r/EPA Hazardous Substance h Centers Program 'oaivim Summary 1990 "/ T. Printed on Recycled Paper ------- TABLE OF CONTENTS TITLE PAGE INTRODUCTION Centers Program at a Glance 3 NORTHEAST CENTER Chapter 1 (Region-Pair 1/2) 1 1 Key Personnel: Table 1 1 3 Science Advisors: Table 2 1 4 Technology Transfer and Training Advisors: Table 3 15 Budget: Table 4 16 Student Support: Table 5 16 Highlights , 18 Summary of Projects: Table 6 22 Project Descriptions 24 Bibliography 50 GREAT LAKES/MID-ATLANTIC CENTER Chapter 2 (Region-Pair 3/5) 57 Key Personnel: Table 1 5 9 Science Advisors: Table 2 6 1 Technology Transfer and Training Advisors: Table 3 62 Budget: Table 4 6 3 Student Support: Table 5 63 Highlights 65 Summary of Projects: Table 6 70 Project Descriptions 7 3 Bibliography 9 6 WASTE MINIMIZATION AND MANAGEMENT CENTER Key Personnel: Table 1 103 Science Advisors: Table 2 104 Technology Transfer and Training Advisors: Table 3 105 Budget: Table 4 106 Student Support: Table 5 106 Highlights 1 10 Summary of Projects: Table 6 114 Project Descriptions 116 Bibliography 152 U.S. Environmental Protection Agency GLNPO Library Collection (PL-12J) 77 West Jackson Boulevard, Chicago, IL 60604-3590 ------- GREAT PLAINS/ROCKY MOUNTAIN CENTER Chapter 4 (Region-Pair 7/8) 157 Key Personnel: Table 1 160 Science Advisors: Table 2 161 Technology Transfer and Training Advisors: Table 3 162 Budget: Table 4 164 Student Support: Table 5 165 Highlights 166 Summary of Projects: Table 6 168 Project Descriptions 172 Bibliography 210 WESTERN CENTER Key Personnel: Table 1 228 Science Advisors: Table 2 228 Technology Transfer and Training Advisors: Table 3 229 Budget: Table 4 230 Student Support: Table 5 230 Highlights 233 Summary of Projects: Table 6 239 Project Descriptions 242 Bibliography 267 ------- HAZARDOUS SUBSTANCE RESEARCH CENTERS PROGRAM: GREATER THAN THE SUM OF ITS PARTS The Hazardous Substance Research Centers form an integrated national program of basic and applied research, technology transfer and training. The attention of the five cooperative multi-disciplinary and multi- university centers is on the problems of managing hazardous substances. Drawing financial support from academia, industry, state and federal government, the centers are able to leverage the research resources provided by EPA. The centers also bring together a critical mass of researchers to conduct complementary and integrated research projects. Industry, regulatory, academic and other representatives come together to help shape the centers' research agenda, through the advisory committee process. Under the leadership of the Center Directors, all of these interests help to focus the centers' activities on practical problems of managing hazardous substances. And also on promoting long-term and "long-shot" exploratory research to find better ways to manage hazardous substances. The results are: o A synergistic, cross-fertilizing environment for gaining knowledge in science, engineering and technology so that results can be shared among researchers; o The opportunity to build on research knowledge through follow-on research efforts, and add needed disciplines and expertise from elsewhere across the research centers; o A concerted technology transfer and training program to promote the rapid transfer of knowledge and technology into practical applications to government, industry and other academic participants. In summary, the whole effort of the HSRC's is greater than the sum of the individual parts of research and technology transfer and training. Organization This report describes the second year activities of the five research centers which comprise the Hazardous Substance Research Centers Program. Following an overview of all five centers, a separate section describes the activities of each. Each center's major researchers are listed in Table 1, and Science and Technology Transfer and Training Advisory Committee members are listed in Tables 2 and 3. Table 4 summarizes each ------- center's budget. Table 5 presents information regarding students supported by research projects of the center. Each director reports on the major accomplishments of the center along with highlights of the year. Table 6 summarizes the individual projects in the HSRC program. Detailed descriptions of individual projects, arranged by major research topic follow. For each project, potential clients/users of the research information are identified. Project reports, presentations, student thesis and dissertations supported by HSRC research are summarized in an outputs section for each center. For more information about any of the projects, contact the director of each center. Background 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 amended Superfund enabled EPA to establish between five and ten university-based HSRCs, with a mission 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 instructs that these centers must be distributed "equitably among the regions of the United States", that recipients dedicate a substantial portion of their resources to technology transfer and training, and that EPA basic grant support of these centers not exceed 80% of the total funding for each center. The law provides 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 be established and that they be established competitively. The EPA Administrator delegated authority for the management of this program to the Director, Office of Exploratory Research (OER). The primary mission of OER is to provide support to the academic environmental research community through several vehicles, including this program of competitively selected research centers. ------- EPA decided to establish five geographic sections of the country, encompasing two adjacent federal regions. Each of these "Region-Pairs" contains one HSRC. THE CENTERS PROGRAM AT A GLANCE There are five HSRC's across the country. The accompanying map indicates the states contained in each Region-Pair and the lead institution of its center. These include: Northeast Hazardous Substance Research Center — Region-Pair 1/2, which includes the New England states, New York, New Jersey, and territories of Puerto Rico and the U.S. Virgin Islands. 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. Great Lakes and Mid-Atlantic Hazardous Substance Research Center — Region-Pair 3/5, comprised of the Great Lakes states and the mid-Atlantic states of Virginia, West Virginia, Maryland, Pennsylvania, and Delaware. 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 Minimization and Management Center — Region-Pair 4/6, which is made up of the Gulf Coast and southern states. 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. Great Plains and Rocky Mountain Hazardous Substance Research Center — Region-Pair 7/8, which contains the states on the eastern side of the Great Basin and the Great Plains. 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 — Region- Pair 9/10, which serves the states of the West Coast plus Idaho, Arizona, Alaska, Hawaii, and Guam. Stanford University and Oregon State University make up this consortium. Dr. Perry McCarty of Stanford University is the Center Director, ------- HRZRRDOUS SUBSTRNCE RESERRCH CENTERS RND DIRECTORS Dr Larry E Erickson D«p( ol Chemical Engineering Durtand Hall Kansas Stale Univerwty Manhanan. Kansas 66506 913/532-5584 Dr Walter J Weber. Jr OepL ot Ovil Engineering 2340 C G Brown Sodding University of Michigan Ann After, Michgan 4« 109-2126 313/763-2274 Dr Richard Mag0«. Director Hazardois Substance Managemeni Research Center New Jersey institute ol Technology Newark. New Jersey 07102 201/596-3233 Region Dr Perry L McCarty Center Director Dept ol Civil Engineering Stanford University Stanford, California 94306 415/723-4131 Dr Micted R. Gvercash Dept of Chemical Engineering North Carokna Stale UreverMy Ratoign. Norti Carolina 27695-7001 «1«r737-232S ------- HAZARDOUS SUBSTANCE RESEARCH CENTERS Research Project Distribution (Number of Projects) 10% Metals (13) 27% Other (36) £ 36% Bioremediation (48) 5% Thermal Treatment (8) 7% Waste Minimization (9) 15% Technology Transfer and Training (20) The Hazardous Substance Research Centers Program includes 134 research and technology transfer and training projects during the report year for Fiscal 1990*. The largest group of projects, 36% (48 projects) explore bioremediation of contaminated soils and groundwater. This represents about half of all of EPA's research effort on bioremediation. For the HSRC's, this includes $3.6 M for the report period, and represents a total bioremediation research project budget of $6.6M. Included among the other 27% (36 projects) of HSRC projects are research efforts on fate and transport of hazardous substances, three dimensional modeling of sub- surface environments, physical/chemical treatment including supercritical fluid extraction, and monitoring and sampling instrumentation. Another major effort is reflected in the 15% (20 projects) which address technology transfer and training. * The Centers operate on a budget year from February to February. possible summary information is reported as of October, 1990. To the extent ------- HSRC STUDENT SUPPORT Undergraduate Graduate Academic Level Post-Doctoral Student Support Undergraduate (40) Graduate (149) Post-Doctoral (34) Total 223 Another important aspect of the HSRC academic research grant program is the number of students who are supported. Included among 223 students supported by the Centers are 149 graduate students, 40 undergraduates and 34 post-doctoral students. This reflects an expenditure of $3.5M in student stipends and support. Sources of HSRC Funding Funding for the HSRC program comes from those organizations that benefit from the research conducted in hazardous substance management. The primary sources of funds are USEPA and other federal agencies, state government and consortia universities, and industry. The Departments of Energy and Navy in particular have been substantial supporters of the research efforts of the HSRC's. The chart below shows the percentage of funds from the various sources which support the HSRC program. ------- HSRC BUDGET COMPOSITION Center Base Grant Other EPA Other Federal State Consortia Private/ Industry Source Center Base Grant EPA Other Other Federal State Consortia Private/Industry Total $5,329,209 290,000 770,000 291,291 1,641,668 601,286 $8,923,454 Each center received an initial grant for a three-year project period. Subject to a successful evaluation, the centers can be renewed for another five-year project period, for a total life span under this program of eight years. In addition to performing innovative research on critical problems associated with hazardous substances, each center is required to dedicate between 10 and 20% of its grant to training and technology transfer activities in support of the center's mission. To assist each center director in selecting research topics and ensure the continued high quality of the research, each center was required to establish and maintain a Science Advisory Committee made up of experts in relevant disciplines from the 8 ------- federal government, academia, the private sector, and state and local government. This body meets at least twice annually. A similar advisory group was mandated to help the center director plan and manage the 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, also meets twice a year. The five centers have complementary missions. Several mechanisms are in place to assist in the coordination of activities among the centers, including shared advisory committee members, an annual meeting of center directors and technology transfer and training directors, mutual attendance at individual center functions, joint sponsorship of conferences and workshops, as well as 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 individual centers should be directed to the center director, whose name, address, and phone number appears at the beginning of the chapter for that center. Questions pertaining to the HSRC program in general may be directed to: Dale Manty, Ph.D., Director Hazardous Substance Research Centers Program Office of Exploratory Research (RD-675) U.S. Environmental Protection Agency 401 M St., S.W. Washington, DC 20460 (202) 382-7445 ------- NORTHEAST HAZARDOUS SUBSTANCE RESEARCH CENTER PARTICIPANTS: DIRECTOR: TECHNOLOGY TRANSFER DIRECTOR: 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, Ph.D Northeast Hazardous Substance Research Center Newark, New Jersey 07102 Phone: 201/596-5883 Fax: 201/802-1946 John Ehrenfeld, Ph.D Associate Director, Massachusetts Institute of Technology Kurt Fischer, Ph.D Associate Director, Tufts University William Librizzi Training and Technology Transfer Program Northeast Hazardous Substance Research Center Newark, New Jersey 07102 Phone: 201/596-2457 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 with the New Jersey Institute of Technology (NJIT) as the lead institution in a seven-member consortium. 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. 11 ------- Regions 1 and 2 have a unique combination of historic industrial activity, population density, 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 Superfund 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 are insufficient. Improved technologies for pre-treatment of industrial wastes are needed. These needs provide the stimulus for the Center's research focus. NORTHEAST HAZARDOUS SUBSTANCE CENTER Research Project Distribution (Number of Projects) 23% Biological/Chemical/ Physical (5) 36% In-Situ Methods (8) 18% Technology Transfer and Training (4) 23% Incineration/Thermal (5) Major Focus: The Center's research programs focus on development and demonstration of treatment and remediation technologies in three broad areas: incineration/thermal methods; in-situ methods; and biological/ chemical/physical methods. The NHSRC is the only one of the five EPA HSRC's focusing on incineration research and this area is considered the major thrust of the NHSRC. The Center recognizes the need for in-situ remediation technologies, while aware that sites will continue to be remediated using removal and treatment biological, chemical and physical 12 ------- technologies. Hence, the development and demonstration of in-situ remediation technologies is another major research thrust of the NHSRC. Researchers pay special attention to intermedia effects, such as impacts on air quality as a result of 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 are encouraged. These include incineration, separation, stabilization and biotreatment technologies. Key personnel currently working for the Center are listed in Table 1. TABLE 1: KEY PERSONNEL IN THE NHSRC New Jersey Institute pf Technology P. Armenante B. Baltzis R. Barat J. Bozzelli L. Dauerman E. Grosse G. Lewandowski W. Librizzi R. Magee E. Ritter Tufts University A. Chabot B. Cole A. Robbat D. Walt Princeton P. Jaffe G. Pinder K. Sirkar University Massachusetts Institute of Technqlogy S. Chisholm J. Ehrenfeld J. Longwell D. McLaughlin J. Nash W. Peters R. Probstein A. Sarofim Rutgers University R. Ahlert M. Finstein D. Kosson Stevens Institute of Technology G. Korfiatis L. Reddi The needs of the region-pair also require increased training and technology transfer as they relate to the Center's research agenda, and to the scientific and engineering advances in the hazardous waste field. The Center focuses its efforts on activities that advance the state-of-the-art in managing hazardous wastes and complement EPA and State on-going training and technology transfer programs. The Center is guided by an 18 member Science Advisory Committee (SAC), and a 14 member Training and Technology Transfer Advisory Committee (TTAC) (see Tables 2 and 3). The Center's funding is shown in Table 4, and support for students in Table 5. 13 ------- TABLE 2: SCIENCE ADVISORY COMMITTEE Dr. Ralph R. Rumer Dr. Halina Brown Richard F. Cahaly Dr. Peter Daley Dr. Richard Denison Joan Denzer Barry Frasco Merrill Hohman Joseph Lafornara Dr. Thomas Lester G. Blair Martin William Muszynski E. Timothy Oppelt Dr. Albert L. Page Dr. Stephen Schmelling Dr. Jost O.L. Wendt Norman Willard Dennis Wynne Academia, S.U.N.Y. at Buffalo Academia, Clark University Industry/GZA/ GeoEnvironmental, Inc. Industry/Chemical Waste Management Environmental Group/ Envir. Defense Fund Environ. Group/ Sierra Club NJDEP U.S. EPA U.S. EPA University of Kentucky U.S. EPA U.S. EPA U.S. EPA University of CA, Riverside U.S. EPA University of Arizona NEWMOA (State) U.S. Army In-Situ Remediation Bio/Chem/Phys Treatment Bio/Chem/Phys Treatment Bio/Chem/Phys Treatment Incineration Thermal/Treatment Pollution Prevention Site Remediation Site Remediation Emergency/ Remedial Response Incineration/ Thermal Treatment Incineration/ Thermal Treatment Site Remediation Bio/Chem/Phys Treatment Soil Remediation/ Contaminant Transfer In-Situ Remediation Incineration/ Thermal Treatment Pollution Prevention In-Situ Remediation Chair 14 ------- TABLE 3: TRAINING AND TECHNOLOGY TRANSFER ADVISORY COMMITTEE Michael Bonchonsky Joseph S. Carra Ronald DiCola Susan Fessenden Meg Kelly James Makris William Muszynski Linda Murphy Metcalf & Eddy Technologies, Inc. U.S. EPA AT&T MADEQE U.S. EPA U.S. EPA U.S. EPA U.S. EPA Remediation R.C.R.A. Remediation State Programs Training/Technology Transfer SARA Title III Multi-media needs in Regions Region al-Sup erf und Dr. Gerald Nehman Michael OToole Kathleen Porter* Jack Stanton John Walker Norman Willard Environmental Institute for Technology Transfer NY DEC MA DEM U.S. EPA COM Federal Programs Corp. NEWMOA (State) Training/Technology Transfer State Superfund State Pollution Prevention Training/Technology Transfer-EPA/ORD Consulting Services State Programs Chair 15 ------- TABLE 4: CENTER FUNDING FUNDING SOURCES EPA: Center's Program EPA: Other Other Gov't: Federal Other Gov't: State Consortium Private Sector TOTAL STUDENT SUPPORT Undergraduates Graduates Post Doctoral TOTAL STUDENT SUPPORT Undergraduates Graduates Post Doctoral TOTAL FY1990 $ 1,606,496 0 0 59,771 550,968 47,587 $ 2,264,822 NUMBER 0 16 3 __ NUMBER 1 20 6 27 FUNDS TO DATE $ 2,606,496 0 0 137,865 888,092 47,587 $ 3,680,040 1989 FUNDS 0 233,018 54,370 "287^388 1990 FUNDS 5,643 314,167 103,978 ~423?788 STUDENT LEVEL Undergraduate Graduate Post Doctoral TOTAL TABLE 5: STUDENT SUPPORT NUMBER 1 36 9 46 FUNDS TO DATE 5,643 547,185 158,348 TTU76 16 ------- CENTER DIRECTOR'S REPORT Over 100 faculty and staff members 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 NHSRC is the nucleus to bring together and focus on hazardous substance problems of concern in Regions 1 and 2. During the second year of the Center's operation, six new research projects were initiated and the 12 original projects continued for a second year. Five of these projects were in the incineration/thermal method area; eight of the projects addressed in-situ methods; and five projects involved treatment technology approaches utilizing biological, chemical, and physical treatment methodologies. Interest and participation from faculty at the consortium schools in the activities of the Center are strong. Thirty-two new research proposals were submitted for funding consideration in 1991. Funding requested exceeded the NHSRC budget by two-hundred percent. Plans are to fund seven to ten of these new proposals dependent upon the funding status of the Center. The Center's program for Training and Technology Transfer focuses on the 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 extent possible, such approaches provide innovative and imaginative concepts that advance the state-of-the-art, meet the defined needs of Regions 1 and 2, and are potentially adaptable for broader national use. Three important areas that can have significant impact on the hazardous substance management program have been identified and include: project management, consideration and use of alternative treatment technologies, and pollution prevention. Further, the Center has been designated as an EPA Superfund University Training Institute (SUTI) and chartered to conduct advanced courses on legal issues, contract administration, and site management for superfund managers and coordinators. Four training and technology transfer initiatives were supported in FY 1990. These included a state-of-the-art review and seminar on emerging waste technologies; a conference on aquifer reclamation and source control; and in-depth training in alternative/innovative technology options for remedial actions at hazardous waste sites. This latter project 17 ------- was a cooperative effort among this Center, the New York State Center for Hazardous Waste Management-State University of New York at Buffalo, and the New York State Department of Environmental Conservation. The NHSRC and the New York State Center for Hazardous Waste Management also co-sponsored the First Hazardous Waste Treatment and Prevention Technologies Conference. And the HSRC has been designated an Advanced Superfund University Training Institute (SUTI) to conduct advanced courses in legal issues, contract administratio and site management. The Center has a strong and 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 to refine its focus and research thrusts. The Center has established an excellent working relationship with the New York State Center for Hazardous Waste Management at S.U.N.Y.-Buffalo which should grow to the benefit of the region-pair. 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 FOR 1990 Real-Time Monitoring and Control of Groundwater Contamination: The subsurface contaminant plumes found at hazardous waste sites can be highly irregular and difficult to locate. The irregularity of these plumes is due to a variety of factors, primarily variations in geological properties (e.g., soil hydraulic conductivity and sorption), variations in recharge, and scattered contaminant sources. Professor Dennis McLaughlin of MIT Civil Engineering Department is developing methods which can be used to construct multidimensional maps of subsurface contaminant plumes. These maps are obtained by combining field measurements with predictions obtained from computer models of groundwater flow and transport. The computer models guide the placement of wells and other aspects of the field sampling program. Hydrologic and chemical measurements are used to improve the models which are, in turn, used to guide additional sampling efforts. Each sampling round yields a more detailed map of the subsurface contaminant plume. This sequential or "real-time" approach to site characterization is very efficient since it makes maximum use of a limited amount of field data. The contaminant plume maps produced by the sequential sampling procedure can be used to plan and monitor site remediation activities. 18 ------- Initial tests of the procedure at a coal tar disposal site in upstate New York have produced encouraging results. The computer models are now being generalized so that they can deal with a range of different hydrogeologic conditions. Additional field tests are also anticipated. This research will result in more timely, and cost-effective site remediation efforts. Incineration of Chlorocarbons: Incineration is currently being 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). A detailed understanding of the effects of chlorine on hydrocarbon oxidation in flames will aid in design and operation of incineration equipment for minimum chlorocarbon emissions. Professors A. Sarofim and J. Longwell of the Chemical Engineering Department of MIT, and Professors J. Bozzelli and R. Barat of the Chemical Engineering, Chemistry and Environmental Science Department of NJIT, examined the destabilizing effects of methylchloride on a fuel lean ethylene/air flame in a torroidal jet stirred combustion (TJSC). The TJSC emulates the highly circulated flame stabilization zone in many large scale burners. It is in this zone where CHC's are most likely to affect incinerator performance. Under fuel rich conditions, destabilization and escape of unburned fuel, during unstable operation, similar to that previously reported for lean conditions, is observed but, in addition, synthesis of a variety of chlorocarbons occurs on quenching the combustion product stream. Detailed chemical mechanisms are currently being developed to offer further insight into PIC formation in this system. The modeling has been used to find mechanisms for optimizing combustion processes when chlorocarbons are present. One method for improvement of chlorocarbon combustion predicted in the future is to add inexpensive steam to the process. Interaction with several incinerator operators has verified the predictions. Once the full effects of chlorine are understood, incinerator operations can be altered to minimize this production of PIC's when disposing of chlorocarbons. A reduction of PIC emissions supports EPA's risk reduction goal when managing hazardous wastes. 19 ------- Removal and Recovery of Heavy Metals from Wastewater: Efficient removal and recovery of toxic heavy metals from industrial waste streams prior to discharge is a major challenge. Not only does removal of heavy metals eliminate toxicity but also it prevents metal accumulation in biological sludge. A novel and robust hollow fiber contained liquid membrane (HFCLM) technique has recently been developed at Stevens Institute of Technology. The efficiency and stability of the novel HFCLM technique for the removal and concentration of toxic heavy metals is being investigated. Using counter transport, copper was transferred from a dilute solution of CuSo4 through an organic membrane containing a chelating extractant to a highly acidic solution and concentrated. Feed solution was brought down to 1-3 ppm level from 100-250 ppm level at the inlet and simultaneously concentrated up to 1700 ppm in the strip side. A month long run indicated that the liquid membrane flux and process are quite stable. Similar experiments with chronium and mercury are in progress. This technique has the potential to provide a simple way of treating aqueous industrial wastes contaminated with metal ions, recovering and recycling the metal back to the process. The process can clean waste streams to contaminant levels in the parts per billion (ppb) range, thus reducing the impact of heavy metals in the environment. Microwave Treatment of Contaminated Soil: The treatment/ remediation of large quantities of contaminated soil is a major challenge facing the states in federal Regions 1 and 2. Contaminants include volatile and semi-volatile organics, and insoluble non-volatile organics, e.g., dioxins, and heavy metals. Alternatives to incineration and land-fill are needed. Microwave treatment of contaminated soils by Dr. Leonard Dauerman at New Jersey Institute of Technology shows great promise. Studies to date are exploring the mechanisms involving the interaction of microwave energy on a variety of contaminants. Results to date indicate that: steam distillation is the governing mechanism for the removal of volatile and semi-volatile organics; insoluble non-volatile organics, e.g., 9, 10- anthraquinone, become "fixed" in the soil at a relatively low temperature; soil impregnated with hexavalent chromium could be rendered non- hazardous as determined by the EP Toxicity Test. While studies continue on these mechanisms, tests are underway in a recently installed 6KW microwave pilot-plant with soil feeder and 20 ------- continuous conveyor. These tests are designed to determine system operating performance and costs and scale-up parameters. This new technology is versatile, cost-effective and capable of treating soils with a mixture of contaminants. Following further development, this technology should offer an attractive alternative to conventional soil treatment/ remediation technologies. Incinerator Monitoring: Monitoring is a key element in building public trust in incineration and ensuring that emissions do not exceed agreed upon standards. A one-day conference entitled "Incinerator-Monitoring: Techniques for Assuring Performance and Building Public Trust," was held at MIT on June 6, 1990. The audience came away from the conference with increased understanding in three areas: First, audience members learned how incinerator monitoring is done currently, what current regulations require, and the capabilities of "state- of-the-art" monitoring systems. Second, participants learned of the limitations of existing monitoring systems. While monitoring techniques have improved dramatically in the past twenty years, monitors cannot provide complete assurances of incinerator safety. Speakers and members of the audience highlighted critical deficiencies in existing technology. For example, several people noted that continuous emission monitors are only available for a handful of pollutants. The pollutants of greatest public concern--dioxins and heavy metals—cannot be monitored continuously. Finally speakers and audience members suggested ways to overcome these limitations. Monitoring should focus upon incinerator inputs, as well as stack emissions. Techniques for monitoring ambient air and soils should be improved, as well as techniques for monitoring community health. Citizens play a key role in incinerator monitoring. Incinerator emissions data should be accessible through a public database, and citizen inspectors should be hired, as is done in Connecticut. The conference demonstrated to participants that it is possible for the diverse interests that play a part in incinerator proposals to work together in a constructive manner. The conference brought together 125 people. Thirty-five corporations sent representatives, as did six environmental groups, four universities, the states of Connecticut, New York, Massachusetts, Maine, New Hampshire, Rhode Island and Virginia, U.S. EPA Regions 1 and 2, and the Department of the Army. Many participants noted in conference evaluation forms the need for more 21 ------- frequent interaction among government regulators, incinerator operators and representatives of the public interest outside of the heated debate that tends to accompany specific incinerator proposals. This conference demonstrated the usefulness of establishing a forum to meet that need. TABLE 6 NORTHEAST HAZARDOUS SUBSTANCE RESEARCH CENTER PROGRAM SUMMARY PRINCIPAL INVESTIGATOR PROJECT IN-SITU TREATMENT END DATE CURRENT BUDGET TOTAL BUDGET Jaffe Methanogenic 1992 $78,481 Bioremediation of Aquifers Pinder Investigation into the 1990 $50,547 Dissolution of DNAPL in the Subsurface McLaughlin Real-Time Monitoring 1991 $72,186 and Control Of Ground- water Contamination Walt Field-Based Testing of 1991 $92,506 a New Remote Sensing Groundwater Monitor Chisholm DNA Characteristics of 1991 $69,159 Indigenous Microbial Communities as Indicators of Mutagenic Waste Exposure Probstein Electrode Emplacement 1992 $80,000 Geometries and Electric Field Strengths for In-situ Extraction of Contaminants from Hazardous Waste Sites by Electroosmosis Korfiatis A Study of the Efficiency 1991 $57,612 of Vibroflotation in In-situ Phase of Separation of Immiscible Contaminants $160,446 $50,547 $122,746 $167,506 $138,318 $188,877 $57,612 22 ------- PROGRAM SUMMARY (CONTINUED) PRINCIPAL INVESTIGATOR Robbat PROJECT Development of Field GC-MS Methods for Hazardous Waste Sites END DATE 1992 CURRENT BUDGET $100,890 TOTAL BUDGET $336,154 INCINERATION/THERMAL TREATMENT METHODS Howard/ Fundamental Studies of 1991 $124,948 $249,896 Peters Solids Devolatilization for Hazardous Waste Destruction Longwell/ The Effect of Chlorocar- 1991 $125,221 $250,442 Sarofim bons on Flame Intermit- tency, Stability, and Efficiency in a Well- Stirred Reactor Bozzelli Hydrocarbon Flames 1991 $250,481 $322,506 Doped with Chlorocarbons Dauerman Microwave Treatment 1992 $107,075 $220,748 of Hazardous Wastes: Underlying Mechanisms Bozzelli Thermal Desorption of 1992 $78,580 $156,760 Hazardous Organic Chemicals from Soils BIOLOGICAL/CHEMICAL/PHYSICAL TREATMENT Armenante Contaminated Ground- 1991 $79,672 $132,172 water Treatment With Bio-reactors Utilizing A White Rot Fungus Finstein Optimization of Biological 1991 $84,857 $171,317 Soil Remediation Baltzis A Dynamic Model of 1991 $67,576 $117,576 Sequencing Batch Reactors Sirkar Removal and Recovery 1991 $71,803 $145,773 of Heavy Metals from Waste Water by Hollow Fiber Contained Liquid Membrane Technique 23 ------- PROGRAM SUMMARY (CONTINUED) PRINCIPAL INVESTIGATOR PROJECT END DATE CURRENT BUDGET TOTAL BUDGET Ahlert Supercritical Fluid Extraction of Organic Contaminants from Soil 1992 TRAINING AND TECHNOLOGY TRANSFER $73,228 $151,894 Librizzi Grosse Librizzi Ehrenfeld In-Depth Training in 1991 $55,226 $55,226 Alternative/Innovative Technology Options for Remedial Actions at Hazardous Waste Sites Aquifer Reclamation 1991 $64,315 $64,315 and Source Control Conference SUTI Advanced courses in 1991 $133,119 $133,119 Legal Issues, Contract Administration and Site Management Emerging Waste Tech- 1991 $28,166 $28,166 nologies:A State-of- the-Art Review and Seminar RESEARCH PROJECT DESCRIPTIONS IN-SITU TREATMENT Methanogenic Bioremediation of Contaminated Aquifers: Jaffe, Princeton University Peter R. Goal: It is known that chlorinated compounds such as trichloroethylene (TCE) can be degraded by reductive dehalogenation under methanogenic conditions. The goal of this research is to investigate if this process can be enhanced and used as a bioremediation technology to decontaminate aquifers. 24 ------- Rationale: In the first part of our research sponsored by the Center, we developed a model to investigate the aerobic bioremediation of aquifers, paying special attention to the interaction between biomass production and changes in the groundwater hydrology (soil plugging). We have shown how to overcome plugging by manipulating the injection of oxygen and the inducer (methane), but the process is essentially limited by the solubility of oxygen. In anaerobic processes, oxygen solubility is not a problem, but a large quantity of low solubility gases is formed (methane) that can, by forming bubbles, affect the soils' permeability and make bioremediation unfeasible. The research focuses, therefore, on the kinetics of TCE degradation under methanogenesis and on incorporating in our existing model the effect of gas formation on the soil permeability. Approach: Degradation kinetics of TCE by mixed methanogenic cultures is being studied to investigate the effect of the carbon source on the degradation of TCE and the production of methane. These studies are being performed in batch reactors. To investigate the effect of methane gas on the soil permeability, a column will be operated under methanogenic conditions at a constant flow rate and spatial changes in pressure, substrate concentration, and chlorinated solvents will be measured as well as biomass and methane accumulation. The latter two parameters will be monitored with the use of a dual gamma attenuation system. Results of both phases will be incorporated into a model which will allow the evaluation of different bioremediation strategies. Status: The kinetic experiments are underway, and the column experiment is being designed. Client/Users: Researchers interested in TCE degradation kinetics, and interested in the effect biogas production has on soil hydrologic properties; EPA Regulators/Industry concerned with the decontamination of hazardous waste sites. Investigation into the Dissolution of DNAPL in the Subsurface: George Finder, Princeton University Goal: The goal of this project is to develop a technique for the removal of Dense Non-Aqueous Phase Liquids (DNAPL) from the subsurface. Rationale: DNAPL is characterized by the fact that it is only slightly miscible with water and is of a density greater than that of water. Because of these two properties, DNAPL once introduced into the soil, migrates 25 ------- downward through the unsaturated zone to the saturated zone and through the saturated zone until it reaches a lithological boundary. There the properties of the encountered layer preclude further movement. It then moves, normally as a thin layer, down the topological gradient of the inhibiting layer. As a result of this behavior, it is extremely difficult to find DNAPL once it enters the subsurface. Moreover, even if it is identified, it is impossible to remove. Thus, due to its low solubility, it acts as a source of contamination for a very long time. This research is dedicated to the discovery of a technique for the removal of the DNAPL. Approach: The project has several parts, two of which constitute the current research effort. In part one, the idea of using a co-solvent, namely alcohol, to enhance the solubility of DNAPL is investigated. Experiments have been run in the laboratory to determine the best alcohol for this purpose and isopropanol was identified. In the second, and current phase of the research, a method for designing a field technique for injection and withdrawal of the alcohol- water mixture has been investigated. The field design must recognize the fact that the exact location of the DNAPL will not be known. Some of the techniques used in oil reservoir simulation appear promising. To test these concepts a numerical model, similar but different than that used in the oil industry, is needed. The research this year has focused on the development of such a model. Status: The initial experimental research has been completed and there has been significant progress in the development of the numerical model. Client/Users: The users of this technology are those companies responsible for the cleanup of aquifers contaminated with DNAPL such as trichloroethylene. This would include not only major corporations and governmental agencies, but also companies who contract to do the required cleanup. Real-Time Monitoring and Control of Groundwater Contamination: Dennis McLaughlin, Massachusetts Institute of Technology Goal: The overall goal of this project has been to develop practical methods for characterizing and controlling contamination at hazardous 26 ------- waste sites when field data are limited. Our more immediate objective has been to test the feasibility of sequential (or real time) methods for designing field sampling programs at such sites. Rationale: The success of groundwater remediation depends strongly on our 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 for designing monitoring and remediation strategies which explicitly recognize the importance of heterogeneity. Approach: The key to the real-time approach is to combine information obtained 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 six months of the project we completed the field work and modeling needed to test our real-time approach. We used results obtained from our two-dimensional stochastic groundwater flow and transport models to guide a well sampling program at a coal tar disposal site in upstate New York. Data collected at the field site convinced us that we need three-dimensional models to provide an adequate description of subsurface conditions. We are currently extending our modeling and sampling design techniques so that they can deal with three- dimensions. We are also incorporating extensions that will allow us to design a sampling network for monitoring the effectiveness of future remediation activities at the coal tar site. Client/Users: Personnel responsible for characterizing the extent and severity of contamination at hazardous waste sites; personnel responsible for designing and carrying out groundwater remediation programs; government regulators; environmental specialists in companies involved in hazardous waste cleanups. Field-Based Testing of a New Remote Sensing Groundwater 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 to facilitate 27 ------- an early transfer of this new technology to the solution of environmental problems through the creation of prototype equipment, materials, and testing protocols. 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 detector is based on a fiber optic sensor that changes its fluorescence properties in contact with volatile organic compounds. The sensor operates on the basis of 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: Professor David Walt and Mr. Steven Barnard of Tufts University Chemistry Department have developed a fiber optic sensor and appropriate field-portable instrumentation that is sensitive to environmentally significant levels of volatile organic contaminants. The sensor is composed of an indicating phase that is chemically immobilized at the distal end of an optical fiber. The indicating phase contains a chemical indicator that changes its fluorescence properties upon interaction with volatile organic hydrocarbons. The delicate distal tip of the fiber containing the sensing chemistries has been field hardened by shielding it with a porous stainless steel sheath. Field studies have indicated that the sheath provides excellent protection from physical damage, adequate permeability to organic vapors, and rejection of ambient light. A portable field instrument has been designed for use with the sensors and has been constructed, laboratory tested, and field tested. Initial field studies were conducted at Pease Air Force Base, New Hampshire, at a site contaminated with JP4 jet fuel. Four different sampling wells were monitored using the sensor and portable instrumentation. The sensor's response correlated well with laboratory measurements, measured by a photoionization detector probe. Client/Users: The users of this technology would be petroleum industries involved in site remediation and site assessment. 28 ------- DNA Characteristics of Indigenous Microbial Communities as Indicators of Mutagenic Hazardous Waste Exposure: Sallie W. Chisholm and Ena Urbach, Massachusetts Institute of Technology Goal: The goal of this project is to develop molecular methods to directly analyze the effects of mutagenic contaminants on bacteria drawn from a potentially contaminated site. Information from the observed mutational spectra could be used to identify mutagenic contaminants. Rationale: Our collaborator, Prof. William G. Thilly, and his co-workers have developed techniques to rapidly analyze mutations caused in the human HPRT gene in cultured cells using denaturing gradient gel electrophoresis (dGGE) and a high fidelity variation on the polymerase chain reaction (PCR). Their results show a good correspondence between particular mutagens and the set of mutations they produce, their "mutational spectra." Work by other researchers has established the reproducibility of mutational spectra in Escherichia coli. so it may be possible to apply Thilly's techniques to the analysis of mutational spectra in naturally occurring populations of the bacteria. Approach: We have chosen Pseudomonas fluorescens. a robust aquatic bacterium as our assay species, and the evolutionary conserved 16s ribosomal RNA (rRNA) genes as target DNA sequences. Our overall approach to the problem is first to establish the natural variability in these genes by DNA sequencing from isolates at different times of the year and at different sites. After we have established that this potential background variability is minimal, we will determine the mutational spectra in field populations from well-characterized contaminated sites. Status: We have isolated several clones of Pseudomonas fluorescens at different times of year from a lake at our study site, and we have sequenced the genes for 16s rRNA from one of these isolates. Work is underway to improve methods for sequencing the other isolates, and on PCR amplification with species-specific primers to eliminate the need for an initial isolation step. Client/Users: People interested in identifying mutagenic contaminants at sites where even the broad class of suspected contaminants is unknown. 29 ------- Electrode Emplacement Geometries and Electric Field Strengths for In-Situ Extraction of Contaminants from Hazardous Waste Sites by Electroosmosis: Prof. Ronald F. Probstein, Massachusetts Institute of Technology Goal: This project addresses a new technique for in-situ decontamination of polluted soils. The technique is based on an electrokinetic phenomenon called electroosmosis. Electroosmosis describes the movement of liquid through a soil as a result of an applied electric field. The electric field is applied via electrodes placed within the contaminated soil. The immediate goal of this project is to determine the optimum placement of electrodes in a hazardous waste site and the optimum field strength applied to these electrodes to achieve the most efficient removal of contaminants from the waste site. Rationale: Previous research conducted in our laboratory has demonstrated that electroosmotic purging of contaminants from saturated soils can remove nearly all of the pollutants under certain conditions. The energy costs required for the decontamination process were also shown to be quite reasonable (<$2.50/ton in some cases). These results were obtained in one-dimensional soil column experiments. To apply this promising technology to actual field site conditions, it is necessary to determine the three-dimensional effects associated with the process. If the technology is shown to be feasible, in terms of degree of decontamination achievable and energy costs, in three-dimensional geometries, then the process could be used in hazardous waste sites to remove pollutants from soil without the need for excavation. Approach: This project is being investigated by combining three- dimensional laboratory experiments with theoretical modeling. Experiments will be conducted in three-dimensional electroosmotic test cells which permit investigation of the effects of electrode spacing and electric field strength on the electroosmotic decontamination process. The results will be compared with a mathematical model developed to stimulate laboratory experiments and field tests. Results of this study will provide design tools, in forms of a computer simulation program and an experimental database, necessary for the optimization of proposed field tests. Status: Experimental and theoretical work is underway and is proceeding as scheduled in the original proposal. Completion is expected January 31, 1992. 