demonstrate the potential for using the process in the field, and to develop methods for applying the process to contaminated sites. Methanotrophic bacteria were found to be naturally present at the field site, and when stimulated to grow by the addition of methane and oxygen dissolved in water, they degraded TCE, DCE, and VC. The latter were degraded faster and more completely than the former. Because of the success of this research, several Center projects 112 ------- are now underway to obtain greater fundamental understanding of the several processes involved, and to speed the application of this in-situ biorenediation method at contaminated sites. An industrial site in Michigan has been chosen for an initial full-scale application of the methanotrophic process. The engineering and economic feasibility of applying the process here is being evaluated through a Center project funded with an industrial contract with the company involved and additional EPA support. Through natural biological processes, TCE at this site has been transformed in the groundwater into DCE and VC, compounds that are degraded faster than TCE itself by the methanotrophic process. Subsurface samples have been obtained with the aid of EPA's Kerr Laboratory in Ada, Oklahoma, to determine whether the methanotrophic bacteria of interest are naturally present in this system, and to assess their respective rates of chemical transformations. A computer model is being used to evaluate alternative ways for adding methane and oxygen, and to select the best operating procedures for the system. One of the significant findings from past studies is the important effect on the rate of groundwater mineral movement when contaminants are sorbed onto these minerals. A new finding is the relatively slow rate at which some chemicals desorb from ground- water minerals, a fact that has important implications for any engineered solution to a subsurface contamination problem as well as for in-situ biodegradation. The sorptive properties of aquifer material at the Michigan site are being studied because of this need. In addition, two Center projects are specifically addressing the question of just how sorption affects the rates of biological degradation. In many subsurface clean-up schemes, contaminated water is pumped to the surface, and volatile organic compounds such as TCA, TCE, DCE, and VC are air stripped and transferred either to the air or onto sorbing material such as activated carbon. Vapor extraction is another process used. In an above-ground surface reactor, biodegradation of the contaminants so removed could lead to their destruction, thus achieving a permanent remedy. Toward this end, one Center project is developing basic information on mass trancf«r and kinetics of biodegradation of chlorinated solvents for application in surface reactors. In enter to implement engineered systems to reduce ground- water contamination, strategies are needed to detect and assess the presence of groundwater contaminants and to design reliable and cost-effective mitigation schemes. Two Center projects are directed towards satisfying these needs. The projects specifically consider the great uncertainties involved in groundwater 113 ------- remediation because of the complexity and variability of subsurface geology. These studies will aid in the design of in-situ bioremediation schemes, such as methanotrophic oxidation, as well as other cleanup approaches. Such studies by the Center cover short term and long term needs for the remediation of contaminated groundwaters and for treatment of contaminated water supplies as well. The approach being taken is to develop a basic understanding of the physical, chemical, and biological processes involved, and to develop as rapidly as possible engineered applications that make use of these processes. The new approach of using co-metabolism for degradation appears very promising for permanent disposal of chlorinated solvents, which are among the most prevalent, difficult, and costly hazardous substance problems before the country. Anaerobic Biological Transformations of Aromatic Compounds Leakage of gasoline and other petroleum hydrocarbons represents another major source of subsurface contamination. Of the many components in gasoline, the compounds benzene, ethylbenzene, toluene, and xylenes (BTX) are the most soluble in water and thus are the ones most commonly found as groundwater contaminants. These aromatic compounds, so named because they all contain the benzene ring structure, are readily degraded by bacteria when oxygen and other inorganic nutrients required for bacterial growth are present. However, oxygen often is deficient in groundwater because of lack of contact with air, and for this reason, aromatic compounds often persist for years. While it has been clearly demonstrated that natural microorganisms exist that can degrade aromatic hydrocarbons such as BTX in the absence of oxygen, the rates are slow, and very little is known about the microorganisms involved or of their biochemistry. Through previous studies by Center faculty and their students, disappearance of BTX under anaerobic conditions was first observed at landfill leachates from North Bay, Canada, and was confirmed through laboratory studies. Aromatic hydrocarbons are also common contaminants in wood preservatives, such as creosotes, and in wastes from consumer-gas production plants, widely used in the past. Recent studies by Center faculty have demonstrated some of the aromatic hydrocarbons in these wastes are also slowly degraded in groundwater under some conditions. Anaerobic degradation of pentachlorophenol, which is another important wood preservative, has also been found. The recent observations that other highly chlorinated aromatic compounds such as polychlorinated biphenyls (PCBs), can be transformed in the absence of oxygen as well, have led to 114 ------- considerable interest in anaerobic processes. Chlorine atoms from highly chlorinated compounds are often removed faster under anaerobic conditions than aerobic conditions. These very recent and important findings indicate that under the proper conditions, some groundwater contaminants of concern will naturally disappear with time so that no costly remediation will be required. If we had the ability to predict when and where such degradation would occur, then scarce financial resources could be used elsewhere to solve more intractable problems. Also, the potential exists for engineered approaches to speed along these natural processes. This requires a much better scientific understanding of the microorganisms involved, pathways of degradation, and factors affecting rates of reaction. Several of the Center projects have these objectives in mind. In aerobic systems, bacteria use oxygen to oxidize organic compounds for energy. In the absence of oxygen, there are bacteria that can use alternative oxidants (electron acceptors) such as nitrate, sulfate, or carbon dioxide. The bacteria capable of using these different oxidants are themselves quite different as is their