30 ------- Client/Users: Researchers interested in in-situ decontamination of soils, particularly soils of low permeability; industries involved in soil remediation; State and EPA regulators concerned with emerging hazardous waste site remediation technologies. A Study of the Efficiency of Vibroflotation in In-Situ Phase Separation of Immiscible Contaminants: George P. Korfiatis and Lakshmi N. Reddi, Stevens Institute of Technology Goal: The goal of this project is to develop an in-situ remediation technology for sites contaminated with Non-aqueous Phase Liquids (NAPLs). The technology is based on vibroflotation, a process involving simultaneous vibration and flotation (localizing waterflooding) of soils. Rationale: The basis for the technology is that vibrations in conjunction with "quick" sand conditions will provide necessary conditions to overcome the capillary stresses binding the NAPL ganglia to soil particles. Vibroflotation is a frequently used in-situ technique in the geotechnical industry to densify sandy soils. Approach: The approach consists of conducting a series of laboratory tests simulating vibroflotation in soil columns 6 ft. high. Several combinations of soils and NAPLs will be used in the tests. Commercial vibrators will be modified to create water jetting and consequent flotation of the soil. For each soil-NAPL combination, the effectiveness of vibroflotation will be assessed. The effect of various equipment-related and soil-NAPL parameters will be identified. Status: Experimental work is underway. Completion expected December, 1990. Client/Users: Industry/State and EPA regulators concerned with remediation of NAPL contaminated sites and researchers interested in in- situ remediation techniques, etc. 31 ------- Development of Field Gas-Chromograph-Mass Spectrometer (GC-MS) Methods for Hazardous Waste Sites: Albert Robbat, Jr., Tufts University Goal: The primary objective of this research is to develop simple, field- practical sample preparation procedures and technology for identifying and quantifying EPA listed organic compounds at Superfund sites. The premise is that it is possible to make chemical measurements in the field that have the same standard of data quality as laboratory measurements. Rationale: GC-MS is the only analytical tool that provides unambiguous identification of organic compounds. GC-MS detection is required by EPA for site assessment, clean-up, and closure. Typically, commercial laboratories in EPA's contract laboratory program (CLP) provide data turnaround times that exceed three months. This means that little on-site remediation work can proceed while waiting for data. This is particularly problematic where clean-up technology performance and community/worker protection from fugitive emissions and particulates must be determined in "real-time." Approach: Two methods of detection are being developed: 1) a quick (five minute analysis/sample) soil screen that involves direct introduction of the contaminant(s) into the instrument (no sample cleanup procedures); and 2) a simple clean-up procedure preceding contaminant(s) introduction into the GC-MS (20 minute analysis/sample). This field-practical sample preparation procedure is in contrast to laboratory methods which require three to five hours/sample. The first field soil screenmethod provides data comparable to laboratory quality. Laboratory and field-based analyses have been compared for Superfund sites in North Dartmouth, New Bedford, Westboro, and Bridgewater, Massachusetts. Status: To date, these methods have been developed for the most commonly found semi-volatile and volatile organics found at Superfund sites in soil and water, respectively. Methods for detection of PCBs and polycyclic automatic hydrocarbons (PAHs) in soil as well as constituents from gasoline and some chlorinated volatile organic solvents (VOCs) have been field tested and forwarded to EPA's Analytical Operations Branch for inclusion in a Field Analytical Methods Compendium. Research will begin on a generic method for the wide range of organics in FY91 which is expected to be field tested by FY92. Client/Users: Expected users of this technology will be state and federal agencies and environmental contractors responsible for the management 32 ------- and clean-up of Superfund sites. This research is expected to benefit the public directly (e.g., cost reduction by elimination of immobilized personnel and equipment, waiting for data to proceed to the next step, and worker/community protection) and indirectly (from both sociological and psychological aspects associated with living next to hazardous waste sites) by speeding the Superfund process along. INCINERATION/THERMAL METHODS Fundamental Studies of Solids Devolatilization for Hazardous Waste Destruction: J.B. Howard, G.S. Darivakis, J. Lee, S. Gerjarusak, and W. Peters, Massachusetts Institute of Technology Goal: The objective of this project is to provide better 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 evolved by thermal decomposition of waste solids such as plastics and contaminated soils. Effects of further thermal treatment of newly formed gaseous and liquid decomposition products are also of interest. Rationale: Initial thermal decomposition of solids and subsequent thermal reactions of the resulting decomposition products 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 clean-up equipment, might escape the process as toxic emissions. Better understanding of these reactions provide guidance on how to design and operate incinerators, advanced thermal destruction reactors and associated equipment such as afterburners, and clean-up apparatus, to achieve desired waste destruction efficiencies without producing adverse emissions. Approach: Small scale research apparatus is used to mimic important features of practical thermal treatment equipment such as temperature, heating rate, and treatment time, under closely controlled conditions. Effects of these and other variables, such as chemical and physical properties of the waste, on the yields, compositions, and generation rates of destruction products are being determined. 33 ------- Status: 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. Major findings are presented in a journal article expected to be published in 1990. An overview paper on the role in hazardous wastes destruction of solids thermal decomposition, and of secondary reactions of the resulting volatiles was published. Exploratory studies of thermal decontamination of soils under rapid heating conditions were also performed. Client/Users: Researchers, industrial practitioners, regulators (local, state, federal), and public interest groups, interested in performance assessment and assurance for solid wastes incinerators and in potential new approaches for thermal destruction of hazardous solids and thermal remediation of contaminated soils. The Effects of Chlorocarbons on Flame Intermittency, Stability and Efficiency in a Well-Stirred Reactor: J. Brouwer, A.F. Sarofim, and J.P. Longwell, Massachusetts Institute of Technology Goal: To acquire a quantitative understanding of the effect of chlorocarbons on escape of unburned material from incinerators and to apply their understanding to diagnosis and correction of the processes responsible for their escape in practical systems. Rationale: 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 here to develop knowledge and techniques for assessment of the effects in practical systems. Approach: The torroidal stirred reactor has been specially developed to provide a well-characterized combustor. Effects of adding chlorocarbons to an ethylene-air mixture are studied by measuring temperature fluctuations with a sample time of 6.5 x 10~9 seconds and a sample volume of 200 x 200 x 20 um^. Unburned material leaving the combustor is determined by chemical analysis of quenched gas samples. The observed 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. 34 ------- 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, developed in cooperation with center Professors Bozzelli and Barat of NJIT is being applied to interpretation of the results. Under excess air conditions, the major unburned materials are carbon monoxide and unburned fuel. Where oxygen is insufficient to completely burn the fuel, many chlorinated hydrocarbons not present in the feed are found. It is believed that these are formed on cooling the flue gas which contains hydrocarbons and chlorine. Expansion of the data base for oxygen deficient combustion and kinetic analysis of these data are major near-term goals. It is believed that the work will provide tools for diagnosis and correction of mixing deficiencies that lead to emission of chlorocarbons caused by locally fuel-rich conditions. Client/Users: These results will be useful to developers and designers of incineration equipment and to the users for fault diagnosis and correction. Hydrocarbon Flames Doped With Chlorocarbons: J. Bozzelli, and R. Barat, New Jersey Institute of Technology Goal: The objectives of this project are to: 1) experimentally study reaction processes in incineration of chlorocarbons, both oxidation and pyrolysis, obtaining information of kinetics of reactant loss, intermediate formation and subsequent reaction of intermediates, and final product formation rates; 2) develop a model (set of elemental reactions) based on fundamental thermodynamic and kinetic principals and validated through experiments by the combined research groups and other published literature; and 3) use this model and experimental data to determine how to improve or provide direction toward optimum operation of incinerators used in the oxidation (complete destruction) of chlorinated hydrocarbons. The project experiments and a model are applicable to incineration processes ranging from refuse recovery to hazardous waste facilities. Rationale: Chlorocarbon incineration is a complex process and has not been studied thoroughly. Incineration is, however, one method which can completely destroy hazardous chemical species converting them into relatively safe basic chemicals - water, (CC>2), and chloride salts (after the HC1 has been scrubbed). Many , industries, in considering their environmental responsibilities, believe it is much better to completely destroy waste chemicals rather than store them, where they can possibly 35 ------- leak into the environment. Thus, there is a demand for safe and effective incineration of hazardous wastes. Approach: Perform experiments in thermal oxidation reaction systems where we can accurately describe the physical properties, temperature, turbulence, and time, in the reactors. We shall then focus on the chemical reactions that are taking place in order to learn and understand the important chemical and mixing processes. The MIT group is a joint participant in the project. The are focusing on actual flame studies and turbulence using our models to explain the chemistry. Status: The project has seen the completion of Chloromethane/ Methane/Oxygen experiments and a reaction mechanism has been developed and validated for flame oxidation of chloromethane - ethylene mixtures. Experiments and modeling are continuing. Client/Users: Researchers interested in chlorocarbon incineration, state, community and EPA regulators interested in optimum incinerator operation with respect to detoxification and minimum effect on the environment. Microwave Treatment of Hazardous Wastes: Underlying Mechanisms: L. Dauerman, New Jersey Institute of Technology Goal: The goal is to explore the interaction mechanism of microwave energy with the following systems: 1) substrates containing volatile and semi-volatile organics; 2) substrates containing insoluble non-volatile organics; and 3) substrates containing heavy metals. Rationale: Microwave treatment of hazardous wastes can only be optimized on specific waste streams if the process development is guided by a mechanism. In bench scale studies, it is necessary to postulate and test mechanisms. Their validity, applicability and feasibility must be tested in pilot plant scale studies. Both bench scale and pilot plant studies are being carried out. Approach: Bench scale and pilot plant studies are being carried out on three different waste streams: 1) substrates contaminated with volatile and non-volatile organics; 2) substrates contaminated with insoluble non- volatile organics; and 3) substrates contaminated with heavy metals. 36 ------- Status: 1) Volatile and semi-volatile organics: Steam distillation is the governing mechanism based upon the following observations: a) the removal of the organic is directly related to the concentration of water; b) the temperature at which removal occurs is approximately 100°C; and c) the substrate need not to be a "lossy" material. 2) Insoluble non-volatile organics: 9, 10-anthraquinone, a surrogate, becomes "fixed" in the soil at a relatively low temperature. We are developing the Fourier Transform Infrared Spectroscopy (FTIR) combined with Attenuated Total Reflectance (ATR) Spectroscopy and Diffuse Reflectance Spectroscopy (DRIFT), respectively, as a method to determine the physical and chemical nature of the soil "fixation". 3) Heavy metals: spectroscopic studies of microwave treated particles, chromium-impregnanted soil (X-Ray powder diffraction Spectroscopy; scanning electron microscopy (SEM); energy dispersive Spectroscopy (EDS)) showed that the hexavalent chromium phase disappeared in the chromium-impregnated soil. Chromium was reduced to the trivalent state and appeared in two new crystalline phases: chromite (FECr2O4) and (Cr2O3), respectively. Studies are now underway to determine if the results of the microwave treatment are unique. Soils treated thermally, in a muffler furnace, are being subjected to similar spectroscopic investigations. Client/Users: Generally, the technology will be of use to a wide spectrum of clients; those with a need to remediate sites with oil spills (e.g., oil companies); those with a need to remediate dioxin-contaminated soils (e.g., chemical corporations); those with a need to remediate chromium contaminated soil (industry and state). Thermal Desorption of Hazardous Organic Chemicals from Soils: J. Bozzelli, New Jersey Institute of Technology Goal: 1) to study the mass transfer mechanisms and equilibrium behavior of volatile and moderately volatile organic contaminants in soil matrices through various experimental measurements; 2) to develop models based upon fundamental principles of thermodynamics and diffusion theory for estimation of mass transfer parameters and equilibrium constants and for prediction of contamination/desorption profiles of organics in heated soil beds; and 3) to obtain fundamental data and optimum operating conditions 37 ------- which may be utilized in practical thermal decontamination of soils containing hazardous substances. Rationale: Removal of suspected hazardous organic pollutants from contaminated soil matrices by thermal desorption combined with a purge flow of air or inert and secondary incineration or recovery of the desorbed vapors is far more energy efficient and feasible than, incineration of an entire soil mass. A number of field studies by EPA and industry have demonstrated the feasibility of this technique for highly volatile organic substances (boiling points less than 125°C). Approach: We have utilized chromatographic response analysis incorporating intra-(pore) and inter-particle diffusion, heats of adsorption, equilibria, in addition to all the normal mass transfer parameters in developing our initial model. The experiments consist of plug flow deposition of the contaminant on a well-characterized soil column and on saturation of the soil bed with contaminants at varied temperatures. Status: We have determined equilibrium constants, heats of adsorption and mass transfer coefficients for eight target compounds, in addition to identification of a "Minimum Allowable Temperature" (MAT) below which, the compound is not completely desorbed from a partial clay soil. Equilibrium constants were strongly dependent on temperature and followed the Van't Hoff equation only above the MAT's. We have developed a model and now use it to predict concentration profiles of target organic pollutants in soil adsorption and desorption experiments, without water vapor. Client/Users: State and EPA regulators and industry concerned with decontamination of soils containing moderately volatile organics. Thermal desorption was recently announced as the Method of Choice for clean-up of the Lipari Hazardous Waste Site in New Jersey. BIOLOGICAL/CHEMICAL/PHYSICAL METHODS Contaminated Groundwater Treatment with Bioreactors Utilizing a White Rot Fungus: P. Armenante, New Jersey Institute of Technology Goal: The main goal of this project is to determine the role of the most significant engineering parameters in the degradation of chlorinated 38 ------- aromatic compounds dispersed in wastewater and contaminated soils, using the white rot fungus Phanerochaete chrysosporium. Rationale: Phanerochaete chrysosporium is a naturally occurring fungus which has been shown in the past to be highly effective against a large number of toxic chlorinated aromatic compounds typically found in wastewater and in contaminated soils. There are a number of engineering parameters, such as the level of agitation to which the fungus is exposed or the type of support to which it is attached, which play an important role in the degradation process. Therefore, the objectives are to assess the role of these parameters in the overall microbial degradation process, and the determination of kinetic rate constants and the optimal reactor configurations best suited for the exploitation of the biotreatment potential of the fungus. Approach: Different reactor configurations were selected as the most appropriate for growing the fungus and stimulating the production of its enzyme system responsible for the degradation activity. Two reactor configurations were considered. The first one consisted of an agitated fermenter provided with multiple axial impellers. The second reactor configuration examined was a packed-bed column. Previous data from our lab showed that this type of system was the most appropriate for the fungus. We improved the basic design by utilizing a newly built column equipped with side ports to monitor the degradation process, and by using wood chips as packing material (instead of synthetic materials). Experiments were also conducted in artificially contaminated sand matrices to which the fungus, previously grown in suspended cultures, was added. Most of the experiments have been conducted with 2-chlorophenol (in the aqueous systems), and lindane (hexachlorobenzene), a commonly used insecticide, in the soil systems. Status: An extensive number of experiments have been carried out. Significant degradation rates were observed when contaminated streams were passed through columns containing the fungus immobilized on a solid support. Similarly, significant degradation of lindane in sand was observed when the sand was mixed with pellets impregnated with the fungus. These results indicate that the fungus can successfully degrade pollutants found in contaminated soils and wastewaters. Client/Users: Researchers studying the degradation of chlorinated aromatic compounds in both wastewater and soil; EPA investigators and regulators interested in biological approaches to remediation of 39 ------- contaminated groundwater and soils; and industry and contractor representatives who are involved in bioremediation activities. Optimization of Biological Soil Remediation: M. Finstein, Cook College, Rutgers University Goal: Based on previous research, the premise is that a mixture of contaminated soil (e.g., coal gasification site) and energy-rich organic waste (cow manure) subjected to controlled composting is a site of 1) biodegradation of problem compounds; and 2) removal of such compounds, hence cleansing of the soil, through "low-temperature steam distillation". System configuration in the laboratory and field lends itself to the capture of distillate. Rationale: Composting is a predominantly aerobic, solid phase matrix, self-heating, thermophilic process. It is initiated and carried forward by a broad range of indigenous microbes, some of which degrade problem compounds. Management of the process is via ventilative heat removal in reference to a microbially favorable temperature ceiling (50°). The vaporization of water is the predominant heat removal mechanism. This accounts for the possibility of an integrated exploitation of biological/ physical action (degradation/low-temperature steam distillation). Approach: In an earlier project, a composting physical model was employed to investigate the fates of 13 polycyclic aromatic hydrocarbons in a rice hull/flour matrix at process control set points of 35, 40, 45, 50, 55, and 60°C. Intrinsic to this system, regardless of set point, is a temperature gradient in the direction of the airflow. Part One of the present project is to determine the fates at fixed temperatures, as above. This is to more precisely assess temperature effects on biological and physical action. Part Two is to determine the fates in the composting physical model in mixtures of soil, soli and cow manure, and soil and sawdust, using a set point of 45°C (best temperature for degradation/distillation as determined in part one) and two creosote doses. Status: Part One: A fixed temperature experimental apparatus was fabricated and employed in runs spanning the design temperatures. The extractions and analyses were completed and the data partly analyzed. Part Two: Three runs were completed using a creosote dose of 3,000 ppm. Although the chemical analyses are not yet completed, this dose 40 ------- suppressed self-heating to temperatures of <45°C (set point). The final three runs will be at a lower dose (probably 1,000 ppm.). Client/Users: Numerous groups have expressed interest in this research, and some are considering full-scale demonstrations. These include: consulting firms, oil and petrochemical companies, investment firms, and citizens groups. A Dynamic Model of Sequencing Batch Reactors: B.C. Baltzis and G. Lewandowski, New Jersey Institute of Technology Goal: The goal of this project is to develop and test mathematical models that describe biodegradation of hazardous wastes in a sequencing batch reactor (SBR). These models, when tested and verified, will provide criteria for optimal engineering designs of industrial units which use biological means for treating hazardous wastes. Rationale: Hazardous wastes need to be treated (detoxified) before they are released to the environment (rivers, sea, lakes, and soil). Biological treatment (when feasible) can be a most economical way to deal with hazardous wastes. Furthermore, it is generally more environmentally benign than alternate technologies such as incineration. Once feasibility is established, it is necessary to have a rational method for designing reactors for biodegradation. Earlier work, has shown that sequencing batch reactors offer a number of operation advantages over conventional continuous flow units. We have derived in the past a mathematical model which was able to describe the dynamic behavior of a SBR when a single pollutant is degraded by a single-type of organism. The model was verified experimentally. Since in practice mixed cultures are used for treating mixtures of substrates, we are currently developing models that would describe these types of processes. Biological systems are extremely complex, and detailed experiments are costly and time-consuming. Furthermore, in the absence of considerable prior experience, it is difficult to design a unit, and optimize its operation, based only on experimental results. A mathematical description of the process, when experimentally verified, can reduce the number of required experiments, and develop engineering design criteria in a rational way. Approach: A number of different microbial species are tested for their ability to individually biodegrade either a single, or a mixture of two pollutants. The kinetics of biodegradation are studied in small scale experiments, and the results are used for predicting the behavior of the 41 ------- system at a larger scale. When mixed cultures are used, the interactions among the species are translated into mathematical models, which are then tested for their validity in experiments with a microprocessor controlled reactor. Status: A mathematical model describing biodegradation of a single pollutant by two competing species has been derived, and experimentally verified for one type of kinetic behavior. Experiments continue for complete verification of the model. Experiments are also under way for biodegrading mixtures of phenol and 2-chlorophenol. Client/Users: Industry concerned with biological treatment of wastes; researchers interested in biodegradation. Removal and Recovery of Heavy Metals from Wastewater by Hollow Fiber Contained Liquid Membrane Technique: K.K. Sirkar, Stevens Institute of Technology Goal: The general 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 first year of this study showed the efficiency and stability of the HFCLM technique for removal of copper from different aqueous waste streams and its simultaneous concentration. The immediate goal is to focus on heavy metals like chronium and mercury. 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 membrane between two sets of microporous hollow fibers in a shell, we have recently obtained a very stable liquid membrane. Since copper removal from wastewater and concentration in the permeate stream for recycle in a stable fashion has been achieved using rh HFCLM technique, similar results should be expected for Cr6+ and Hg. A number of general issues such as volumetric mass transfer rate in such a process, membrane stability, upperlimit purification and enrichment, selection of membrane liquid and its environmental impact, and a predictive model to describe observed purification are to be addressed before the technique can be taken up for technology development. 42 ------- Approach: Our approach consisted of the following steps: 1) Measure distribution coefficient for chromium and mercury between aqueous solution and alkylamine containing diluent; 2) Carry out short term and 1- month long studies of individual removal rates of chromium and mercury in a HFCLM permeator; 3) Develop a model to predict the extent of removal of a metal in a HFCLM permeator; 4) An experiment will be done to study copper removal and chromium removal using vegetable or mineral oil instead of the diluents currently used. In one case, feed containing sodium and calcium salts will be used, For chromium and/or mercury removal, an experiment will be pursued also to see the effectiveness of other extractants like oleic, linolic acids, etc., instead of long-chain amines, and 5) Explore the purification limits of an individual metal (e.g., Chromium) removal and its simultaneous concentration. Status: Both experimental work and modeling activity are underway, with completion expected January 15, 1992. Client/Users: Plants in electroplating, electronics, chlo-alkali, rayon processes can use such a technique once commercialized. The treated streams obtained from remediation of highly polluted sites e.g., Berry's Creek in Meadowlands, may also be processed to concentrate mercury salts and other metallic salts prior to recovery and reuse. It can be used in small or large scale anywhere. Supercritical Fluid Extraction of Organic Contaminants from Soil: R.C. Ahlert, D.S. Kosson, and A. Andrews, Rutgers - The State University of New Jersey Goal: The primary goal of this investigation is acquisition of fundamental equilibrium and rate data for supercritical fluid extraction of complex organic contaminants from soils. A sequential goal is the formulation of models to correlate data, test for thermodynamic consistency, and provide a basis for process design and on-site pilot-scale demonstrations by interested organizations. Rationale: Supercritical fluids (SCFs) can achieve high efficiencies in the extraction of organic contaminants from soil, due to the unique properties of fluids near the critical point. Separations of extract and solvent are facilitated through depressurization. Adsorptive interactions between a complex matrix such as soil, nonpolar organic species, and nonpolar SCFs are not well defined. Fundamental understanding of these interactions 43 ------- may enhance the potential for application of SCF technology in Superfund clean-up actions. Approach: Solubility and adsorption measurements are being carried out in a novel apparatus that incorporates circulation of high-pressure supercritical carbon dioxide (SC CO2) through a fixed bed extractor. This apparatus provides precise temperature/pressure control, on-line sampling, and on-line monitoring of fluid phase concentration via UV absorbance. Both equilibrium pure solid solubility and solid adsorption data have been obtained with the apparatus. Calibration of fluid phase concentrations by on-line sampling/off-line HPLC analysis gives results within 5% of actual values, with reproducibilities within +_ 2%. The solubilities of anthracene, phenanthrene, triphenylene, chrysene and perylene in SC CO2 have been measured at temperatures of 25 to 70°C. The constant density, isothermal adsorption behavior of the same species on a sandy loam has been characterized at SC CO2 densities of 0.69 to 0.85 g/ml. Status: Solubilities and adsorption isotherms on soil have been studied for five PAHs in SC CO2- The solubilities of other organic contaminants, polar and non-polar, in SC CC>2 and other SCFs will be studied. Adsorption of these compounds will be characterized, also with alternate soils, and other SCFs/co-solvent couples. An overall extraction model, incorporating sorption equilibria and mass transfer rates, will be developed in the second year of the project. Client/Users: SCF-based processes seem attractive for remediation of soils contaminated by organic species that are poorly soluble in aqueous media. Possible target substances include chlorinated dioxins, polychlorinated biphenyls, gasification residues and still bottoms. The U.S. EPA Risk Reduction Engineering Laboratory and several industries have expressed interest in process application. 44 ------- TRAINING AND TECHNOLOGY TRANSFER In-Depth Training in Alternative/Innovative Technology Options for Remedial Actions at Hazardous Waste Sites: W. Librizzi, New Jersey Institute of Technology, and R. Rumer, New York State Center for Hazardous Waste Management. Goal: This project developes and delivers technical workshops in two critical technology areas: thermal destruction and treatment of soils, and groundwater contaminated with metals. The workshops specifically provide participants with a basic knowledge and understanding of these technologies that will promote the consideration, evaluation and implementation of appropriate alternative/innovative treatment technologies for Federal Superfund, State Superfund and Potentially Responsible Party Sites. This training should enhance compliance with prohibitions on land disposal under Hazardous and Solid Waste Amendments and the preference for permanent remedy under Superfund Amendments and Reauthorization Act. Rationale: Thermal destruction and treatment of soils and groundwater contaminated with metals are of critical importance because: most National Priorities List (NPL) sites (over 75%) have soil and groundwater contaminated with heavy metals, four of the five most prevalent organics found at inactive sites are ignitable and incineration systems offer the highest degree of reduction of toxicity, mobility, and volume. Approach: The project was initiated as a joint effort between the EPA NHSRC, the N.Y State Center for Hazardous Waste Management at Buffalo, N.Y. and the New York State Department of Environmental Conservation (NYDEC). Four two-day technical workshops were conducted for NYDEC staff by faculty with experience in the training areas. Several steps have been carried out by the Principal Investigators and the Faculty: finalization of workshop agenda, development of curriculum/methodology, preparation of student materials, development of classroom exercises and conduct of technical workshops. Emphasis was placed on presentations that combine lectures, case studies and group participation. Status: The four two-day technical workshops were presented to an average of 40 NYDEC personnel per session (160 people total). The workshop agenda for treatment contaminated soil included such topics as: overview of the soil pollutant extraction process, heavy metals characteristics, remediation technologies, treatment of extraction fluids, 45 ------- and residual management. The thermal destruction workshop agenda included overview of thermal destruction fundamentals, thermal technologies (types, design, operating characteristics, performance systems, etc.), environmental controls, risk, and public perspectives. Both workshops concluded with an exercise that enabled the participants to apply the material learned in class. Client/Users: Federal and State project mangers who are responsible for hazardous waste site remediation. It may also have use by the private sector who have hazardous waste problems. Conference on Incinerator Monitoring: J. Ehrenfeld, Massachusetts Institute of Technology Goal: The purpose of the conference was to: 1) define the state-of-the-art of incinerator monitoring - what current regulations require and the capabilities of current monitoring systems; 2) highlight new technologies for monitoring which may emerge in the next few years; and 3) consider how monitoring should be improved to ensure regulatory compliance and build public trust. Thus, the ultimate goal was to spur new developments in the policy, regulation and technology of incinerator monitoring to satisfy the demands of a concerned public. Rationale: Monitoring is a key element in building public trust in incineration and ensuring that emissions are within agreed upon standards. Monitoring technologies have improved dramatically in the last two decades. "State-of-the-Art" monitors can detect dioxins, furans, and heavy metals - the pollutants of greatest public concern - in the part per billion or part per trillion range. Concentrations low enough to ensure that stringent health-based emission standards are not exceeded. The public is largely not aware of these new capabilities. In addition, regulatory officials and representatives of industry may not be aware of public concerns. For example, officials may not be aware of the importance to many environmental group representatives of monitoring incinerator inputs, as well as outputs. A dialogue among regulators, industry and environmental advocates could help to set the direction for future improvements in monitoring policy and technological development. Approach: A one-day conference addressed specific issues to explore how incinerator monitoring is done today, and how it should be improved in the future. 125 people representing government, industry, environmental groups, and academia participated in the conference, which 46 ------- also featured two lively discussion sessions. Exhibits of incinerator monitoring technology were displayed. Copies of papers presented at the conference were distributed to participants in a bound proceedings. Status: The conference was held on June 6, 1990, and proceedings were distributed in August, 1990. The project has been completed. Significant Results: 125 conference participants increased their understanding of the capabilities and limitations of existing and emerging incinerator monitoring technologies. In addition, participants came to understand how these capabilities and limitations are viewed by the diverse interest groups represented at the conference. The conference helped to bring these different perspectives to the surface in a non- confrontational, constructive setting. Participants offered suggestions for building public confidence in incineration, such as making incinerator emissions data accessible through a public database and hiring citizen inspectors. Many participants noted in conference evaluation forms that these suggestions were among the most useful insights they gained. Several noted the need for more frequent interaction among government regulators, incinerator operators, and representatives of the public interest outside of the heated debate that tends to accompany specific incinerator proposals. This conference demonstrated the usefulness of establishing a forum to meet that need. Aquifer Reclamation and Source Control Conference: E. Grosse, New Jersey Institute of Technology Goal: To provide a structure whereby researchers, professional and technical personnel can share information on new developments, applications, and innovative technologies in aquifer restoration. Rationale: Groundwater resources in the United States have a volume greater than that of all surface water. In EPA Regions 1 and 2, aquifers account for nearly 70% of all potable groundwater. Protection against aquifer contamination and pollution are therefore, major issues in these regions. Approach: Two conferences, one in Region 1, and the other in Region 2, are to be conducted. At the conference, presentations are given by representatives from industry, universities, and governmental agencies, dealing with various aspects of the aquifer problem. 47 ------- Status: The first conference, was held in New Jersey in November, 1990. Client/Users: Researchers and technical personnel responsible for all aspects of aquifer preservation or restoration will benefit from the conference. Superfund University Training Institute (SUTI): William Librizzi, New Jersey Institute of Technology Goal: This project develops, delivers and administers in-depth advanced technical instruction for Regional Project Managers (RPM's), On-Scene Coordinators (OSC's), and Project Officers in three critical areas: legal issues, contract administration and site management. Rationale: Successful implementation of a sustained and effective hazardous waste program required under superfund legislation will require a well trained cadre of On-scene Coordinator/Regional Project Managers (OSC/RPM). These SUTI's provide high level advanced training that aids ERPA in developing experienced and knowledgeable OSC/RPM's. The OSC/RPM's are called upon to manage the cleanup of an expanding number of sites that have complex administrative, legal, and technical challenges. Approach: Experts in the areas of focus conduct the sessions using lecture, case studies and simulation exercises. These provide the OSC/RPM's with a substantial understanding of the technical concepts, their practical applications and the available tools that enhance their ability to fulfill their responsibilities. Case studies and the workshop agenda are based upon SARA laws and regulators plus field experience. EPA participation is required to ensure that the most current critical issues and solutions are included in the activity. Training materials have been developed for use throughout the training experience which are also useful as reference documents. Status: Pilot courses have been completed in Site Management for Remedial Project Managers and Legal Issues. Following evaluations of these pilot courses, modifications to course content have been implemented and the revised courses are scheduled for delivery. Client/Users: Participants in the course will be Federal or State On-Scene Coordinators, or Remedial Project Managers with a minimum of two years experience, 40 hour, 29CFR.1910.120 training, some field experience 48 ------- preferred, and are or will be involved in remedial actions. All participants are expected to have a recommendation from their Division Director. SUMMARY OF OUTPUTS IN FY 90 Refereed Journal Articles 1 4 Articles Submitted or In Press 10 Books and Bound Proceedings 3 Chapters In Other Books or Bound Proceedings 0 Project Reports 3 Conferences and Workshops Held 8 49 ------- BIBLIOGRAPHY REFEREED JOURNAL ARTICLES Barat, R.B., J.W. Bozzelli, W.P. Ho, "Mechanisms of Acceleration and Inhibition in Hydrocarbon Combustion by Chlorocarbons and HC1," Chemosphere. Dioxin '90. June, 1990. Barat, R.A., J.W. Bozzelli, J.P. Longwell, A. Sarofim, "Effects of Chlorocarbons on Flame Intermittency and Stability in a Jet-Stirred Reactor," Combustion Science and Technology. November, 1990. Bozzelli, J.W., E.R. Ritter, "Chlorobenzene Hydro-Pyrolysis Initiated by 02. Combustion Fundamentals and Applications. Vol. 17, p. Ill, 1990. Bozzelli, J.W., E.R. Ritter, "Chlorobenzene Reactions in H2 and H2/O2 Mixtures - Thermodynamic and Kinetic Analysis of Pathways to Dioxin Formation," Combustion and Science Technology. November, 1990. Bozzelli, J.W., E.R. Ritter, "Production of Chloro and Dichlorobiphenyls, Terphenyls and Triphenylenes from Pyrolysis of Chloro and Dichloro Benzenes," Chemosphere - Dioxin '90. June, 1990. Bozzelli, J.W., E.R. Ritter, V. Desai, "Mechanistic Considerations for Cyclopentadiene and Cyclopentadienyl Radical Conversion During Benzene Oxidation," Combustion Fundamentals and Applications. Vol. 19, p. 123, 1990. Bozzelli, J.W., E.R. Ritter, and Y.P. Wu, "Thermodynamic Insights on Pathways to Formation of Chlorinated Dioxins and Dibenzofurans," Chemosphere - Dioxin '90. June, 1990. Bozzelli, J.W., J. Wan-Dong, Jong-In, "Removal of Hazardous Organic Compounds from Soil Matrices Using Thermal Desorption with Purge," Proceedings of the American Chemical Society. Division of Environmental Chemistry. Boston, April, 1990. Bozzelli, J.W., H. Karim, M. Dean, and M.S. Chou, "Detailed Reaction Mechanism for Prediction of NO, NH, CH, CN and OH in Rich Methane Flames," Combustion Fundamentals and Applications. No. 11, p. 71, 1990. 50 ------- Dauerman, L., N. Ibrahim, E. Sedhom, G. Windgasse, "Microwave Treatment of Hazardous Wastes: Immobilization of Chromium in Soil," Environmental Science and Technology Dauerman, L. and G. Windgasse, " Microwave Treatment of Hazardous wastes: Removal of Volatile and Semi-Volatile Organics from Soil," Environmental Science and Technology Graham, W. and D. McLaughlin, "Stochastic Analysis of Non- Stationary Subsurface Transport., 1. Unconditional Moments," Water Resource Res.. Vol. 25, No. 2, pp. 215-231, 1989. Graham, W. and D. McLaughlin, "Stochastic Analysis of Non- Stationary Subsurface Transport., 2. Conditional Moments," Water Resource Res. Vol. 21, No. 11, pp. 2331-23355, 1989. Peters, W.A., G.S. Darivakis, and J.B. Howard, "Solids Pyrolysis and Volatiles Secondary Reaction In Hazardous Waste Incineration Implications for Toxicants Destruction and PIC's Generation," Hazardous Waste and Hazardous Materials. Vol. 7, pp. 89-102, 1990. ARTICLES SUBMITTED OR IN PRESS Andrews, A.T., R.C. Ahlert, and D.S. Kosson, "Supercritical Fluid Extraction of Aromatic Contaminants from a Sandy Loam Soil," Journal of Hazardous Materials. Barat, R.B., A.F. Sarofim, J.P. Longwell, 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. In Press, Combustion. Barat, R.B., J.W. Bozzelli, W. Ho, "Thermal Reactions of CH2C12 in O2/H2 Mixtures: Implications for Chlorine Inhibition of CO conversion to CO2," Accepted - In Press, Combustion and Flame. September, 1990. Barat, R.B., C.V. Wikstrom, J.P. Longwell, and A.F. Sarofim, "Characterization of the Mixing/Chemistry Interaction in the Torroidal Jet- Stirred Combustor," submitted to the American Institute of Chemical Engineers. 51 ------- Bozzelli, J.W., and I. Jong, "Mass Transfer Parameters and Equilibria of Organic Contaminants in Heatred Soil Matrices," to be presented at the AIChE Annual Meeting, Chicago, November 11-16, 1990, Group II, Fundamentals, Mass Transfer. Bozzelli, J.W. and W. Ho, "Mechanisms of Chlorine Acceleration and Inhibition in Pyrolysis and Oxidation of Chlorocarbon/Hydrocarbon Mixtures, submitted to Combustion and Science 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, August 2-4, 1989. Accepted for publication in Combustion Science and Technology, c. 1990. Li, S.G., and D. McLaughlin, "A Non-Stationary Spectral Method for Solving Stochastic Groundwater Problems, 1. Theory," submitted to Water Resour. Res.. July, 1990. Li, S.G., and D. McLaughlin, "A Non-Stationary Spectral Method for Solving Stochastic Groundwater Problems, 2. Examples," submitted to Water Resour. Res.. July, 1990. Taylor, S.W., and P.R. Jaffe, "Enhanced In-Situ Biodegradation and Aquifer Permeability Reduction," Journal of Environmental Engineering. ASCE, in press. BOOKS AND BOUND PROCEEDINGS Dauerman, L., H. Gu, N. Ibrahim, E.H. Sedhom, G. Windgasse, Applications of Microwave Treatment of Hazardous Wastes: a) Non-Volatile Organics. b) Heavy Metals." Proceedings of the Materials Research Society, Spring meeting, Symposium on Microwave Processing of Materials, San Francisco, CA, April 16-21, 1990. Incinerator Monitoring: Techniques for Assuring Performance and Building Public Trust. Massachusetts Institute of Technology, Cambridge, MA, June 6, 1990. 52 ------- Singhal, N., P.R. Jaffe, and W. Maier, "Effect of Carbon Source on The Biodegradation of Trichloroethylene by Mixed Cultures of Methanogens and Fermenters" proceedings of the 1990 ASCE National Conference on Environmental Engineering. Washington, July 1990, C.R. O'Melia (Ed.), ASCE, N.Y. pp. 915-916. CHAPTERS IN OTHER BOOKS OR BOUND PROCEEDINGS None. PROJECT REPORTS Armenante, P.M. and G. Lewandowski, "Contaminated Groundwater Treatment with Bioreactors Utilizing A White Rot Fungus," Project Report submitted to the Northeast Hazardous Substance Research Center for Federal Regions 1 and 2, February, 15, 1990. Darivakis, G.S., J.B. Howard and W.A. Peters, "Fundamental Studies of Solids Devolatilization for Hazardous Waste Destruction," Technical Progress Report for Fiscal Year ending February 15, 1990, submitted to the Northeast Hazardous Substance Research Center. Korfiatis, G.P. and L.N. Reddi, "A Study of the Efficiency of Vibroflotation in In-Situ Phase Separation of Immiscible Contaminants," Project Report #1, April 11, 1990. THESES/DISSERTATIONS Andrews, A.T., "Supercritical Carbon Dioxide Extraction of Polycyclic Aromatic Hydrocarbons from Contaminated Soil," Doctoral Dissertation in Chemical and Biochemical Engineering. Rutgers - the State University of New Jersey, Piscataway, New Jersey, October, 1990. Aquilar, E., "Efficiency of Vibroflotation as an In-Situ Remediation Technique," MS Thesis, Department of Civil, Environmental, and Coastal Engineering, Stevens Institute of Technology, 1990. Dong, J.I., "Mass Transfer Parameters and Equilibria of Organic Contaminants in Heated Soil Matrices," Ph.D. Chemical Engineering, New Jersey Institute of Technology, July, 1990. 53 ------- Fan, S., "Microwave Treatment of Organic Contaminated Soil," MS Thesis, New Jersey Institute of Technology, October, 1989. Garni, A.C., "Biodegradation of Hexachlorocyclohexane in Sand and Wastewater Using Immobilized Phanerochaete Chryosporium," MS Thesis, New Jersey Institute of Technology, in preparation, (expected completion date is December, 1990). Gu, H., "The Application of Microwave Technology to the Remediation of Non-Volatile Organic Contaminated Soil," MS Thesis, New Jersey Institute of Technology, May, 1990. Hyman, J.A., "Groundwater Monitoring in Three Dimensions Using the Multi-Level Sampler," MS Thesis, Massachusetts Institute of Technology, 1990. Ibrahim, N., "Scanning Electron Microscopy and Energy Dispersive Spectroscopy; Study on Microwave Heated Soil Bearing Chromium," MS Thesis, New Jersey Institute of Technology, May, 1990. Jou, G., "Immobilization of Chromium in Soil as A Result of Microwave Treatment," MS Thesis, New Jersey Institute of Technology May, 1989. Ko, Y.S., "Biodegradation of Phenol by Two Competing Microbial Species in A Sequencing Batch Reactor," New Jersey Institute of Technology, 1990. Mahesh, K.C., "Microwave Treatment of Spent GAC to Effect Regeneration On-Site," MS Thesis, New Jersey Institute of Technology, October, 1989. Windgasse, G., "A New Hazardous Waste Treatment Technology Utilizing Low Power Density Microwave Energy" MS Thesis, New Jersey Institute of Technology, May 1989. 54 ------- CONFERENCES AND WORKSHOPS HELD "Applications of Microwave Treatment of Hazardous Wastes: a) Non- Volatile Organics, b) Heavy Metals," Symposium on Microwave Processing of Materials. - L. Dauerman, H. Gu, N. Ibrahim, E.H. Sedhom, G. Windgasse, Materials Research Society, Spring Meeting, San Francisco, CA, April 16-21, 1990. "Biodegradation of Single and Multiple Hazardous Substances in A Sequencing Batch Reactor: Theory and Experimental Results," B.C. Baltzis G. Lewandowski, S. Dikshitulu, Y.S. Ko, and K.W. Wang, AIChE Annual Meeting. Chicago, November 13, 1990. "Investigations on Retention and Recovery of Immiscible Contaminants in Soils," - L.N. Reddi, G.P. Korfiatis, D.A. Vaccari, and A. Hadim, EPA Region 1 and 2, Conference on Aquifer Reclamation and Source Control, November, 1990, Woodbridge, NJ. "Microwave Treatment of Hazardous Wastes: Chemical Mechanisms," L. Dauerman, G. Windgasse, Industrial Microwave Processing Conference, Deakin University, Geelong, Australia, July 12, 1990. "Microwave Treatment of Hazardous Wastes," L. Dauerman and G. Windgasse, The International Conference on High Frequency/Microwave Processing and Heating. KEMA Laboratories, Arnhem, The Netherlands, 1989. "Selective Separations Using Contained Liquid Membranes," R. Basu and K.K. Sirkar, Pollution Prevention for the 1990's: A Chemical Engineering Challenge. Washington. D.C.. An AIChE Symposium, December, 4-5, 1989. "Supercritical Fluid Extraction of Toxic Organics from Soil," A.T. Andrews, R.C. Ahlert and D.S. Kosson, 1989 AIChE Annual Meeting. San Francisco, CA, November, 1989. "Supercritical Fluid Extraction of Aromatic Contaminants from A Sandy Loam Soil," A.T. Andrews, R.C. Ahlert, and D.S. Kosson, 1990 AIChE Spring National Meeting. Orlando. Florida, March, 1990. 