biochemistry. A potentially important group of anaerobic bacteria are the sulfate reducers because sulfate is commonly found in groundwater. However, knowledge about their ability to degrade aromatic compounds is almost nonexistent. For this reason, three Center projects are concerned with biotransformation of aromatic compounds under sul fate-reducing conditions. One is directed towards evaluating the degradation of chlorinated aromatic compounds in pulp mill bleaching effluent, and the other is directed towards the polycyclic compounds (PAHs) that are commonly present at creosote sites and consumer gas plants. Another Center project funded by the U.S. Navy and the Orange County Water District is directed towards understanding factors affecting rates as well as nutrient requirements in BTX destruction by the different groups of bacteria that use nitrate, sulfate, or carbon dioxide as oxidants. These studies are difficult because of the necessity to exclude oxygen from the cultures, and the slow rate of organism growth and adaptation to these hydrocarbons. However, because of the long residence times of groundwaters , transformation processes that are very slow can be quite significant, and thus are worth understanding. In spite of the slow and complex nature of this research, significant progress is being made. International A significant event co-sponsored by the Center this year was the International Symposium on Processes Governing the Movement and Fate of Contaminants in the Subsurface Environment. This three-day meeting, held at Stanford University on July 23 to 26, 1989, was also sponsored by the International Association on Water Pollution 115 ------- Research and Control, with financial support from EPA, the National Science Foundation, and the U.S. Geological Survey. The purpose of the meeting was to bring together leading research scientists and engineers from around the world to evaluate the current knowledge about the processes that affect the way in which chemicals interact with the soil, move with the flow of water and air through the subsurface environments, and are transformed or degraded by both abiotic and biotic processes. A total of 175 individuals attended the meeting, including 28 foreign participants from 14 different countries. There were 35 oral and 40 poster presentations. The symposium focused on the physical, chemical, and biological processes that are most important to chemical migration and transformation in both the saturated and unsaturated zones. Considerable scientific interaction occurred at this meeting, and it sharpened the focus of the Center faculty, staff, and students on the important issues requiring further research. The symposium was highly successful in meeting its objectives. SUMMARY OF ONGOING PROJECTS Investigators Project Title Above-Ground Treatment Systems Reinhard, McCarty, Treatment of Complex Mixtures Roberts, Grbic'-Galic', Leckie McCarty, Roberts Oxidation of Chlorinated Solvents by Methanotrophs Woods Interactions Between Electron Acceptors in the Treatment of Wastewaters Containing Sulfate, Chlorophenols and Acetate Williamson, Nelson Enhancing Biodegradation with Sorption and Alternating Aerobic/Anaerobic Environments julyurface Assessment and Treatment Kitanidis Detection and Assessment of Subsurface Contamination Corelick Design of Reliable and Cost-Effective Mitigation Schemes 116 ------- Roberts, Kitanidis Reinhard, Roberts Istok, Woods McCarty, Reinhard McCarty, Roberts Reinhard, McCarty Kitanidis, Freyberg Reinhard, McCarty Spatial Distribution and Mass Transfer of an Organic Liquid Contaminant in a Porous Medium Gaseous Stripping of Nonaqueous Liquids from the Vadose Zone Development and Verification of a Numerical Model to Predict the Fate and Transport of Chlorinated Phenols in Groundvater In-Situ Biological Treatment of Aromatics in Groundwater In-Situ Bioremediation of Chlorinated Aliphatics with Methanotrophs The Effect of Surfactants on Biodegradation of Chlorinated Biphenyls in Soils FASTCHEM Application and Sensitivity Analysis Long Term Chemical Transformation of 1,1,1-Trichloroethane (TCA) and Freon 113 under Aquifer Conditions Mechanistic Studies Grbic'-Galic' Mccarty, Roberts Leckie Reinhard Anaerobic Microbial Transformation of Homocyclic and Heterocyclic Polynuclear Aromatic Hydrocarbons Effects of Sorption on Biodegradation of Halogenated Organics Trace Metal Removal Processes Abiotic Dehalogenation of Haloaliphatic Compounds in Aqueous Solutions Containing Hydrogen Sulfide 117 ------- Training and Technology Transfer McCarty, Roberts International Symposium on Processes Governing the Movement and Fate of Contaminants in the Subsurface Environment Williamson, Nelson Fundamentals of Chemistry of Hazardous Substances Williamson, Nelson, Fundamentals of Hazardous Substances Istok, Woods Grbic'-Galic, Biological Transformation of Chlorinated McCarty, Roberts, Solvents in Subsurface Systems Semprini PROJECT DESCRIPTIONS Above-Ground Treatment Systems Treatment of Complex Mixtures: M.R. Reinhard, P.L. McCarty, P.V. Roberts, D. Grbic'-Galic1, and J.O. Leckie, Stanford University Goal: The long term goal of this project is to develop a computer based information system which can be used to develop criteria for choosing appropriate treatment combinations for complex wastes. Rationale; Waste streams and waters containing complex mixtures generally cannot be treated using a single treatment process. Depending on the types of contaminants present and their physical, chemical, and biological properties, combinations of several different processes must be employed. Approach; A computerized data base will be developed which may be used to retrieve or to estimate the compound properties that are relevant for assessing their behavior in treatment systems, such as physico-chemical properties of contaminants, energetics concepts for evaluating the thermodynamic feasibility of biotransformations, and correlations for estimating mass transfer rate coefficients. Status: Presently, two chemical information systems, EICHEM and SECHEN are being employed. These were developed at the Technical University in Munich. Dr. Drefahl, the developer of the two systems, has joined the Center and is currently in the process of setting them up. EICHEM is capable of estimating a range of environmentally relevant substance properties, such as n-octanol/water partition coefficients, vapor pressure, and heat 118 ------- of evaporation, on the basis of substituent constants. SECHEM is designed to evaluate contributions of substructures based on discriminant analysis techniques and a test set of data. Work during this project period is focusing on the implementation of algorithms which consider the effect of solution variables, such as cosolutes, temperature, pH, and ionic strength, on solute properties. In future work, programs for the evaluation of contaminant behavior in treatment processes will be developed. Oxidation of Chlorinated Solvents by Kethanotrophss P.L. Mccarty and P.V. Roberts, Stanford University Goal; Methanotrophic