55 ------- GREAT LAKES AND MID-ATLANTIC HAZARDOUS SUBSTANCE RESEARCH CENTER PARTICIPANTS: DIRECTOR: TECHNOLOGY TRANSFER DIRECTOR: University of Michigan Michigan State University Howard University Walter J. Weber Ph.D. Great Lakes/Mid-Atlantic Hazardous Substance Research Center The University of Michigan Office Ann Arbor, Michigan 48109-2125 Phone: 313/763-1464 Fax: 313/763-2275 James H. Johnson, Jr. Ph.D., Assistant Director Great Lakes and Mid-Atlantic Hazardous Substance Research Center Department of Civil Engineering Howard University Washington, DC 20059 Phone: 202/806-6570 Fax: 202/806-5961 Karen E. Vigmostad, Program Manager Technology of Transfer and Training Great Lakes and Mid-Atlantic Hazardous Substance Research Center Michigan State University Office C231 Holden Hall East Lansing, Ml 48824-1206 Phone: 517/353-9718 Fax: 517/355-4603 THE CENTER AT A GLANCE The University of Michigan, and Michigan State University and Howard University have combined forces to pursue cooperative efforts in multi-disciplinary hazardous substance research. The partnership developed a successful proposal to the U.S. Environmental Protection Agency (EPA) for designation and funding as one of five new regional hazardous substance research centers. Since February 1989, when the three universities were funded by the EPA to establish the Great Lakes and Mid-Atlantic Hazardous Substance Research Center (the Center) for 57 ------- federal Regions 3 and 5 with matching fund support provided by the Michigan Department of Natural Resources (MDNR). GREAT LAKES/MID-ATLANTIC HAZARDOUS SUBSTANCE RESEARCH CENTER Research Project Distribution (Number of Projects) 19% Technology Transfer and Trainina 37% Bioremediation (10) 44% Engineered Systems (12) Major Focus: The Center's research is focused on the development and refinement of biological remediation technologies that are effective, efficient in their use of energy and other resources, and environmentally sound. Center projects emphasize the types of contamination commonly found in these two heavily industrialized regions. The Center's programs are designed particularly to serve the people, industry, agencies, and other organizations in federal Regions 3 and 5. These regions encompass all of the Great Lakes and most of the mid-Atlantic states: Delaware, the District of Columbia, Illinois, Indiana, Maryland, Michigan, Minnesota, Ohio, Pennsylvania, Virginia, West Virginia, and Wisconsin. The Center's mission is to provide the philosophical framework, organizational structure, and resources required to support integrated and collaborative research designed to advance the science and technology of hazardous substance management and control. The Center promotes 58 ------- coordinated efforts focused on common objectives in selected research subject groupings, and encourages and facilitates participation by researchers from diverse disciplines and perspectives in each subject group. Cooperative interactions with industry, government, other academic institutions, and the public sector are key elements of the Center's comprehensive program of research, education, and technology transfer. The Center brings together a resource of more than 100 faculty and staff with expertise in hazardous substance control and environmental engineering and sciences. Dr. Walter J. Weber, Jr., of The University of Michigan's Department of Civil and Environmental Engineering serves as Center Director. Dr. Weber has primary responsibility for the Center's overall research focus and implementation. Dr. Thomas C. Voice of the Department of Civil and Environmental Engineering at Michigan State University is the Associate Director. Dr. Voice coordinates the research at Michigan State University and oversees the training and technology transfer programs with Karen E. Vigmostad who is the Program Manager for Training and Technology Transfer. Dr. James H. Johnson, Jr., Chair of the Department of Civil Engineering at Howard University is the Assistant Director. Dr. Johnson has primary responsibility for coordinating the research and training activities of that Region 3 institution with the two Region 5 institutions in Michigan. A list of key individuals currently associated with the projects and activities of the Center is given below (Table 1). TABLE 1: KEY PERSONNEL IN THE CENTER University of Michigan Dr. Linda M. Abriola Dr. Marilyn Barger Mr. Michael C. Berger Dr. Avery H. Demond Dr. Kim F. Hayes Dr. Jerome J. Kukor Dr. Paul F. Nowak Dr. Ronald H. Olsen Dr. Milagros S. Simmons Dr. Keeran R. Srinivasan Dr. Timothy M. Vogel Dr. Walter J. Weber, Jr. Dr. Steven J. Wright Michigan State University Dr. Stephen A. Boyd Dr. Simon H. Davies Dr. Robert F. Hickey Dr. Susan J. Masten Dr. Patrick J. Oriel Dr. James M. Tiedje Ms. Karen E. Vigmostad Dr. Thomas C. Voice Dr. Roger G. Wallace Howard University Dr. Joseph N. Cannon Dr. James H. Johnson, Jr. Dr. Edward J. Martin 59 ------- The activities of the Center are guided by two advisory groups that include members from academia, government, and industry: a Science Advisory Committee and a Training and Technology Transfer Advisory Committee (members of these committees are identified in Tables 2 and 3, respectively). The Science Advisory Committee provides general policy guidance and specific technical assistance in the solicifications review review of research projects. Personal attention is provided for each research project by small groups of committee members (i.e., Project Oversight Teams). These groups monitor progress and serve as resources to individual researchers on a "standing" basis during the course of the project. By staggering the terms of committee members from one to three years, we ensure continuity while bringing in fresh ideas as new members replace those whose terms have expired. The Training and Technology Transfer Advisory Committee works with Center administrators to develop efficient and effective ways to communicate research and technological developments to those who can benefit from it. This committee reviews the Center's training and technology transfer program and projects and suggests ways to refine our approaches and activities in this important area of responsibility. Members are drawn from state, federal, and independent training and technology transfer organizations. The Center's budget is summarized in Table 4 and the number of students supported by the Center is presented in Table 5. 60 ------- MEMBER Mary P. Anderson Univ. of Wisconsin, Madison Gary F. Bennett** Univ. of Toledo Robert J. Bowden U.S. EPA Region 5 Richard L. Brunker U.S. EPA Region 3 Torrey C. Brown Maryland D.N.R. John J. Convery U.S. EPA Office of Res. & Dev. Stacy L. Daniels Dow Chemical Co. Gary E. Guenther Michigan D.N.R. Robert L. Irvine Univ. of Notre Dame S. Job. Kang McNamee, Porter, Seeley William L. Mills H.H. Atlantic Corp. Joseph V. Osterman* U.S. Dept. of Defense Irwin H. Suffet Drexel University John T. Wilson U.S. EPA TABLE 2: SCIENCE ADVISORY AFFILIATION University University Government Government Government Government Industry Government University Industry Industry Government University Government COMMITTEE EXPERTISE Subsurface systems Process engineering Regulatory research needs Regulatory research needs Technology implementation Treatment and remediation techno-logies Process engineering Technology implementation Process engineering Process engineering Environmental resources Biological processes Chemical processes Subsurface systems *Chairman **Vice Chairman 61 ------- TABLE 3: TECHNOLOGY TRANSFER AND TRAINING ADVISORY COMMITTEE MEMBER AFFILIATION EXPERTISE William C. Arble Pennsylvania State Univ. University Lois R. DeBacker Government Michigan Dept. of Commerce Patricia B. Easley U.S. EPA Region 5 Margaret Kelly U.S. EPA Michael J. Senew* Haz. Materials Training & Research Institute Steven Smagin U.S. EPA Region 3 John J. Stanton U.S. EPA, Hdq., Wash. *Chairman Government Government Industry Government Government Technical assistance Waste reduction services Regulatory needs Regulatory needs Training Regulatory needs Technology transfer 62 ------- TABLE 4: CENTER FUNDING FUNDING SOURCES FY 1990-91 FUNDS* FUNDS TO DATE EPA: Centers Program $944,473 $2,944,473 EPA: Other 0 0 Other Govt: Federal 0 0 Other Govt: State 0 500,000 Consortium 236,119 236,119 Private Sector Q Q TOTAL $1,180,592 $3,680,592 *October 1, 1990 - September 30, 1991 TABLE 5: STUDENT SUPPORT STUDENT LEVEL NUMBER FY 1990-91 FUNDS* Undergraduate 2 $ 6,425 Graduate 21 238,274 Post-doctoral 6_ 88.200 TOTAL 29 $332,899 *Includes tuition, travel, etc. CENTER DIRECTOR'S REPORT Since its founding in February 1989, the Center has developed and refined our initial focus on research and technology transfer programs related to on-site remediation, with special emphasis on bioremediation. Center research programs continue to emphasize remediation schemes which integrate biological with complementary chemical and physicochemical technologies. The focusing process helps identify and target logical new research areas to pursue as well as refine ongoing efforts. Identification and prioritization of research needs and topics is done in partnership with two standing advisory committees. This process is iterated regularly as research in certain areas matures and other promising areas of pursuit emerge. In this context, the funding structure of the EPA's Centers Program allows what normal granting procedures 63 ------- would not. Specifically, the Centers Program enables the structuring of flexible research groups, or "teams", to meet the specific needs of emergent research problems and projects. The research teams are restructured as required to maintain relevance and compatibility as projects logically mature. To capsulize, the Center provides a climate of cooperation and excellence for research that is: • multidisciplinary in scope; • state-of-the-art in character and quality; • problem-focused in selection of research topics; and • solution-oriented in approach. The Center has made a strong commitment to foster multi- disciplinary research efforts. The success of the Center's problem-focused research program stems from the flexible research teams referred to above; research teams structured to have specific combinations of scientific and engineering expertise. During this past year, this commitment has been pursued in two specific ways. Namely, existing interactions have been strong there and two new areas of cooperative research have been added: free radical oxidation processes (including natural and engineered photolytic processes), and open-water site remediation processes. Because the ultimate success of research depends on the collaborative sharing of information and ideas, the Center has initiated a series of satellite research retreats as catalysts for the Center's interdisciplinary, multi-investigator research activities. These retreats bring together groups of investigators working on related topics to discuss research directions, progress, and other issues of mutual concern. Common sets of goals and understandings are sought. The first of these retreats brought together over twenty-five research personnel from the three member institutions working on various facets of the use of surfactants (surface active agents) for in-situ (in place) soil decontamination. Retreats on biological processes and free-radical oxidation processes are being scheduled. A plan to expand the satellite research retreat concept to all five EPA centers is also planned. The Center will host an on-site remediation workshop a May, 1991. Using a format similar to that of a Gordon Conference, groups of specific investigators from all five centers will gather to discuss their research activities in an informal and uninterrupted setting. The workshop will also provide a session led by experts from 64 ------- business and government for discussion of problems involved with the practical applications of specific technologies. The last day will be devoted to the development of consensus regarding: 1) the current status of on- site remediation research; and 2) an agenda for ongoing cooperation and collaboration in the research efforts of the five centers. The five-center workshop is one of a number of projects being coordinated in concert with the Center's training and technology transfer program. The Center strives to make its research more useful and accessible to others through its technology transfer projects. Related outreach activities of the program include a variety of types of publications, conferences and workshops, training and audiovisual materials, and direct assistance to faculty and regional personnel. Publications distributed or in press include the Center's research chronicle, synergos, specific research summaries, and a manual on reactor design for treatment and remediation process research. The Center also funds technology transfer-related research and demonstration projects. For example, we are currently developing approaches to technology transfer using the videotape medium. One of the projects in this area involves a joint effort with EPA Region 3 personnel on a bioremediation videotape targeted for field staff. The tape will provide baseline scientific information on what bioremediation is, how it works, and what we know about applications of the technology. In an attempt to gain a clearer understanding of which techniques work best and why, we are currently developing a new project to analyze the process of technology transfer itself. Several responses to a request for proposals are currently under external peer review, and will be considered for funding at the next meeting of the Training and Technology Transfer Advisory Committee. HIGHLIGHTS FOR 1990 Nine new research projects we initiated in September of this year, including several in two new areas: free-radical oxidation processes and open-water site remediation. Marilyn Barger, Stephen Parus, and the Center Director are investigating laser-aided photodegradation of polychlorinated biphenyls (PCBs) and related compounds, particularly with respect to concentrated mixtures extracted from soils and sediments. Susan Masten and Simon Davies are examining ozone-induced free radical oxidation of chlorinated benzenes and chlorinated biphenyls in both solution phase and with adsorbed soils and sediments. Simon Davies and 65 ------- Thomas Voice are studying mechanisms governing the release of contaminants from sediments resuspended during dredging operations. The initiation of open-water remediation projects is designed to help the Center address critical issues facing the Great Lakes states. Two additional bioremediation projects have also started. Patrick Oriel will compare the advantages and disadvantages of bioremediation of enzene, toluene, ethylene and xylene (BTEX)-contaminated sites using thermophilic bacteria and anaerobic respiration with nitrate. BTEX is shorthand notation for a suite of compounds which are major constituents of gasoline; namely, BTEX. James Johnson and Edward Martin will analyze solid phase aerobic/anaerobic treatment of polycyclic aromatic hydrocarbon compounds (PAHs). This work is an extension of current investigations of the biodegradation of PAH compounds under aerobic conditions. Ongoing surfactant research efforts have been strengthened by several new projects begun in September. Steven Wright is studying the role of "fingering"--preferential channeling—of surfactant solutions during their use in aquifer remediation schemes. Linda Abriola's newest surfactant project looks at phase equilibria and transport properties of surfactant systems of interest to soil remediation. Avery Demond is examining the effects of surfactants on the transport properties of aquifer systems during remediation. She intends to develop quantitative descriptions of capillary pressure and relative permeability relationships to be used in the mathematical modeling of aquifer behavior during remediation processes. Kim Hayes and Keeran Srinivasan are assessing the effects of surfactant sorption and desorption during their use in the remediation of contaminated aquifers. In the training and technology transfer area, James Johnson and faculty from Howard University, with input by faculty from the University of Michigan, have extended our Center's workshop for high school science and math teachers to presentations in the states of Pennsylvania and Michigan. This workshop, is a three-day session designed to acquaint teachers with current issues in hazardous substances and with career opportunities in the environmental sciences and engineering. There is a special emphasis on encouraging minorities to pursue careers in these vital areas. The workshops have been videotaped, and plans are being made to produce three video segments covering various aspects of the sessions. 66 ------- In September of this year the first issue of our research chronicle, synergos, was mailed to over 3,000 people in the 11 states and the District of Columbia represented by our Center as well as to many other interested parties across the country. The name synergos, a Greek word meaning "bringing together", captures the essence of our Center: a "bringing together" of diverse resources in a coordinated and focused program of environmental research. The past year also witnessed several specific research accomplishments in our ongoing research programs, some of which are highlighted below. Linda M. Abriola reports that a joint experimental model verification program was initiated between surfactant investigators with Project R8 at the University of Michigan and Project R9 at Michigan State University*. Laboratory column studies being conducted in Project R9 are being used to validate modeling approaches being developed in Project R8. This cooperative effort was a direct result of our surfactant satellite retreat held in January 1990. Milagros Simmons believes that the potential analytical applications of supercritical fluid extraction techniques being developed in Project R13 are enormous. She sees the field moving towards this technique as an alternative to conventional solvent extraction of organic contaminants from soils and sediments for subsequent analytical determination. Several contract laboratories are developing these test methods for specific applications. Symposia and workshops have facilitated discussions about the potential as well as the limitations of this technique. Walter J. Weber. Jr. and Marilyn Barger and their research team have completed the design, construction, and shakedown testing of a unique completely mixed batch reactor for investigating supercritical water oxidation (SCWO) processes in Project R12. This reactor is capable of accommodating viscous organic concentrates, slurries, and solids, as well as the aqueous type waste streams commonly studied in more conventional flow-through SCWO systems. The project is initially investigating the thermodynamics, kinetics, and mechanisms of the oxidation of PCB-laden sludges and oils. These compounds are often the "critical" or "limiting" components of wastes in which they are present due to their resistance to oxidation and their potential toxicity, even at low concentrations. The Projects are identified by number in the next section of this report. 67 ------- results of this research will thus provide insight to the design of SCWO reactors for "worst-case" type wastes. Paul Nowak reports significant developments in both of his Center- funded Project 2T technology transfer videotape activities. He feels that the cooperative efforts between EPA field people and university researchers on these projects will reap large rewards. These efforts make investigators more aware of the need for state-of-the-art technical training and technical information in the field. Ramesh Chawla and Joseph Cannon report conclusions from project RIO that trichloroethylene (TCE) adsorption on top soils exhibits nonlinear behavior and that desorption in both water and surfactant solutions is typically marked by hysteresis. They note that these trends are more pronounced with increasing aging of the adsorbed TCE. While naturally occurring soil microbes can be stimulated to degrade TCE after it has desorbed, Chawla and Cannon have found that the biodegradation process is inhibited by the presence of the surfactants used to enhance the desorption. Roger Wallace has developed time-lapse color films that show the dynamics of the flow of a surface oil spill and the formation of oil lenses at the water table, as well as the downward migration patterns of surfactant solutions and the sequence of events that follow the penetration of the surfactant into oil lenses. This visualization work being conducted in Project R9 should facilitate a better understanding of complexities encountered in field applications of surfactant flushing techniques. Ronald Olsen and Jerome Kukor have fingerprinted a novel metabolic pathway for BTEX degradation in the studies they are conducting in Project R3. The regulation of this new pathway has been defined, and this information will be used in the "design" of BTEX-degrading bacteria for "seeding" in bioremediation schemes. Olsen and Kukor have also shown that xylene degradation by bacteria isolated from BTEX-contaminated aquifers must be induced by toluene or, less frequently, by benzene. Thomas Voice and Robert Hickey report that their cooperative efforts in Projects R6 and Rll demonstrate that the use of fluidized bed reactor systems for biological activated carbon processes provides enhanced system stability and overall removal efficiency. This work, which is coordinated with pilot-scale studies at the Michigan Biotechnology Institute in East Lansing, Michigan, also confirms that systems which combine the removal mechanisms of adsorption and biological degradation 68 ------- generally provide performance superior to that of systems employing only adsorption or biological action. James M. Tiedje believes that the isolation and stimulation of indigenous microorganisms provides an effective and practical means for propagating active PCB-dechlorinating communities for bioremediation of PCB-contaminated sites. The success he has had in Project Rl with respect to serially transferring communities active on Aroclor 1260 is particularly important because of the complete recalcitrance of this mixture to aerobic degradation. 69 ------- TABLE 6 GREAT LAKES/MID-ATLANTIC HAZARDOUS SUBSTANCE RESEARCH CENTER PROGRAM SUMMARY PRINCIPAL INVESTIGATOR PROJECT BIOREMEDIATION END DATE CURRENT TOTAL BUDGET BUDGET J.M. Tiedje T.M. Vogel R. Olsen/ JJ. Kukor T.M. Vogel S.A. Boyd R. Chawla/ J.N. Cannon T.C. Voice W.J. Weber, Jr. (Rl) Isolating organisms which dechlorinate PCBs (R2) Investigation of mechanisms controlling rates of dechlorination of halogenated organic solvents by methanogens (R3) Engineered organisms: development of microbial strains with enhanced potential for degradation of volatile organic carbon compounds (VOCs) (R4) Factors affecting attachment and release of microorganisms to aquifer solids (R5) Bioavailability of aged residues in contaminated soils (RIO) Use of microorganisms and surfactants for in-situ detoxification of hazardous wastes in soils (Rll) Design and operation of biological activated carbon adsorption systems (R12) Destruction of biologically resistant organics by supercritical water oxidation $72,000 $42,000 $58,000 $34,000 $80,000 $71,000 $70,000 $117,000 $90,000 $105,000 $110,000 $47,000 $91,000 $100,000 $98,000 $140,000 70 ------- PRINCIPAL INVESTIGATOR PJ. Oriel PROJECT (R20) Thermophilic bio- remediation* END DATE J. Johnson, Jr. (R22) Solid phase/ E.J. Martin anaerobicaerobic treatment of polycyclic aromatic hydrocarbon compounds* CURRENT BUDGET $0 $0 TOTAL BUDGET $0 $0 ENGINEERED SYSTEMS/SURFACTANT OXIDATION R.F. Hickey (R6) Development of modular laboratory-scale reactors for investigation of hazardous waste treatment schemes J. H. Johnson L.M. Abriola R.B. Wallace M.S. Simmons L.M. Abriola M. Barger/ S.J. Parus/ (R7) Detoxification of hazardous and substances via in-vessel composting (R8) Modeling surfactant mobilization of entrapped organic liquids in groundwater systems (R9) Physical models for examining in-situ use of surfactants to achieve Non-aqueous Liquid Phase (NAPL) clean up (R13) Methods for isolation of hazardous substances from complex mixtures (R14) Phase equilibria and transport properties of surfactant systems of interest to soil remediation* (R15) Laser photodegrada- tion of polychlorinated $80,000 $72,000 $36,000 $71,000 $42,000 $1,000 $1,000 $91,000 $90,000 $73,000 $100,000 $53,000 $1,000 $1,000 W.J. Weber, Jr. biphenyls and related compounds* *Note, some projects were initiated during the last month covered by this report. 71 ------- PRINCIPAL INVESTIGATOR PROJECT END DATE CURRENT BUDGET TOTAL BUDGET S.J. Wright A.H. Demond K.F. Hayes/ K. Srinivasan S.J. Masten S.H. Davies S.H. Davies/ T.C. Voice (R16) The role of fingering during aquifer remediation with surfactants* (R17) The effect of surfactants on the transport properties of aquifers during remediation* (R18) Remediation of contam- inated aquifers with surfactants: The effect of surfactant adsorption and desorption (R19) Use of oxidants for the degradation of chlorinated benzenes and PCBs in aqueous systems and sediments* (R21) Mechanisms governing the release of contaminants from sediments resuspended during dredging operations* $2,000 $0 $4,000 $0 $2,000 $0 $4,000 $0 TRAINING AND TECHNOLOGY TRANSFER J.H. Johnson, Jr P.P. Nowak K.E. Vigmostad K.E. Vigmostad K.E. Vigmostad/ W.J. Weber, Jr. (Tl) Materials and hazardous $53,000 %79,000 waste workshop (T2) Waste minimization information $30,000 $30,000 and training/Bioremediation videotape development (T3) State/industrial assistance $0 $0 (T4) synergos, the research chronicle $4,500 $4, 500 (T5) Five-center on-site remediation $0 $0 research workshop 72 ------- RESEARCH PROJECT DESCRIPTIONS BIOREMEDIATION Isolating Organisms Which Dechlorinate Polychlorinated Bi- phenyls (PCBs): James M. Tiedje, Michigan State University Goal: To stimulate, enrich and hopefully isolate microorganisms from PCB- contaminated river sediments which have the capacity to dechlorinate PCBs, thus making them less harmful. These organisms must be propagated in some way in order to magnify this activity and make bioremediation of PCB-contaminated sites feasible. 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: Isolation of dechlorinating organisms has proven very difficult. With no known single route to success, it is important to explore several routes to determine which is most likely to be promising for PCB dechlorinators. Thus, the following approaches are being evaluated. First, dechlorinating organisms are being enriched by virtue of the dechlorinating reactions serving as the only electron acceptor for growth, and perhaps as an energy source. While this rate of enrichment is likely slow, it is the best strategy yet known to selectively enrich dechlorinators over other indigenous microorganisms. Second, information learned about isolated dechlorinators, especially strain (DCB-1), will be used as a clue to recognize unique features that may also occur in other dechlorinators. Such features are the unique 16S RNA sequences, the presence of (CO) dehydrogenase, and unique sulfur metabolizing pathways. Third, use of simplified fractions of communities and more defined conditions that result in active PCB dechlorination. Status: Enrichments were established using electron donors (pyruvate, fornate) and medium found to be most effective for dechlorination by strain DCB-1, and Aroclor 1242 as the sole electron acceptor. The following was found: 1) a stable meta dechlorinating community was established through nine serial transfers. It removes about 0.5 mole/mol biphenyl. The rate of dechlorination has not increased with transfer; 2) this enriched 73 ------- community does not need the normal sediment microflora since the same dechlorination activity occurred when inoculated into sterile and nonsterile sediments. Dechlorination does not occur in aqueous medium nor with inorganic matrices (sand, clays); 3) dechlorination activity of the inoculum was inhibited by BBS and sulfate, but not by nitrate, CC>2, ferric- oxyhydroxide, nor is it stimulated by the addition of hydrogen or acetate; and 4) the enriched community has activity on Aroclors 1242, 1248, 1254, and 1260 (to a lesser extent) but not on 1221. Because the above enrichment might be dependent on an expensive electron donor, we also established enrichments using native sediment carbon as the donor. The concentration of Aroclor was increased in 5000 ppm, Aroclors 1254 and 1260 were also used as electron acceptors and inocula from other sites (4) were used. These enrichments removed approximately 1 Cl/mole biphenyl and have been carried through three serial transfers on Aroclor 1254 and 1260. The more successful inocula were from an industrial lagoon and a lake receiving industrial effluent that had been exposed to these higher chlorinated congeners. Studies were initiated with trichlorinated biphenyls (2,2',3' and 2,3',4' congeners), which are the congeners most readily dechlorinated in Aroclors. It is hoped that a factor rate would speed the study of PCB dechlorination. More than 50% of these congeners were dechlorinated within two weeks, confirming the faster rate. Attempts to increase the bioavailability of these trichlorinated biphenyls by placing them in an emulsifier (ligninsulfonate) or encapsulating them in liposomes did not increase dechlorination. Client Audiences: People interested in this research include industrial and academic researchers. Presentations have been made before many individual groups and academic researchers. Audiences with large industrial representation include the Gordon Conference on Aquatic Chemistry, the NIEHS Symposium on Biodegradation, the International Biodegradation Symposium, the UNEP Symposium on Biodegradation and the European Environmental Research Organization Symposium on Biodegradation. Individual discussions with approximately 10 environ- mental engineering firms and companies have taken place on their specific PCB issues. 74 ------- Investigation of the Mechanisms Controlling the Rates of Dechlorination of Halogenated Organic Solvents by Methanogens: Timothy M. Vogel, University of Michigan Goal: To identify the chemical characteristics of microbial dechlorination of chlorinated solvents. The dechlorination of organics generally reduce their health hazard. Microbial dechlorination may be applicable to cleaning hazardous waste sites. Rationale: Previous research illustrates the ability of some anaerobic microbes to dechlorinate hazardous waste compounds. We have shown previously that this is a fortuitous process not requiring any natural selection. Development of techniques that enhance this process could potentially be applied in clean-up activities. Approach: Several approaches to understanding the chemical characteristics of microbial dechlorination are being investigated. First, experiments deciphering the mechanisms and kinetics of dechlorination by metal-organics are underway. This requires examination of the influence of different metals chelated in porphyrins, which model different biomolecules in microorganisms. Second, microbes grown under different conditions, such as substrate and metal concentrations, are exposed to chlorinated compounds. The dechlorination is compared with microbes not previously acclimated and with nonviable microbial cells. Status: Experimental work is underway. Metal preference for dechlorination is in the order cobalt, magnesium, and iron, which would imply that cobalt containing reduced biomolecules will be more effective at dechlorinating solvents. Completion of this set of experiments is expected by 1991. Client Audiences: People interested in this research include consulting engineering companies and industries which either use or produce chlorinated solvents. Engineered Organisms: Development of Microbial Strains With Enhanced Potential for Degradation of Several Volatile Organic Compounds: Ronald H. Olsen and Jerome J. Kukor, University of Michigan Goal: Five goals describe our participation in Center-sponsored research: 1) isolate and characterize microbial strains competent for the degradation of VOCs which show adhesion to soil and/or granulated carbon particles; 2) 75 ------- determine the effect of attachment (adhesion) on the metabolism of VOCs; 3) determine the effect of environmental fluctuations on the performance of selected strains; 4) extend the substrate range of selected bacterial strains employing genetic technology; and 5) evaluate the performance of selected bacterial strains in generic and modified bioreactors. Rationale: Prior research suggests that noxious contaminants accumulating in soil as a consequence of gasoline spills can be degraded under anoxic conditions 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, these noxious contaminants are removed in excess of the capacity of the granulated carbon to absorb them. It has been postulated that the disappearance of these contaminants is a reflection of their degradation to carbon dioxide and water by microbial species indigenous to soil which are transported to the carbon filtration units where such microbial species grow and multiply using the contaminants as food. If the degradating activities of such microorganism can be optimized through the design of appropriate bioreactors, or, nutrients can be added to the spill in-situ, then removal of these contaminants can occur at an accelerated rate and limit further dissemination into the environs of the spill. Optimization of the degradating activities of microorganisms indigenous to spill areas and/or genetic enhancement of such microorganisms has the potential for economical remediation at the site of a spill and obviates the need to transport contaminated soils to landfills. Approach: Microorganisms are being isolated from carbon filtration units and sandy soil samples from gasoline-contaminated environments. These microorganisms are being screened for their ability to degrade the BTEX constituents of petroleum products in the presence of air, as well as when only small amounts of oxygen are present (anoxic conditions). From a group of many microbial strains differing in their physiological characteristics, a few microbial strains showing superior degradation 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 the degradating activity towards the target chemicals. Status: We have isolated numerous bacterial strains which show BTEX degradation under denitrifying conditions. Such degradation is dependent on nitrate. We have described the gene arrangement and mode of regulation for one isolate and are currently studying two more isolates. 76 ------- Client Audiences: We have had numerous inquiries from federal laboratories and private sector remediation companies concerning our work. These studies are germane to activities concerned with environmental problems stemming from oil or gas exploration and production, to regulatory agencies, and to engineering contractors in the biotreatment industry. Factors Affecting Attachment and Release of Microorganisms to Aquifer solids: Timothy M. Vogel, University of Michigan Goal: To understand and describe the fate of microorganisms that move through the subsurface environment by examining the microbial attachment and detachment phenomena in the presence and absence of other microbes and contaminants. Rationale: Microbes are or will be used for many applications related to degradation of hazardous waste. One application is the use of microbes in cleaning groundwater contaminants. The added microbes must move to the location of the contaminant and attach to a surface in order to remain for sufficient time to degrade the contaminant. Nutrients must also be available. Hence, if microbes in the local region of the contaminants are unable to degrade the compound or are not induced to degrade it, then other microorganisms moving into the area must make the transition from a suspended organism to an attached one. The ability of useful microbes to attach in regions of contaminants should be studied. Approach: Sterile and nonsterile aquifer columns packed with uncontaminated subsurface material will have a specific microorganism pumped through them at effective velocities reflecting groundwater speeds. Breakthrough curves of microbes will be compared for sterile versus nonsterile material. Mass balances on total carbon will be performed. The distribution of microbes retained in the columns will be determined along with the influence of growth stage and flow rate on the movement of microbes. Status: Microbial breakthrough curves for sandy aquifer material with indigenous microbes and sterile conditions have been compared to conservative tracers. Considerable cell lysis occurs to cells pumped through sand column. Work is in progress on 14c_iabe}ec| bacteria. Completion of this set of experiments is expected by 1991. 77 ------- Client Audiences: People interested in this research include those that would use added microbes for detoxifying contaminated groundwater aquifers such as consulting engineering firms, industries, and state departments of natural resources/environment. Bioavailability of Aged Organic Contaminants in Soils and Sediments: Stephen A. Boyd, Michigan State University Goal: Our goal is to determine whether soil- and sediment-bound organic contaminants may become unavailable to microbial degraders resulting in increased persistence of the contaminants. The potential limits on biodegradation imposed by reduced bioavailability need to be understood and overcome to successfully implement bioremediation technologies for the restoration of contaminated soils and sediments. Rationale: The majority of environmental contaminants are associated with soils or sediments. Previous research in this laboratory and elsewhere have indicated that such soil- and sediment-bound organic contaminants are biologically unavailable. Therefore, these contaminants must desorb (or disassociate) from soil and sediments solids before biodegradation can occur. If this disassociation proceeds rapidly, then target contaminants should be bioavailable and biodegradable. However, if contaminant disassociation from soils and sediments is a slow process then they may be biologically unavailable and protected against biodegradation. It is necessary to evaluate the existence of situations where contaminants are biologically unavailable and to understand the factors that lead to reduced bioavailability. This will enable us to predict when limited bioavailability may occur and to know how to overcome this problem so that bioremediation technologies can be successfully implemented in the field. Approach: We have examined the bioavailability of PCBs in contaminated sediments and of the herbicide Simazine in an agricultural soil. The contaminants present in these actual field samples have long residence times and are referred to as aged contaminants. To test the effects of contaminant aging on bioavailability, the soil and sediment samples were amended with PCBs or Simazine in the laboratory. The bioavailability of these newly added compounds was then simultaneously compared to that of the aged contaminants. For the PCB sample, an active PCB dechlorinating consortium was used to test biodegradability of the newly added and aged PCBs. For Simazine, soil incubations were used to determine if bioavailability to soil bacteria was different for the added and aged residues. Also, the herbicidal activity, i.e., plant availability to sugar 78 ------- beets, of added and aged Simazine was compared as a second test of bioavailability. Status: We have now documented that the aged PCB and Simazine residues are biologically unavailable to microbial degraders. This was shown by the degradation of newly added PCBs and Simazine while the aged PCB and Simazine residues, present in the same samples, were completely protected against biodegradation. Similarly, aged Simazine had no herbicidal activity against sugar beets, whereas, newly added Simazine at the same concentration resulted in damage to greater than 50% of the seedlings. Thus, the process of contaminant aging has apparently rendered the indigenous PCBs and Simazine biologically unavailable. These results demonstrate that limited bioavailability will likely be encountered in the field and will need to be considered when designing and implementing bioremediation technologies. Client Audiences: These results should be of direct interest to all those attempting to develop and utilize bioremediation technologies. This would include industries that have environmental restoration efforts, the U.S. Department of Defense, EPA, and biorestoration companies. Use of Microorganisms and Surfactants for In-situ Detoxification of Hazardous Wastes in Soils: Ramesh C. Chawla and Joseph N. Cannon, Howard University Goal: The goal of this research is to determine the feasibility of using surfactants and naturally occurring microorganisms at hazardous waste sites for in-situ cleanup of contaminated soils. Rationale: Properly formulated surfactants under controlled laboratory conditions have 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: Batch studies with TCE were designed and carried out to determine or develop the following: 1) the adsorption/desorption rates and limits in TCE/soil/surfactant systems; 2) a microbial consortium from 79 ------- natural sources which would survive the exposure to TCE; and 3) the TCE biodegradation rates and limits in liquid phase surfactant/microorganism systems with and without the presence of TCE-contaminated soil. Status: Adsorption/desorption studies have been completed. A microbial consortium capable of degrading TCE was successfully developed. The constituent members of the consortium have been isolated and are being tested for TCE biodegradation ability. Client Audiences: People interested in this research include all industries which are involved in the generation, storage or disposal of hazardous waste. Additionally, people and organizations charged with treatment and cleanup of hazardous waste sites such as state and federal regulatory agencies, would be interested in some aspects of this research. Design and Operation of Biological Activated Carbon Adsorption Systems: Thomas C. Voice, Michigan State University Goal: The goal of this project is to investigate the use of systems employing both activated carbon adsorption and biodegradation for groundwater contaminated with VOCs. The research will seek to produce a better understanding of how these two mechanisms affect each other when both are operating in a single system, how the reactor type and hydraulic characteristics of the reactor affect these mechanisms, and how to best design and operate such treatment systems so as to obtain optimal performance. Rationale: Previous research has established that biodegradation of waste constituents frequently occurs in activated carbon adsorption systems. This has generally been regarded as desirable, in that biodegradation serves to extend the life of the carbon adsorbent. Although negative impacts, such as bed fouling by the growing biomass, have been noted. Most of this work has involved incidental biodegradation occurring in systems designed as adsorbers. Little attention has been given to designing biological activated carbon (BAC) systems in order to exploit the benefits of both mechanisms, thereby producing superior overall system performance. This study is attempting to do this for an important class of treatment problems: groundwater contamination by VOCs. Approach: The approach involves the study of two primary types of treatment systems: packed-bed systems in which the water being treated flows through a stationary "bed" of carbon particles, and fluidized-bed 80 ------- systems in which the carbon particles are suspended in a stream of upward-flowing water. Experiments involve operating these systems in three modes: 1) adsorption only (biodegradation inhibited); 2) biodegradation only (non-adsorbing particles); and 3) combined biodegradation and adsorption. Additional experiments are being conducted to investigate the biological degradation of the benzene, toluene and xylene (BTX) constituents both singly and in combination. This information will be combined in computer models to predict overall system performance and the results compared to bench-scale experiments for different designs and operating conditions. Status: Both types of experimental systems have been studied for the treatment of water containing the petroleum derived hydrocarbons BTX. The fluidized bed system is clearly superior, being able to degrade BTX from near saturation levels (low parts per million) to acceptable discharge levels (below 1 part per billion) with detention times under two minutes. While this result is primarily a biological phenomenon, the activated carbon provides for much faster system start-up, treatment during start- up, and considerable protection against shock loads that can disrupt or destroy traditional biological systems. Characterizing the ability of these systems to handle shocks, which are inevitable in practice, is the focus of current work. Biological systems have not been widely accepted for treatment of VOC contamination problems, in part because of shock-load problems. BAG systems may prove to overcome this limitation and allow the benefits of biodegradation to be realized for this class of problems. Packed-bed systems are also of interest because this design is widely used for adsorption-only designs. Our efforts are addressing how the separation of solutes in the bed as a result of different adsorption characteristics can be exploited when one solute inhibits biodegradation on another. Future work will investigate ways to encourage biodegradation in existing packed-bed adsorbers without otherwise degrading system performance. Client Audiences: Since this project is highly focused on an application, specifically on the design and operation of treatment systems for contaminated groundwater, there has been considerable interest in the work by potential users. We are in regular contact with Envirex, a major treatment system manufacturer, and are conducting a related study for this firm at the Michigan Biotechnology Institute. We have had additional discussions with several engineering design firms, oil companies, the Michigan Office of Underground Storage Tanks, and the EPA to secure funding to demonstrate at the pilot-scale that fluidized-bed BAG systems are sufficiently efficient and reliable to be used for BTX groundwater 81 ------- problems. We believe that such a demonstration will result in widespread acceptance of this technology. Destruction of Biologically Resistant Organics by Supercritical Water Oxidation: Walter J. Weber, Jr., University of Michigan Goal: To explore and develop the use of Supercritical Water Oxidation (SCWO) as a means for destroy biologically resistant hazardous organic substances, such as PCBs and higher molecular weight 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 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 oxidations are studied in a completely mixed batch reactor system designed to handle viscous organics and solids, as well as more ordinary organic solutions. The initial experiments involve the injection of small amounts of organics into a supercritical mixture of water and oxygen, and subsequent monitoring of the resulting reactions. Analyses include characterization of intermediate products, mechanisms, and reaction kinetics. Status: The reactor system has been built, peripheral systems have been calibrated, and preliminary oxidations of phenol have been performed. These preliminary runs have shown the system to be functional, and have resulted in very high destruction efficiencies. Current work involves improving the accuracy of the data to allow for more quantifiable estimates of reaction kinetics. Oxidation of PCBs is expected to begin this fall. Client Audiences: This work should be of interest to those who are working on the development of chemical oxidation and thermal destruction treatments for concentrated aqueous wastes and residues containing recalcitrant organic compounds such as, or similar to, PCBs or PAHs. 82 ------- ENGINEERED SYSTEMS/SURFACTANT OXIDATION Development of Modular Laboratory-scale Reactors for Investigation of Hazardous Waste Treatment Schemes: Robert F. Hickey, Michigan State University and Michigan Biotechnology Institute Goal: The goals of this project are two-fold: 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 intensively monitor these reactors to develop a data base 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 treatment of hazardous wastes. These are: 1) isolate organisms with the desired capabilities; 2) improve understanding and optimization of the enzymatic processes; 3) "house" the organisms in reactor systems that best exploit the capabilities of the organisms; and 4) develop process monitoring and control strategies that assure reliable performance and help overcome any user confidence hurdle(s) that may impede application of bioprocesses. Approach: Sets of one and two-inch diameter reactors of varying heights were constructed. These reactors are versatile enough so that 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 biodegrading 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 such that it can be continuously monitored for both major and trace gases via an on-line 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: A series of modular reactors have been completed and ancillary equipment such as gas transfer devices have also been constructed and tested. A series of trace studies have been performed to define system hydraulics for aerobic and anaerobic operation. A two-inch diameter 83 ------- reactor has been linked to the on-line data acquisition system. Steady- state gas composition information is currently being collected. A special chemostat has been constructed for TCE-degradation studies using methanotrophic bacteria. The reactor is designed to allow headspace monitoring of the TCE and gaseous substrates and products either by manual sampling or in conjunction with the on-line data acquisition system. This reactor is now being tested. Drawing and materials sheets are currently being put together to allow others to construct similar systems. Client Audiences: This project is mainly a service-based project for the Center. The main interactions have been with Project 11. Three one-inch reactors have been operational as aerobic fluidized bed reactors for the past six months. A manual of more general interest is being prepared describing laboratory reactor design and specifications. Detoxification of Hazardous Substances via In-vessel Composting: James H. Johnson, Jr., and M. Mohan Varma***, Howard University Goal: The primary goal is to optimize operating conditions to degrade pyrene using in-vessel composting technology. The success of pyrene degradation was evaluated by the mineralization of pyrene. The research effort also included two secondary areas; namely, the investigation of the metabolic pathways of pyrene degradation, and the initiation of a future project on "Solid phase aerobic/anaerobic treatment of PAH compounds". Rationale: Previous research has indicated that biodegradation of PAH compounds with three or less rings is possible. However, mineralization of PAH compounds via biodegradation with more than three rings has not been demonstrated. Pyrene, a four-ring PAH compound was chosen as the model compound for this study because it is a recalcitrant and poses a potential health hazard. Approach: Most of the experiments conducted during this period were in a laboratory-scale self-heating composter. Sewage sludge contaminated with pyrene served as the test material. Experiments were conducted which included the variation of initial pH, composting temperature, type of bulking agent, and C:N ratio. The compost was monitored for quality of Dr. Varma passed away in September, 1990. Dr. Johnson is completing the project on his own. 84 ------- effluent gas, pH, temperature and initial and final C:N ratio and moisture content. 4,5, 9,1 0-1 ^C pyrene was used as a marker for monitoring ^^CO2 which is an end-product of pyrene degradation. The second experimental approach used amber-colored Erlenmeyer flasks placed in a water bath. A flask was drawn every two days up to the experiment's end and analyzed for the parameters mentioned above as well as pyrene and several metabolites postulated in the literature. Status: Two batch and four continuous experiments with -C labeled and cold pyrene have been conducted during the project period. Reduction of up to 72% in concentration of pyrene in the batch composter and 10-20% mineralization of l^c pyrene in continuous composter have been achieved. More experiments are currently in progress to complete the necessary experiments needed to determine optimum conditions. The selected combination of operating conditions is based on a fractional factorial experiment design. Client Audiences: Persons interested in remediating soils in the vicinity of coal conversion facilities, petroleum plants, waste disposal facilities, and wood preserving plants. Modeling Surfactant Mobilization of Entrapped Organic Liquids in Ground water Systems: Linda M. Abriola, University of Michigan Goal: Surfactant enhanced in-situ soil flushing (SEISF) appears to hold much promise for the remediation of groundwater formations contaminated by NAPL organics. This process has been proposed to reduce residual saturation of entrapped NAPL organics. A variation of this process primarily based on the ability of surfactant solutions to dissolve sparingly water soluble organics by increasing their availability to microorganisms. The primary goal of this research effort is to develop a mathematical model capable of describing surfactant mobilization and solubilization of NAPL organics entrapped within a groundwater system and to implement this model in a computer simulator capable of analyzing the relative importance of SEISF process variables. Rationale: Such a simulator will be a useful tool in the design and evaluation of SEISF processes and could be used, for example, to explore the hydraulic parameters which control the mobilization of entrapped 85 ------- contaminants and predict the level of contaminant removal for a given system of chemical and surfactant. Earlier research efforts in the petroleum industry have been successful in modeling the process of enhanced oil recovery using surfactants. Thus, as a basic rationale for this project it is presumed that, with some adaptation, the approach used in the petroleum industry in the modeling of surfactant-enhanced oil production can be employed to simulate the process of cleaning up contaminated groundwater systems. Approach: Two distinct, but simultaneously occurring mechanisms of removal of entrapped organic liquids will be considered. These are: 1) mobilization of organic liquids by immiscible displacement due to reduction of interfacial 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 equilibrium phase relationship among the fluids. The physical model can be described as follows. A contaminated zone is initially assumed to exist in a saturated region of the aquifer. The surfactant solution is assumed to exist in a saturated region of the aquifer. The surfactant solution is then 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 the University of Michigan and Michigan State University. Status: The project is currently into its second year. During the first year, the majority of the efforts were directed toward the review of the pertinent literature, conceptualization of the physical model, and formulation of the governing equations. These tasks have been successfully completed. We currently have a mathematical model capable of describing the process of surfactant mobilization and solubilization of NAPL organics entrapped within a groundwater system. 86 ------- During the second year, we have been primarily concerned with the implementation of the model in the form of a one-dimensional computer simulator along with its experimental validation. Representation of the phase behavior of the ternary system (water, organic and surfactant), which is a critical step in the code development, has been successfully completed. In this second project year, we have been working in close cooperation with Project R9 investigators. A joint experimental program with Roger Wallace and David Wiggert, principal investigators of Project R9 [Michigan State University (MSU)], has been developed for model validation. This program is well underway. At a recent September 28 meeting with the MSU group in Ann Arbor, preliminary experimental results showing the importance of solubilization as a principal contaminant removal mechanism for certain types of surfactant were discussed. Based upon these experimental observations, a variation of the one-dimensional surfactant flushing simulator for comparison with experimental measurements is being implemented. This simulator treats solubilization as the principal contaminant removal mechanism. In addition, we are currently exploring the extension of the modeling to a two-dimensional visualization experiments. Client Audiences: This research will be of interest to federal and state agencies, industry, and private consultants involved in the remediation of NAPL organic contaminated sites. Physical Models for Examining In-situ use of Surfactants to Achieve NAPL Clean Up: Roger B. Wallace, Michigan State University Goal: Immediate--to identify the gross characteristics of surfactant flow through contaminated capillary fringe in order to better understand how to deliver surfactant near that region for NAPL cleanup. Long-term—to use the physical model developed in this study to investigate alternative remediation strategies near the water table. Rationale: Oil spills collect in large pools at the water table. Such pools must be removed for remediation success. However, traditional methods of gravitational drainage and pumping are not sufficient to provide complete cleanup of the aquifer. Results of earlier studies show the potential of surfactant flushing to solubilize and/or alter the interfacial tension of oils. This also can increase the yield of traditional cleanup 87 ------- methods by either solubilizing the NAPL or removing some of the capillary forces that immobilize it. Approach: A physical two-dimensional model has been developed for visual observation of NAPL and surfactant flow regimes in the unsaturated zone near an established water table. The flow visualizations are recorded using 16 mm time-lapse movies. In addition, one-dimensional column experiments are being formed in collaboration with the University of Michigan modeling group (Abriola) in order to verify the numerical model they are currently developing. Status: A small glass tank (1 m x 1 m x 5 cm) was constructed with a sand packer and controlled flow system to study the migration of oil spills to the water table and the penetration of surfactants into the oil pool. Preliminary experiments were completed in order to gain experience in methods of sand packing, strategies of delivering oil and surfactant, and photography. A time lapse movie of a refined and controlled experiment showing the downward flow of surfactant into an oil layer was completed. A large glass tank (Imx2mxl5 cm) was constructed in order to study introduction of surfactants through wells at or near the water table in order to promote oil removal. A bench top design of the one-dimensional experiment was developed and the results of several preliminary experiments are being used for initial comparison with the numerical simulation of the modeling group at Michigan. Client Audiences: Our audience includes researchers dealing with remediation problems as well as those involved in the basic aspects of immiscible fluid flow in soils such as fingering. It also includes people interested in development of commercial field applications for oil spill cleanup. Methods for Isolation of Hazardous Substances from Complex Mixtures: Milagros S. Simmons, University of Michigan Goal: To establish conditions for extractions of bound organics from soils and other materials using supercritical fluid extraction techniques. Rationale: Methods of extractions for hazardous organics from complex mixtures are not only tedious but also inefficient. Extractions using 88 ------- supercritical fluid which possess good solvating power as well as diffusivity offer potential means to successfully isolate bound organics from different matrices associated with hazardous wastes. One of the skepticisms for 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 will focus on the comparison of the extraction efficiency and selectivity for selected organics using both conventional techniques and supercritical fluid extractions. Approach: Mixtures of selected chemicals representing a wide range of polarity will be used. Selection criteria are based on the frequency of the chemicals in hazardous wastes 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. Status: Mixtures of chemicals have been selected and conditions for their analyses have been established using gas chromatography. Several sorbent samples have been selected to be spiked with standard mixtures and split for both conventional methods of extraction and supercritical extraction. The initial studies were carried out using BTX representing the volatile organics, spiked in a variety of sorbent materials, such as activated carbon, sand, limestone, soil sample, and wood charcoal. The results showed the good recoveries (90%+) of BTX from these materials. Another set of chemicals representing acid, base and neutrals (AB/N) were chosen for the study. They were sorbed on to limestone and activated carbons at different time incubation and their recoveries from these materials were compared using AB/N extraction and supercritical extraction. The results show the remarkable efficiency of supercritical carbon dioxide over methylene chloride in extracting the AB/N compounds from the sorbent materials. Client Audiences: This research will be of interest to agencies engaged in routine analysis of organics from environmental samples such as contract laboratories, government and industrial laboratories processing a large number of samples using conventional extraction techniques. 89 ------- TRAINING AND TECHNOLOGY TRANSFER State/Industrial Assistance Requirements: Karen E. Vigmostad, Michigan State University Goal: To assess the current situation of site remediation activities in Region 3 and 5 states to determine what contributions the Center can make to fill any unmet needs. Rationale: All states are involved in cleaning-up sites of environmental contamination. The federal government, state and local agencies, and private industry are all funding these costly activities. With our emphasis on site remediation research, we want to find efficient and useful ways to transfer our research findings and technological developments to people who will use it. The latest information can help people decide between clean-up technologies, improve analytical procedures, reduce costs, and improve the actual clean-up of contaminated materials. This project will design targeted information and assistance—such as research summaries, videotapes, short courses, laboratory demonstrations—once individual state needs are identified. Approach: Each Region 3 and 5 state as well as EPA regional offices will be called or visited in order to determine individual state needs. People in private industry will also be contacted to try to dovetail projects that meet their needs also. Information and needs for other types of assistance will be evaluated. A final report with recommendations will be written and presented to our Training and Technology Transfer Advisory Committee. Status: Initial one-on-one telephone contacts have been made and information will be stored in a simple database. Existing information such as brochures, fact sheets, project reports, and legislation is being collected and will be assessed. Follow-up and more detailed calls will be made. Completion of a final report is expected in 1991. Client Audiences: People involved in all aspects of site remediation. For example, federal Superfund employees, site remediation companies, state agency personnel, consulting engineers, and equipment manufacturers. 90 ------- Research Chronicle: Karen E. Vigmostad, Michigan State University Goal: To produce a written chronicle to effectively communicate our research activities and progress to individuals interested in the research findings of Center investigators. Rationale: A periodic chronicle is a useful tool for timely communication of information to a given audience on a specified topic. While there are currently many excellent "newsletters" available on a range of hazardous substance research and training topics, there are none which communicate the general 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. Approach: Rather than trying to be all things to all people, the Center's research chronicle 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 chronicle will also serve as an information referral service, rather than primary source, steering people to existing sources of information. It will be written for 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 chronicle over time as needed. Status: The first issue of our research chronicle, synergos, was mailed to over 3,000 people in 11 states and the District of Columbia in September 1990. The next Winter 1990/91 issue—currently in early stages of research—will examine PCB contamination and Center and other research efforts to attack the problem. Synergos will be an ongoing semi-annual Center publication. Client Audiences: People involved in all aspects of site remediation. For example, federal Superfund employees, site remediation companies, state agency personnel, consulting engineers, and equipment manufacturers. 91 ------- Five-center On-site Remediation Workshop: Karen E. Vigmostad, Michigan State University, and Walter J. Weber, Jr., University of Michigan Goal: To summarize and share the latest on-site remediation research information being conducted at the five EPA regional hazardous substance research centers, as well as review some of the practical site restoration problems. Rationale: The five EPA Centers are all conducting site remediation research. Our Center has found that our satellite research retreats for investigators conducting research within research groupings are excellent ways to share information and foster close collaboration. Therefore, we want to use this model to bring together investigators at all five centers to improve communication and foster collaboration. Approach: Participants will take part in a one-week intensive workshop, modeled after a Gordon Conference, in a retreat-like setting. People from government and industry will make presentations of the practical problems in site-remediation activities. Graduate students and postdocs will also participate. Workshop reports and summary conclusions will be recorded and distributed to all participants. Significant findings will be more generally distributed. Status: An initial "straw man" program was distributed to the five center directors for discussion in November 1990. The Kellogg Biological Station, located on Gull Lake in southwestern Michigan, has been reserved for the week of May 19 - 24, 1991. Client Audiences: Summary of proceedings will be of interest to people involved in site remediation activities and we will distribute to our comprehensive list. Science and Math Teacher Training Materials and Hazardous Waste Workshop: James H. Johnson, Jr., Howard University Goal: The goal of this project was to orient science and mathematic teachers to environmental issues and career opportunities and challenges in the field. The teachers are expected to share this information with students in their junior and senior high school classes, other teachers, and eventually develop teaching modules and/or class projects which can be incorporated into course curricula. 92 ------- Rationale: Several professional groups have projected a severe shortage of trained environmental professionals for the year 2000. Educators have the opportunity to play an important role in the process of empowering students and encouraging entrance into professions. By training teachers, it is expected that they will influence the career choices of their students to include environmental professions. Approach: Three-day workshops were held in Lansing, Michigan and Philadelphia, Pennsylvania. Each workshop was divided into two parts. The first part provided an orientation to hazardous substances, and how hazardous substances are regulated and managed. The orientation was structured to stress underlying career requirements particularly in engineering and the physical sciences. The second part provided demonstration of training aids and materials which can be used to supplement the course curriculum in the classroom. Theses materials are useful in stimulating young people's interest in mathematics, science and engineering as a career choice and elevating students' awareness of environmental issues. Lectures, discussions, interactive sessions, and demonstrations were given by faculty members from Howard University, University of Michigan, and Michigan State University. Each workshop also included a session on a local water quality issue such as the Great Lakes and Chesapeake Bay, respectively. Status: Two workshops were held in August 1990. A follow-up session is not planned for the workshops. However, a follow-up meeting was held in early 1990 for participants of a similar five-day 1989 workshop. Ten of the 20 participants of the 1989 workshop attended. Each attendee presented projects which they had developed or adopted to reflect environmental topics. Examples of projects included a film, an environmental awareness classroom corner, and science fair projects. Of particular note are the participation of two of the teachers in more formal environmental programs: Ms. Yvonne Lewis participated in the Department of Energy's (DOE's) summer program at Batelle's Pacific Northwest Laboratory and Ms. Carolyn Kornegay accepted an assignment in a pilot program in the Washington, D.C. school system. The pilot program provides environmental education to 10th graders by using environmental topics in all classes, including english and history. Client Audiences: Middle and secondary school educators and agencies involved in promoting environmental education. 93 ------- Waste Auditing/Waste Minimization and Bioremediation Training: Paul F. Nowak, University of Michigan Goal: Waste Auditing—The production of a proposal on Waste Auditing/Waste Minimization for use in developing funding from private industry to support a major training program for the electroplating industry. Bioremediation—The production of written and video materials that can be used by EPA and State field professionals to help them understand bioremediation and the special aspects of it that affect their field responsibilities. Rationale: Previous results of questionnaires and direct contact with working professionals have shown a great need for the development of techniques that can effectively transfer knowledge about specific research topics to field personnel and other professionals. These types of information are critical in many very important and expensive decisions that are currently being made in the field of hazardous substances. Using a wide range of educational and communication techniques, we are interested in finding out how to best develop these kinds of materials and, once developed, how they can be effectively delivered to those who need them. An important aspect of this system is the evaluation process which focuses on using evaluation to modify the product so that it develops into an evolving program rather than being one which is only used once. Approach: Working with both researchers and professional field people, an overview of the material that needs to be transferred is developed and organized into a logical flow pattern. Both written and video materials are then built from this material. Once the materials are written, they are then carefully reviewed before they are finalized. They are then piloted and again revised, if necessary, based on the pilot evaluations. While this is our main development system, each of the projects for the Center is somewhat unique. This fits in well with our interest in exploring different development and delivery models. Status: Waste Auditing—This project has developed written materials on Waste Auditing which form the basis for the proposal to the electroplating industry. We have contacted a number of major companies such as Dow, Kodak, Chevron, and IBM and have acquired a great deal of video footage from them. They have also shown real interest in the project and its materials. We have developed a script for the video and are in the video development stage of this project. Bioremediation—A set of questions that EPA and Michigan Department of Natural Resources (MDNR) field people 94 ------- want answered about bioremediation have been formulated, and we are ready to videotape the EPA and MDNR officials asking questions and researchers answering them. The congested schedules of the researchers has been a limiting factor in this effort. We have also deferred some time from the Waste Auditing Project to put emphasis on this effort. Client Audiences: Waste Auditing-The Waste Auditing project is aimed at the electroplating industry. It should be specifically useful for small to medium-sized companies. The materials should be easily adaptable to other industries once completed. Bioremediation--The Bioremediation Project is designed for EPA and state agency field professionals who must make decisions about the viability of various remediation techniques. The materials should also be useful to the private sector. SUMMARY OF OUTPUTS IN FY 1990 Referred Journal Articles 2 Articles Submitted or In Press 10 Books and Bound Proceedings 6 Chapters in Books or Proceedings 2 Project Reports 1 Conferences and Workshops 10 95 ------- BIBLIOGRAPHY This is a compendium of 1990 publications and related activities resulting directly from work supported by the Center during the one-year period from October 1, 1989 through September 30, 1990. REFERRED JOURNAL ARTICLES Boyd, S.A. and S. Sun, "Residual Petroleum and PCB-oils As Sorptive Phases for Organic Contaminants in Soils," Environ. Sci. Technol. Vol. 24, pp. 142-144, 1989. Kukor, J.J., and R.H. Olsen, "Molecular Cloning, Characterization, and Regulation of a Pseudomonas pickettii PK01 Gene Encoding Phenol Hydroxylase and Expression of the Gene in Pseudomonas aeruginosa PAOlc," J. Bacteriol.. Vol. 172, pp. 4624-4630. ARTICLES SUBMITTED OR IN PRESS Chawla, R.C., A.E. Helou, J.N. Cannon and A.A. Shafagati, "Adsorption/Desorption Characteristics of Soil-TCE Surfactant Systems," Presented at the 1990 Summer National Meeting of the American Institute of Chemical Engineers, San Diego, California, August, 1990. Submitted to AIChE Chenet, B.P., M.E. Egbe, R.C. Chawla, J.N. Cannon and F.L.A. Buckmire, "A Laboratory Assessment of Trichloroethylene Biodegradation in the presence of surfactants in Aqueous Media," Presented at the 1990 Summer National Meeting of the American Institute of Chemical Engineers, San Diego, California, August, 1990. Submitted to AIChE Kaphammer, Bryan, Jerome J. Kukor, and Ronald H. Olsen, 1990, "A Novel Toluene/Benzene Degradative Pathway Cloned," from Pseudomonas pickettii PK01, (Submitted to J. Bacteriol., August 28, 1990). Kukor, J.J., and R.H. Olsen, "Genetic Organization and Regulation of A Meta Cleavage Pathway for Catechols Produced from Catabolism of Toluene, Benzene, Phenol and Cresols by Pseudomonas pickettii PK01," (Manuscript in preparation). 96 ------- Scribner, S., S. Sun, T. Benzing and S.A. Boyd, "Bioavailability of Aged Simazine Residues in Soils," Environ. Sci. Technol. submitted October, 1990. Shreve, G.S., Olsen, R.H., and T.M. Vogel, "Development of Pure Biofilms of P. Putida on Solid Supports," Biotechnology and Bioengineering. Simmons, M.S., and Shih, K.C., "Comparison of Supercritical Fluid Extraction of Selected Priority Pollutants with Conventional Extraction Methods," (manuscript in preparation). Simmons, M.S., Bloem, T., and Kim, J., "Supercritical Extraction of Benzene, Toluene and Xylenes (BTX) from Spiked Sorbent Materials," (manuscript in preparation). Sun, S. and S.A Boyd, "Sorption of PCB Congeners by Residual PCB-oil Phases in Soils," J. Environ. Qual. submitted October, 1990.. Wallace, R.B., Wiggert, D.C., Shabana, M.D., and Chevalier, L., "A 2-D Experimental Observation of Surfactant Movement in the Capillary Fringe in the Presence of an Oil Phase," In preparation. BOOKS AND BOUND PROCEEDINGS Jeffrey, Wade H., Stephen M. Cuskey, Peter J. Chapman, and Ronald H. Olsen, Isolation of A Pseudomonas Chromosomal DNA Fragment Able to Substitute for TOL Plasmid XylSregulatory Gene, Abstr., Bacteriol. Proc. K144, p. 243, 1990 Kaphammer, Bryan, Jerome J. Kukor, and Ronald H. Olsen, "Cloning and Characterization of A Novel Toluene Degradative Pathway," from Pseudomonas pickettii PK01. Abstr., Bacteriol. Proc. K145, p. 243, 1990 Kukor, Jerome J., and Ronald H. Olsen, "Genetic Organization of Phenol Degradation Cloned into Pseudomonas aeruginosa PAO," from A Soil Pseudomonad. Abstr., Bacteriol. Proc., p. 254, 1989 Kukor, Jerome J., and Ronald H. Olsen, "Genetic Characterization of A Phenol Hydroxylase Cloned from Pseudomonas sp. PK01 and Expressed in P. aeruginosa PAO," Pseudomonas '89, ASM Conference, Chicago, Illinois, 1989 97 ------- Kukor, Jerome J., and Ronald H. Olsen, "Molecular Cloning and Regulation of Genes Encoding Meta Cleavage of Catechols Produced from Catabolism of Phenol and M-cresol by Pseudomonas pickettii PK01," Abstr., Bacteriol. Proc., K143, p. 243, 1990 Mikesell, Mark D., Jerome J. Kukor, and Ronald H. Olsen, "Isolation of Hydrocarbon-degrading Bacteria from Contaminated Aquifer Material," Abstr., Bacteriol. Proc. Q59, p. 298, 1990 CHAPTERS IN BOOKS AND BOUND PROCEEDINGS Kukor, Jerome J., and Ronald H. Olsen, "Diversity of Toluene Degradation Following Long-term Exposure to BTEX In-situ," I n Biotechnology and Biodegradation (D. Kamely, A. Chakrabarty, and G. Omenn, Eds.), Gulf Publishing Co., Houston, Texas, 1989 Yusuf, Mohammed, "Detoxification of Hazardous Substances Via In- Vessel Composting (Poster Abstract)," Environmental Engineering Proceedings of the 1990 Specialty Conference. O'Melia, C.R. (ed.), American Society of Civil Engineers, pp. 929-930, 1990 PROJECT REPORTS Olsen, Ronald H., and Jerome J. Kukor. Reports to the Great Lakes and Mid-Atlantic Hazardous Substance Research Center project oversight team. 1990. CONFERENCES AND WORKSHOPS One-day internal workshop -- "First Surfactant Group Retreat" -- Linda M. Abriola, University of Michigan, January 16, 1990. Assaf-Anid, N. and T.M. Vogel, "Dehalogenation of Chlorinated Aliphatics by A Variety of Porphyrins and Corrins," Society for Environmental Toxicology and Chemistry, Toronto, Canada, November, 1989 Three-day workshop — "A Hazardous Waste Workshop for Science and Mathematics Teachers"; James H. Johnson, Jr., East Lansing, MI, August 1-4, 1990 and Philadelphia, PA, August 13-15, 1990 98 ------- Kukor, Jerome J., and Ronald H. Olsen, "Diversity of Toluene Degradation Following Long-term Exposure to BTEX in-situ," Biotechnology and Biodegradation Workshop, Lisbon, Portugal (by invitation). Kukor, J.J., B. Kaphammer, and R.H, Olsen, "Cloning and Characterization of a Novel Toluene Degradative Pathway from Pseudomonas pickettii PK01," 8th Annual Biodeterioration and Biodegradation Symposium, University of Windsor, Windsor, Ontario 1990 Kukor, J.J., and R.H. Olsen, "Molecular Cloning and Regulation of Genes Encoding Met a Cleavage of Catechols Produced from Catabolism of Phenol and M-cresol by Pseudomonas pickettii PK01, 8th Annual Biodeterioration and Biodegradation Symposium, University of Windsor, Windsor, Ontario, 1990 Presentation by Dale Manty and Paul Nowak on the project at the, "Conference on the Adult Learner," University of South Carolina at Columbia, May 27-May 30, 1990 Olsen, R.H., Two-day workshop, "Deep Microbiology Program Review Workshop," U.S. Department of Energy, Gaithersburg, Md., August 27, 1990 Olsen, R.H., One-day workshop, "Natural Bioremediation As An Alternative UST Remediation Strategy, API/U.S.E.P.A., Oklahoma City, Ok., September 6, 1990 Two-day workshop — "Workshop on Supercritical Fluid Processing of High Risk Wastes" -- Walter J. Weber, Jr. Hosted by Los Alamos National Laboratory, August 1-2, 1989 99 ------- PARTICIPANTS: CENTER FOR WASTE MINIMIZATION AND MANAGEMENT North Carolina State University The University of North Carolina, Chapel Hill Texas A & M University, Galveston and College Station DIRECTOR: TECHNOLOGY TRANSFER DIRECTOR: Michael Overcash, Ph.D. Center for Waste Minimization and Management Department of Chemical Engineering North Carolina State University Raleigh, North Carolina 27695-7905 Phone: 919/737-2325 Fax: 919/737-2463 Dale Denny, Ph.D. Technology Transfer and Training Program 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 (NCSU). The consortium is referred to as the Center for Waste Minimization and Management. 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: • to develop practical means for industry to eliminate the use and generation of hazardous substances; • treat those wastes that cannot be eliminated; and 101 ------- to provide secure containment for treatment residues. WASTE MINIMIZATION AND MANAGEMENT CENTER Research Project Distribution (Number of Projects) 44% Treatment and Containment (7) 50% Waste Minimization (8) 6% Technology Transfer and Training (1) Major Focus: Since the inception, an increasing emphasis has been given to the primary Center mission, industrial process modification to reduce pollution. This area is clearly the largest Center focus for research and technology transfer. Even projects in the other waste management areas have been developed to generally have a waste minimization component. The opportunities to jointly fund future work with various other organizations have occurred in the pollution prevention field involving diverse industries and multi-media research activities. The role of the partner institutions in the Center is dictated by the scientists and engineers brought together at each school. Under the direction of Dr. Kirk Brown, Texas A & M University has taken the lead in research on long-term containment and remediation. 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 102 ------- environments. Waste minimization and transportation research efforts are spearheaded by the researchers at North Carolina State University. The faculty and staff who direct the Center's research training and technology transfer activities are listed in Table 1. The Center's Engineering and Science Advisory Committee and Training and Technology Transfer Advisory Committee members are listed in Tables 2 and 3. The budget for the past year is summarized in Table 4, and student supported by the Center are presented in Table 5. TABLE 1: KEY PERSONNEL IN THE CENTER North Carolina State University Dr. Michael R. Overcash Dr. Peter S. Fedkiw Dr. Ruben G. Carbonell Dr. Christine S. Grant Dr. H. Henry Lamb Dr. Dale A. Denny Dr. Cliff M. Kaufman Dr. Thomas W. Joyce Dr. Josef S. Gratzl Dr. John R. Stone Dr. John Sutton Dr. P. K. Lim Dr. Morton A. Barlaz University of North Carolina at Chapel Hill Dr. William Glaze Dr. Fran DiGiano Dr. Rich Kamens Dr. Debbie Amaral Dr. Judi Charles Dr. Don Francisco Texas A & M University Dr. Kirk Brown Dr. C. S. Giam Dr. Robin L. Autenrieth Dr. Kevin J. Mclnnes 103 ------- TABLE 2: ENGINEERING AND SCIENCE ADVISORY COMMITTEE MEMBER Dr. Norvin Clontz Dr. H. T. Davis Mr. Jack Divita Mr. Leo Duffy Mr. Carl Fromm *Dr. Donald Paul Mr. Ralph W. Jennings Dr. Merle Lefkoff Dr. Frank Loprest AFFILIATION Milliken and Company Spartanburg, SC University of Minnesota Minneapolis, MN USEPA-Region 6 Dallas, TX US Department of Energy Washington, DC Jacobs Engineering Pasadena, CA University of Texas Austin, TX USEPA-Region 4 Atlanta, GA Merle Lefkoff & Assoc. Santa Fe, NM Colgate-Palmolive Co. Piscataway, NJ Dr. Philip X. Masciantonio USS Corporation Monroeville, PA Mr. E. Timothy Oppelt USEPA Cincinnati, OH EXPERTISE Textile Industry Academic Member, National Academy of Engineering, Chemical Engineering Deputy Director, Hazardous Waste Management Division Special Assistant to the Secretary of the Department of Energy for Coordination of Waste Management Chemical Process Design Engineer Academic, Chemical Engineering Senior Scientific Advisor EPA Region 4 Administrator Conflict Resolution and Public Involvement Research Director, Consumer Products Vice President, US Steel Corporation; and Chairman, Business Roundtable Environmental Committee Laboratory Director in Office of Research and Development 104 ------- MEMBER Mr. Robert Hangebrauck Mr. Lee Thomas AFFILIATION USEPA Research Triangle Park, NC Law Environmental, Inc. Kennesaw, GA EXPERTISE Laboratory Director in Office of Research and Development Chairman and Chief Executive Officer, Law Environmental, Inc.; Former Administrator of the USEPA ""Chairman TABLE 3: TECHNOLOGY TRANSFER AND TRAINING ADVISORY COMMITTEE MEMBER AFFILIATION EXPERTISE Mr. David Ebenhack Mr. Norman Dyer Ms. Ann Griffith Ms. Meg Kelly Ms. Elizabeth Kraft Ms. Ann Mason* Dr. Ed Morris Mr. Tom Nessmith Dominec Forcella Chemical-Nuclear Systems Technology and Public Raleigh, NC Communication - Waste USEPA-Region 6 Dallas, TX Containment Technology Transfer Coordinator North Carolina Citizens Industry for Business and Industry USEPA Washington, DC Director Technology Staff League of Women Voters Public Interest Group Washington, DC Chemical Manufacturers Industry Association Washington, DC Arkansas Department of State Government Pollution Control Little Rock, AK USEPA Atlanta, GA National Governors Association Washington, DC USEPA-Region 4 State Government *Vice Chairman 105 ------- TABLE 4: CENTER FUNDING FUNDING SOURCES EPA: Centers Program EPA: Other Other Govt: Federal Other Govt: State TOTAL FY 19901 $926,080 $20,000 $70,000 $ 231.520 $1,274,600 FUNDS TO DATE $2,926,080 $20,000 $70,000 $1.124.984 $4,141,064 TABLE 5: STUDENT SUPPORT STUDENT LEVEL NUMBER Undergraduate 28 Graduate 36 Post-Doctoral/Research Associates 13 TOTAL 77 FUNDS TO DATE $ 13,444 339,353 235.887 $588,684 CENTER DIRECTOR'S REPORT The Center for Waste Minimization and Management continues as the largest national research effort directed at pollution prevention. Projects and future results are pivotal to the improved understanding of manufacturing processes, chemical losses, and waste generation. This critical research is opening doors for new waste minimization, but is also discovering doors that were never known to exist thus leading to further pollution prevention. Activities stimulated by the Center and a variety of advocates in industry and government have established waste reduction as a major technology to improve human health and the environment. With the cost of existing environmental regulation compliance by industry estimated at $75 billion per year, the incentive to avoid these costs through pollution 106 ------- prevention is large. In addition, the balance shifts even further with new costs of $30-$40 billion per year toward reducing chemical loss or waste generations with regulatory amendments to the Clean Air Act. These economic facts have stimulated very real waste minimization by virtually all major manufacturers, including government departments. In addition, over 30 states have active technical assistance programs for small and medium manufacturers. Into this picture of activities, the major missing element is active research to go beyond the application of existing technology and to create new approaches to waste reduction. This is the principal role served by this EPA Research Center and is currently the largest university research organization in this new field. The success and growth of industrial waste minimization must be balanced with the recognition that complete elimination of pollution at the source will not be achievable. Thus, treatment and long-term containment will remain necessary technologies. It is our Center's mission to recognize that the full hierarchy for waste management will be needed and to invest in critical leading-edge research to improve treatment, containment, and remediation. Thus, between 30% - 40% of the Center is devoted to these areas. This work occurs at the University of North Carolina and at Texas A & M University. At this time, some of these projects have a direct impact on improving the ability to set priorities for prevention of chemical losses through a more focused understanding of important constituents with respect to discharge in the environment. This positive interaction among research goals in the Center is an important facet of these EPA resources. Thus, the criterion for our Center research, both in the primary field of waste minimization, but also in the full-range of waste management, has been high-quality research projects. Emphasis must be given to fundamental issues to enhance the broader use of results and many projects are for three years. Reviews since the first year of work and, more recently in the critical evaluation by the Engineering and Science Advisory Board (ESAB), have been very favorable and no projects have had to be greatly modified. As the Center completes the second year, the emphasis on pollution prevention is increasing in research, as well as in industrial accomplishments to apply technology. Our research projects have played a direct role in the advancement of this new national approach to reducing pollution. However, in its special role as a research leader, the Center has helped define the concept of research in this field of both environment and manufacturing. The projects in the Center have illustrated clearly that basic unanswered questions on the role of chemicals and the specific circumstances of loss are critical research needs. These needs exist in all 107 ------- manufacturing sectors and hence pollution prevention is a broad opportunity. Projects in the Center are established to meet these needs and, because of the underlying process fundamentals studied, the transfer potential to multiple facilities in a particular industry is large. In some cases, the research results are useful in very diverse industries, such as the Center's fundamental work on surface contamination and cleaning. There have evolved six areas for research in pollution prevention from the work at North Carolina State University. These are: • wastes from surface preparation and cleaning; • chemical losses as trace toxics or reaction improvements; • volatile losses in manufacturing of products; • chemicals altered to be compatible with the environment; • recovery and reuse; and • overall waste reduction strategies. Direct industrial participation is vital in achieving clear and important research goals and this has been received in all of the Center's projects. Thus, the goal of identifying underlying process issues for research and the generic areas of pollution prevention efforts have been some of the Center's contribution to the overall national effort to achieve waste reduction. This field is undergoing rapid growth, beginning at about the start of the Center, and will clearly be an important element in the overall environmental field for the next decade. The challenge for the Center is to expand the role of research in the pollution prevention field and to continue the cooperative efforts with the industrial base that must implement actual waste reduction. The primary research projects in waste minimization and management were structured and remain three-year activities. As the research has continued to progress, the investigators have continued to develop the technology transfer opportunities for their work. However, since the primary role of the Center is research, the transfer of information and utilization of results depends primarily on the commitment of industry and other organizations focused on utilization. The Center's research activities have involved 24 faculty, 36 graduate students, and 28 undergraduate project participants during the first two years. This has been a very positive outcome and as these individuals continue to make professional contributions will represent an important facet of the Center for Waste Minimization and Management. 