bacteria, which oxidize methane for energy, have been found capable of oxidizing chlorinated solvents by co-metabolism. The goals of this project are: (1) to obtain a better basic understanding of the relationship between the relative concentrations of methane and chlorinated compounds and the overall chlorinated solvent degradation rate, (2) to assess the importance of mass transfer limitations to methanotrophic reactions, and (3) to use the knowledge gained about reaction kinetics and mass transfer limitations to determine the most suitable reactor design for enhancing chlorinated solvent degradation. Rationale: There are many current attempts to devise treatment processes for degrading chlorinated aliphatic compounds. However, there is a lack of basic understanding of the factors affecting reaction rates for co-metabolized compounds. In addition, since the energy substrates, methane and oxygen, and the contaminants are all poorly soluble in water, mass transfer properties of treatment systems become of great significance. Approach! It is hypothesized that oxidation rates for methane and chlorinated contaminants can be described by a competitive inhibition model. Here, the rate limiting step is the oxidation of either methane or TCE by methane monooxygenase (MMO). To evaluate this hypothesis, reaction coefficients for methane and TCE alone are being evaluated using a mixed methanotrophic culture derived from the Moffett Field aquifer. Reaction rates when they are used in combination will then be predicted and measured in order to test the hypothesis. In mass transfer studies, model calculations are being made for a variety of fixed-film reactor configurations in order to determine flow patterns that are realistic and optimal for given treatment objectives. These calculations consider mass transfer effects and biological reaction kinetics. The model results are expected to guide reactor design as well as help to determine important knowledge gaps that may be in need of further research. 119 ------- statusi Preliminary laboratory studies have been conducted to determine basic reaction coefficients for methane and trichloroethylene utilization alone by methanotrophs. Model calculations have been carried out for a fluidized bed reactor, and results are being evaluated to determine where knowledge gaps may exist. Interactions between Electron Acceptors in the Treatment of Wastewaters Containing Sulfate, Chlorophenols and Acetate: S.L. Woods, Oregon State University Goal; The goal of this project is to develop and verify a mathematical model for anaerobic biodegradation in the presence of competing electron acceptors. Biodegradation constants will be measured to describe sulfate reduction, acetate fermentation, and reductive dechlorination. Resulting kinetic expressions and constants will be used to: (1) develop an effective anaerobic biological treatment process for wastewaters from the pulp and paper industry, (2) model sequential reductive dechlorination of chlorophenols in soils, and (3) model the anaerobic/aerofc_c treatment of chlorophenols in biological wastewater treatment systems. Rationale; A better understanding of biodegradation in the presence of multiple substrates is needed. Additionally, kinetic constants for biodegradation are necessary to understand the fate of hazardous wastes in soils and to develop bioremediation or wastewater treatment systems. Approach: Progress curves for compound biotransformation are generated in batch reactor systems, and biodegradation constants are determined by fitting a mathematical model to the progress curves generated under varying initial conditions (concentrations of acetate, sulfate, and chlorophenols). The initial biomass is held constant. The reactor system has been designed and constructed to permit strictly anaerobic transfers. The system consists of two 9-liter mother reactors and 2-liter batch reactors. The mother reactors are operated at a 10 hour hydraulic retention time. The first reactor is fed a solution of pentachlorophenol, acetate, and nutrients. The second reactor is fed a similar solution except for the addition of sulfate. Progress curves are developed with the 2-liter batch reactors. statusi S«v«ral batch experiments have been conducted. Reductive dechlorination of pentachlorophenol has been observed in the presence and absence of sulfate. Experimental work is continuing to evaluate biodegradation kinetics under varying initial conditions. Completion of the project is expected in February 1992. 120 ------- Enhancing Biodegradation with florption and Alternating Aerobio/Aaaerobia Environment*: K.J. Williamson, P.O. Nelson, Oregon State University Qoalt The goal of this project is to develop and verify a mass transport and biokinetic model of the sorption and biological degradation of chlorophenols by an aerobic-anaerobic layered biofilm on granular activated carbon. Rationale! Granular activated carbon (GAG) has been shown to be useful for enhancing biological treatment of toxic organic compounds by adsorption, resulting in reduced aqueous concentrations to below inhibitory levels. This enables biological degradation by both suspended bacteria and the biofilm attached to the GAG. Haloaromatic compounds undergo different biodegradation pathways under anaerobic and aerobic conditions. Either anaerobic or aerobic pathways may result in the production of metabolites that cannot undergo further metabolism in that particular pathway. It may be possible to increase the potential for biodegradation of these compounds and their metabolites by alternating their exposure to aerobic and anaerobic conditions. GAG will serve as an adsorbing medium for the halogenated organic compounds and their metabolic products that do not undergo rapid biodegradation. GAG will also serve as a support medium for the biofilm to allow physical separation from the liquid stream and transfer between aerobic and anaerobic environments with a controlled frequency. Approach: The project has been broken down into several individual tasks to meet the overall project goal. The tasks are: (1) determine the aerobic biodegradation kinetics of chlorophenols in batch biological reactor experiments, (2) determine the anaerobic biodegradation kinetics of chlorophenols in batch biological reactor experiments, (3) measure the sorption and desorption kinetics and equilibria of chlorophenols on granular activated carbon in complete-mix batch reactors, (4) investigate the combined sorption-biodegradation of chlorophenols sorbed on GAG in alternating aerobic-anaerobic complete-mix flow reactors, and (5) develop a combined kinetic model. Status* Experiments are in progress for the first three tasks identified above. Reactors are being designed for the experiments in task four. Individual components of the combined kinetic model are under development for representing the results of aerobic biodegradation, anaerobic biodegradation, and sorption experiments. Expected completion date for the project is February 1991. 