108 ------- New projects were added in year two. The opportunities for new activities were based on one of two tenets, to open new research areas or to round out existing suites of research projects. As new projects, one recommended from the ESAB and Region 4 was consumer- or public- related waste reduction. A new project was begun to assist the solid-waste issues of municipalities, by using Center expertise to clarify technical capacity for recycling of plastic and tires at the level of an entire state. This study of the technologies and size considerations is also structured to define the wastes for which there are not viable alternatives and hence the need for research. Two new projects in waste minimization were also begun. One focuses on the fundamental role of cyanide for those electroplating processes in which non-cyanide alternatives are not available. The second project expands the collection of surface cleaning research to a large industrial need for waste minimization, the decontamination of process equipment to maintain product quality or process operation. In the treatment field, the Center had a focus in air and aquatic media. Thus, a new project was initiated in terrestrial systems to complete the range of media under investigation for the treatment of hazardous substances. This project will examine the behavior of chlorinated high-molecular weight constituents in land treatment of pulp mill sludges. This project receives supplementary support from industry. Finally, a review of the research in improved long-term containment identified two important elements missing from the current program. These were the use of absorbing liner materials and an overall integrating effort that would utilize all available aspects of landfill containment. Initiation of these two projects at Texas A & M was begun in year two. Results from the containment research are expected to improve municipal solid waste, as well as hazardous waste containment. The Center for Waste Minimization has continued to achieve important research contributions for issues important in Regions 4 & 6, as well as the nation as a whole. The primary emphasis on research in pollution prevention should be a major and unique part of the overall EPA commitment to risk reduction. Industrial progress in actual waste reduction, using available technology, is a major stimulus to our Center as we strive to identify the difficult chemical losses for which research is needed to sustain the U. S. pollution prevention momentum. Information dissemination has continued to occur in the Center as a means to initiate actual transfer of research. The Center's primary goal in technology transfer is to achieve in-plant or more full-scale demonstration of the results from the research projects. This is a difficult activity, being increasingly realized in various government programs and thus the 109 ------- experience of the Center will be relevant. The first step in demonstration is identifying potential users and in the original identification of research needs. The Center has thus developed active interfaces with Regions 4 & 6, with industry, and specialized organizations involved in dissemination of information. Over 50 such activities were conducted in the initial two years of the Center. HIGHLIGHTS FOR 1990 Pollution Prevention in Semiconductor Manufacturing: Improvements in current liquid cleaning of chips are aimed at reducing use of chlorinated solvents, high-strength acids, and alkaline cleaners. The alternatives depend on obtaining a firm understanding of the actual processes by which particles and organic films are removed from silicon surfaces. Little information existed as the Center's research began. We now have established and demonstrated experimentally a firm theory to explain the mechanism of particle-wafer adhesion and removal. For particles and wafers with the same charge contamination is controlled when the semiconductor is passed through the bath/air interface. With differences in charge the diffusion/adsorption processes control contamination while the wafer is in the bath. These mechanisms allow evaluation of a variety of particles, organics, and wafer surfaces. Advances in gas-phase cleaning is another important development from the Center's research. A new spectroscopic technique was developed to monitor semiconductor contamination in-situ. This is important to improved understanding of cleaning alternatives. Ultraviolet light and ozone were found to potentially replace one of the major wet cleans used widely by the industry, and hence offer a mechanism for waste reduction. The hydrocarbon-free silicon surface with hydrogen-terminated sites is very desirable for semiconductor processing and may allow the development of an integrated gas-phase clean sequence for full-scale manufacturing. Superfund Fugitive Emission Research: Reduction in volatilization losses of organic chemicals is a wide-spread goal in numerous industrial sectors. The Center's program is focused on first understanding the mechanisms of loss. Virtually no information on molecular-level processes in the context of actual industrial devices (such as valves) was available to help in making changes to reduce losses. In this year, the initial model for chemical-volatile emissions has been verified for the important case of pipeline valves and a new model developed to describe the ubiquitous 110 ------- rotating seal in pumps. The experiments have identified capillarity, packing compression, and line pressure factors and the relation to controlling loss. Results will indicate directions that, in design or maintenance, will lower fugitive losses. Further, the existence of a firm mechanistic description will reduce the trial-and-error procedural methods currently used by industry. Another Superfund waste reduction focus has been methylene chloride, CFC's, or acetone when used as auxiliary blowing agents in flexible polyurethanes. Center research has provided some of the first quantification of actual loss rates, dependence on temperature, and position in the continuous manufacturing process with the largest mass loss. About 60% of the auxiliary blowing agent is lost in the foaming tunnel and a mathematical description of the factors controlling gas stream concentration has been developed. The emphasis now is on the design of a plant retrofit to allow the comprehensive measurement of both foam- product quality and chemical-loss rates. This is an important step in understanding if and how much chemical recovery can be achieved in a product plant situation. These answers could have a profound impact on the existence of this industry in the U. S. Trace Organic Minimization in Manufacturing: The complex chemistry and conditions that allow the formation of dioxin in pulp bleaching processes has been a good illustration of trace organics. This research project has verified the chlorinated dioxin precursors (chemical speciation was developed at the University of Washington, Seattle) in relation to actual pulp bleaching. Of potentially greater importance, the researchers discovered that the conditions of chlorine use may be as important as the existence of chlorine in controlling chloro-organic formation. This would have potentially large benefits in an overall strategy to reduce not just dioxin but other chlorinated organic species. The conditions of continuous, low-dose chlorination appear superior to current industry practices. Waste Reduction Strategies: Research to understand the complex interactions among industrial inputs, outputs, and energy usage is critical to determining whether total waste reduction can occur. The current progress has completed an important energy element or subroutine, the coal-fired production of energy. A mass envelope for air, aqueous, solid, and hazardous waste streams has been done and a chemical constituent envelope for each of these streams is complete. The data framework has been developed initially using the Smalltalk© software. This permits multi-dimensional comparisons necessary to establish net waste reduction. Ill ------- In most states, there has emerged in the last 1-2 years a goal of greater (sometimes 25%) recycling of municipal solid wastes. For plastics, tires, and paper, this has meant an emphasis on technologies to actually take these waste streams and produce recycled materials. What are these technologies and specifically how much of each type will be needed for recycling at the much-larger scale envisioned by 25% of an entire state solid waste? These are the issues to be addressed as the Center assists the state process of municipal solid-waste recycle. We have established the estimated mass of plastic and tire material generated in each county. Technologies for plastics, by type, and for tires have been evaluated. This new project will assist in state planning and defining future Center research on the technical barriers for even greater recycling. Improved Waste Characteristics: As a new project, preliminary results on the role of cyanide in electroplating are encouraging. This fundamental understanding is essential in developing possible further shifts away from cyanide usage in this industry. Initial results have measured copper deposition from the cyanide complex and found potential process inefficiencies associated with competing H2 generation from water. Hazardous Substance Transportation: Research using artificial intelligence concepts has developed a routing strategy for risk reduction. A micro computer system is now available for the State of North Carolina to assist in selecting improved routes. Usage by city or county staff is now available, but full expansion, using full geographic information systems (GIS) has to be developed. This research could be of use in other states in Regions 4 & 6. Treatment Technologies and Risk Reduction: Aquatic toxicity testing is increasingly used for wastewaters, but without much mechanistic knowledge of the test or the environmental significance. This area is studied in the Center because such test-only approaches may have a high occurrence of results for which action is not needed, but "required" or is needed, but "unrequired". The initial research identified the inconsistencies in various databases of Region 4 available to select priority wastewaters for evaluation. As a demonstration of the ability, on a chemical class basis, for utilizing the EPA Toxicity Identification and Evaluation protocol, a textile dyestuff wastewater was selected. Considerable cooperation of the manufacturer was received, and over 700 bioassays and analyses were conducted. The research has identified the potential for more selective fractionation testing. Direct use of the EPA protocol is currently very expensive and time consuming. The research 112 ------- identified for this wastewater that the chronic safety factor was 20-25 fold too high using a previous rule-of-thumb approach rather than the direct methods of this project. Coupling these results to a waste minimization strategy is now a goal. Air emissions and control technologies have been examined in an integrated fashion with another Center research project. The relation between incinerator stack concentration of polybrominated dibenzo dioxins (PBDD) and (PBDF) furans and the safety issues of flame retardants has been measured. Atmospheric exposure to sunlight found the PBDD and PBDF to be very stable and not rapidly photolyzed. A technique was developed to estimate exposure risks from different levels of these chemicals in products sent to incineration. Wastes treated by soil systems were studied in a new project on land spreading of paper-mill sludges. The focus of these experiments is on total organic halides (TOX) as a measure of constituents in sludges. The TOX procedure was found to be reproducible, but very dependent on the test procedure used, thus greatly reducing wide-spread utility. Also, the natural formation of TOX is significant thus further confounding the use of this test. Specific experiments on chlorolignin and chlorinated low- molecular weight compounds from wood pulp indicate degradation occurs. This suggests wider use of land treatment may be viable. Containment and Remediation Technologies: As a part of an integrated research evaluation of landfill containment, it was found that lime and cement addition to soil liners reduced shrinkage by 50%. Such desiccation shrinkage is critical in permitting movement of liquids which occurs in the building and usage of landfill cells. Neither amendment was very effective in reducing movement of pure organics. Further, this project has discovered the potentially primary failure mode in synthetic liners. This is vapor transport, and appropriate diffusion coefficients were measured in this project. An important expansion was made with a new project to examine alternate liner materials. A complete simulation of containment facilities is envisioned in a second new project that links the various experimental landfill studies underway in the Center. Currently contaminated land is often managed with source removal and bioremediation. Sources are cleaned up from the upper soil zone (1-2 meters) and microbial processes used in this upper zone to reduce residual levels of organics. Bioremediation is also used in groundwater zones. However, our Center's research is directed at the critical middle zone (vadose zone) between surface and groundwater. In this area, little 113 ------- research existed and our results have discovered the potential to use bioremediation here, as well. In contaminated sites, vadose zones microbial populations were increased 50% using available enhancements. Degradation of dimethyl naphthalene was measured and some of the factors that improve the losses in the vadose zone were examined. It is expected that larger-scale decontamination trials can now be conducted based on this research. TABLE 6 CENTER FOR WASTE MINIMIZATION AND MANAGEMENT PROGRAM SUMMARY PRINCIPAL INVESTIGATOR PROJECT WASTE MINIMIZATION Carbonell Lamb Lim Gratzl/Joyce/ Felder Overcash Barlaz Surface Cleaning of Particles in Micro- electronics Fabrication Surface Cleaning in Microelectronics Fabrication: Alternatives to Aqueous Replacements for Conventional (RCA) Cleaning Controlling Mechanisms of Fugitive Emissions of Volatile Substances from Industrial Equip- ment & Devices Formation of PCDD's & PCDF's in Chloride Bleaching of Kraft Pulp Development of Multi- Industry Waste Reduction Model Assessment of Tech- nology Capacity Needed to Develop Recycle Markets for Plastics & Tires in NC END CURRENT TOTAL DATE BUDGET BUDGET 1992 1992 24,148 47,957 109,932 135,504 1992 78,066 261,573 1992 1992 1993 41,556 76,464 23,912 240,000 211,109 47,824 114 ------- PRINCIPAL INVESTIGATOR Fedkiw Stone PROJECT The Role of Cyanide in Electroplating of Copper Highway Routing Strategies for Safely Transporting Hazardous Wastes TREATMENT AND CONTAINMENT DiGiano Kamens Joyce Brown Autenreith Mclnnes Giam Aquatic Toxicity Mechanisms of Compounds in Industrial Wastewater Discharges Strategy for Analyzing Hazar- dous Waste Incineration & Other Treatment Technologies Decomposition in Soil of Specific Chlorinated Organics Related to Paper Industry Sludges Effectiveness of Multiple Liner Systems for Hazardous Waste Containment Facilities Evaluation of Alternative Leachate Liner Materials as a Function of Chemical & Liner Characteristics Mechanistic Model to Aid in Design of Composite Liners In-situ Bioremediation of Hazardous Substance in the Vadose Zone TRAINING AND TECHNOLOGY TRANSFER END DATE 1993 1992 1992 1992 1993 1992 1991 1991 1992 Denny/ Overcash Technology Transfer & Training 1992 CURRENT TOTAL BUDGCT BUDGCT 21,898 15,000 97,999 98,000 5,000 102,000 42,243 37,750 90,000 196,361 43,796 45,000 293,999 293,999 10,000 306,000 84,485 75,500 270,000 376,338 115 ------- RESEARCH PROJECT DESCRIPTIONS WASTE MINIMIZATION Surface Cleaning of Particles in Microelectronics Fabrication: R. G. Carbonell, North Carolina State University Goals: The objective of this project is to understood the mechanisms of particle deposition from solvents onto silicon wafers during microelectronics fabrication, and to use that information to develop alternative techniques for particle removal. 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 should lead to rational selection and use of alternative solvents and cleaning techniques. One of the main objectives of the work is to understand the role of particle physical properties and the surface properties of the wafer on the deposition mechanism; in particular, whether deposition takes place during wafer immersion into the liquid, while the wafer is immersed in the bulk solution, or during withdrawal from the liquid bath. Some of the variables that can influence the amount and rate of deposition include the particle concentration, the degree of stirring of the liquid, the time of immersion, the particle size and charge, the wafer surface composition and the wafer surface structure. In addition, this work aims at classifying the types of particles that are found in liquid processing baths so that alternative processing procedures can be developed, based on an improved understanding of the particle deposition process. Approach: Micron- and submicron-sized particles of different materials 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 the concentration of suspended particles in solution, immersion time, ionic strength of the solution. The wafers can be either hydrophilic, or hydrophobic, and they can be either patterned or unpatterned. In addition, the degree of stirring of the liquid can play a role in the rate of particle deposition. 116 ------- Status: This year, we have found that the charges on the wafer and the particles can play a significant factor on the amount of particle deposition, and the mechanism for particle adhesion. Particles with charges opposite the wafer deposit primarily in the bulk. Particles with the same charge deposit at the air-water interface. Client/Users: Cleaning to achieve pure surfaces is a wide-spread practice in many advanced technology manufacturing facilities. Circuits, optical disks, plastic and ceramic components are examples along with semiconductors in which the basic understanding of contamination/ decontamination is needed to reduce wastes due to cleaning. Surface Cleaning in Microelectronics Fabrication: Alternatives to Aqueous (RCA) Cleaning Solutions: H. H. Lamb, North Carolina State University Goal: To aid in the development and implementation of gas-phase cleaning processes for semiconductor surfaces. These are acceptable RCA chemistries, thereby enabling the industry to reduce significantly the generation of dilute aqueous wastes. Rationale: Although cleaning effectiveness is key to high-chip yields in microelectronics fabrication, the basic surface chemistry of silicon wafer cleaning is not well understood. Gas-phase alternatives, such as (UV/C»3), (UV/C12) and vapor-phase HF treatments, have been identified by simple analogy to conventional RCA cleaning chemistries. Basic knowledge of surface cleaning should provide insights leading to a more rational development of cleaning technologies for semiconductors, optical disks, and magnetic storage media. Understanding the basic chemical engineering science for gas-phase alternatives for silicon wafer cleaning will provide predictive models for use by chip manufacturers in the changeover from wet-chemical cleaning to more efficient, less polluting dry cleaning. Approach: In prospect, Ultra Violet (UV) photo-assisted oxidation of organic contaminants and vapor-phase HF etching of the resultant (SiC>2) layer comprise a gas-phase cleaning sequence to produce hydrocarbon- free, hydrogen-terminated silicon surfaces. Langmuir-Blodgett transfer of fatty acid surfactants from the air-water interface is used to reproducibly and quantitatively apply films of these common organic contaminants to silicon surfaces. Multiple-internal-reflection infrared (MIR) and Auger 117 ------- electron spectroscopies are applied in-situ to monitor: 1) organics removal and concomitant oxide growth in the presence of C«2 and UV light; and 2) vapor-phase HF etching of the resultant oxide layer. MIR spectroscopy uniquely provides submonolayer sensitivity to organics and to hydrogen adsorbed on silicon surfaces. Parameters to be investigated in UV photo- assisted oxidation include oxygen and water partial pressures, radiation intensity, total pressure, lamp-to-substrate distance, substrate temperature and chemical structure of the organic film. The effects of hydrogen fluoride and water partial pressures on oxide etch rate and on hydrogen versus fluorine termination of the resultant silicon surfaces will be investigated. Status: MIR spectroscopy has been applied to in-situ monitoring and evaluation of UV photo-assisted removal of Langmuir-Blodgett fatty acid films on Si(lOO). UV/O3 cleaning was found superior to the conventional RCA SCI (H2O2 : NIfyOH : H^O) cleaning step in removing submonolayer organic contamination from silicon. Hydrocarbon-free, hydrogen- terminated silicon was produced by UV/O3 cleaning followed by oxide etching in aqueous 1% HF solution. An integrated gas-phase cleaning tool, developed through collaboration with the NCSU Center for Advanced Electronic Materials Processing and Sematech, is nearing completion. The modular system will include processing chambers for UV-assisted removal of organics and metals, vapor-phase HF etching of native oxide, and ultra- high vacuum surface analysis. Client/Users: Development and implementation of gas-phase cleaning technology in microelectronics fabrication will result in a significant reduction in aqueous wastes generated by this industry. Current wet- chemical RCA wafer-cleaning processes generate large volumes of dilute hydrofluoric acid, sulfuric acid, ammonium hydroxide, and hydrochloric acid. These solutions, contaminated with organics, metals, and silicon must be treated and disposed of properly. The alternative gas-phase processes will eliminate these aqueous wastes and will use chemical reagents more efficiently. For example, it has been estimated that 5 Ibs. of anhydrous HF is sufficient to etch 90,000 silicon wafers by a vapor-phase process. In contrast, 2,000 Ibs. of 10% aqueous HF would be required by conventional wet-chemical etching. 118 ------- Controlling Mechanisms of Fugitive Emissions of Volatile Substances from Industrial Equipment and Devices: Robert All (Graduate Assistant), Dr. Sang June Choi (Visiting Professor), and Dr. P. K. Lim (Principal Investigator), North Carolina State University Goals: The goal is to identify and study the principal loss mechanisms by which fugitive emissions of volatile substances occur from industrial devices (such as valves, flanges, pressure-relief devices, drains, and the seals of compressors, pumps, and agitators). Ultimately, cost-effective measures may be taken to reduce the emissions. Rationale: SARA Title III regulations mandate the public disclosure of the fugitive emissions of listed chemicals from industrial sites, but reliable emission data are scarce and hard to interpret, and estimates of chemical emissions based on refinery emission factors are considered 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 SARA regulations. Approach: An experimental program is being undertaken to verify, improve, and extend the mechanistic models which have been developed earlier in an analysis of some plant-site data. Status: The capillary model has been extended to account for the emission of a condensable vapor from pores formed by two different wall materials. A separate viscous dissipation-evaporation model was developed to describe the emission from the wetted (lubricated) mechanical seal of a pump or compressor. Confirmation of a key prediction from the capillary model was made by experiments. This was a reduction of the surface tension driving force will lower the rate of emission of a condensable vapor. A second key prediction of the capillary model, namely the emission rate of a condensable vapor, should be relatively insensitive to the bulk pressure driving force and this was also demonstrated in the laboratory. An open valve was found also to give a consistently lower emission rate than a closed valve. Client/Users: The research findings are useful to commercial facilities that have a significant number of the devices mentioned above. A confirmation of the capillary model suggests the number of practical applications. Some of these are control measures which can complement the existing maintenance and repair program utilized by industry. A non- wetting packing material will lower emission. Application of an 119 ------- appropriate compressive stress on the packing material reduces the pore sizes through which the fugitive emission occurs. Minimization and Recovery of Volatile Organic Losses Manufacture of Flexible Polyurethane Foam: C. Kaufman, North Carolina State University Goals: Quantification of the volatilization dynamics of blowing agent loss and examination of innovative means to maintain safe worker conditions and current soft polyurethane product formulations while recovering the auxiliary blowing agent are the primary goals of this project. Increasing the process vent concentration of auxiliary blowing agents would lead to a potentially economical recovery/recycle process. Subsequently, air emissions of ozone-depleting CFC's or of a volatile organic (methylene chloride) would be minimized. Rationale: Polyurethane foam density is currently reduced to meet consumer specifications by the use of methylene chloride or chlorofluorocarbons as auxiliary blowing agents. These 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. Flexible foam manufacturers are under severe pressure to significantly reduce (VOC) emissions (methylene chloride) and to eliminate the use and emission of chlorofluorocarbons. Modification of the manufacturing process to allow for recovery/recycle of the auxiliary blowing agent or chemical substitution with an environmentally acceptable material would promote cleaner air. Approach: 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. 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: Magnitude and rates of auxiliary blowing agent losses have been established as a function of plant location. A model has been developed which predicts foam tunnel concentrations of methylene chloride as a function of formulation, tunnel length, conveyor speed, and exhaust rates. 120 ------- The next step is to form an industrial coalition of foam manufacturers and chemical suppliers to develop the necessary design modifications for tunnel retrofit/isolation and collection of tunnel emissions on one foam line. The goals of this demonstration project would be to determine collection efficiencies, specifications for recovered auxiliary blowing agents, product qualities of foam prepared with recycled materials, and a cost analysis of the process change. Client/Users: The technology of identifying magnitudes, rates, and plant location of hazardous emissions is a typical starting point for many industrial waste minimization schemes. The concentration/recovery/ recycle strategy has applications in many chemical process industries using large amounts of non-aqueous solvents where air is used to protect worker safety. Examples include the manufacture of other foams like expanded polystyrene (blown with hydrocarbons or ethyl chloride) and the manufacture of cellulose acetate (spun in acetone). Formation of PCDD's and PCDF's in Chlorine Bleaching of Kraft Pulp: J. S. Gratzl, C. L. Chen, and T. W. Joyce, North Carolina State University Goals: The objectives of this project are: 1) to determine the fundamental chemistry by which organic chlorine compounds, particularly dioxin, are formed; and 2) to develop engineering strategies to minimize the amount of chlorinated organics formed. Rationale: The paper industry generates large quantities of chlorinated organics each year as a byproduct of the pulp bleaching process. It is now realized that the continued discharge of these chlorinated compounds should be reduced. Recent research suggests that there may be process strategies by which these compounds can be minimized. Since the paper industry has already invested heavily in bleaching technology and equipment, it is much preferable to reduce the formation of unwanted pollutants by process modifications rather than by installation of new equipment. Approach: A systematic study of the basic chemistry of pulp bleaching was made in the laboratory. From these studies, further research on the effect of process variables on the production of specific pollutants was carried out. 121 ------- Status: We have now progressed to the point of understanding the basic chemistry of formation of chlorinated compounds in the bleach plant. Dioxin precursors have been identified in conjunction with work at the University of Washington, Seattle. From this understanding flows the ability to change process variables for bleaching thereby decreasing the discharge of pollutants by process modification. We are now discussing with the Department of Chemical Engineering how our discoveries can be applied on an industrial scale. Client/Users: At present, the paper industry generates large quantities of chlorinated organics during the pulp bleaching (chlorination) process. Because of potential regulation and a concern for generation of these pollutants, the industry is searching for means to minimize these constituents. Much effort has been directed to chlorine-free bleach processes. However, these processes would require the construction of expensive new equipment which the industry is reluctant to do. Our concept is to take existing equipment and change the conditions by which it is operated. This approach serves two purposes. First, we will be able to avoid investment in new equipment and secondly, we hope to minimize operating costs by reducing the quantity of chemicals used in the process. Multi-Industry Waste Reduction Model: M. R, Overcash, G. Rutledge, J. Sutton, North Carolina State University Goals: 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. 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 deterioration in another. The result is not net minimization of waste, but relocation. Approach: In the first phase of this study, data are being collected from available sources to couple energy expenditures or savings with increases or decreases in pollutant emissions to the surface, water and air. The analyses 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 122 ------- materials and influence, if any, on product use. These will better describe the mass and thermodynamic information on which the computer framework will be built. Status: The initial study of the first phase has been restricted to collecting data on coal-fired power plants. These are a prime energy source for industrial production. An extensive literature search, limited to an inside-the-walls approach, has produced a substantial amount of pertinent information. Meetings with industry, EPA, and other federal and state representatives provided us with current facts. The relevant data from all sources are being used to construct a model 500 MW bituminous coal-fired electric power generating plant with a once-through water system for the first frame of the computer framework utilizing Smalltalk© software. Test manipulations of the data collected indicate that Smalltalk will be satisfactory for analysis and graphic presentations. The inside-the-plant approach is being used to identify the pollutants in the waste streams and the existing technology for minimization and management including energy requirements. Four streams, wastewater, solid, air, and hazardous waste are included in the mass envelopes. These can be broken down to identify the compounds and then calculate an overall chemical envelope containing the energy cost per kilowatt hour. The Smalltalk subroutines of the mass, chemicals, and totals of multiple waste streams can be linked to manufacturing waste reduction and decreased or increased energy requirements. Client/Users: Similar envelopes from a variety of manufacturing operations can be used for the first comparison of waste reduction case studies. These pioneering evaluations are for the determination of the methodologies for net waste minimization in a wide variety of industrial categories. The focus is on pollution prevention in areas of total net reduction rather than transfers along a manufacturing sequence. Assessment of Technology Capacity Needed to Develop Recycle Markets for Plastics and Tires in North Carolina: M. A. Barlaz and D. M. Russell, North Carolina State University Goals: The objectives of this project are to: 1) critically evaluate existing technologies for recycling post-consumer plastics and tires; 2) identify the processing technology and manufacturing capacity required to recycle all of the waste plastic and used tires generated in North Carolina; and 3) determine whether there is sufficient demand for products made from 123 ------- recycled plastic to support the recycling of all of the post-consumer plastic generated in North Carolina. Similarly, to evaluate whether there are sufficient markets products manufactured from recycled tires. Rationale: Recent regulations proposed by the EPA under Subtitle D of the Resource Conservation and Recovery Act (RCRA) require that, as a nation, we commit ourselves to reducing the mass of non-hazardous solid waste requiring disposal by 25%. A similar goal has also been adopted by several states including North Carolina. Meeting this goal will require an increase in the amount of waste reused either prior to, or after reprocessing (recycling). Plastic and tires are two components of the solid waste stream for which recycling rates are low. Only about 1% of the 22 billion pounds of waste plastic generated annually is recycled. However, the numerous plastics recycling projects which have been initiated in the last two years provide evidence of the recyclability of specific plastics and suggest that there is the potential to increase plastics recycling if appropriate collection infrastructure and manufacturing capacity are available. The critical element missing in the search to increase recycling in North Carolina is the development of stable, large markets for materials. Specifically, if all 100 counties in North Carolina are collecting plastics and tires for recycle, then "What manufacturing capacity do we need?" Without this technology capacity information, little state-wide planning and policy development can be implemented. Since the amount of material the state might collect is not known, nor goals set precisely, we must understand the relationship between technical capacity and generation for recycle. In addition, with realistic goals and capacity, the state can then develop better policies to encourage use of the recycled materials. North Carolina will be used as a model for this study, although the findings will be generally applicable to other states. Approach: The first step is development of the quantities of waste which would be available for recycling if policies were to be enacted to mandate the segregation of all or most of the waste plastic and tires in North Carolina. Estimates of these quantities will be developed from state population data and waste composition data available in the literature. Technologies suitable for recycling the target waste streams will then be identified. Next potential markets for recycled plastic, including both the types of products and the total weight of production, will be identified. From these data, we will evaluate whether we have the technology, manufacturing capacity, and long-term markets to recycle the post- 124 ------- consumer waste plastic and tires generated in North Carolina. Our findings will be published as technical resource manuals whose central theme will be to answer the question, "What is required at the state-wide level to recycle plastics and tires, or otherwise reuse these such that there is a viable alternative to land burial?" Status: We have completed our design basis for the quantity, composition, and demographics of waste plastic generation. Based on an initial survey of processing requirements and collection technology, we assume that high-density polyethylene (HDPE) milk containers and polyethylene terephthalate (PET) soft-drink containers will be segregated and the remainder of the plastics stream must be handled as mixed plastic. We are currently assessing available manufacturing capacity and the viability of long-term markets for segregated PET and HDPE. Next, we will perform a similar assessment for commingled plastics. Client/Users: States must determine whether the manufacturing capacity is in place to handle the increased waste loads which will develop as the rate of plastics recycling increases ten- to twenty-fold. Manufacturing capacity will only develop if there is sufficient demand for resin generated from post-consumer plastics. We will evaluate the demand for recycled resin relative to the expected future supply. Old tires are generated at the rate of 240 million per year. Our analysis of viable alternatives for recycling old tires will proceed along a path similar to that described here for post-consumer plastics. The Role of Cyanide in the Electroplating of Copper: P. S. Fedkiw and D. Chu, North Carolina State University Goals: Our objective is to understand the unique electrochemical role that cyanide plays in the overall metal-deposition process, and effects on the resulting deposit properties. In particular, we are studying the copper- cyanide system. The chemical and physical interactions of cyanide with the other bath constituents is also being examined. Ultimately, with the results of our research, chemical, electrochemical, and physical criteria for ligands to replace the environmentally noxious cyanide will have been identified. Rationale: Copper is electroplated from basic pH plating baths containing copper cyanide and higher cyanide complexes, excess sodium cyanide, and sodium carbonate and hydroxide. Such baths have excellent "throwing power" (i. e., the ability to distribute the metal plate uniformly along an 125 ------- odd-shaped workpiece), and the deposit has good adherence to the substrate, particularly on ferrous metals. Copper cyanide baths are routinely used in so-called "strike baths" as the first layer upon which other metals are deposited; for example, chromium is the third metal plated in the sequential copper-nickel-chromium process. Even in the electrodeposition of copper from acid sulfate baths, a copper cyanide strike is first typically applied so that the deposit is a better adherent. The rinse waters from the cyanide plating line must be treated before discharge, and are commonly oxidized by hypochlorite to form CNO" which ultimately decomposes to nitrogen. The added complexity of treating cyanide- containing wastewaters and the potential catastrophic failure of the treatment system are strong motivating factors for the replacement of cyanide plating baths. It is our point of view that the search for cyanide replacements should be guided by a fundamental understanding of the functionality of cyanide in the plating process so that the search for replacement ligands may be scientifically, rather than empirically, guided. Approach: We have identified the following electrochemical experiments to achieve our objectives: cyclic voltammetry (CV), rotating disk (RDE) and ring disk (RRDE) hydrodynamic voltammetry, all of which are standard electroanalytical tools. We have performed some preliminary CV measurements using a standard electroanalytical tools. We have performed some preliminary CV measurements using a standard copper cyanide bath formulation from which we make two interesting observations: 1) the potential for copper deposition overlaps that, for water discharge to hydrogen; and 2) the potential along the more recessed portions of a workpiece can be such that a copper oxide is formed. In addition to the electrochemical experiments, post-run (SEM) analysis and Auger spectroscopy of the surface will be performed to examine the morphology and chemical composition of the surface layer of the deposit. Client/Users: Surface-finishing and electroplating industrial processes which have been unsuccessful in converting away from cyanide usage. These often involve strike-plating or other special applications. The replacement of cyanide must be based on improved understanding of the role in plating. North Carolina Industry SARA Section 313 Data Analysis: D. Denny, North Carolina State University Goals: Categorize North Carolina industry air toxics emissions by industry category, chemicals released, sources, and geographical distribution. 126 ------- Generally identify and describe source reduction and recycling potential for each industrial category using case studies where possible. Identify areas where new technologies need to be developed. Approach: Review existing computerized inventories of North Carolina industry discharge submissions, as required by SARA, Section 313. Prepare summary reports describing the air toxics portions of the inventories by industrial category, pollutant, and geographical location. Identify and summarize all case studies in the Pollution Prevention Pays library for relevant case studies. Provide general summaries of existing technologies for source reduction and toxics pollutant recycling potential. Provide engineering analysis to identify the applicable technologies by source category supported by case studies when available. Identify those sources and source categories that need additional research. Status: The North Carolina SARA 313 air toxics emission inventory has been obtained. The inventory has been segregated by pollutant, industry segment (SIC Code), and geographic location. Summaries remain to be prepared. The North Carolina Pollution Prevention Pays library has been researched and all pertinent case studies have been summarized. Material has been gathered describing generally existing applicable technologies. The industry by industry analyses are in process. Highway Routing Strategies for Safely Transporting Hazardous Wastes: J. R. Stone, North Carolina State University Goals: The goal of this project is to develop a computerized method which will aid planners of hazardous wastes routes and to demonstrate the utility of artificial intelligence as a management information method. Rationale: Current research indicates that documented guidelines for routing hazardous waste have effectively reduced highway accidents and spills. The premise of this effort is that such guidelines and other heuristic rules can successfully be incorporated in computer-based expert systems and geographic information systems in order to facilitate the route planning task. Approach: A flexible approach has been taken in this project. Initially, the USDOT Routing Guidelines were programmed and validated in a spreadsheet model. Next, an expert system shell provided the user interface with the spreadsheet. It also provided a link to the most recent truck accident models and a weighted evaluation scheme for selecting the 127 ------- routes. In the future, cost models will be added, and the adaptability of the method to a geographic information system will be explored. Status: A prototype using standard USDOT guidelines has been computerized and successfully applied to a hypothetical case study. Extensions to the computer method will be made as necessary, and a real case study will be evaluated in future work. Client/Users: This method is directed to public agencies and trucking firms which plan the routes for hazardous waste collection and delivery to disposal sites. Aquatic Toxicity Mechanisms of Compounds in Industry Wastewater Discharges: F. A. Di Giano, J. Charles, D. Amaral, D. Francisco, University of North Carolina Goals: The immediate goal of this project is to identify a direct industrial discharger willing to cooperate in a study of fractionation schemes aimed at identifying the specific chemical source(s) of effluent toxicity. The ultimate goal is to develop and test laboratory protocols that can be adopted by various classes of industry important to Regions 4 & 6 to solve their aquatic toxicity problems. The approach expands upon protocol being developed by the U. S. EPA to examine toxicity of municipal effluents rather than specific industrial effluents. Rationale: The fractionation schemes developed so far by EPA are focused 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 dyes used in the textile industry, may contribute 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. Approach: A listing of industries causing aquatic toxicity and discharging organic chemicals of possible human health concern has been generated for North Carolina, South Carolina and Tennessee. A list of industries with 128 ------- potential problems in meeting toxicity limits has been received from EPA Region 6. General classes of organic chemicals in use by different industries will be developed using available data from NPDES permits and effluent guideline documents. One industry representative of an important class (those using textile dyes) was selected for investigation of fractionation procedures. Having completed three rounds of sampling and submitted the results to the industry for their consideration, another case study will soon be selected. This may be a representative of EPA Region 6. Additional analytical approaches for specific identification of those chemicals causing acute toxicity to Ceriodaphnia are warranted. This includes more precise segregation of organic from inorganic sources of toxicity and a more efficient scheme to narrow the list of potential organic compounds. The identification of sources with chronic toxicity is in the long-range plans, but will await the results of research on testing protocol being done by EPA at the Duluth Laboratory. Another important aspect of the research is a broad-based, regional profile of industry classes to examine (a) the range of effluent toxicity from different classes, (b) the variability in effluent toxicity from site to site for a given class, and (c) the variability in dilution afforded by receiving streams for a given class. Status: A textile dyestuff manufacturing plant was selected for study. Three samples were taken in January, April and July of 1990 and subjected to toxicity identification and evaluation procedures. A protocol was established whereby the amount of toxicity due to chloride and to organic compounds was calculated. Over 700 bioassays were conducted in an attempt to isolate specific sources of toxicity. A list of organic compounds suspected of contributing toxicity has been established and is being further refined with the help of the industry. Client/Users: Major industrial classes found in EPA Regions 4 & 6 which are likely to have difficulty in meeting more stringent effluent toxicity limits. The focus is on industries having complex effluents containing both inorganic and organic compounds. Given that toxicity due to metals is fairly easy to identify, this research deals with segregating and identifying organic compounds. As examples, in Region 4, both the textile industry and organic chemicals manufacturing industry are of interest. In Region 6, the general category that includes various aspects of the petrochemicals industry is of interest. 129 ------- Strategy for Analyzing Hazardous Waste Incineration and Other Treatment Technologies: R. Kamens, D. Amraal, J. Charles, University of North Carolina Goals: The main 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 are comparing, as a model situation, the thermal treatment of flame-retardant materials such as polybrominated biphenyl ethers (PBBEs) with other physical or chemical disposal alternatives. 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. Hence, we have chosen to investigate these compounds as representing an ideal test case for looking at disposal alternatives with a class of compounds that have not received a lot of attention. As an example, we expect the developed model to provide information which would help one decide between discarding materials containing fire retardants in a landfill (knowing all the costs, risks, and societal concerns associated with this option) versus incineration, with all of its costs risks, and societal concerns. Approach: The potential treatment alternatives for discarded materials which contain fire-retardant materials are being 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 then add emissions directly to existing 25m3 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: A method has been implemented and is being refined for evaluating options for managing a troublesome waste. This method relies on calculating the probabilities of a range of possible exposures resulting from a given management scheme. These exposures are then compared to risk-related health guidelines or standards. Two situations are currently being studied, one in Charlotte and the other in Wilmington, NC. Aerometric and ground water models have been adapted for estimating 130 ------- probability related exposures. In our current example, atmospheric stability estimates of PBDDs and PBDFs are needed in the aerometric model. Progress on the outdoor chamber part of this project shows that measured PBDDs and PBDFs on real soot particles are not very reactive in the atmosphere. We are currently: a) implementing a model to estimate total environmental dose; b) generating a method to characterize PBDDs and PBDFs toxicity; c) collecting data on industry production of PBDEs and use in plastics; and d) integrating cost information into the models for different treatment options. Client/Users: We view local communities, governments, and industry as the ultimate users of this work. For example, the Brominated Fire Retardant Industry Panel has expressed interest in our outdoor chamber experiments and has asked for the results of our PBDDs and PBDFs atmospheric stability studies. They have also co-funded the purchase of brominated dioxin and furan standards for this project. In the future, we expect to provide a generalized methodology which can be used to plan for the best way to manage a given toxic waste in light of potential health risks and costs to the community. Decomposition in Soil of Specific Chlorinated Organics of Importance Related to Paper Industry Sludges: T. W. Joyce, M. R. Overcash, North Carolina State University Goals: The objectives of the project are: 1) to develop a test procedure for measuring organic chlorine compounds in paper mill sludges and sludge/soil mixtures as might be found when paper mill sludge is landspread as an ultimate sludge treatment technique; and 2) to determine if the chlorinated lignins found in paper mill sludges are degradable when spread on land. Rationale: The paper industry is rapidly running out of landfills to dispose of sludges. It is also unlikely that incineration of sludges will be permitted since, particularly for paper mill sludges, there is a likelihood that chlorinated dioxins will be formed during the combustion process. Thus, landspreading is one of the most attractive sludge-management alternatives remaining. However, regulatory officials still have a concern that the chlorinated species in paper mill sludges are not biodegradable and may accumulate in the soil, perhaps even reaching and polluting the groundwater. 131 ------- Approach: Sludges were obtained from operating paper mills and subjected to various preparation methods to determine if a method could be developed to measure chlorinated species in a reproducible manner. A "model" sludge, the first chlorination stage pulp, was used as a base case. Chlorinated lignins were prepared in the laboratory and incubated in soils thought to be suitable for landspreading. In a similar manner, specific, low molecular weight chlorinated species commonly found in paper mill sludges were also incubated in the soils. The rate of carbon dioxide evolution was measured for the lignin supplemented soils, while the specific chlorinated species were extracted from the soil and measured by gas chromatography. Status: A procedure for measuring the sum of chlorinated organics in sludges and sludge/soil mixtures has been developed. Of the seven specific compounds incubated in soil, only one was not quickly degraded. It must be pointed out, however, that the compounds were added to the soil in concentrations several-fold higher than would be found in a paper mill sludge. This was necessary to ensure that a sufficient amount of the compound would be available for measurement over the time course of the experiment. We have found that chlorinated and unchlorinated lignins evolve carbon dioxide at essentially the same rate. The rate is somewhat lower than naturally occurring lignins, such as corn stalks, and the total amount of carbon dioxide evolved indicates a rather low degree of stabilization. We attribute this to the lignin becoming a part of the humic matter of soil and not indicative of potential environmental problems. Client/Users: The landspreading of paper industry sludges will probably be practiced widely in the future. Sludges are always produced from all paper mills in significant quantities. Landfilling is now the most common means of sludge disposal. However, regulatory agencies are not permitting landfills as easily now as in the past. Incineration is usually not an acceptable option because of the concern for dioxin formation during the combustion of paper industry sludges. Thus, landspreading is the most obvious choice for future sludge disposal; the one concern is the fate of the chlorinated organics in the soil and whether these would ever pose a hazard to the groundwater. Landspreading will not be permitted until this concern is addressed. 132 ------- TREATMENT AND CONTAINMENT Effectiveness of Multiple Liner Systems for Hazardous Waste Containment Facilities: K. Brown, R. Lytton, C. Giam, Texas A&M University Goals: The immediate goal of this project is to evaluate the potential use of stabilizing agents and additives to the clay to enhance the ability to withstand chemical attack and to retard the migration of organic contaminants. Future goals include: 1) the development of a laboratory testing protocol to be used to evaluate soils for suitability in a clay liner; 2) the evaluation of ventilation systems to extract the volatile constituents from the leachate collection and leak detection systems; and 3) the development of mathematical models to describe the transport of organic contaminants through a composite liner system. Currently, we have achieved our immediate goal, and are well underway in the studies needed to accomplish goal 1. Studies needed to accomplish goal 2 have been designed and should be conducted in the upcoming year. Design and development of the overall model (goal 3) is being done in a companion study under the direction of Dr. Mclnnes. Rationale: Many of the wastes resulting from RCRA waste treatment and cleanup of superfund sites which need to be disposed in landfills still contain small quantities of hazardous constituents which could drain from the waste, adversely impact the integrity of landfill liners, and migrate to the groundwater. Recent data by Haxo indicate that certain organic contaminants, even when these occur 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 including the addition of stabilizing agents to prevent chemical attack, better laboratory testing protocols to allow better evaluation of the suitability of soil materials for use in constructing clay liners, the addition of polymeric chemicals to clay to increased the sorption capacity, and the use of ventilation systems to remove volatile organic vapors before these can penetrate the liners. Approach: The effects of several stabilizing agents on the hydraulic conductivity of compacted clay soils will be evaluated through a laboratory study employing fixed wall parameters 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 133 ------- constants of various organics through several thicknesses of high density polyethylene (HOPE). Laboratory testing methods will be developed to measure soil properties such as shrinkage and cracking and correlate these properties to the final hydraulic conductivity in the field situations. A mathematical model to describe the movement of chemicals through a multi-component 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. Status: The laboratory testing of amendments (lime and cement) is nearing completion. Diffusion measurements have been conducted for trichloroethylene and toluene in HOPE and compared to modeled data for these compounds. Future testing will expand this data base to other chemicals representative of various chemical classes. Modeling work to create an overall model of the liner system has been transferred to a companion project under the direction of Dr. Mclnnes. Client/Users: This project is developing information which will be of assistance to regulatory agencies, as well as those professionals involved in the design and construction multi-component landfill liners. New testing procedures to be developed will aid in predicting which soils will perform best under field conditions. New municipal landfills will depend on this information. Evaluation of Alternation Leachate Liner Materials as a Function of Chemical and Liner Characteristics: R. L. Autenrieth, Texas A&M University Goals: The primary goal of this research project is to determine if readily available inexpensive materials when added as a protective layer to landfills as currently designed will be able to provide an adequate barrier to the movement of leachates. We will specifically be testing lignite, peat moss, compost, cotton gin trash (type of activated carbon), and activated carbon (as a standard reference material) as potential liner materials with exposure to individual and mixtures of organic solvents representative of leachate components. We will determine how much of the leachate components can be held and what effect a mixture of these solvents has on the effectiveness of these materials. Rationale: The synthetic liner materials and compacted clay which compose the primary barrier materials in a landfill have been shown by numerous investigators to allow certain components of leachates to move 134 ------- through these liners, sometimes quite readily. These chemicals are able to escape from the landfill either due to imperfections in the liners, by dissolving, or by diffusing. By adding an additional layer to the liner sequence which has properties enabling it stops the further movement of these leaching chemicals would significantly reduce the risk of further contamination. Since this layer is likely to be more expensive than clay or synthetic liners, it is meant as a safeguard and would not necessarily be considered a primary liner material. Placement of the material would be flexible depending on the anticipated leachates. Approach: The ability of the selected liner materials to prevent the movement of a range of chemicals frequently found in leachates from hazardous landfills will be evaluated. First, the affinity of the chemicals for the liner materials will be quantified. These tests will be conducted for single chemicals and mixtures to determine if mixtures alter the performance of the individual compounds. Then the mass of chemicals that the liner can hold will be determined by using specially designed chambers. Status: This project was initiated in July 1990. We have finished our literature review, procured our solid materials, and selected our organic solvents. We have completed preliminary sketches of the breakthrough chamber and are testing components of this chamber for use. We are currently developing our analytical techniques and the quality control/quality assurance measures in the laboratory. We anticipate initiating the experiments at the beginning of December. Client/Users: All those involved in the design, construction, compliance, and monitoring of landfills will be interested in this research. This would include government agencies, those who would be using landfills to dispose of wastes, and those responsible for landfill construction and monitoring. With new landfill regulations for municipal solid waste, these results should be of direct benefit. Mechanistic Model to Aid in the Design of Composite Liners: K. J. Me Inness and K. W. Brown, Texas A&M University Goals: The goal of this project is to develop a user-friendly mechanistic computer simulation model based on physical and chemical properties of liner materials that predicts the transport of organic and non-organic contaminants through composite liners. The model is intended to allow researchers working on individual components of multiple-liner systems to 135 ------- combine research results with those of others to allow an estimate the future loss of pollutants through the liner to groundwater. The first version of the user interface and simulation model have been completed. Rationale: A well-constructed, multiple-liner system should minimize the possibility that present waste disposal activities will require future remediation. The design must be based on our combined knowledge of contaminant movement through individual layers and how these layers interact. Liners should be engineered for the optimal combination of flexible membrane and clay layers. A simulation model based on physical and chemical principles and actual experimental data can be used to predict the proper combination of barriers, amendments, and control measures to contain hazardous waste. In addition, modeling should be part of a standardized protocol for the design of RCRA-type landfills. Approach: A numerical simulation model is being developed to study the transport of metals and organic compounds through a composite liner consisting of a combination of carbon filter layers, compacted clay layers, drain layers with potential vapor extraction, and flexible membrane liners. The model is based on an implicit finite difference solution of the combined flow equations for each layer. The solution technique guarantees mass balance. The flow equations account for both diffusion and mass flow and combine the concept of the mobile phase having different mobilities. The model is coded in C programming language for the IBM PC and the Apple Mac II computers. The user will be able to choose the order, number, and thickness of layers along with the physical and chemical properties without directly editing, recompiling, and linking source code. A library of common individual compounds and properties will be kept available to the user in the model. The user interface will stress ease of use. Status: On the Mac II, Version 1 of a user-friendly HyperCard interface, a simple two-phase convective dispersion model programmed in C are operational. Further development of the HyperCard interface and the C code are underway. The C code simulation is running on both the IBM PC and the Macintosh. Client/Users: The model is to be used by researchers working on individual components of multiple-liner systems to combine their research results with those of others to allow and estimate the loss of pollutants through the liner. In addition, this tool may be used by engineers to predict the proper combination of barriers, amendments, and control 136 ------- measures for a particular site when designing a multiple-liner system to contain hazardous waste. In-Situ Bioremediation of Hazardous Substance in the Vadose Zone: C. Giam and K. Brown, Texas A&M University Goals: The overall 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. Laboratory and field data will be collected and used for calibration of the model. Rationale: Microorganisms indigenous to soils are capable of degrading most 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. In the first level, a mathematical model is being developed to 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 levels 1 and 2 studies. Status: Preliminary work on assembling the model (level 1) has been completed and collection of laboratory data for calibration of the model is well underway (level 2). The laboratory system designed to evaluate the effects of various environmental parameters on the biodegradation rate is now operational and has been used to evaluate the ability of vadose-zone microorganisms to utilize one of three model compounds. Collection of additional laboratory data and calibration of the model will continue through the upcoming year. Client/Users: The data and model developed in this study will be of value to both industrial and regulatory personnel who are involved with the design and operation of in-situ bioremediation activities. The data should help in the design of systems of optimal operation and thereby 137 ------- reduce both the time and cost for clean up. The model will be a major advance in our ability to reclaim subsurface soils which would otherwise pose major pollution threats. TRAINING AND TECHNOLOGY TRANSFER Research Presentations for Technology Transfer: M. R. Overcash, North Carolina State University Goal: The open discussion of the Center's research agenda is to be utilized in the dissemination of important results. Rationale: Interaction with the public and industry is vital in the research on pollution prevention. The presentation of current research, even at the early stages of work, is helpful in maintaining potential user interest in the results generated. Approach: During the year, a series of efforts were initiated to transfer Center research through detailed presentations. These activities assist in maintaining interaction with the Center and hence a constant interchange of ideas. We conducted the following presentations: • Pollution Prevention Approaches, Earth Day Alliance of the Lower Cape Fear River; • Reducing Volume and Toxicity of Hazardous Waste, teleconference from Oklahoma State University to 200 locations in 33 states plus Canada, Japan, Mexico (about 2,500 persons); • Waste Minimization Research, N. C. Governor's Waste Management Board and public attendees; • Computer System for Transport of Hazardous Wastes (Dr. John Stone), N. C. Governor's Waste Management Board and public attendees; • Reduction in Municipal Solid Waste - University Perspective, Video Conference for Earth Day across North Carolina; 138 ------- • Pollution Prevention and the Process Industries, First Pollution Control Conference of the Mexican Institute of Chemical Engineers; • Chemical Waste Minimization and Management, Our Island Earth Symposium, Wesleyan, NC; • Process Improvement in Pollution Prevention, 1990 Industrial Energy Technology Conference, Houston; • Research Center Presentation at the New Jersey Water Pollution Control Federation Conference; and • Future of Recycling - University Research, presentation to Annual Conference of North Carolina Recycling Association. Status: These presentations to large and diverse audiences have been completed and more are scheduled in the effort to disseminate information from the Center. Regional, National, International Research Needs and Information Exchange: M. R. Overcash, North Carolina State University Goal: The evolution of research issues in waste minimization and management is enhanced by the interactions with groups in our region pair, as well as at a national level. Rationale: Research and technology transfer activities of the Center must continually interpret the input from diverse organizations in order to refine the research projects over the longer terms of a Center. This interpretation includes discussions with state agencies and regional EPA offices as the issues of waste minimization and management are developing. Approach: There have been several circumstances in which the Center has sought and received input on possible new or enhanced research projects. Since all the initial research efforts were three-year projects and were proceeding very effectively, the region-pair and national inputs were used for a limited number of new activities. • The input on research needs included a complete briefing of EPA Region 6 staff responsible for the various regulatory 139 ------- programs. Specific follow-up to each of the 7 areas was made in writing to identify detailed technical issues that evolved from this meeting. In addition, a half-day seminar on the Center was given for the technical staff of Region 6 offices in Dallas. One specific area identified was by the water/ wastewater program as a need to evaluate toxicity testing data in Region 6. This has become a part of the research program. The National Clearinghouse on pollution prevention is managed by EPA in Washington, D. C. All of our relevant projects have been listed and are thus accessible to nation-wide users. A certain fraction of the inquiries we receive derive from our participation in this clearinghouse. The environmental conference conducted by our Center provided a wide variety of technical and user input from the region-pair. The expansion of the Center into terrestrial systems for treatment and the enhancement of the residue containment research were a result of regional-pair input and discussion at that conference. Further input on research needs was sought from the Engineering and Science Advisory Board and the Technology Transfer Advisory Committee of this Center. These individuals have a broad view of regional and national issues. From these groups, the new Center-funded research in municipal solid waste recycle was implemented in response to a recommendation on consumer and public issues for waste reduction. We jointly conducted a two-day conference with industry and university faculty, and published a proceedings entitled Waste Minimization Research Needs. Developed and presented an information booth on all Center projects for a major energy x and industrial conference in Houston. Described in detail the concepts of pollution prevention and the Center role to legislative representatives of about 18 states comprising the Southern Legislative Conference. These discussions focused on research infrastructure and specific State needs. 140 ------- • Participated in decision-makers Forum for all industry of North Carolina to establish priorities and assistance in waste reduction. • The eight states of Region 4 meet periodically to focus on waste reduction and their respective programs. The Center has met with all eight states and presented the detailed research projects. These discussions have established a mechanism for the pollution prevention research needs to be directed to the Center. • Conducted discussion with the Director of the United Kingdom Department of the Environment programs on pollution prevention research and national progress in clean technologies. • Provided materials for establishing a research program for pollution prevention in universities of Spain as a part of their national 3R Program. • Provided an in-depth seminar to assist the Ministry of Environment in Norway as a research and technical assistance program is established. Status: The active transfer of information to refine or expand research in response to region-pair or national needs is on-going and has already demonstrated effectiveness. Technical Assistance in Waste minimization and Management to Legislatures, Government, and News Media: M. R. Overcash and D. Denny, North Carolina State University Goal: The engineering and technical expertise from the Center should serve a role in providing information to a variety of decision makers and others responsible for public education. Rationale: As various government organizations examine environmental issues, it is important that greater factual and descriptive material be available. This process improves decision making. The same is true with preparation of news media coverage of environmental issues. The Center program and personnel represent a valuable source of information as those 141 ------- involved with various research activities conduct these projects. Thus, this Center is committed to providing information and presentations to government and news media personnel. Approach: From our national and regional activities that focus attention on developments in pollution prevention and the EPA Center, a number of more specific assistance opportunities have occurred. These include: • Discussions to help the S. C. Department of Health establish a waste minimization program for South Carolina; • Hazardous waste recycling technology presentation at public hearing on a recycling industry siting, Franklin County, NC; • Limits of hazardous waste reduction for off-site materials, Raleigh News and Observer; • Assessment of solar treatment of hazardous wastes for staff of N. C. Senate President; • Review of proposals for research fellowships in environmental restoration, U. S. Dept. of Energy; • Detailed review of N. C. Senate Bill [63] to identify criteria for local input to siting and site management, N. C. Dept. of Environmental Health and Natural Resources; • Pollution prevention review of N. C. capacity assurance plan for national hazardous waste management compliance; • Testimony before U. S. House of Representatives, Subcommittee of Science, Space, and Technology Committee, topic Pollution Prevention Research - Future Potential; and • One-day scientific instruction and training for site managers of Illinois EPA by K. C. Donnelly, Texas A & M University. Status: These assistance activities have been completed and with the interest in environment and waste minimization, further technical participation for Center staff is envisioned. 142 ------- Industrial Technology Activities: M. R. Overcash, North Carolina State University Goal: The opportunities to implement the research program results are to be expanded through specific industry interaction in pollution prevention. Rationale: Experience gained in actual waste minimization projects or through in-depth process discussions is instrumental in developing routine techniques for technology transfer. Approach: A series of activities were conducted to develop specific waste reduction case studies or to develop industry-related applications of the Center's research: • Dr. Stahel assisted in the evaluation and specification of recovery equipment for solvent- and petroleum-contaminated rags and cloth; • Developed information package to assist the Electronic Chemicals Manufacturer Association utilize the waste reduction research results; • Provided a review and then dissemination of a process manual to be used by small manufacturers based on the waste management hierarchy and procedures developed at NCSU (for Ontario Waste Management Corporation); • Organized and chaired a technical conference session on Waste Minimization Design Methodologies and Material Substitution to disseminate research to industry and chemical engineers (Orlando, FL, American Institute of Chemical Engineers); • Conducted an in-depth research and technology development meeting for major corporation staff focusing on pollution prevention and process innovation business opportunities; and • Presented detailed overview of all Center projects and discussed research implementation with Chemical Industry Council of North Carolina. 143 ------- Journal and Database Materials to Disseminate Center Mission and Research: M. R. Overcash, North Carolina State University Goal: Broad exposure of the Center's research in waste minimization should be achieved using electronic and printed summaries of information. Rationale: It is effective to utilize the growing number of catalogs prepared by U. S. and overseas organizations to document the field of pollution prevention. These sources are broadly utilized and thus provide exposure for the Center's research projects. The approach is more toward transfer of information instead of the research needs solicitations described elsewhere. Approach: The Center has been active in identifying and contributing to various journals and database summaries that can broadly disseminate the Center research: • The research in polyurethane foams was described from information provided by the Center in local newspapers near such manufacturing facilities; • Descriptions provided for the National Research Centers Directory; • Best North America data base was used to outline the Research Center mission; • A National Science Foundation research catalogue section was prepared on all waste reduction research projects; • International dissemination of the EPA Center program and projects was accomplished through the research publications catalog for the Danish Technological Institute; • Pollution Prevention catalog entries for center research projects, State University of New York at Buffalo Compendium on R&D in Hazardous Waste Management; and • Listing of research projects and services for environmental catalog of Inform Corporation, New York. Status: We continue to search for these databases in order to disseminate the Center research results. 144 ------- Newspaper Recycle Technology: Development of Undergraduate Participation and Research: R. Bailie, J. Heitman, T. Joyce, M. Overcash, North Carolina State University Goal: Considerable public interest and concern is directed at recycle and reuse programs to reduce landfill usage. In order to have options available to achieve recycle, there must be technology alternatives. Hence, a project was developed to broaden the options for one municipal solid waste stream, post-consumer newspapers. Rationale: While the level of municipal solid-waste recycle of newspaper is principally limited by public habits and interest, there is always a technical challenge to keep generating more and better options. University students are both consumers and trained undergraduates capable of generating options for greater newspaper recycle. This project utilizes the opportunity to educate individuals on the full issue of newspaper recycle and to employ the scientific and engineering education process to develop technical recycling options. Approach: The support and interest of a Raleigh newspaper was brought to the Center through our information transfer activities. The Raleigh News and Observer believed that more information and innovation would be valuable for the issue of newspaper recycling. At NCSU, the educational course structure was augmented for Chemical Engineering Process Design (ChE 451), Wood and Paper Science Project Management and Analysis (WPS 415), and Chemical Engineering Independent Research (ChE 497 and ChE 498) to include the specific issues of newspaper recycling technology and public perceptions. A number of lectures to about 50 students were given on current technical approaches and the magnitude of this portion of the municipal solid waste. The students then developed a report describing 16 technical alternatives. Of these, 6 were chosen for in-depth design evaluations. Interdisciplinary teams from both Departments were employed to produce the detailed process descriptions. To assist in this development, the students were taken to four related manufacturing facilities to better understand the issues and limitations in newspaper recycling. As a part of the final report, these teams taught the broader chemical engineering senior design class the information generated in this project. Status: This project is scheduled for completion in 1991 and has involved 50 undergraduates and one ChE graduate student. 145 ------- Research Dissemination: D. Jurczak, North Carolina State University Goal: The broad access by industry and the public to the research of the Center is an important criterion for technology transfer. A commitment to writing articles for broad publication has been made in this project on all aspects of the Center's activities. Rationale: Research technology transfer is in part enhanced by general public and industry knowledge of activities by the Center faculty. This information makes individuals aware of the potential for future changes that will improve the environment through pollution prevention. The contacts that are initiated from this information dissemination are utilized to begin the resources-intensive process of implementing full-scale utilization technology advances. Approach: The various Center research and technology transfer projects are reviewed periodically. Determinations of groups potentially related to the technical areas sponsored by the Center for Waste Minimization and Management are made to establish articles for preparation. Information collection and writing are conducted to prepare articles of necessary length or level of detail for technical or non-technical audiences. These articles are valuable to identify areas of research transfer, to increase attendance at training sessions, and to establish a dialogue with the public and industry groups that would benefit from the Center program. These communications include print and electronic media. Status: Activities have generated information transfer items on about half of the Center's projects. About seventy five items for dissemination of Center activities have been prepared. Research Conference: C. Kaufman, North Carolina State University Goals: Transfer environmental research information from Sunbelt university and government laboratories to regional industries. Rationale: There is a very large amount of relatively unknown, steadily developing environmental research underway at universities and research institutions. It is important for industry and government personnel to better understand these efforts since few resources exist to duplicate this 146 ------- 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 were complimented with a poster session. Status: A two-day regional conference, the First Annual Exposition: Environmental Research in The Sunbelt -- 1989, was held in Raleigh, NC on November 14 and 15, 1989, with approximately 100 individuals representing industry, academics, and government attending 11 plenary lectures and viewing 30 posters. In addition to the plenary lectures and poster papers, approximately 200 research summaries were received from southeastern universities and government laboratories and included in the conference proceedings (475 pages). These research summaries were indexed by types of study, types of waste, regulatory media, treatment/disposal methods, major industries affected, and key words. Hydrofluoric Acid Reuse: D. Denny, North Carolina State University Goals: The goal is to identify users of spent hydrofluoric acid from the electronics industry. Rationale: Electronics component manufacturers are hydrofluoric acid for etching and cleaning purposes. The spent acid must be neutralized or 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. Approach: A survey of hydrofluoric-acid users and waste generators will be conducted to identify potential suppliers of spent acid for aluminum and steel treating operations. If a match can be found where the spent acid meets the quality and volume specifications of the potential user, a test will be set up to determine, in a commercial environment, the technical and economic feasibility of hydrofluoric acid reuse. Status: Two of the three companies that supplied spent hydrofluoric acid for the research study now neutralize the spent acid waste and no longer have a need to find a user for the spent acid. One aluminum-can manufacturer has expressed interest in the program. One electronics manufacturing supplies has been located to date that could satisfy the aluminum-can manufacturer's volume or quality requirements. Work is in 147 ------- process to determine if the HF waste would be satisfactory for aluminum- can treatment. Hydrofluoric Acid Reuse: D. Denny, North Carolina State University Goals: Provide training to industrial participants in compliance procedures for all aspects of RCRA. The workshop content must be suitable to certify students as compliant with RCRA training requirements. Approach: The workshop, for large-quantity generators, is conducted under the auspices of the North Carolina State University Industrial Extension Service (IBS), the North Carolina Department of Environment, Health, and Natural Resources, and the NCSU Center for Waste Minimization and Management. A workshop manual has been prepared and is updated annually. External consultants, environmental service personnel, lawyers, and IES staff present and interpret material in the manual and provide supplementary material as appropriate. The workshop is two and one-half days long with the first half-day dedicated to participants who have no RCRA experience. Of the remaining two days, about one half day is dedicated to waste minimization which is a new emphasis from the North Carolina efforts in this field. Status: The workshop has been in continuous operation for about 10 years. It is offered eight times per year at various North Carolina locations. Typically, there are over 200 participants per year who earn RCRA training certificates. The Center provides quality monitoring to the small quantity generator workshops. Workshop - Land Treatment Technology for Wastes: M. R. Overcash, North Carolina State University Goals: Government regulatory, municipal, and industrial personnel can benefit by an in-depth state-of-the-art course on the use of land treatment for wastewaters and sludges. Rationale: There are no detailed continuing education offerings in Regions 4 and 6 or in the U. S. on the use of land treatment technology. With over 20,000 such systems, training, design, and compliance are important roles for the course. 148 ------- Approach: A two-day course is taught at various locations in the U. S., by Professor Wade Nutter of the University of Georgia. This course covers all types of land treatment approaches and includes both the fundamentals of design and engineering. Many of these systems are in Regions 4 & 6. The course is linked to the American Institute of Chemical Engineers to provide marketing and administrative functions. Status: The course was taught three times (Houston, Philadelphia, and Orlando). Workshop - Prevention, Management, and Compliance of Hazardous Wastes: M. R. Overcash, North Carolina State University Goals: Provide continuing education to industrial and governmental personnel regarding the field of hazardous waste management. Rationale: With the new emphasis on waste minimization and changes in the practices of compliance, individuals need convenient means to understand the technologies for hazardous wastes. Individuals with newly assigned responsibilities in this field need an overview and detailed sources of information to perform their jobs. Approach: A three-day course taught by Dr. Al Wentz of Argonne National Laboratory and Mr. Don Miller with Law Environmental Services is offered periodically across the U. S. The course is also offered at a specific industry if enough attendees are available. Equal thirds of the course are on minimization, treatment, and containment/remediation, thus matching the structure of the Center. Status: The course was taught six times (Houston, Philadelphia, San Francisco, Orlando, San Diego, and Chicago). The course is linked to the American Institute of Chemical Engineers to provide marketing and administrative functions. Waste Minimization - Legal, Technical, Human Factors University Education: D. Denny, North Carolina State University Goals: The goal is to develop and implement a senior-level chemical engineering course that will provide the necessary background for engineering students to design, sell, and implement a waste reduction program in an industrial environment. 149 ------- Rationale: Current engineering 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 has been formed consisting of representatives from academia, state government, federal government, national industry, state industry, and environmental groups. The course responsibilities include reviewing the course outline and associated instructional materials and providing constructive input regarding improvement of those materials. Status: The course outline was prepared and sent to the advisory committee for comment. The course materials was assembled over the spring semester during which the course was taught on an experimental basis. Twenty-five students completed the course. Feedback from the students indicated a very useful component of the course was a real-world case study of a manufacturing facility. The students actually performed a site audit and proposed waste reduction alternatives to the company that participated in the program. Delays in receiving materials from the company, precluded a detailed engineering and cost analysis of the proposed pollution reduction techniques. That problem will be remedied in the planned second offering of the course in the spring of 1991. Course materials are in the process of being documented and summarized. These materials will be sent to the advisory committee for review when completed. Integration of Pollution Prevention in Core Chemical Engineering Curriculum: D. Denny, North Carolina State University Goals: As a part of basic chemical engineering principal courses, the concept of illustrating this knowledge to develop means to reduce pollution in manufacturing processes can be a useful part of university education. Rationale: There are numerous instructional elements in chemical engineering courses. Practical examples, involving independent evaluation by students or teams, are effective in university teaching. Since the concept of pollution prevention is prevalent in industry, which typically hire these students, the opportunity to include case studies was appropriate. 150 ------- Approach: A first course was a junior offering and the waste minimization issue was finish oils from a textile mill. The textile mill was visited. Information was obtained that described the amount of waste oil generated and the reasons why the oil was discarded and not reused. Several alternate uses, such as burning as fuel, recycling, and use in fabric softener formulations were identified. The source and causes of the waste generation were also evaluated, and several options to reduce the amount of waste oil through process changes were also identified. A second offering was a senior design course and the recovery of methylene chloride from polyurethane foam plants was undertaken. Options proposed for reducing exposure to emissions from the plant included tall stacks, containment of the foam manufacturing process with a reduced air flow followed by either condensers, carbon adsorption or incineration of the off-gas stream. Preliminary economic analysis showed tall stacks to be the least-costly option to comply with the state of North Carolina air toxics pollution laws. Work is proceeding to find an industrial site where the containment and reduced-plant air flow portion of the proposed solution can be tested. The objective would be to demonstrate the economically recoverable concentrations of methylene chloride can be generated in stacks without exceeding OSHA in-plant limits for TDI. A third course is an advanced undergraduate/graduate student seminar series. Emphasis is given to waste minimization and management for both hazardous and low-level radioactive wastes. Status: These courses demonstrated the viability of using pollution prevention to illustrate chemical engineering principles. The junior course (Spring 1989) had 45 students while the senior course (Fall 1989) had 15 students. The seminar course had about 25 students. The magnitude of instructional effort and the industry participation were high as this was a developmental effort in training. 151 ------- BIBLIOGRAPHY REFEREED JOURNAL ARTICLES Giam, C. S., T. L. Holliday, J. L. Williams, R. R. Weller, and J. A. Mayernik. 1990. "Laser Desorption-Ionization FT-ICR Mass Spectrometry: DNA-Adduct Bases, Nucleosides and Nucleotides". Marine Environmental Research. Vol. 28, pp. 309-312. Donovan R., A. C. Clayton, D. J. Riley, and R. G. Carbonell. V. B. Menon, "Investigating Particle Deposition Mechanisms on Wafers Exposed to Aqueous Baths," Microcontamination. August, 25-29, 1990. ARTICLES SUBMITTED Donnelly, K. C., C. S. Anderson, J. C. Thomas, K. W. Brown, D. J. Manek, and S. H. Safe. 1990. "Mutagenic Potential of Soil Samples From a Wood- Preserving Bioremediation Facility," Submitted to Journal of Hazardous Materials. Riley, D. J., and R. G. Carbonell. "Liquid-Based Particle Deposition: An Investigation of Double-Layer Effects Using Hydrophilic Silicon Wafers," Microcontamination. in press. ARTICLES IN BOOKS, PROCEEDINGS, AND OTHER JOURNALS Kozub, D., and J. R. Stone. "An Expert Support System for Routing Hazardous Materials by Trucks," Proceedings of the Seventh Conference on Computing in Civil Engineering. Washington, DC, May 6-8, 1991. Kaufman, C. M. and M. R. Overcash, "Waste Minimization Strategy in the Manufacture of Flexible Polyurethane Foams" in Proceedings of the International Association of Clean Technologies Conference. Washington, DC, June 1990. Jurczak, D., Training Course Description: "Hazardous Waste Workshop," 20 Articles, Newspaper, and Radio, 1990. Jurczak, D. Environmental Conference Topics, 4 Articles, Industry and Public Journals, 1990. 152 ------- Jurczak, D. Training Course Description: "Minimization of Hazardous Waste Workshop," 10 Articles, Newspaper and Radio, 1990. "NCSU Engineers Seeking Wafer-Cleaning Options," September 1989, Special to Microcontamination. (Santa Monica, CA). "NCSU Research Team Seeking Answers to Dioxin Issues," September 1989, Special to American Paper Convention Daily. (Park Ridge, IL). "NCSU Research Develops New Recovery Method for Foam-Blowing Agents," October 1989, sent to Modern Plastics. (New York, NY) and Plastics World. (Newton, MA). "Conference Highlights Hazardous Substance Research In Southeast," November 1989, sent to Chemical Engineering Progress. (New York, NY) and Oil and Gas Journal. (Tulsa, OK). "Helping Industry Help the Environment," December 1989, Special To Research Initiatives For The New Decade. (NCSU, Raleigh, NC). "Waste-Reduction Researchers Seeking Industrial Support," January 1990, Special to NCSU College of Engineering Newsletter. (Raleigh, NC). "NCSU Environmental Researchers Aided In Weapons Complex Study," March 1990, sent to The Chemical Engineer. (Rugby, England) and Waste Tech News. (Denver, CO). "NCSU Waste Reduction Research Keeps Industrial Budgets In Mind," March 1990, sent to Forbes. (New York, NY) and Wall Street Journal. (New York, NY). "Waste Reduction Researchers Seeking Cooperation And Industrial Support," April 1990, sent to League of Women Voters. (Washington, DC). "NCSU Engineer Testifies In Congress For Stronger Pollution Prevention Steps," April 1990, sent to Chemical Processing. (Chicago, IL) and Chemical Business. (Massapequa, NY). "NCSU-Based Minimization Center Targets Industrial Waste Reduction," April 1990, sent to Chemical and Engineering News. (Washington, DC) and National Geographic News Service. (Washington, DC) and National Geographic News Service. (Washington, DC). 153 ------- "NCSU Engineer Studies Jet Sprays For Cleaning Chemical Reactors," July 1990, sent to Advanced Manufacturing Technology. (Fort Lee, NJ), Chemical Engineering. (New York, NY) and Food Engineering. (Radnor, PA). "NCSU-Based Minimization Center Targets Industrial Waste Reduction," July 1990, sent to U. S. News & World Report. (Washington, DC) and Technical Insights, Inc., (Fort Lee, NJ). "NCSU Waste Reduction Research Keeps Industrial Budgets In Mind," July 1990, sent to Technical Insights. Inc.. (Fort Lee, NJ). "NCSU-Based Research Center Explores Ways to Reduce Waste, Improve Processes," August 1990, special to North Carolina Magazine. (Raleigh, NC). "NCSU Engineer Studies Jet Sprays For Cleaning Chemical Reactors," September 1990, sent to Mullmagazin. (Berlin, Germany). "NCSU-Based Minimization Center Targets Industrial Waste Reduction," September 1990, sent to Mullmagazin. (Berlin, Germany) "How to Join the Center," September 1990, sent to Mullmagazin. (Berlin, Germany). Riley, D. J., and R. G. Carbonell, "The Deposition of Liquid-Based Contaminants onto Silicon Surfaces." 1990 Proceedings of the Institute of Environmental Sciences. New Orleans, LA. April 23-27, 224-228. 1990. Riley, D. J., and R. G. Carbonell. "The Deposition of Liquid-Base Contaminants onto Hydrophilic Silicon Surfaces." TECHNON '90. San Jose, CA, October 16-18, 1990. PROJECT REPORTS Jefcoat, I., and M. Overcash, "Research Needs for Waste Minimization," Gulf Coast Hazardous Substance Research Center. Beaumont, TX, p. 46, 1990. 154 ------- THESES/DISSERTATIONS Kozub, D. "An Expert Support System for Routing Hazardous Materials by Trucks, Masters Thesis," Department of Civil Engineering. North Carolina State University. Raleigh, NC. June 1990. CONFERENCES First Annual Exposition: Environmental Research in the Sunbelt 1989, Raleigh, NC, November 14-15, 1989. 155 ------- GREAT PLAINS/ROCKY MOUNTAIN HAZARDOUS SUBSTANCE RESEARCH CENTER PARTICIPANTS DIRECTOR: TECHNOLOGY TRANSFER DIRECTOR: Kansas State University Montana State University University of Iowa University of Missouri University of Montana University of Nebraska University of Utah Larry E. Erickson, Ph.D. Great Plains/Rocky Mountain Hazardous Substance Research Center Durland Hall Kansas State University Manhattan, KS 66506-5102 Phone: 913/532-5584 Fax: 913/532-7810 Richard Hayter, Ph.D. Great Plains/Rocky Mountain Hazardous Substance Research Center Engineering Extension Service Ward Hall Kansas State University Manhattan, KS 66506-5111 Phone: 913/532-6026 Fax: 913/532-6952 THE CENTER AT A GLANCE Kansas State University (KSU) leads the seven-institution consortium comprising the Great Plains/Rocky Mountain 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 on the identification, treatment and reduction of hazardous substances resulting from agriculture, forestry, mining, mineral processing, and other activities of local interest. The Center has a major research focus on soils and soil contamination and remediation. 157 ------- The States in the Great Plains and Rocky Mountains region have a curious diversity of interests. This results 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 defined its original mission in terms of these wide-ranging activities and has undertaken research in the following areas: • Soil and water contamination by heavy metals and other sources; • Simplified methods for analyzing contaminated soil; • Safe concentration; • Hazardous waste minimization; and • Incineration, biodegradation, and immobilization technology. GREAT PLAINS/ROCKY MOUNTAIN HAZARDOUS SUBSTANCE RESEARCH CENTER Research Project Distribution (Number of Projects) 18% Technology Transfer and Training (7) ^^~^ 24% 2% / : ^^^^^ Heavy Metal (10) Other (1), 18% Analysis/Treatment (7) / 38% Organic Chemical Contamination of Soil (16) Major Focus: Based on the recommendation of the Science Advisory Commitee in May, 1990, a decision was made to assign the highest priority to research on soil and processes to clean up contaminated soil. Research 158 ------- Major Focus: Based on the recommendation of the Science Advisory Commitee in May, 1990, a decision was made to assign the highest priority to research on soil and processes to clean up contaminated soil. Research proposals were requested based on the following needs and problems which are listed here in order of their priority based on the current mission of the Center: • Soil and water contaminated by heavy metals such as cadmium, chromium, copper, lead, and zinc associated with mining wastes and other industrial activities. Mine tailings from past mining operations have resulted in contaminated surface and groundwater; • Soil and groundwater contaminated by organic chemicals from a variety of sources. Wood preservatives including pentachlorophenol and creosote, polynuclear aromatic hydrocarbons, carbon tetrachloride, trichloroethylene, vinyl chloride, and other chlorinated aliphatic hydrocarbon, polychlorinated biphenyls (PCBs), and dioxin have been identified as priority substances for research. 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; • Development of improved methods for analysis of contaminated soil. Simple inexpensive analyses are desired; and • Development of innovative treatment technologies for remediation of contaminated soil and for rendering wastes nonhazardous. The Center is supporting research projects at two non-consortium institutions within the region-pair through contracts. Less than 10% of the Center's funds are allocated for projects at the University of Colorado and Utah State University. Training and technology transfer events offered by consortium universities and other institutions are listed in the newsletter. The Center is headed by Dr. Larry E. Erickson, Professor of Chemical Engineering at KSU. Dr. Erickson is assisted primarily by Dr. Richard Hayter, of KSU's Engineering Extension Service, who oversees the conduct of the Center's training and technology transfer program. Researchers from several specialties interact through the Center, bringing a diversity of perspectives to address complex problems 159 ------- associated with hazardous substances. Table 1 provides a list of key personnel from each participating consortium institution. TABLE 1: KEY PERSONNEL IN THE CENTER Kansas State P.L. Barnes B.R. Biles L.E. Erickson L.T. Fan R.E. Faw S.J. Galitzer L.A. Glasgow Hayter Klabunde Pierzynski Schlup Schwab Steichen Walawender Wang University R.B. K.J. G.M. J.R. A.P. J.M. W.P. C.K. University of Missouri S.H. Anderson R.K. Bajpai S.K. Banerji B.J. Brazos T.E. Clevenger C.O. Harbourt E.J. Hinderberger S. Kapila J.T. O'Connor T.J. O'Keefe R.L. Peyton D.S. Viswanath J.L. Watson A.F. Yanders Montana State W.G. Characklis F.D. Culver A.B. Cunningham D.J. Dollhopf R.S. Hunter W.L. Jones Z. Lewandowski University of Iowa D.T. B.C. G.F. J.L. R.L. Gibson Kross Parkin Schnoor Valentine University of Montana J.J. Bromenshenk University of Nebraska B.C. Dickey M.W. Gilliland G.B. Keefer W.E. Kelly D.P. Shelton C.W. Walton University of Utah S. Ghosh The Center benefits from guidance supplied by a Science Advisory Committee which meets twice a year and a Training and Technology Transfer Advisory Committee. The members of these committees are listed in Table 2 and 3. 