121 ------- Detection and Assessment of Subsurface Contamination: Peter K. Kitanidis, Stanford University Goal; The thrust of this project is the development of better techniques for characterizing contaminated sites. Objectives include the development of better methods for the detection and assessment of groundwater contamination and the determination of the mechanisms and parameters which govern the transport and fate of pollutants. Another important objective of this project is to develop practical methods for determining the effective properties of heterogeneous media from measurements of the local parameters. Rationale: There is seldom enough information to determine with certainty the precise values of all parameters, especially at the local scale. Measurements of some critical transport parameters, such as hydraulic conductivity, indicate variability of orders of magnitude over short distances. Other parameters, such as thermodynamic constants and rate coefficients, are also quite variable. In many cases, one is interested in the "effective" parameters of the heterogeneous formation, meaning those which govern the net or "macroscopic" rate of advection, dispersion, and chemical attenuation, rather than the highly variable local rates. Approach; The developed approach combines measurements, mechanistic models describing the transport and fate of pollutants, and statistical methods. In recognition of spatial variability and scarcity of information, the parameters which determine flow transport and fate of solutes, such as conductivity, retardation, and reaction coefficients, are characterized in statistical terms. The mathematical formalism of random functions is used to describe spatially variable quantities through statistical moments, such as mean and covariance functions. These moments are obtained from data and other information using geostatistical techniques. Then, through the governing flow and mass transport equations, the statistics of solute concentration can be derived. These methods are applied to two problems of practical interest: the evaluation of the macroscopic or field-scale flow and transport parameters and the conditioning of predictions on data. Status: Initial efforts have focused on determining the relation between the measurable but highly erratic local parameters and the effective parameters which govern the flow and solute transport at macroscopic scales of interest. Significant progress was achieved in the problem of effective conductivities. Consider the problem of flow in a porous medium with hydraulic conductivity which fluctuates locally about a mean value. The flow is unsteady but gradually varying, i.e., the scale of head fluctuations is 122 ------- larger than the scale of hydraulic-conductivity fluctuations. The equations have been derived which must be satisfied by the effective conductivity tensor under general conditions using a method of volume averaging and spatial moments. The effective conductivity is defined as the conductivity of a fictitious homogeneous medium which would effect the same rate of spreading on a pressure mound as the actual heterogeneous medium. The key result of the analysis was that the effective conductivity matrix of the hydraulically heterogeneous medium is given by solving a well-defined boundary value problem and carrying out an integration. Even if those have to be performed numerically, this approach is potentially a significant improvement over other numerical methods. Another numerical method is being developed which takes advantage of the structure of the problem at hand. Work is also progressing on the problem of effective dispersion coefficients. Design of Reliable and Cost-Effective Mitigation Schemes: S.M. Corelick, Stanford University Qoalt The aim of this project is to develop and test methods for design of pump-and-treat aquifer remediation systems. These methods can target reliable strategies that identify the best well locations and pumping rates to successfully capture contaminant plumes. Reliable strategies also must be made cost effective by determining the lowest pumping rates that assure contaminant capture. Rationale: Simulation models can be powerful tools for designing aquifer remediation schemes. Unfortunately, there is tremendous uncertainty associated with our predictive models of subsurface contaminant transport, even for substances whose chemical behavior is well understood. This uncertainty stems from the spatial variability of aquifer properties which dictate flow. Given this uncertainty, one must over-design any pump-and-treat system. Knowledge of the nature of simulation model uncertainty and the development of risk-based design strategies are therefore essential. Approach: The project is being conducted in cooperation with Environment Canada. Efforts focus on the Gloucester Special Waste Compound in Ontario, Canada. In 1989, work began to design a pump-and-treat remediation scheme for this research site which contains hazardous organic solvents. The best remediation design requires optimal well selection and the determination of optimal pumping rates. This research team approaches the problem by developing stochastic simulation models based upon available field data, then combining these models with nonlinear optimization methods in order to identify reliable strategies. Model parameter 123 ------- uncertainty is considered as an indicator of design reliability. In this approach, model parameters are first described statistically and these statistical measures of uncertainty are then used to overdesign the remediation system. Status: Preliminary analysis of the hydraulic and chemical field data for the Gloucester site has been completed. A stochastic simulation model of the site is currently under development. The model is a two-dimensional plan view finite-element simulation model in which the transmissivity, porosity, and dispersivitiy are considered the critical uncertain parameters. Geologic characterization is complete and calibration of the model is underway. Completion is expected by 3/92. Spatial Distribution and Mass Transfer of an Organic Liquid Contaminant in a Porous Medium: P.V. Roberts and P.Kitanidis, Stanford University Goal; The goal of this project is to improve understanding of the physical processes that govern the distribution and mass transport of residual organic liquid contaminants in the subsurface, in par- ticular the effects of mass transfer limitation and heterogeneity. Rationale; These phenomena are believed to influence significantly the design and economics of groundwater quality restoration efforts in situations where immiscible organic liquids have contaminated the subsurface. Approach; This project will proceed by formulating a conceptual model for the distribution of the residual liquid, applying interphase mass transfer models to the situation of a uniform medium, testing the models against the results of laboratory experiments, and developing mathematical models to simulate behavior in nonuniform media. Status; The evaluation of mass transfer of residual liquid contaminant phases has commenced with the development of a simple conceptual model which envisions the residual contaminant as being held in the form of pendular rings in the narrow spaces surrounding the solid contact points. The relationship between the relative saturation and the interfacial area for various packing geometries has been calculated under these idealized conditions. A manuscript in preparation summarizes the basic theory and results of the preliminary computations, and points out the implications for groundwater contamination problems. Also, a new modeling approach was developed for simulating transport of a sorbing solute under conditions of spatially variable retardation; a closed-form analytical solution was obtained using the method of small perturbations (Chrysikopoulos, Kitanidis, and Roberts, 1989). 124 ------- Gaseous stripping of Nonaqueous Liquids from the Vadose zona: M.Reinhard, P.V. Roberts, Stanford University Goal: The goal of this project is to develop an understanding of the basic processes which govern the behavior of organic vapors in the unsaturated zone. Rationale» Vapor stripping has become a widely used method for removing volatile organics from the subsurface. However, there is no basis for assessing when conditions are favorable for this procedure, nor is there any way of predicting the rate of contaminant removal. Approacht Chromatographic columns packed with aquifer material and model sorbents are being used to simulate vapor phase sorption in the vadose zone. The data will be used to to evaluate the existing transport models. Statusi Two similar vapor sorption systems consisting of a soil column connected to a gas Chromatographic detector have been constructed and tested. Work with two aquifer materials and several model solids is expected to be completed in early 1992. Development and Verification of a Numerical Model to Predict the Fate and Transport of Chlorinated Phenols in Groundvatert J.D. Istok and S.L. Woods, Oregon State University Goal: The objectives are to develop a numerical model to predict the fate and transport of 2,4-dichlorophenol, pentachlorophenol, and their primary anaerobic degradation products in field soils and groundwater aquifers, and to verify the model using laboratory and field experiments. Rationale: Predictive models are needed for site characterization and to design effective biological remediation strategies. Approach! A preliminary mathematical model was developed based on processes of advection, dispersion, diffusion, sorption, and anaerobic degradation for each solute species in the anaerobic degradation pathway for pentachlorophenol, an electron donor (acetate), and biomass. Monod kinetics and a "macroscopic bulk concentration" concept are used to describe growth. The resulting set of nonlinear differential equations are solved by the finite difference method. Experiments are conducted using a Chehalis soil in batch reactors, columns, and in large soil tanks consisting of an aluminum box (2m wide x 4 m long x 20 cm deep) supported by a steel framework. The tanks each hold 1500 kg of soil and are designed to provide controlled temperature, atmosphere, and water pressure and flow rate during long-term (many months) experiments. The tanks are instrumented with pressure and temperature sensors and sampling ports for liquid, solid, and gas phases. 125 ------- status: Soil samples have been collected from an uncontaminated site. Batch sorption experiments with chlorophenol to determine sorption kinetics and equilibrium have been completed. Continuous flow column experiments are underway and should be completed by February 1990. The results will be used to validate numerical models of movement and transformation, following which larger-scale studies in the tanks are planned. In-aitu Biological Treatment of Aromatics in Groundvater: P.L. Mccarty and M. Reinhard, Stanford University Goal: This project attempts to evaluate the rate of aromatic hydrocarbon biotransformation under methanogenic, sulfate, and nitrate reducing conditions under field and laboratory conditions, and to assess the potential of these processes for aquifer remediation. Rationale: Although most gasoline constituents are readily degraded under aerobic conditions, the groundwater environment impacted by the gasoline spills is typically anaerobic, thus precluding aerobic degradation pathways. In the absence of oxygen, there is the potential that alternate electron acceptors, such as nitrate, sulfate, and carbon dioxide may be utilized. Approach: This study is a combined field and laboratory study. The laboratory study concerned with anaerobic biotransformation is being conducted at the Center. Laboratory studies concerned with aerobic conditions are being conducted at the Laboratory of the Orange County Water District (OCWD) in Southern California under the direction of Dr. Harry F. Ridgway. The field study is being conducted at the Seal Beach field site which is near the OCWD laboratory. In the field studies, degradation rates will be determined in 30 L bioreactors which will be emplaced in the ground at the site. Both aerobic and anaerobic conditions will be studied. Status: The laboratory studies have focused on the growth conditions of denitrifying microorganisms which utilize aromatic hydrocarbons as their sole carbon and energy source. At the field site, a mobile laboratory is being developed and within the next few months, the reactors will be installed and instrumented. In-8itu Biorraediation of Chlorinated Aliphatic* with Methanotrophss P.L. Mccarty and P.V. Roberts, Stanford University Goal: The goal is to evaluate the feasibility of remediating a groundwater contaminated with trichloroethylene (TCE), dichloroethylene (DCE), and vinyl chloride (VC) through stimulation of the growth of indigenous methane oxidizing bacteria (methanotrophs). 126 ------- Rational*: A four-year field steady of in-fiitil biodegradation of chlorinated solvents by methanotrophs at the U.S. Navy Moffett Field site, funded by EPA and conducted by Stanford University, demonstrated the potential of this process for aquifer clean-up. Stimulation of the growth of indigenous methanotrophs at this site by injection of water containing dissolved methane and oxygen resulted in in-situ degradation of chlorinated aliphatic compounds injected into the aquifer. The next step in application to full-scale is a technical and economic evaluation of the feasibility of the process, as is being conducted here. Approach: A contaminated groundwater site in Michigan was found to have suitable conditions of aquifer homogeneity and permeability, distribution of TCE, DCE, and VC contaminants, and access to make in-situ bioremediation attractive. Aseptic samples of aquifer material from two separate wells were obtained from this site with the assistance of the EPA Robert S. Kerr Environmental Research Laboratory, Ada, Oklahoma. The possible presence of indigenous methanotrophic bacteria and their rates of chlorinated chemical transformation are being determined through laboratory studies with these materials, as are