160 ------- TABLE 2: MEMBER Dr. Joseph Fernandes Dr. John Wilson Dr. Dermont Bouchard Dr. Thomas Holloway Dr. Henry Schroeder Dr. Makram Suidan Dr. David Constant Dr. Robert Ahlert Dr. Dunja Grbic-Galic Dr. Richard Speece Dr. Randy Freeman Mr. Dennis Murphey Dr. Eddie Hsu Dr. Hugh Stirts Dr. Robert Peters SCIENCE ADVISORY COMMITTEE AFFILIATION U.S. EPA U.S. EPA U.S. EPA, Region 7 U.S. EPA, Region 7 U.S. EPA, Region 8 University of Cincinnati EXPERTISE Chemical engineer Microbiologist; soil micro- biology Soil scientist Chemist Microbiologist; mining wastes Environmental engineering Louisiana State University Hazardous waste engineering; chemical engineering Rutgers University Stanford University Vanderbilt University Monsanto Chemical Company Roberts/Schornick and Associates Shell Oil Company DOD, Air Force Argonne National Laboratory Chemical engineering Microbiologist Environmental engineering Chemical engineering Biochemistry Chemical engineering Environmental science Chemical and environmental engineering Chair 161 ------- TABLE 3: TECHNOLOGY TRANSFER AND TRAINING ADVISORY COMMITTEE MEMBER Richard Bauer Tom Blewett Dave Finley Felix Flechas Gil Greenwood Tom Gross Ray Haner Dave Henney William Hotchkiss Vonni Kallemeyn John Konefes Jack Lonsinger* Rusty Lundberg Chet McLaughlin Edward Mead Keith Potts Richard Scalf Richard Schlenker AFFILIATION Industry State Government State Government USEPA Industry State Government Industry USAF USGS Government State Government Industry Industry State Government USEPA Industry Industry USEPA State Government EXPERTISE Industrial processes State regulation management State regulation management Federal program management Industrial processes State regulation management Industrial processes Industrial processes Industrial processes State regulation management Industrial processes Industrial processes State regulation management Federal program management Industrial processes Industrial processes Federal program management State regulation management Chair 162 ------- TABLE 3: TECHNOLOGY TRANSFER AND TRAINING ADVISORY COMMITTEE (CONTINUED) MEMBER Martin Schock David Shorr Joan Sowinski John Stanton Rich Steimle Roger Thorvilson AFFILIATION State Government State Government State Government USEPA USEPA State Government EXPERTISE State regulation management State regulation management State regulation management Federal program management Federal program management State regulation management 163 ------- TABLE 4: CENTER FUNDING FUNDING SOURCES FY1990* FUNDS TO DATE EPA: Centers $926,080 $2,926,080 Program EPA: Other 70,000 70,000 Other Govt: Federal 250,000 250,000 Other Govt: State Consortium 774,961 2,305,029 Private Sector 16.000 26.000 TOTAL $2,037,041 $5,577,109 *Oct. 1, 1989 - Sept. 30, 1990 Fiscal Year TABLE 5: STUDENT SUPPORT STUDENT LEVEL NUMBER* FUNDS TO DATE** Undergraduate 9 $20,000 Graduate 18 523,000 Post Doctoral _3_ 45.000 TOTAL 30 $588,000 *Full-Time Equivalents **Includes Tuition and Travel (Rounded Values) The diversity of the region-pair's interests and the large geographic area represented are further reflected in the training and technology transfer program the Center currently supports. 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 collects audio and video training materials relating to hazardous substances and makes these materials available for loan, seven 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 164 ------- carefully selected special audience functions, provide for the dissemination of needed technical information across this large and varied area. The Center's base support comes from USEPA. However, the participating schools have all made substantial contributions as well. Contributions have been received from individuals and private industry. The U.S. Department of Energy is partially supporting several research projects. It is hoped that private industry and other public sector organizations will find the center concept attractive and will contribute additional funds in the future. The Center's funding is summarized in Table 4. CENTER DIRECTOR'S REPORT Establishing the Center has provided a focal point for hazardous substances research, training, and technology transfer in the Great Plains and Rocky Mountain area of 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, Center staff have emphasized inclusiveness and the idea of "working together for a better environment." Center personnel have made visits to all of the consortia 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 attended. Approximately 5,000 individuals have benefitted directly through the center activities. Many of the research and technology transfer and training projects currently underway were selected prior to the designation 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 consortia universities. The advisory committees have been most valuable in guiding the Center in selecting research and technology transfer and training areas to pursue. The decision to assign the highest priority to research on soil and processes to clean up contaminated soil reflects the desire of the science advisory committee for the Center to have a major focus. Several new projects, which reflect the priority on soil-related research, have been approved for funding. One other aim of the Center is to use the resources provided by USEPA to solicit support for academic environmental research from other 165 ------- federal agencies, states, and private industry. Representatives from the U.S. Department of Energy expressed interest in participating in Center activities in the Summer of 1989. They have reviewed research proposals, selected projects which are of interest to the Department of Energy, presented information at our annual conference on their research needs and programs, and provided $250,000 to partially fund eight research projects. HIGHLIGHTS FOR 1990 One of the most important aspects of research is to report the results so that they are available to other professionals and practitioners for their use. A new book, Biofilms. edited by William G. Characklis and Kevin C. Marshall, was published by John Wiley in 1990; a review appeared in the July 1990 issue of HazTech Transfer. The Proceedings of the 1989 Conference on Hazardous Waste Research were published in November 1989; eleven papers describing work which was partially supported by the Center were included. The Proceedings of the 1990 Conference on Hazardous Waste Research will be published; it contains more than 500 pages. Most of the researchers supported by the Center presented their work at the 1990 Conference. The Center co-sponsored the February 20-21, 1990, Cluster of Conferences and assisted with publicity; four conferences "Agricultural Impacts on Ground Water Quality," "Ground Water Geochemistry," "Ground Water Management and Wellhead Protection," and "Environmental Site Assessments: Case Studies and Strategies" were held, simultaneously. The Proceedings of the 1990 Cluster of Conferences were distributed at the February Conferences in Kansas City; this 953 page volume entitled Ground Water Management is available from the National Water Well Association. The Association of Ground Water Scientists and Engineers co-sponsored this conference. Dr. Gary B. Keefer submitted a final project report for the project entitled "Metal Recovery and Reuse Using an Integrated Vermiculite Ion Exchange - Acid Recovery System." The work has been presented at three conferences and submitted for publication. This metal recovery process appears to be economically competitive for treating zinc at concentrations below 25 mg/liter. Strong Lite Manufacturing of Pine Bluff, Arkansas has expressed interest in commercializing the process. 166 ------- Dr. J.L. Schnoor at the University of Iowa, is directing an investigation of the effects of trees on the bioremediation of contaminated soil and groundwater. He has planted deep-rooted poplar trees at a field site in Iowa where experiments with atrazine and alachlor show that vegetative buffer strips can alter contaminant fate in the subsurface environment. The uptake of nitrate and the pesticides was significant, especially for a plot planted densely with poplar trees. An objective of this research is to reduce the amount of nitrates and pesticides reaching streams by planting plants and trees along water way channel banks. Planting, fertilizing, and watering plants and trees at sites contaminated with organic compounds to achieve in-situ bioremediation is a potential, low-cost solution. 167 ------- TABLE 6 GREAT PLAINS/ROCKY MOUNTAIN HAZARDOUS SUBSTANCE RESEARCH CENTER PROGRAM SUMMARY PRINCIPAL INVESTIGATOR PROJECT END DATE HEAVY METAL CONTAMINATION OF SOIL/WATER Clevenger/ Hinderberger Keefer Ghosh O'Keefe/ Watson Hansen/ Stevens Walton Lewandowski Faw/ Wang Reclamation of Metal 1992 and Mining Contami- nated Superfund Sites Using Sewage Sludge/ Fly Ash Amendments Metal Recovery and 1990 Reuse Using an Inte- grated Vermiculite Ion Exchange - Acid Recovery System Removal of Heavy Metals 1991 from Hazardous Wastes by Protein Complexation for Their Ultimate Recovery and Reuse The Characterization and 1991 Treatment of Hazardous Materials from Metal Mineral Processing Wastes Optimal Bioreactor Design 1991 for Biological Removal of Mercury An Electrochemical Method 1992 for Acid Mine Drainage Remediation and Metals Recovery Heavy Metals Removal 1992 from Dilute Aqueous Solutions Using Biopolymers Neutron Activation 1991 Analysis for Heavy Metal Contaminants in the Environment CURRENT BUDGET $76,000 $14,000 $70,000 $76,000 $76,000 $72,000 $44,000 $32,000 TOTAL BUDGET $147,000 $54,000 $140,000 $129,000 $76,000 $72,000 $44,000 $32,000 168 ------- PRINCIPAL END CURRENT TOTAL INVESTIGATOR PROJECT DATE BUDGET BUDGET Pierzynski/ Reducing Heavy Metal 1992 $42,000 $42,000 Schwab Availability to Perennial Grasses and Row-Crops Grown on Contaminated Soils and Mine Spoils Dollhopf Sulfide Size and 1992 $68,000 $68,000 Morphology Identification ORGANIC CHEMICAL CONTAMINATION OF SOIL/WATER Banerji Migration and Biodegrada- 1992 $116,000 $224,000 Bajpai of Pentachlorophenol in Soil Environment Yanders/ Time Dependent Movement 1992 $112,000 $217,000 Kapila of Dioxin and Related Compounds in Soil Schnoor/ Modeling Dissolved Oxygen, 1991 $99,000 $238,000 Parkin Nitrate, and Pesticide Contamination in the Subsurface Environment Glasgow Vadose Zone Decontamina- 1992 $41,000 $73,000 tion by Air Injection Schlup Adsorption of Hazardous 1991 $32,000 $60,000 Substances onto Soil Constituents Illangasekare Distribution and Recovery 1992 $95,000 $95,000 of Refinery Waste Products in Groundwater Aquifers: Experimental Study and Model Evaluation Ghosh Biodetoxification of 1992 $131,000 $131,000 Hazardous Solid Wastes by Staged Anaerobic Fermentation Conducted at Separate Redox and pH Environments Schnoor/ Deep-Rooted Poplar Trees 1993 $70,000 $70,000 Licht as an Innovative Treatment Technology for Pesticide and Toxic Organics Removal from Groundwater 169 ------- PRINCIPAL INVESTIGATOR Schnoor/ Licht Dickey/ Shelton/ Steichen/ Barnes Parkin/ Gibson Erickson/ Fan Kross O'Connor/ Brazos END DATE 1993 1992 PROJECT The Role of Deep-Rooted Poplar Trees in Adding Organic Carbon to the Soil for Pesticides and Toxic Organic Removal Alachlor and Atrazine Losses from Runoff and Erosion in the Blue River Basin Feasibility of In-Situ 1992 Anaerobic Bioreclamation of Mixtures of Toxic Chemicals; Feasibility of Using Genetically Engineered Bacteria To Degrade Trichloroe- thylene in Activated-Sludge Systems Development of In-Situ 1992 Biodegradation Technology Removal of Nitrogenous 1991 Pesticides from Rural Well Water Supplies by Enzymatic Ozonation Process The Response of Natural 1991 Groundwater Bacteria to Groundwater Contamination by Gasoline in a Karst Region CURRENT BUDGET $31,000 TOTAL BUDGET $31,000 $163,000 $163,000 $63,000 $170,000 $77,000 $57,000 $145,000 $160,000 $61,000 Characklis/ In-Situ Bioremediation Jones/ of Organic Groundwater Cunningham/ Contaminants Lewandowski 1992 Hunter/ Culver Computer Method to Estimate 1990 Safe Level Water Quality Concentrations $152,000 $0 $61,000 $247,000 $28,000 ANALYSIS/TREATMENT OF CONTAMINATED SOIL Klabunde Nano-Scale Metal Oxide Particles as Reagents for Destruction and Immobiliza- tion of Hazardous Substances 1993 $53,000 $53,000 170 ------- PRINCIPAL INVESTIGATOR Valentine Peyton/ Anderson Fan Walawender/ Fan Viswanath/ Kapila/ Clevenger Parkin END PROJECT DATE In-Situ Soil and Aquifer 1993 Decontamination Using Hydrogen Peroxide and Fenton's Reagent Simulation of Three- 1992 Dimensional Transport of Hazardous Chemicals in Heterogeneous Porous Media Using X-Ray Computed Tomography Experimental Study of 1992 Stabilization/Solidification of Hazardous Substances Thermochemical Treatment 1992 of Hazardous Wastes Development, Characteriza- 1992 tion, and Evaluation of and Evaluation of Adsorbent Materials for Waste Streams The Effect of Redox Condi- tions on Transformations of Carbon Tetrachloride 1991 CURRENT BUDGET $60,000 $76,000 $53,000 $79,000 $158,000 $31,000 TOTAL BUDGET $60,000 $76,000 $98,000 $149,000 $305,000 $31,000 WASTE MINIMIZATION Fan Computer-Aided Design and 1992 Control of Systems for Treatment of Hazardous Waste and Minimization of Waste Production $87,000 $138,000 TRAINING AND TECHNOLOGY TRANSFER Hayter Hayter Biles Hayter HSRC Newsletter, HazTech 1992 $42,000 Audio and Video Training 1992 $8,000 Technology Data Base 1992 $17,000 HSRC Contribution 1992 $19,000 Repository and Information Clearinghouse $76,000 $12,000 $18,000 $26,000 171 ------- PRINCIPAL END CURRENT TOTAL INVESTIGATOR PROJECT DATE BUDGET BUDGET Hayter Video Conference 1992 $44,000 $44,000 Hayter Conferences 1992 $54,000 $96,000 Harbourt Introduction to Hazardous 1992 $62,000 $179,000 Waste Management Gilliland/ Hazardous Waste Manage- 1991 $78,000 $128,000 Kelly ment in Rural Communities in EPA Regions 7 and 9 RESEARCH PROJECT DESCRIPTIONS HEAVY METALS Reclamation of Metal and Mining Contaminated Superfund Sites Using Sewage Sludge/Fly Ash Amendment: T.E. Clevenger, University of Missouri-Columbia and E.J. Hinderberger, University of Missouri, Environmental Trace Substances Research Center. Goals: The objectives of this study are to determine the feasibility of using sewage sludge and fly ash as a method of reclaiming Superfund metal-contaminated sites. Rationale: Through the use of a mixture of sludge and fly ash, it is possible to increase the organic content of the soil. As a result, plant cover can be established, pH is increased, and the mobility and availability of metals are controlled. Approach: An old, abandoned lead tailings pile in Desloge, Missouri has been selected for the study site. This site is unusual because of the presence of a pristine Ozark stream running along the edge of the tailings pile and the use of part of the site as the St. Francois County sanitary landfill. Samples have been obtained and initial analyses completed. Speciation methods as well as total metal analysis are being used to evaluate the potential for mobilization of the metals in the tailings piles. Because the chemical form is critical in predicting mobility and toxicity, the investigators felt that total metal analysis would not provide enough information. The principal investigator has developed an extraction 172 ------- scheme that will selectively extract several different lead compounds (PbSC>4 , PbCO3, PbO, PbS). This method and X-ray diffraction are being used to determine chemical forms. Preliminary results indicate that the predominant forms of lead in the tailings are oxide and sulfide. Column studies were conducted to determine the effect of adding fly ash and sewage sludge to the Desloge lead tailings. During the course of this project, the investigators have been told of the importance of their speciation work by many different scientists (federal, state and industry). The development of a valid method for speciation has become one of the primary goals of the project. Status: The project has been moving forward smoothly. Results indicate that the fly ash changed the availability of the metals, primarily to unavailable forms. However, it was observed that at the high pH (12) which was produced by the leachate from the fly ash and tailings columns, the leachate contained 5-20 ppm lead, depending upon sample, while the control column of tailings alone gave a leachate of about 0.1 ppm (pH 7). Lead is forming a hydroxide complex and actually is more soluble at pH 12 than pH 7. The Desloge site has been sampled during each of the two years of the project. During the last year, samples from southwest Missouri (Tri-State mining region) have been obtained. The tailings are different from those at Desloge. They contain more Zinc and Cadmium. Typical samples from southeast Missouri have been compared to two typical Tri-State samples. The speciation of each has been evaluated and the significance of the difference is currently being studied. Client/Users: The results of this work are of interest to other researchers, regulatory personnel, and those responsible for the remediation of sites contaminated with heavy metals. Metal Recovery and Reuse Using an Integrated Vermiculite Ion Exchange-Acid Recovery System: G.B. Keefer, University of Nebraska- Lincoln. Goal: The Goal of this research is to evaluate and optimize a system for zinc recovery and reuse from plating wastewaters or contaminated groundwater. 173 ------- Rationale: 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 research evaluated 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: A system which uses a multiple countercurrent, vermiculite, and ion exchange column treatment process has been developed to treat zinc 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: 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. Work on this project has been completed and a final report has been submitted. The results are described in manuscripts which have been submitted for publication. Strong Lite Manufacturing of Pine Bluff, Arkansas has expressed interest in commercializing the process. There is currently a proposal to continue the research with funding from Strong Lite. Client/Users: The results are of interest to private industry, those developing pollution prevention technologies, and other researchers. Removal of Heavy Metals from Hazardous Wastes by Protein Complexation for Their Ultimate Recovery and Reuse: S. Ghosh, University of Utah. Goals: The overall objectives of this research were: to develop a better understanding of the mechanisms, kinetics, and parametric dependence of complexation of selected heavy metals with microbial proteins and biopolymers; and to ultimately develop an innovative continuous-flow, 174 ------- bioprocess consisting of a "biotrap" for the uptake of heavy metals from aqueous wastes and a "metal extractor" for releasing and recovering the complexed metals, thus liberating the metal-complexing cells, organelles and biopolymers for recirculation to the biotrap for complexing more incoming heavy metals. Rationale: There is an increasing public concern for the potential dangers posed by heavy metals, metal ions, and organometallic compounds to the environment and human health. These potentially toxic substances have their origins in mining, mineral processing, metallurgical, and various manufacturing operations. They are found in surface and ground waters and in soils. The biological approach takes advantage of the fact that many species of bacteria, and other uni- and multi-cellular organisms have the capability to remove heavy metals as part of their natural defense mechanism for survival in environments contaminated with hazardous heavy metals. Some microorganisms can remove heavy metals at high efficiencies of up to 10% or higher in terms of mass of metals removed per unit dry weight of cell mass. Heavy metals are complexed by various organelles (predominantly cell wall and cell membrane), and extracellular and intracellular biopolymers (mainly proteins, exopolysaccharides, and lipoproteins) which offer ample anionic sites for metal uptake. The major metal-removal mechanisms are adsorption and ion-exchange (or chemisorption), chelation by ligand complexation, and precipitation. The predominance of one or more of these mechanisms depends on the culture environment, prevalent growth phase and other factors. Heavy metal uptake efficiency is also dependent on the presence of various species of metals, cell viability, cell acclimation, and other factors. Approach: This research project focuses on biological metal removal and recovery by mixed bacterial cultures. Mixed cultures are preferred since it has been reported that metal uptakes by mixed cultures are usually higher than those by pure cultures. Also, mixed cultures are more appropriate because it is not practical to maintain a sterile environment in wastewaters. Laboratory-scale experiments were conducted to this end to obtain information on: 1) the kinetics of heavy metal uptake by aerobic and anaerobic cultures; 2) metal removal efficiencies; 3) the effect of microbial growth phase on metal uptake; 4) the relative importance of such removal mechanisms as adsorption, ion-exchange, chelation and chemical precipitation; 5) the effects of metal uptake on cell viability; 6) hierarchy 175 ------- of metal uptake; and 7) the effects of the culture environment (e.g., C/N and C/S ratios, pH, cation concentration, substrate composition) on heavy metal removal. Status: Considerable progress has been made towards achieving the objectives of the project. Work completed to date shows that unacclimated aerobic and anaerobic cultures are capable of removing the test heavy metals of silver, copper, cadmium, and lead rapidly at high efficiencies. With the exception of cadmium, these heavy metals were removed in less than half an hour of batch incubation. Even dilute bacterial suspensions containing less than 2,000 mg/1 of dry solids could effect metal removal efficiencies up to 9.5%. Cultures maintained in the endogenous growth phase could remove significantly higher amounts of heavy metals than those in the exponential growth phase indicating the importance of exopolymers in complexing heavy metals. At low metal concentrations (less than 50 mg/1), lead, silver, cadmium and copper were removed at efficiencies of 23.5, 7.6, 4.1, and 3.7 mg of metal/lOOmg of protein, respectively. However, much higher uptake efficiencies of up to 210 mg/100 mg protein were observed at higher metal concentrations. The viability of the cultures decreased dramatically with metal uptake, but metal uptake continued unabated despite the drop in cell viability. The cultures exhibited the following hierarchy of metal uptake: Pb>Ag>Cd>Cu. Client/Users: The results of this research are of interest to other research investigators. The Characterization and Treatment of Hazardous Materials from Metal/Mineral Processing Wastes: TJ. O'Keefe and J.L. Watson, University of Missouri-Rolla. Goals: The objective of the research is to develop processing procedures to treat waste oxides generated by mining and metals industry. Rationale: 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 slags generated by lead smelters have been processed in a small furnace to obtain a nonhazardous residue and an oxide fume 176 ------- containing zinc, cadmium, and lead. Characterization and processing feasibility tests are being conducted on the oxide fumes. Status: Experimental research has been carried out with three different slags. Sulfuric acid leaching has been employed and found to be the most adequate process for the treatment of fumes having high zinc and lead oxides content. Other separation processes are also under investigation. Clients/Users: The results of this research are of interest to the mining and metals industry. Regulatory personnel have also expressed interest in the research. Optimal Bioreactor Design for Biological Removal of Mercury: C.L. Hansen and D.K. Stevens, Utah State University. Goal: Biological removal of mercury (Hg) has been adequately demonstrated from the microbiological and biochemical viewpoint. The goal of this aspect of the work was to characterize the fate of Hg°, and the effect of hydraulic retention time (HRT) and aeration rate on disposition of Hg°. Rationale: Biological removal of Hg involves enzymatic reduction of Hg2 + to Hg°. The Hg° can then be volatilized and separated from contaminated water and sediments. Approach: Mercury resistant bacteria were used to reduce Hg^+ as (HgCl2) in a 1.4 liter continuous, complete mix, stirred tank reactor (bioreactor) to Hg°. Volatile traps consisting of oxidizing solution of 3% potassium dichromate and 14% sulfuric acid were used to remove mercury. Aeration rates from 0.36 to 6.1 liters/liter min. were employed to test the effect of aeration rate on Hg volatilization. Influent Hg^ + concentration was held constant at 75 mg/liter. HRT, defined as reactor volume/flowrate, was varied from 10 to 55 h to determine the effect of HRT on Hg volatilization. Status: Several experiments have been completed. The percent of volatilized was varied from 10 to 68% of influent Hg2+ by varying HRT at an aeration rate of 1.1 1/1-min. The correlation between HRT and percent Hg volatilized was positive and linear with R^ = 0.97. Intense aeration of 6.1 1/1-min reduced total Hg concentration in the bioreactor to below 177 ------- detection limit (»0.5 mg/1) by inductively coupled plasma spectrophotometry analysis. Client/Users: Other researchers have expressed interest in this project. Contractors and those in private industry can use this technology for mercury recovery. An Electrochemical Method for Acid Mine Drainage Remediation and Metals Recovery: C.W. Walton, University of Nebraska-Lincoln. Goals: The major goal of this project is to obtain the necessary experimental information required to determine the feasibility of an electrodialytic ion exchange (EDIX) cell-based metal recovery system as applied to acid mine drainage. This includes the evaluation of various process configurations and the experimental measurement of the performance of a laboratory-scale EDIX cell and the membranes of which it is constructed when exposed to the chemicals found in the acid mine water. Rationale: As a means for eliminating the problem of water contamination and resource loss caused by acid mine drainage, a new method for waste management has been proposed. The intent of the EDIX cell is to minimize both of these problems. The initial design criteria is to produce a residual wastewater stream which would meet EPA effluent guidelines for metal content and a concentrated metal ion stream which could be further recovered by electrowinning. The process also has direct application to metal recovery from electroplating wastewaters. Approach: This research project is composed of three major parts: evaluation of individual membrane performance, EDIX laboratory-cell performance, and projected economic performance and scaleup, Dow Chemical Company was contacted to obtain cation permeable membranes and negotiations on a secrecy agreement were initiated (Dow plans to donate the membrane to the project.) Bipolar membranes and additional cell stacks are still being obtained, also. The Lincoln Plating Company (Lincoln, Neb.) has generously offered in-kind donation of analytical services. This will allow us to have the water samples evaluated in a laboratory which already must meet the quality assurance requirements of the U.S. EPA. A more detailed literature review of existing and potential methods of treatment for acid mine drainage (AMD) was initiated. This included 178 ------- gathering articles with information on quality assurance and work related to AMD. Finally, process modeling of the EDIX cell system as applied to acid mine drainage is being pursued. The preliminary process modeling work on the use of the EDIX cell concept for metal recovery from electroplating rinsewater is being extended to AMD. Status: Currently, equipment for construction of the laboratory test cell is being obtained and assembled. Initial papers on process modeling have been submitted for publication. A database of literature references has been constructed. Client/Users: The results of this research are of interest to industry, regulatory personnel, and other researchers. Several companies have already expressed interest in the research. Heavy Metals Removal from Dilute Aqueous Solutions Using Biopolymers: Z. Lewandowski, Montana State University. Goal: The goal of this work is to develop a theoretical basis for designing metal biosorption processes. The metal binding properties of microorganisms and polymer extracts from microorganisms will be studied and compared. Tools to study the kinetics of metal-biopolymer binding will be developed. Rationale: Knowledge of both thermodynamic and kinetic parameters of metal binding are needed to evaluate biosorption as a process for heavy metals removal and to design large scale processes. Approach: Two major approaches are used to describe the biopolymer- metal binding process: adsorption and complexation. Both models perform well when a polymer has a limited number of metal binding sites and the binding sites have equal or similar affinity for the metal. In more complex cases, where the polymer has many binding sites of different affinities for the metal, neither model is adequate. A binding model based on the multi- equilibrium reaction between polymer and metal satisfactorily describes the polymer-metal binding process. The model assumes that all interactions between metal and biopolymer can be described as chemical binding. 179 ------- Status: A model which describes the binding of metals to biopolymers has been developed. A technique to experimentally investigate the kinetics of heavy metal binding has been developed. Client/Users: The results are of interest to other researchers, private industry, and regulatory personnel. Neutron Activation Analysis for Heavy-Metal Contaminants in the Environment: R.E. Faw, and C.K. Wang, Kansas State University. Goals: The goal of this research is the determination of the extent to which instrumental neutron activation analysis might contribute to the characterization of hazardous waste sites through the analysis of soils and other solids for heavy metal content. Rationale: A need exists for inexpensive rapid methods of instrumental analyses to identify hazardous contaminants in soils and other solids. Instrumental neutron activation analysis has the potential to be used for rapid screening of multiple samples using nondestructive analyses involving no chemical separations. Approach: A literature review will be conducted. Protocols for instrumental neutron activation analysis of heavy metals in soils and other samples will be developed with special emphasis on sample collection and mixing. Standards will be prepared and the methods will be compared to other available methods. Status: This is a new project. Client/Users: The results are of interest to regulatory personnel and contractors who need to determine the concentrations of heavy metals in soil. Reducing Heavy Metal Availability to Perennial Grasses and Row-Crops Grown on Contaminated Soils and Mine Spoils: G.M. Pierzynski and A.P. Schwab, Kansas State University. Goals: The objective of this research is to develop and evaluate methods to reduce heavy metal availability to grasses and crops grown on contaminated soils and mine spoils. The relative tolerance to high 180 ------- concentrations of heavy metals of grasses and cover crops will be evaluated. Rationale: The soils in southeast Kansas, southwest Missouri, and northeast Oklahoma are contaminated with heavy metals because of past mining activities. Reclamation efforts aimed at establishing vegetation are needed. Organic amendments, pH adjustments, increased cation exchange capacity, soluble phosphorous additions, and dilution with uncontaminated soil are potential methods to improve vegetation. Metal-tolerant grass species can also be seeded. Approach: Greenhouse studies will be conducted on soil and mine spoil material from selected sites. Chemical, physical, and mineralogical characterization of the soil will be carried out to determine plant nutrient status, pH, organic matter, lime requirements, particle size analysis, clay mineralogy, total metal content, and chelate extractable metals. Experiments with amended soils and controls will be carried out with several plant species. Status: This is a new project. Client/Users: The research is of interest to those responsible for remediation of soils contaminated with heavy metals. Sulfide Size and Morphology Identification for Remediation of Acid Producing Mine Wastes: D.J. Dollhopf, Montana State University. Goals: The purpose of this research is to develop methods to predict waste acid production at mine waste sites. Pyrite size and morphology will be investigated. Rationale: Acid production from mine and mill wastes has produced one of the largest hazardous waste problems in Regions 7 and 8. Better methods are needed to predict whether acid will be produced during site remediation. Approach: Sulfide size and morphology will be investigated in potentially acid-producing mine waste. Mine waste samples containing six different forms of pyrite morphology will be collected and their acid-producing characteristics will be evaluated by laboratory weathering. Status: This is a new project. 181 ------- Client/Users: The research is of interest to regulatory personnel and contractors responsible for managing acid-producing mine wastes. ORGANIC CHEMICAL CONTAMINATION OF SOIL/WATER Migration and Biodegradation of Pentachlorophenol in Soil Environment: S.K. Banerji and R.K. Bajpai, University of Missouri- Columbia. Goal: The overall goal of the study is to determine the migration rate of pentachlorophenol (PCP) in soil environment and to evaluate the feasibility of above ground and in-situ biodegradation of PCP. Rationale: Wood preservatives are used extensively throughout the country. Research on the migration and biodegradation of pentachlorophenol will be useful in developing plans to clean sites affected by wood preservative wastes containing pentachlorophenol. Approach: The research program for determining the migration and biodegradation behavior of PCP in soil environment was divided into the following parts: 1) PCP volatilization studies; 2) PCP/soil interaction studies; 3) PCP photodegradation studies; 4) PCP biodegradation using bacterial species; a) pure culture studies using Pseudomonas cepacia in liquid culture and in soil system, and b) mixed culture studies using acclimated culture from a local wastewater plant; and 5) PCP biodegradation using the fungi, Phanerochaete crysosporium. Status: The project has been fully functional for 14 months. The progress made in each category is good. The goals set up for the project will be completed as planned. Clients/Users: Contractors and regulatory personnel can use the results of this work in developing plans to clean up sites contaminated with wood preservatives. The work is also of interest to other researchers. Time Dependent Movement of Dioxin and Related Compounds in Soil: A.F. Yanders and A. Kapila, University of Missouri, Environmental Trace Substances Research Center. 182 ------- Goal: The primary objective of the study is to determine the rate of migration and loss of polychlorinated dibenzo-p-dioxins and related compounds under varied contamination scenarios, such as the accidental surface contamination which occurred at Times Beach, Missouri, and the effects of co-contaminants in the contamination of saturated, deep-soil zones over long periods of time at wood treatment facilities. Rationale: It is anticipated that the results obtained will aid in the design and selection of the most appropriate mitigation strategies for sites contaminated with dioxin and other chlorinated hydrocarbons. Approach: The degree of translocation and loss of 2,3,7,8 tetrachlorodibenzo-p-dioxin (TCDD) in contaminated soil is being determined at Times Beach, the state's most extensively contaminated site. The concentration profiles of TCDD in experimental plots and soil columns located at the experimental site and in the laboratory are being measured. Status: The project is on schedule. The investigators have completed the initial laboratory studies on TCDD in soil columns. The studies involving column exposures of higher levels of contamination at Times Beach have been set up there and are underway. The sampling and analysis of cores from the experimental plots at Times Beach continue to provide useful data. This study is taking advantage of the unique opportunity to study the behavior of dioxin in a real-world contamination situation. The column teachability and adsorption studies have now been completed for incubation periods of one year and the results are being tabulated. Clients/Users: The results of this research are of interest to other investigators, regulatory personnel, and private contractors. Modeling Dissolved Oxygen, Nitrate, and Pesticide Contamination in the Subsurface Environment: J.L. Schnoor and G.F. Parkin, University of Iowa Goals: The objectives of this project are three-fold: 1) to develop better mathematical model formulations for the fate and transport of pesticides in the unsaturated zone and saturated groundwater; 2) to perform field and laboratory experiments on the fate and transport of alachlor and atrazine to test the model formulations; and 3) to assess the effects of best management practices and reduced pesticide application rates on groundwater contamination and runoff of agricultural pesticides. 183 ------- Rationale: Both models and field studies are necessary to improve the ability to estimate toxic organic concentrations in groundwater using different agricultural management practices. Better kinetic formulations that can be used in models are being 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 site. Three types of plots have been examined: one of 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 is being used to test the model formulations. Status: The results show that alachlor is more mobile than atrazine. It showed greater runoff rates and percolation to the groundwater, but also disappeared at a more rapid rate than atrazine. Atrazine was tightly bound to the soil, especially in the small plot planted in poplar trees. The investigators have written three research articles on the results of the field study. Client/Users: The results of this research are of interest to other researchers, regulatory personnel, and all who are involved in pesticide management. Vadose Zone Decontamination by Air Injection: L.A. Glasgow, Kansas State University. Goals: The feasibility of vadose-zone soil decontamination by venting or vacuum extraction has been proven in field demonstrations. In many cases it is both effective and economical. The purpose of this project is to explore methods by which alternative venting strategies can be compared with the objective of producing more efficient process designs. This task is obstructed by the large number of variables affecting performance of soil venting systems. Rationale: The efficiency of and coverage provided by air injection and venting have not been reliably characterized. It is necessary to develop design methods that can be used to employ air injection and venting processes efficiently and economically to remove volatile contaminants. 184 ------- Approach: The investigators have developed a simple computer code that can be used to calculate gas flow patterns obtained with various venting arrangements. Numerical simulation is being used to investigate the effects of injection and withdrawal well placements. Status: The investigation has made considerable progress in three specific areas: 1) A review of reported effects of contaminant partitioning among the Non-acqueous Phase Liquid (NAPL), aqueous, vapor, and solid phases on soil venting performance has been completed; 2) Extensive numerical modeling of the equilibrium pressure distributions with different extraction/injection arrangements has been completed; the systems studied have included both vertical wells and horizontal trench extraction; and 3) A gas-phase transport model has been developed and tested numerically with the objective of providing a quantitative comparison of contaminant removal rates for different operational strategies and process designs. Client/Users: Soil venting research results are being used at field sites by contractors, private industry, and regulatory personnel. Other researchers are also interested in the results of this research. 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: The objective will be accomplished by obtaining adsorption isotherms for these systems along with infrared spectra of the samples obtained as a consequence of measuring the adsorption isotherms. In this way fundamental data concerning the mechanism of adsorption (obtained via infrared spectroscopy) can be correlated with macroscopic data of engineering interest (the adsorption isotherms). Status: Silica, alumina (gibbsite), kaolinite, and montmorillonite have been chosen as the adsorbents characteristic of soil constituents to be used 185 ------- in this study. Fourier transform infrared photoacoustic spectra (FTIR-PAS) have been obtained for these materials. Naphthalene, phenanthrene, pyrene, and anthracene have been selected as model compounds representative of PAH systems. FTIR-PAS spectra of these compounds were obtained for use as future library spectra. 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. Client/Users: This research is of interest to other researchers and to contractors involved in the design of remediation processes. Distribution and Recovery of Refinery Waste Products in Groundwater Aquifers: Experimental Study and Model Evaluation: T.H. Illangasekare, University of Colorado. Goal: The goal is to obtain a fundamental understanding of the processes associated with the entrapment and movement of oil refinery waste products (both LNAPL and DNAPL) in heterogeneous soil and water systems. Rationale: There is a lack of understanding of the physical and chemical behavior of organic compounds in naturally heterogeneous soil and water systems. Research is needed to understand the processes associated with the entrapment and movement of organic liquids in soil so that better recovery processes can be developed. Approach: An experimental investigation of entrapment and transport behavior of organic compounds in soil systems is being conducted. The effectiveness of direct recovery techniques for oil products from groundwater is being investigated. The adequacy and effectiveness of models are being studied. Status: Laboratory experiments have been conducted using two test fluids and three soils in vertical columns and in two soil tanks. Clients/Users: This research is of interest to other investigators, regulatory personnel, and contractors. Those who investigate hazardous chemical spills are also potential clients of this work. 186 ------- Biodetoxification of Hazardous Solid Wastes Including Heavy Metals by Staged Anaerobic Fermentation Conducted at Separate Redox and pH Environments: S. Ghosh, University of Utah. Goals: The objective of the project is to develop a staged anaerobic fermentation system for the simultaneous biodegradation of mixed solid and hazardous organic substances with removal of heavy metals in separated redox and pH environments of acidogenic and methanogenic bioreactors. The staged fermentation system will consist of a solid-phase acid fermenter operated in tandem with a packed-bed, upflow methanogenic bioreactor. Solubilized heavy metals contained in the solid- bed fermenter effluent will be removed, as necessary, in a metal separator. Rationale: Large quantities of hazardous and nonhazardous wastes are disposed of on land in landfills, mine tailings, gob piles, waste heaps, and other deposits. Unconventional and innovative approaches to simultaneous destruction of hazardous substances and stabilization of nonhazardous wastes need to be explored. Biochemical treatment offers an attractive alternative for remediation of large as well as small deposits of mixed hazardous and nonhazardous solid wastes. Approach: This research is aimed at developing an anaerobic bioprocessing technology for the simultaneous destruction of hazardous organics and inorganics, removal of heavy metals, and stabilization and gasification of nonhazardous organic wastes. In this system, costabilization of mixed hazardous and nonhazardous solid wastes and bioleaching of heavy metals are accomplished in a staged, anaerobic fermentation system. This system is designed and operated to promote solid-phase hydrolysis, acidification, and methanogenesis at separate redox and pH environments characteristic of the prevalent fermentation steps. This fermentation system is expected to provide ecological niches for such degradative reactions as hydrolysis, hydration, dehydrohalogenation, carboxylation, 6- oxidation, reductive dehalogenation and others for solubilization, acidification and gasification of hazardous and nonhazardous pollutants. Status: The major activities during the last two months were concerned with the design, fabrication, and installation of equipment, compilation of data on about 100 hazardous substances, collection of processed municipal solid waste, and conducting preliminary adsorption runs with two priority pollutants, phenol and p-nitrophenol, and sterilized and unsterilized municipal solid waste samples. 187 ------- Client/Users: The results of this work are of interest to private industry, contractors, and regulatory personnel. Other researchers have also expressed interest in this work. Deep-Rooted Poplar Trees as an Innovative Treatment Technology for Pesticide and Toxic Organics Removal from Groundwater: J.L. Schnoor and L. A. Licht, University of Iowa. Goals: The research has three main objectives: To determine if deep- planted poplar trees can be grown in a riparian zone buffer strip to remove pesticides and other toxic organic chemicals as an innovative technology for treatment of groundwaters and contaminated soils; to construct a mass balance on toxic organics (and pesticide inerts) in the field, and pesticides (atrazine and alachlor) in plant growing chambers with radio-labeled Carbon-14; to provide further mechanistic data and kinetic formulations for a mathematical model of pesticide dynamics in the field. Rationale: Deep-rooted poplar trees may be used to protect groundwater from pesticide contamination. A vegetative buffer strip at the bank of the receiving stream may beneficially reduce the concentrations of nitrates and pesticides. Approach: The pesticides alachlor and atrazine and nitrogen fertilizers have been applied at two application rates on three small plots: one grown with corn, one with poplar trees, and one barren plot. Pesticides and nitrate have been sampled at different depths at regular intervals after application. Toxicity studies with other hazardous chemicals have been conducted. Status: The results are encouraging. Poplar cuttings have grown steadily in concentrations of m-xylene, m-dichlorobenzene, toluene, carbon tetrachloride, benzene, and trichloroethylene up to 120 mg/liter. Field studies with these chemicals are in progress. Research with pesticides has been encouraging; poplars have reduced atrazine concentrations relative to the reference plots. Client/Users: The results of this research are of interest to other researchers, regulatory personnel, and all who are involved in pesticide management. 