their sorptive properties. Computer simulation models will be used to help design a treatment strategy that will be used by the engineering firm involved in a comparative evaluation of in-situ bioremediation with other treatment alternatives. Status: Aquifer samples have been obtained and laboratory studies have been initiated. The feasibility study should be completed by June 1990. The Effect of surfactants on Biodegradation of Chlorinated Biphenyls in Soils: M. Reinhard and P.L. Mccarty, Stanford University Goal; The goal of this study is to develop a data base which can be used to judge the feasibility of surfactant treatment of PCB contaminated soils, and to study the effect of surfactants on the aerobic biotransformation of PCBs. Rationale: Addition of surfactants has been proposed as a means to desorb and solubilize hydrophobic contaminants in groundwater aquifers and from contaminated soils. Because sorption of PCBs onto solids Bay slow or prevent biotransformation, solubilization using surfactants followed by biotransformation is a potential treatment scheme to purify soils contaminated by PCBs. Approach: First, PCB sorption onto a sorbent such as diatomaceous earth will be studied using a single PCB congener, such as para- chlorobiphenyl (PCB). Then, a microbial culture will be developed (derived from the Palo Alto Sewage Treatment Plant) which is capable of degrading PCB. Finally, the effect of surfactant on the biotransformation rate will be studied with and without solids added. 127 ------- statust Currently, analytical quality assurance and control protocols are being developed and current models of the solubilization process are being reviewed. The expected completion date is September 1990. FASTCHEM Applications and Sensitivity Analysis: P.K. Kitanidis and D.L. Freyberg, Stanford University Goalt FASTCHEM is a collection of computer programs which can be used to predict the advection, dispersion, and geochemical transformation of chemicals emanating from utility waste disposal sites. The objectives of the work to be performed include: (i) quantifying the sensitivity and uncertainty of predicted parameters, and (2) developing a set of computer programs which apply state-of-the art estimation methods for the interpolation of parameters from sparse measurements. Rationalei Amendments to the Resource Conservation and Recovery Act in 1984 and reauthorization of the Safe Drinking Water Act in 1986 have prompted the formulation of several new regulations to protect groundwater quality. To respond to new regulations and to develop a capability to assess the potential success of remedial actions, the Electric Power Research Institute (EPRI) has supported the development of the interim hydrogeochemical modeling package FASTCHEM. This package of codes can be used to simulate the advection, dispersion, and chemical attenuation of inorganic chemicals that may be leached from electric utility waste disposal sites. EPRI is interested in determining the applicability the model and in incorporating subroutines for the utilization of data. Approach: The model's sensitivity and uncertainty will be evaluated using first-order analysis and Monte Carlo simulations. Methods for incorporating available measurements will be based on linear estimation methods. status: Since the project was initiated in September 1989, the computer codes have been installed and tested. Next, the sensitivity and uncertainty of predictions will be evaluated. Long Term Cneaical Transformation of 1,1,1-Trichloroethane (TCA) and Freon 113 under Aquifer Conditions: M.Reinhard and P.L. Mccarty, Stanford University Goal: This project is designed to determine the transformation rate of TCA and Freon 113 under conditions closely simulating those of a contaminated aquifer. 128 ------- Rational*i It is generally difficult to determine transformation rates occurring at contaminated field sites from field data because of uncertainty about the input, the variability of the data, and the lack of mass balances. Moreover, extrapolation of laboratory data obtained in pure water to field conditions is fraught with uncertainty, because environmental factors such as the role of sorption and nucleophilic and redox active reagents are not considered in pure water experiments. Therefore, laboratory experiments are needed which simulate the natural conditions, and which allow us to determine products, accurate mass balances, and rates. Approacht TCA and Freon 113 will be added to flame sealed vials which contain groundwater and sediment from the site and the organic contaminants at realistic concentrations. The glass vials will be incubated at ambient temperature and disappearance and product formation will be analyzed at regular intervals over a period of four years. Status; All quality assurance and control protocols have been developed, the soil and the water have been characterized, and the rate experiment will be set up in the near future. The project should be completed in 1993. Mechanistic studies Anaerobic Microbial Transformations of Romocyclic and Hetarocyclic Polynuclear Aromatic Hydrocarbons: 0. Grbic'-Galic', Stanford University Goali Recently, this research team demonstrated that monoaromatic hydrocarbons such as toluene and benzene, and some of the nitrogen- and sulfur-heterocyclic polynuclear aromatics such as quinoline or benzothiophene, could be anaerobically degraded by complex microbial communities derived from groundwater aquifers or from municipal sludge, under the conditions of methanogenic fermentation. The goal of this project is to investigate the capabilities of bacteria under two types of strictly anaerobic conditions — sulfate-reducing and methanogenic — to transform polynuclear aromatic hydrocarbons (PAH), more complex nitrogen and sulfur hetsrocycles, and oxygen heterocycles (NSO-compounds). The transformation routes, intermediates, and products are to be studied for single compounds of interest, as well as for mixtures of compounds, such as occur in real contamination incidents. Rationale: PAH and NSO, which are constituents of fossil fuels and creosote and are also formed through incomplete combustion processes, are common environmental pollutants characterized by relative chemical stability, toxicity, and potential carcinogenicity. These compounds had been shown to biodegrade efficiently due to the activity of aerobic microorganisms, in the 129 ------- presence of molecular oxygen which serves as a reactant for the PAH or NSO oxygenation and also as an ultimate electron acceptor for the microorganisms. However, oxygen is frequently limited — and sometimes completely absent — in certain contaminated habitats, such as numerous ground water aquifers. Therefore, it is of interest to learn how significant the anaerobic microbial processes may be in determining the fate of PAH and NSO in anoxic environments, how complete the anaerobic transformations of these compounds are, and whether the intermediates and products of these transformations are more or less hazardous than the parent compounds. Approach; It is hypothesized that relatively small PAH and NSO molecules (such as naphthalene, acenaphthene, acridine, dibenzothiophene, etc.) are amenable to anaerobic microbial transformations, and that the transformation routes are similar to those determined for monoaromatic hydrocarbons and simpler heterocycles under identical conditions. It is not known how PAH and NSO influence the transformation of one another in complex mixtures, where the interactions may range from transformation inhibition, over sequential transformation, to acceleration (through cometabolism, or other mechanisms) of transformation of certain compounds by other compounds in the mixture. In order to evaluate the hypothesis and answer these questions, batch microcosms containing single PAH or NSO or mixtures thereof as substrates, and sulfate or carbon dioxide as electron acceptors, are being studied. These microcosms contain microbial inocula derived from PAH- and NSO-contaminated ground water aquifers, or from stable methanogenic cultures degrading aromatic hydrocarbons, which were developed in this laboratory. Several different analytical techniques (gas chromatography, high performance liquid chromatography, and GC/mass spectrometry) and 14C-labeling of the substrates, are used to detect and identify the intermediates and products of transformation, and to follow the degradation of substrates over time. The most active microcosms will be used to inoculate larger-size microcosms (batch-fed glass columns containing saturated aquifer material) in which the transformation processes on a larger scale can be evaluated. They will be used also to attempt to enrich stable suspended cultures of the active microorganisms, in which details of the transformation pathways and mechanisms of interactions in mixtures can be studied. Status: Batch microcosm studies are underway and the tested microbial inocula have been shown to transform some of the model substrates under anaerobic conditions. Degradation routes for these compounds are being determined. Upon completion of this stage of research, the scale-up of microcosms to column size, as well as enrichment of suspended microbial cultures, will be undertaken. 130 ------- Effect* of Sorption on Biodegradation of Halogenated Organ!cs: P.L. McCarty and P.V. Roberts, Stanford University Goa^i The goal of this project is to determine how compound sorption onto solid surfaces such as soil and sorption media (e.g., activated carbon) affects the rates of biological degradation of organic compounds. Rational*t Rates of biodegradation of organic compounds are known to be affected by sorption onto surfaces, but the nature of this effect is not well understood. Whether it enhances or reduces transformation rates appears to depend upon properties of the sorbed compound, the surface to which it is sorbed, and the biological process involved. Greater knowledge of the effect of sorption is needed in order to better predict fate of chemicals in the environment, and to devise treatment schemes where sorption is involved. Approach; An experimental approach is being used to determine the availability of trichloroethylene (TCE) to biological degradation by methanotrophic bacteria. First, biotransformation kinetics for methanotrophic oxidation of TCE are being determined, using existing laboratory cultures derived from the Moffett Field site, and then parameters associated with sorption kinetics of TCE on a well-defined synthetic media (silicalite) as well as aquifer solids are being determined. A numerical model is also being developed to relate desorption and biotransformation kinetics, using the hypothesis that transformation rates are directly related to solution concentration of TCE. If this hypothesis does not prove correct, then alternative hypotheses that are consistent with experimental results will be sought and tested. Statust Preliminary kinetic studies of methanotrophic transformation of TCE have been completed, as has been the development of sorption isotherms on aquifer material and silicalite. Preliminary biodegradation rate studies have also been conducted with sorbing solids present. Progress is on schedule. Trace Metal Reaoval Processess J.O. Leckie, Stanford University Goal: The long term goal of this project is to develop a mathematical model of mass transport limited adsorption of toxic trace metal* in porous particles. The premise is that hydrous metal oxide particles with the proper pore structure can be used to concentrate and remove the trace metals in engineered processes. Rationale! Previous experimental work with both porous and nonporous particles indicates that the porous particles can dramatically increase the capacity for removal of the trace toxic metals from solution. The engineering application of particles 131 ------- with tailored pore size distributions could provide a means of removing the trace metals in a sufficiently concentrated form to allow economic recycle where appropriate. Approach: The approach taken on this project involves the design and implementation of a parametric study of the adsorption of cadmium and selenite onto porous amorphous alumina particles. The first phase of the project involves the physical-chemical characterization of the alumina particles, including particle size distribution, pore size distribution, site density, specific surface area, surface acidity constants, and the surface complexation constants for the trace elements. The second and longest phase will be the experimental work evaluating the mass transfer limited adsorption process. On the basis of the data developed in the second phase, a mathematical model describing the overall physical-chemical process will be developed to allow simulations over a range of operational variables such as pH, solid to liquid ratio, and adsorbate and adsorbent concentrations. Status: Experimental work has begun, with completion expected in March 1992. Abiotic Dehalogenation of Haloaliphatio Compounds in Aqueous Solutions Containing Hydrogen sulfide: M. Reinhard, Stanford University Goal: The goal of this project is to study the reactivity of hydrogen sulfide towards simple haloaliphatic compounds. Rationale: Relatively little research has been directed towards studying the rates and pathways of abiotic reactions that may be significant under anaerobic conditions. Recent research of this and other laboratories has shown that hydrogen sulfide may promote the dehalogenation of haloaliphatic contaminants at rates that are significantly faster than the competing reactions with water, i.e. hydrolysis and dehydrohalogenation. Approach; 1,2-Dichloroethane and 1,2-Dibromoethane (EDB) were reacted in glass ampules under anaerobic and aseptic conditions for periods of months to years. Products and rates were analyzed using chromatographic techniques. Statusi This project was initiated several years ago and was brought to conclusion under the aegis of the WRHSRC. The results will be published in Environmental Science and Technology in 1989. 132 ------- Training and Technology Transfer International Symposium on Process** Governing th* Movement and Fat* of Contaminant* in th« 8ub*urfae* Environment: P.L. Mccarty and P.V. Roberts, Stanford University Goal: The goal of this symposium, co-sponsored by the Center and the International Association on Water Pollution Research and Control, was to bring together leading scientists and engineers from around the world to evaluate the current knowledge about the processes that affect the way in which chemicals interact with the soil, move with the flow of water and air through the subsurface environments, and are transformed or degraded by both abiotic and biotic processes. Rationale: Basic understanding of such processes is necessary in order to develop realistic models for the movement and fate of contaminants in the environment. Approach: The symposium was held at Stanford University from July 23 to 26, 1989. There were presentations on eight special topics by invited speakers, twenty-seven additional oral presentations, and forty-four poster presentations. The symposium focused on the physical, chemical, and biological processes that are most important to chemical migration and transformation in the unsaturated zones above aquifers as well as in the groundwater zone. This includes information regarding both equilibrium and rate processes, and the various environmental variables that affect them. Among the processes of importance that were emphasized at the symposium were sorption, dissolution, volatilization, diffusion, multi-phase flow, and abiotic and biotic transformations. Experimental investigations were stressed, but presentations were also included that were oriented toward simulation of transport if they emphasized fundamentals of processes affecting the transport and fate of contaminants. The meeting was partially supported financially by EPA, the U.S. Geological Survey, and the U.S. National Science Foundation. statue t The symposium went very well, with much valuable interchange of information. From all indications, the meeting was highly successful in meeting its objectives. Fundamental* of Cbeaiatry of Hasardoue Substances, Training Course, Portland Metropolitan Area: K. Williamson and P. Nelson Goal: The goal of this course was to meet a need for training hazardous waste personnel in the electronics industry. 133 ------- Rationale* Employees who are involved with management, transport, or treatment of hazardous substances at manufacturing firms need a better basic understanding of chemistry related to hazardous substances in order to address the many hazardous substance issues with which they are faced. Approach; The class was held in six 4-hour sessions in the Spring, 1989. A total of 34 individuals completed the course. The class focused upon chemical nomenclature, hazardous waste identification, and chemical processes including oxidation, reduction, acid-base hydrolysis, and precipitation. One session involved a series of laboratory exercises. Status: The class provided strong educational development to most of the participants. The greatest difficulty proved to be meeting the wide variety of interests and abilities of the students. Fundamentals of Hazardous Substances, Training Course, Portland Metropolitan Area: K. Williamson, P. Nelson, J. Istok, and S. Woods Goal; The goal of this course was to provide professional level education concerning the fate and transport of hazardous materials to hazardous waste managers, regulatory personnel, and professional engineers. Rationale: Many engineers, managers, and regulators who have degrees in environmental engineering or related fields find a need now to deal with hazardous substance problems, but have not had formal training in the current approaches for handling and disposal of these materials. This course was developed to help correct this deficiency. Approach; The class consisted of 10 three-hour sessions in the Spring, 1989. Twenty-one persons attended the sessions. The approach was to focus on fate and transport mechanisms including biodegradation, volatilization, precipitation, oxidation-reduction, and sorption. A wide variety of organic and inorganic hazardous substances were described. For each fate and transport mechanism, an example problem was developed and an above-ground treatment process was described. Status; The class successfully provided professional-level development for the students. Student evaluations were excellent. Biological Transformation of Chlorinated Solvents in Subsurface systems, Workshop, Portland Metropolitan Area: P.L. Mccarty, P.V. Roberts, D. Grbic'-Galic1, and L. Semprini Goal; The goal of this workshop was to provide information on the current knowledge concerning chemical movement and fate, and bioremediation of subsurface environments contaminated with chlorinated solvents. 134 ------- Approach: The workshop was offered at Intel Corporation in Hillsboro, Oregon, on April 18, 1989, to a variety of attendees including hazardous substance managers, regulatory personnel, professional engineers, academic personnel, and graduate students. The information included physical transport processes, biological reaction rates and pathways, sorption and desorption processes and rates, and mathematical modeling of a field application. Information was provided on a variety of small-molecular-weight chlorinated solvents. Status: The workshop was well received. It was decided to repeat the workshop at other locations within EPA Regions 9 and 10 during 1990. SUMMARY OF OUTPUTS IN FY 1989 Refereed Journal Articles Published 0 Articles Submitted or In Press 2 Books and Bound Proceedings 1 Chapters in Books or Bound Proceedings 2 Proj ect Reports 0 Conferences and Workshops Held 2 TOTAL 7 135 ------- BIBLIOGRAPHY Articles Submitted or In Press Lee, S.B., J.O. Istok, and S.L. Woods, "A Numerical Model for Interpreting Results of Column Transport Experiments with Nonlinear, Nonequilibrium Sorption." Submitted to Computer and Geosciences. 1989. Kitanidis, P.K., "Effective Hydraulic Conductivity for Gradually Varying Flow." Water Resources Research. 1989. Books and Bound Proceedings International Symposium on Processes Governing the Movement and Fate of Contaminants in the Subsurface Environment, Abstracts, Stanford University, July 23-26, 1989. Chapters in Other Books or Bound Proceedings Gorelick, S.M., "Incorporation of Uncertainty Analysis into Management of Groundwater Quality," Report from the SCOPE Workshop on Groundwater Contamination, Stanford University, Stanford, California, July 27-28, 1989. Gorelick, S.M. and R.M. Gailey, "The Relationship Between Model Calibration and Engineering Overdesign for Heterogeneous Aquifers," Proceedings of International Conference on Calibration and Reliability in Groundwater Modeling, The Hague, the Netherlands, September 3-6, 1990. Conferences and Workshops Held International Conference on Processes Governing the Movement and Fate of Contaminants in the Subsurface Environment, Stanford University, July 23-26, 1979. SCOPE Workshop on Groundwater Contamination, Stanford University, July 27-29, 1989. 136 ------- |