188 ------- The Role of Deep-Rooted Poplar Trees in Adding Organic Carbon to the Soil for Pesticides and Toxic Organics Removal: J.L. Schnoor and L.A. Licht, University of Iowa. Goals: The objective of this research is to investigate the enhanced rate of biotransformation that occurs due to the addition of organic carbon from deep-rooted poplar trees. Rationale: Carefully conducted experiments are needed to understand the effects of plants and trees on biodegradation processes that occur in the root zone. This information is needed to advance the science and application of bioremediation. Approach: The research will be carried out in laboratory growth chambers so that controlled and reproducible results can be obtained. Experiments will be designed with controls to detect any stimulation of biotransformation due to the poplar trees. Status: This is a new project. Client/Users: The research is of interest to those responsible for bioremediation of contaminated soil. Alachlor and Atrazine Losses from Runoff and Erosion in the Blue River Basin: E.G. Dickey and D.P. Shelton, University of Nebraska- Lincoln; J.M. Steichen and P.L. Barnes, Kansas State University. Goals: The objectives of this research are to measure the losses of alachlor and atrazine through runoff and erosion from cropland and to determine relationships to tillage practice, land slope, and soil texture. The effects of rainfall intensity and duration on herbicide losses will also be investigated. Rationale: Conservation tillage is an effective management practice for controlling soil erosion. It leaves at least 30% of the soil surface covered with residue after planting. There is a need to understand the effects of tillage practices on surface water quality. Approach: Investigations will be conducted at four experimental sites on farmer tilled fields that have a known pesticide and cropping history. A clean tillage system having less than 5% cover, a conservation tillage system having about 30% cover, and a no-till system having more than 50% cover will be evaluated at each site. 189 ------- Status: This is a new project. Clients/Users: The results are of interest to regulatory personnel and those responsible for pesticide management. Feasibility of In-Situ Anaerobic Bioreclamation of Mixtures of Toxic Chemicals: 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. 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 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. Studies will also be conducted in soil-water systems. Status: The project initially focused on the ability of anaerobic organisms to degrade the target compounds under "optimal" conditions. After this ability has been established and interactions observed, acetate concentration was decreased because in-situ applications will obviously require low acetate additions. The importance of acetate has been demonstrated. Now carefully controlled kinetic studies and experiments with soil-water systems will be conducted. Client/Users: The results of this research are of interest to other researchers and those who are attempting to apply bioremediation to chlorinated hydorcarbons at hazardous waste contaminated sites. 190 ------- Feasibility of Using Genetically Engineered Bacteria to Degrade Trichloroethylene in Activated-Sludge Systems: G.F. Parkin and D.T. Gibson, University of Iowa. Goal: The general goal of this research is to investigate the feasibility of using genetically engineered bacteria to degrade trichloroethylene (TCE) in laboratory activated-sludge reactors. Rationale: Genetically engineered organisms may be superior to natural populations; their addition may enhance the rate and extent of biodegradation. This study is the first step towards assessing the feasibility of using these types of organisms for treatment of contaminated groundwaters. Approach: The general project approach has been modified somewhat in the past year due to results from preliminary experiments and constraints imposed on the design of the reactor system used for the laboratory studies. The research is now assessing the following: 1) addition of phenol and/or toluene to induce the toluene dioxygenase enzyme system in a mixed culture of organisms; 2) addition of phenol and/or toluene to a pure culture of P.putida Fl. P.putida Fl will also be added to the mixed culture; and 3) addition of the genetically engineered E. coli (GEEC) to the mixed culture. Status: Dr. Gibson and co-workers have isolated a toluene dioxygenase enzyme system with demonstrated ability to degrade TCE. They have developed a pure culture of Pseudomonas putida (P.putida Fl) containing this enzyme system. They have also developed a genetically engineered pure culture of E. coli containing the cloned P.putida Fl toluene dioxygenase genes. It has been shown that phenol and toluene will induce the TCE-degrading capacity of this enzyme. Client/Users: The research results are of interest to other investigators and to regulatory personnel. Development of In-Situ Biogradation 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 through both experimentation and model-based simulation. 191 ------- Rationale: In-situ bioremediation has many potential applications. However, a better understanding of the factors which influence the rate and extent of biodegradation in field applications is desirable. Laboratory experiments and model-based simulation are being conducted to generate new knowledge. The heterogeneous structure of the soil is an important consideration in the formulation of models because diffusion within soil aggregates can limit the rate of bioremediation. Approach: The investigators have formulated mathematical models to describe in-situ biodegradation processes in the saturated zone. One of the models assumes that rates of transport of oxygen and organic contaminants in the micropores of soil aggregates are controlled by the rate of diffusion, while the rate of transport at the surface of the aggregates in saturated soils is determined by the rate of convective flow through the macropores. Computer simulation is being conducted to investigate the effects of aggregate radius, partition coefficient for the contaminant, and initial contaminant concentration on the time and mechanism of bioremediation. The investigators have conducted microcosm studies with various levels of soil moisture to investigate the effects of soil moisture on the rate and extent of biodegradation. Status: Modeling and simulation of in-situ bioremediation in the saturated zone was conducted; the results show that the rate of biodegradation may be limited by the rate at which oxygen is transported to the microorganisms, the rate of diffusion of the contaminants within the micropores of aggregates, and the growth rate of the microorganisms. The results have been presented in several manuscripts. Additional research is in progress. Clients/Users: The results are important for those who are working to develop field applications of bioremediation. Regulatory personnel, contractors, other researchers, and those with manufacturing companies have expressed interest in the results. 192 ------- Removal of Nitrogenous Pesticides from Rural Well Water Supplies by Enzymatic Ozonation Process: B.C. Kross, University of Iowa. Goals: The goals of this study are to determine optimal ozone dose and the mechanisms by which nitrogenous pesticides are removed from well water using an enzymatic ozonation process. Rationale: This research is designed to 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 was built and tested. Optimal ozone dose and other operating conditions for the ozonation of an aqueous alachlor solution at a concentration of about 10 mg/L were studied. Reaction mechanisms and mass transfer phenomena were evaluated and a computer program based on an explicit numerical method was developed to predict the ozone residual during ozonation of alachlor. Status: The bench scale study of ozonation of alachlor in an ozone-purged reactor is nearly complete. At low pH, the direct ozonation of alachlor was found to be second order with respect to alachlor and first order with respect to ozone residual. Client/Users: The results of this research are of interest to those who are developing water treatment systems for rural residents. Other researchers are also interested in the results. The Response of Natural Groundwater Bacteria to Groundwater Contamination by Gasoline in a Karst Region: J.T. O'Connor and B.J. Brazos, University of Missouri-Columbia. Goals: The objective is to investigate the response of natural bacteria to groundwater contamination by gasoline in a Karst region. Rationale: An underground storage tank has leaked 3,000 gallons of gasoline into highly fractured bedrock at Osage Beach, Mo. This spill provides a unique opportunity for investigations, coordinated with a state 193 ------- regulatory agency and its contractor, relative to the spread and bioremediation of components of gasoline in a Karst region. Approach: The levels of contaminants in water wells in the area are being monitored. The rate of contaminant depletion as influenced by well operation, dilution, volatilization, adsorption, and degradation is being investigated. Laboratory studies are being conducted using columns packed with limestone. Status: A literature review has been completed. Three columns for laboratory study have been constructed. Methods for field sampling are being tested and established in the laboratory. Clients/Users: This research is of interest to other researchers, regulatory personnel, and contractors. In-Situ Bioremediation of Organic Groundwater Contaminants: W.G. Characklis, A.B. Cunningham, W.L. Jones, and Z. Lewandowski, Montana State University. Goal: The goal of this research program is to develop improved strategies for in-situ bioremediation of contaminated groundwater and soil. Bioremediation systems typically involve injection or infiltration of nutrients, reactants, and microbial cells, and definitely require an understanding of 1) mass transport; and 2) contaminant biotransformation phenomena in order to be successful. 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. 194 ------- Approach: The project is being carried out through a carefully designed program of laboratory experimentation. Image analysis is being used to monitor microbial processes including transport rates, adsorption and desorption, growth and filtration. Status: Based on experiments, the investigators have correlated porous media biofilm thickness with media porosity, permeability, and friction factor under the following conditions: a Ps. aeruginosa biofilm developed within uniform diameter porous media reactors, operated under a constant piezometric gradient, with a sterile influent. With these experimental conditions in mind, the following conclusions can be drawn: 1) the maximum biofilm thickness varied directly with the initial (clean surface) permeability of the media. Biofilm accumulation followed the same sigmoidal-shaped progression observed in conduit reactor systems; 2) when biofilm accumulation becomes large enough to substantially reduce pore space, medial permeability and porosity will decrease substantially and friction factor will increase substantially; 3) as the accumulation process progressed in the experiments, the permeability of the biofilm- media matrix stabilized at a minimum value (3 to 7xlO"°cm^), regardless of media particle diameter; and 4) predictions of formation plugging and biofilm accumulation in porous media can be accomplished based on biofilm kinetics and the concept of theoretical porosity. Client/Users: The results are of interest to those responsible for bioremediation. Researchers contractors, regulatory personnel, and others have expressed interest in this research. 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. Rationale: 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. Approach: Two concentration levels are necessary to estimate water quality criteria for a chemical: the criterion maximum concentration (CMC) 195 ------- 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 investigators have developed the necessary software. The basic requirements to estimate ambient aquatic life advisory concentrations have been identified. The final report is being prepared. Clients/Users: The results of this research are of interest to regulatory personnel. ANALYSIS/TREATMENT OF CONTAMINATED SOIL Nano-Scale Metal Oxide particles as Reagents for Destruction and Immobilization of Hazardous Substances: K.J. Klabunde, Kansas State University. Goal: The investigators are involved in a two-stage program to evaluate new ultra-fine inorganic substances as destructive adsorbents for toxic substances. The first stage deals with the use of new and novel methods for synthesizing ultra high surface area metal oxides and hydroxides using aerogel, hypercritical drying methods and other related sol-gel methods. The second stage is to evaluate these new materials for their effectiveness at adsorbing toxic chemicals and destroying them during the adsorption process. Organophosphorus compounds and organohalogen compounds are the toxic adsorbates being studied. Rationale: Organic compounds containing halogens can be completely destroyed under mild conditions using metal oxides. Further research is needed to develop this technology so that is can be used in field applications. Approach: Further synthetic work on the production of magnesium oxide in nano-scale particle size is planned. Reactivity studies will be carried out 196 ------- using a pulsed flow reactor. Chlorinated hydrocarbons, phenols, and phosphorous compounds will be studied. Status: Magnesium hydroxide and magnesium oxide with very high surface areas have been synthesized. Studies on the adsorption and destruction of organophosphorus compounds are in progress. Carbon tetrachloride is being used as a model compound with calcium oxide; calcium chloride is produced. Client/Users: The results of this research are of interest to other researchers and to those in private industry. Representatives from several government agencies have expressed interest in the research. In-Situ Soil and Aquifer Decontamination Using Hydrogen Peroxide and Fenton's Reagent: R.L. Valentine, University of Iowa. Goals: The general purpose of this project is to provide a better understanding of the physical and chemical processes, and soil properties affecting degradation of organics, hydrogen peroxide decomposition, and oxygen production in the subsurface environment. Specific goals are to: 1) evaluate the effectiveness of hydrogen peroxide and Fenton's reagent to decontaminate soils and aquifer material and produce oxygen under a variety of reaction and contacting conditions; 2) conduct mechanistic studies with focus on understanding the role of iron and manganese oxides, natural organic matter and mass transfer limitations; and 3) characterize the products of the reactions in so far as possible. Rationale: Hydrogen peroxide, either alone or with ferrous iron ("Fenton's reagent"), has been recently proposed for use as a chemical oxidant for treatment of contaminated soils, as well as to provide oxygen in bioremediation processes. However, the use of this technology has not been generally demonstrated for destruction of contaminants in soil, and factors and processes controlling the efficacy of hydrogen peroxide use in the subsurface environment are poorly understood. Approach: Studies will initially focus on loss of chlorophenols as a class in soils and soil solutions with future work likely including one or more quinoline derivatives, and atrazine. Several real soils, as well as "laboratory" soils and soil components made from purified or chemically produced hydrous iron and manganese oxides, kaolinite (a clay), feldspar (an aluminosilicate mineral) and sand, will be used. Organic material will be extracted from a soil or purchased. Experiments conducted with real 197 ------- soils will focus on demonstrating the effectiveness of the overall process under a variety of reaction conditions. Studies will be conducted in batch and column reactors. Status: A few preliminary experiments have been conducted to determine gross behavior in the presence of ferrous iron, ferric oxides, and ferrous-ferric iron mixtures. As expected, hydrogen peroxide was found to decay more rapidly in the presence of ferrous iron compared to equal concentrations of paniculate ferric oxide. While little work has been done to date with soils, hydrogen peroxide loss was evaluated in an organic rich soil taken from a Perks series (0.5 to 2% organic carbon, 10-15% clay). Essentially, 100% loss was observed when added to 1:2 (v/v) soil:water solution and dosed at 0.26 M. Clients/Users: The results are of interest to other researchers and those responsible for the remediation of contaminated soil and water. Simulation of Three-Dimensional Transport of Hazar-dous Chemicals in Heterogeneous Porous Media Using X-ray Computed Tomography: R.L. Peyton and S.H. Anderson, University of Missouri- Columbia. Goal: The purpose of this study is to develop and test a three-dimensional computer model which can simulate chemical transport through heterogeneous porous media taking advantage of small-scale measurements of spatial variability of soil and chemicals using X-ray computed tomography (CT). Rationale: The unique feature and the anticipated major contribution of the project is the development of CT to nondestructively collect data within an undisturbed soil core. These data can be input into a convection- dispersion transport model to improve our ability to predict chemical movement in heterogeneous media. This research is significant because of the present difficulty in mathematically simulating and predicting the complex movement of chemicals through heterogeneities. These include fractures, root channels and other macropores which greatly increase contaminant arrival times over that predicted for homogeneous media. Approach: The approach is to formulate a transport theory and numerical methodology into a computer model, collect experimental data using CT during breakthrough curve experiments, and compare model 198 ------- predictions with measurements. Four possible approaches to the computer model have been developed and are under examination. The first approach measures pore water velocities throughout the soil core using CT and inputs these velocities into the three-dimensional transport equation to predict chemical transport. The remaining three approaches circumvent this limitation by estimating intrinsic permeability values throughout the core. Status: The experimental apparatus for conducting breakthrough curves in the CT scanner has been designed, fabricated and successfully tested. Our testing has shown that breakthrough curve plots of X-ray attenuation coefficient vs. time at the downstream face of the core compare well to breakthrough curve plots of outflow solute concentration vs. time. These data, along with pixel pore water velocity distributions over the core cross section, were included in recent conference presentations. Client/Users: The results are of interest to other researchers and to those responsible for predicting the fate of chemicals in soil systems. Experimental Study of Stabilization/Solidification of Hazardous Waste: L.T. Fan, Kansas State University. Goals: The goals of this research are to examine experimentally the feasibility and suitability of stabilization/solidification for typical or prevailing wastes in EPA Regions 7 and 8, and to establish extensive knowledge and data bases necessary for optimal treatment of such wastes. Rationale: Numerous Superfund sites in EPA Regions 7 and 8 involve contaminated soil and mine tailings for which stabilization and solidification are often the only feasible techniques for treatment. This combination of techniques is also applicable to a variety of other hazardous wastes. Approach: Various factors affect the immobilizing mechanism of stabilization and solidification of hazardous wastes. These include the type and amount of pozzolanic materials and solidification-aiding reagents, and the characteristics of the wastes. The necessity and desirability of pretreating these wastes has also been examined. The available methods for pretreatment include dilution with solid or liquid materials, grinding, and absorption and adsorption with porous substances, e.g., activated carbon and natural zeolite. 199 ------- An attempt has been made to utilize a wide variety of inexpensive pozzolanic materials, such as fly ash, silica fume, lime-kiln dust, cement- kiln dust and ground blast-furnace slag for stabilization and solidification. Status: Several wastes have been investigated. Three specific studies were undertaken during the current reporting period. The results have been presented in three manuscripts. Additional research on the effects of various solidification-aiding reagents on the stabilization and solidification process is in progress. Client/Users: The results of this research can be used in the field by contractors, private industry, and state, EPA, and DOE personnel. The work is also of interest to other researchers. Thermochemical Treatment of Hazardous Wastes: W.P. Walawender and L.T. Fan, Kansas State University. Goals: The long-term objectives of this research are to obtain experimental data on the influence of key operating parameters on the thermal destruction of chlorinated liquid hydrocarbons in a bench-scale incinerator and to develop models for the design and effective operation of hazardous substance incinerator systems. Rationale: 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 developing models for the design and effective operation of hazardous waste incineration systems. Approach: A 3-inch ID, 30-inch long, bench-scale tubular incinerator was designed and constructed. The incinerator is a novel design, employing secondary gaseous fuel (propane) and liquid hydrocarbon carrier (hexane) for the chlorinated substance. The secondary fuel is introduced from three jets placed symmetrically about the incinerator axis, while the chlorinated substance and liquid carrier are mixed and atomized about the vessel center line. Such a design minimizes cold zones, promotes mixing, and provides dispersion of the chlorinated hydrocarbons, which are important characteristics for efficient destruction of chlorinated substances. Status: The preliminary evaluation of the incinerator was conducted with carbon tetrachloride (CC14) as the model chlorinated hydrocarbon. The preliminary trials consisted of: 1) combustion of secondary fuel (propane); 200 ------- 2) combustion of liquid carrier (hexane); and 3) combustion of CC14 with the liquid carrier and secondary fuel. Incinerator off-gas analyses were obtained under steady-state operation for air-rich, stoichiometric, and fuel-rich conditions, by both on-line gas chromatography (GC) and on-line mass spectrometry (MS), along with the incinerator operating temperature. Client/Users: The results of this research are of interest to those who are developing hazardous substance incinerators, other researchers, and regulatory personnel. Development, Characterization, and Evaluation of Adsorbent Materials for Waste Streams: D.S. Viswanath, S. Kapila, and T.E. Clevenger, University of Missouri-Columbia and Environmental Trace Substances Research Center. Goals: The project is designed to address two important areas of hazardous waste management: 1) the reduction/elimination of hazardous waste; and 2) the rapid characterization of waste for toxic organic constituents. The objectives 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 organics 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. Approach: Experiments have been carried out to determine the efficacy of desorption and regeneration of bonded alkyl siloxane adsorbents with supercritical carbon dioxide. Substances are desorbed and analyzed chromatographically. Sensitivities below parts per trillion can be measured with this method. Supercritical fluid extraction is being used to remove hazardous substances from soil, also. Status: Several manuscripts have been submitted for publication. Considerable progress has been made in supercritical fluid-based desorption and regeneration of surface-bonded siloxane adsorbents. Initial experiments to evaluate the applicability of supercritical fluid extraction for decontamination of soil and other solid matrices have been completed. 201 ------- Client/Users: The results of this research will be used by those responsible for analytical methods development and by other researchers. Regulatory personnel are interested in the sensitivities of the methods. The Effects of Redox Conditions on Transformations of Carbon Tetrachloride: G.F. Parkin, University of Iowa. Goal: The objectives of this research are: to investigate the effects of redox conditions on the transformation of carbon tetrachloride, to identify pathways and metabolites and to investigate abiotic transformation and the effect of carbon tetrachloride concentration on its transformation. Rationale: Redox conditions are important for the transformation of carbon tetrachloride. Since bioremediation is a potentially efficient method for remediating contaminated soil and groundwater, further research to identify suitable operating conditions should be carried out. Approach: Experiments will be conducted in laboratory reactors under aerobic denitrifying, sulfate-reducing and methanogenic conditions. Redox potential will be measured using an electrode system. Status: This is a new project. Client/Users: The research is of interest to other researchers and to those responsible for the remediation of soil contaminated with carbon tetrachloride. WASTE MINIMIZATION Computer-Aided Design and Control of Systems for Treatment of Hazardous Waste and Minimization of Waste Production: L.T. Fan, Kansas State University. Goal: To develop intelligent computer-aided design and control tools for creating optimal systems for the treatment of hazardous wastes and the minimization of waste production. Rationale: Waste minimization can be realized through source reduction and recycling. Source reduction is an activity that reduces or eliminates the generation of waste at a source or sources, usually within a process. To 202 ------- reduce the source of waste, source control is considered as one of the major techniques. Efficient process design and synthesis, robust control, reliable diagnosis, and flexible production scheduling are all considered important techniques for source control. The effort to minimize waste at the process network level so far described can be greatly reduced if the network is embedded in an overall process structure which is synthesized with waste minimization in mind. Approach: A knowledge-based approach has been employed to develop: 1) systematic strategies for the synthesis of mass and heat exchanger networks; and 2) the expert system for cyanide waste minimization. Furthermore, a modern control theory has been applied to the design of a robust control system for a severely disturbed process in which waste generation is to be minimized. In addition, an approach based on graph theory and combinatorial techniques has been proposed for the synthesis of process systems with minimum generation of waste. Status: Four studies have been completed. The first study was the synthesis of combined exchanger networks for the recovery of waste materials and energy. The second study was the development of an expert system for the cyanide waste minimization in an electroplating plant. The third study was the development of a synthesis approach applicable to the design of a novel robust controller. The fourth study was the development of a combinatorial or graph-theoretic approach for process synthesis. Client/Users: The results of this research are being used by design engineers to incorporate waste minimizaiton into process synthesis. Other researchers and regulatory personnel have expressed interest in the research. TRAINING AND TECHNOLOGY TRANSFER HSRC Newsletter, "HazTech Transfer": R.B. Hayter, Kansas State University. Goal: The goal is to provide information to hazardous substance professionals who are involved in research, management, and technology transfer. 203 ------- Rationale: 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. Approach: The newsletter, HazTech Transfer, is published quarterly and distributed without charge to professionals in Regions 7 and 8. It is distributed to professionals throughout the 10 states in the two regions who are actively involved in the development of new technology or who have need for applying that technology. Included in the distribution of approximately 3,000 are state and federal regulatory agencies, researchers and educators, generators of hazardous waste, and consultants. HazTech Transfer contains announcements of research and training projects, a calendar of meetings, workshops and conferences within EPA Regions 7 and 8, research abstracts and newsworthy details of HSRC accomplishments and activities. The HazTech Transfer also details progress in the HSRC library, calls for HSRC proposals, and articles on the annual Hazardous Waste Research Conference at KSU. Status: The HazTech Transfer was published in January, April, July, and October 1990. To date, information has been contributed by Colorado, Iowa, Kansas, Missouri, Montana, Nebraska, and Utah. Copies of the newsletter are distributed at hazardous waste meetings within the two regions. Audio and Video Training: R.B. Hayter, Kansas State University Goal: 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. Rationale: The effective transfer of new technology is inhibited by the distances and time of travel previously required in traditional on-site delivery formats. Video and audio programming include simple teleconferencing between researchers to discuss research results, capturing presentations before live audiences, transmitting live satellite presentations with interactive audio, or entire noncredit courses. Opportunities for inexpensive training occur when materials developed at other locations are made available at reasonable cost. 204 ------- Approach: Audio and video materials are produced and collected from a variety of sources and made available through the Center and the Kansas State University Farrell Library. The Training and Technology Transfer Advisory Committee will assist in identifying special needs for technology transfer that could be delivered electronically. The availability of the tapes are promoted through the Center's newsletter and are maintained on file in the HSRC special collection in Farrell Library. These tapes are available for loan through the Interlibrary Loan System which can be reached via any public library. Status: The collection of audio and video materials continues to grow. This year tapes of the Hazardous Waste Management in Rural States project were added, as well as waste minimization conferences in Omaha, Nebrasja and Kansas City, Missouri. Several SITE video tapes were received from EPA Region 8 that are now included in the holdings. In addition, two live video teleconferences were brought in for local viewing. The first was "Ask the Experts: 3rd Annual Hazardous Materials Teleconference" and the second was "The Executive's Approach to Managing Risk" both originated from Oklahoma State University. Technology Data Base: B. Biles, Kansas State University. Goal: The goal is to catalog the resources of the consortium universities. A Faculty Profile System will be created to catalog people resources, and the Technical Resources Data Base to catalog institutional resources. 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 industry. Approach: The Faculty Profile System will be an adaptation of the FPS, Version 2.1, now being implemented at KSU and at several other Midwestern universities. The system is a data base that catalogs faculty interest, skills, and abilities related to research and other scholarly interests. Through trained "access" or "gateway" persons, the system will enable public users to quickly identify expertise related to hazardous substances. The system will also facilitate contact with individuals at the other participating institutions. Status: Preliminary work has been accomplished and the collection of data will begin in 1991. 205 ------- 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 EPA Regions 7 and 8, 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. Rationale: An important aspect of any research program is the practical dissemination of the results. Since the technology generated by the Center is developed by a number of individuals, it is critical that there be a convenient, single source of information. 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 videos, technical reports, thesis, dissertations and other publications produced as a result of Center funding. The library will make these materials available to all interested parties through the Interlibrary Loan Program. The library is developing a collection of hazardous substance 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 the EPA Center for Environmental Research Information as well as other agencies and research centers to insure receipt of appropriate documents on a timely basis. Status: The library staff continues to collect, store, bind, or otherwise provide a source for preserving Center materials. Several members of the library staff assist with this project. A database was created that insures bibliographic access to all items in the hazardous substance collection. Hazardous Waste Management in Rural Areas: Video Conference: R.B. Hayter, Kansas State University. Goal: The goal of the video conference is to make available to the public information on hazardous substances that may impact their lives. 206 ------- Rationale: One primary objective of the Center is to educate the public concerning hazardous substances. This aspect of the Center's technology transfer is to present in an informative and understandable manner the management of hazardous waste in the rural parts of the 10 states. The video conference will serve to heighten the awareness of the audience to the hazardous waste problems facing the rural community and provide means for the audience to seek further assistance in addressing their individual problems. Approach: A video conference via satellite uplink was conceived as a novel approach to reaching all parts of the 10 state region. Since the consortium universities, as well as many modern offices, and hotels, all have satellite downlink capabilities, it was thought that in this way the largest population could be reached. Status: This project has been slow to start but the staff is currently planning a February, 1991, video conference. The title of the conference is Hazardous Waste Management in Rural Areas. Conferences: R.B. Hayter, Kansas State University. Goals: 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 good opportunities for the exchange of information. 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 technically stronger, 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. 207 ------- Status: A conference on hazardous waste research was held May 21-22, 1990. The Center co-sponsored a conference on hazardous waste minimization, organized by the Iowa Department of Natural Resources and the Nebraska Department of Environmental Control, on January 23, 1990. The Center co-sponsored a cluster of conferences February 20-21, 1990, organized by the National Water Well Association/Association of Ground Water Scientists and Engineers. The Center co-sponsored a conference on controlling water contamination organized by the Kansas Water Resources Research Institute on March 7-8, 1990. The Center cosponsored a conference July 18-20, 1990, on interfacial microbial process engineering organized by the Center for Interfacial Microbial Process Engineering, Montana State University. The Center cosponsored a conference on mineral and hazardous waste processes organized by the Advanced Mineral and Hazardous Waste Processing Center of Excellence, Montana College of Mineral Science and Technology held September 30-October 5, 1990. Introduction to Hazardous Waste Management: C.O. Harbourt, University of Missouri-Columbia. Goal: The three-year goal is to make the three-day short course available in the 10 states of U.S. EPA Regions 7 and 8. This course is intended for individuals responsible for hazardous waste management programs at facilities regulated under 40 CFR Parts 264 and 265. Rationale: The development and evolution of federal and state regulations for the handling of hazardous waste materials within the past 20 years has created a need for specific and detailed training programs for many persons in industrial and nonindustrial employment. The number of organizations coming under regulation continues to grow as hazardous material regulatory threshold quantities are reduced and as specific lists and generic categories of regulated materials are extended. The total number of persons sharing responsibility for hazardous materials handling is growing rapidly from year to year. This course offers a broad introductory treatment of the reasons for hazardous waste regulations, content of current regulations, responsibilities of organizations that generate or handle such wastes, and current problems and practices relative to hazardous wastes. Approach: In 1982, the University of Missouri-Columbia began offering a week-long summer institute on hazardous waste management. By 1988, this institute had evolved into a combination of an introduction to 208 ------- hazardous waste management and an "update" on the subject, including current research results. A course including a two-day introduction plus one day divided between a regulatory update and industry presentations of hazardous waste management practice was derived from the successful Missouri summer institutes. This course was proposed and accepted as a training project for the Hazardous Substances Research Center for Regions 7 and 8. Status: In the first project year, the course was offered in Missouri, South Dakota, Nebraska, Colorado, Kansas, and Montana. The project continued in its second year with funding for three offerings in Missouri, Iowa, and Utah. The total registration for the seven completed courses was 294. Many speakers from industry as well as state and federal agencies have shared their expert knowledge in this project. Participant evaluation responses have been overwhelmingly favorable. Hazardous Waste Management in Rural Communities in EPA Regions 7 and 8: M.W. Gilliland and W.E. Kelly, University of Nebraska- Lincoln. Goals: The goal of this project is to develop video training material on managing hazardous waste suitable for rural officials and decision makers in EPA Regions 7 and 8. Rationale: The project was developed in recognition of the need to provide training materials tailored to rural communities in our region pair. Approach: Videos were developed interactively with an advisory group consisting primarily of state environmental officials from each of the 10 states in the region pair. This group, and others in the region pair, assisted in developing resource materials specific to the region pair as well as in reviewing and developing the scripts. Status: Two of the three planned videos have been produced. The script for video three has also been prepared but the tape has not yet been produced. Supporting notebook materials have been prepared for all three videos. 209 ------- BIBLIOGRAPHY REFEREED JOURNAL ARTICLES Clevenger, T.E., "Use of Sequential Extraction to Evaluate the Heavy Metals in Mining Wastes," Journal of Air. Water, and Soil Pollution. Vol. 50, pp. 241-254, 1990. Wu, J.C., L.T. Fan, and L.E. Erickson, "Modeling and Simulation of Bioremediation of Contaminated Soil," Environmental Progress. Vol. 9, pp. 47-56, 1990. 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 & Chemical Engineering. Vol. 14, pp. 679-685, 1990. ARTICLES SUBMITTED OR IN PRESS Al-Sheriadeh, M., T. Illangasekare, and D. Znidarcic, "Testing a Multiphase Flow in Porous Media for Silty Soils Using Centrifuge," Centrifuge 1991. University of Colorado, Boulder, June 13-14, 1991. Anderson, S.H., R.L. Peyton, and C.J. Gantzer, "Overview of the Use of Computed Tomography for Quantitative Evaluation of Soil Physical Properties," Proceedings of the Conference on Analytical Methods for Quantifying Root and Soil Dynamics. St. Louis, Mo., 1990. Atteya, M., and KJ. Klabunde, "Nano-Scale Metal Oxide Particles as Chemical Reagents. Heats of Adsorption of Heteroatom Organics on Heat Treated Magnesium Oxide," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. I, pp. 230-256, 1990. Atteya, M., and K.J. Klabunde, "Nano-Scale Metal Oxide Particles as Chemical Reagents. Heats of Adsorption of Heteroatom Organics on Heat Treated Magnesium Oxide," Chemistry of Materials. 1990. Cady, J.C., S. Kapila, S.E. Manahan, D.W. Larsen, and A.F. Yanders, "Evaluation of a Novel Carbon Adsorbent for Fractionation and Treatment of Halogenated Organic Wastes," Chemosphere. 1990. 210 ------- Cady, J.D., S. Kapila, S.E. Manahan, and D.S. Viswanath, "Evaluation of Counterflow Oxidation for Regeneration of Granular Carbon Adsorbents," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. II, pp. 739-750, 1990. Chou, S.T. and L. T. Fan, "Influence of the Type and Amount of Binding Agent on the Characteristics of Solidified Arsenic Waste," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. II, pp. 866-876, 1990. Chou, S.T. and L. T. Fan, "Influence of the Type and Amount of Binding Agent on the Characteristics of Solidified Arsenic Waste," Environmental Progress. 1990. Chou, S.T. and L.T. Fan, "Solidification of K061 Waste," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. I, pp. 385-394, 1990. Chou, S.T. and L.T. Fan, "Solidification of K061 Waste," Hazardous Waste and Hazardous Materials. 1990. Coffin, D. and L. Glasgow, "Some Engineering Considerations in the Application of Soil Venting," Proceedings of the Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. I, pp. 257-297, 1990. Coffin, D. and L. Glasgow, "Effective Gas Flow Arrangements in Soil Venting", Water. Air, and Soil Pollution. 1990. Cunningham, A.B., W.G. Characklis, F. Abedeen, D. Crawford, "Influence of Biofilm Accumulation on Porous Media Hydrodynamics," Environmental Science & Technology. August, 1990. Dave, S., T.E. Clevenger, and E. Hinderberger, "Effect of Cover Material on Leachability of Lead Mine Tailings," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. I, pp. 395-416, 1990. Dhawan, S., L.E. Erickson, and L.T. Fan, "Modeling the Bioremediation of Contaminated Soil Aggregates: A Phenomenological Approach," Proceedings of the Twentieth Annual Biochemical Engineering Symposium. Kansas State University, Manhattan, Kansas, 1990. Erickson, L.E., L.T. Fan, S. Dhawan, and P. Tuitemwong, "Modeling, Analysis, and Simulation of Bioremediation of Soil and Water," Proceedings 211 ------- of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. I, pp. 17-46, 1990. Erickson, L.E. and P. Tuitemwong, "Growth Yields, Productivities, and Maintenance Energy of Methylotrophs," Biology of Methylotrophs. I. Goldberg and J.S. Rokem, (eds.), Butterworths, Stoneham, MA, 1990. Friedler, F., K. Tarjan, Y.W. Huang, and L.T. Fan, "Graph-Theoretic Approach to Process Synthesis: Application to Waste Minimization," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. II, pp. 877-892, 1990. Ghosh, S., S. Bupp, and L.M. DeBirk, "Removal of Heavy Metals by Biopolymers," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. I, pp. 449-476, 1990. Ghoshal, S., S.K. Banerji, and R.K. Bajpai, "Photodegradation of PCP," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. II, pp. 806-816, 1990. Gilliland, M.W., W.E. Kelly, and D. Lokke; "Hazardous Waste Management in Rural Areas," Journal of Professional Issues in Engineering. 1990. Hsieh, M., R.K. Bajpai, and S.K. Banerji, "Degradation of PCP by Ligninase Produced by Phanerochaete crysosporium" Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. II, pp. 797-805, 1990. Huang, Y.L., and L.T. Fan, "A Distributed Strategy for Integration of Process Design and Control: A Knowledge Engineering Approach to Incorporation of Controllability into Process Network Synthesis," Computers and Chemical Engineering. 1990. Huang, Y.L., G. Sunder, and L.T. Fan, "An Expert System for Cyanide Waste Minimization in Electroplating Plants," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. II, pp. 500-522, 1990. Huang, Y.L., G. Sunder, and L.T. Fan, "An Expert System for Cyanide Waste Minimization in Electroplating Plants," Environmental Progress. 1990. 212 ------- Hughes, J.B. and G.F. Parkin, "The Effect of Influent Acetate Concentration on the Transformation of Chlorinated Aliphatic Compounds in Fixed Film Anaerobic Filters," Proceedings Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. I, pp. 1- 16, 1990. Illangasekare, T.H., E.J. Armbruster, D.N. Yates, D. Szlag, and D. Reible, "Effect of Heterogenity on Transport and Entrapment of Nonaqueous Phase Waste Products in Aquifers," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. I, pp. 523-540, 1990. Isbell, L., S. Kapila, K.S. Nam, A.F. Yanders, and R.K. Puri, "Application of Support Bonded Siloxanes and Supercritical Carbon Dioxide for Trace Analysis for Organic Compounds," Journal of Chromatography. 1990. Isbell, L., S. Kapila, K.S. Nam, A.F. Yanders, and R.K. Puri, "Application of Support bonded Siloxanes and Supercritical Carbon Dioxide for Trace Analysis of Organic Compounds," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. I, pp. 113-122, 1990. Keefer, G.B., and G.J. Thies, "Metal Recovery and Reuse Using an Integrated Vermiculite Ion Exchange-Acid Recovery System," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. I, pp. 417-437, 1990. Lewandowski, Z., "Biosorption of Metals from Aqueous Solutions," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. II, pp. 477-499, 1990. Licht, L.A., "Poplar Tree Buffer Strips Grown in Riparian Zones for Nonpoint Source Control," Proceedings of the National Conference on Enhancing the State's Lake Management Programs. U.S. Environmental Protection Agency, Chicago, 1990. Liu, M.H., S. Kapila, T.E. Clevenger, D.S. Viswanath, "Evaluation of Supercritical Fluid Extraction for Removal of Organic Contaminants from Soil," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. I, pp. 152-169, 1990. 213 ------- Lo, Y-H., A.F. Yanders, R.K. Puri, and S. Kapila, "Effect of Co-Pollutants on the Movement of Polychlorinated Dibenzo-P-Dioxins and Polychlorinated Dibenzofurans in Saturated Soils," Proceedings of the Conference on Hazardous Waste Conference. Kansas State University, Manhattan, Kansas, Vol. I, pp. 77-88, 1990. Nair, D.R. and J.L. Schnoor, "Modeling of Alachlor and Atrazine at a Small Plot in Amana, Iowa," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. I, pp. 89- 112, 1990. Nam, K.S., Kapila, A.F. Yanders, R.K. Puri, and D.S. Viswanath, "Supercritical Fluid Extraction and Cleanup Procedures for Determination of Xonobiotics in Biological Samples," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. I, pp. 138-151, 1990. Nam, K.S., S. Kapila, A.F. Yanders, and R.K. Puri, "Supercritical Fluid Extraction and Cleanup Procedures for Determination of Xenobiotics in Biological Samples," Chemosphere. 1990. Paterson, K.G. and J.L. Schnoor, "Fate and Transport of Alachlor and Atrazine in an Unsaturated Riparian Zone," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. II, pp. 561-591, 1990. Paterson, K.G. and J.L. Schnoor, "Fate of Alachlor and Atrazine in Riparian Zone Field Site," Research Journal of the Water Pollution Control Federation. 1990. Paterson, K.G. and J.L. Schnoor, "Vegetative Alteration of Nitrate Fate in an Unsaturated Riparian Zone," Journal of Environmental Engineering. ASCE. 1990. Peyton, R.L., S.H. Anderson, CJ. Gantzer, J.W. Wigger, and H. Wang, "X- Ray Computed Tomography as a Tool in Contaminant Transport Research," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. II, pp. 715-732, 1990. Puri, R.K., S. Kapila, Y-H. Lo, C. Orazio, T.E. Clevenger, and A.F. Yanders, "Effect of Co-Contaminants on the Disposition of Polychlorinated Dibenzo-p- dioxins and Polychlorinated Dibenzofurans in Saturated Soils," Chemosphere. 1990. 214 ------- Rayavarapu, R., S.K. Banerji, and R.K. Bajpai, "Biodegradation of PCP by Pseudomonas cepacia," Journal of General Microbiology. 1990. Rayavarapu, R., S.K. Banerji, and R.K. Bajpai, "Biodegradation of PCP by Pseudomonas cepacia," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. I, pp. 47- 62, 1990. Thies, G.J., and G.B. Keefer, "Vermiculite Ion Exchange-Acid Recovery System," Proceedings of the 1990 Summer National AIChE Meeting. Thies, G.J., G.B. Keefer, and B. Larsen, "Vermiculite Ion Exchange Treatment of Zinc Bearing Plating Shop Waste waters," Environmental Progress. 1990. Tuitemwong, P., B.M. Sly, S. Dhawan, L.E. Erickson, and J.R. Schlup, "Microcosm Treatability of Soil Contaminated with Petroleum Hydrocarbons," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. II, pp. 893-925, 1990. Utamapanya, S., K.J. Klabunde, and J. Schlup, "Nano-Scale Metal Oxide Particles/Clusters as Chemical Reagents. Synthesis and Properties of Ultra- High Surface Area Magnesium Oxide," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. I, pp. 170-203, 1990. Utamapanya, S., K.J. Klabunde, and J. Schlup, "Nano-Scale Metal Oxide Particles/Clusters as Chemical Reagents. Synthesis and Properties of Ultra- High Surface Area Magnesium Oxide," Chemistry of Materials. 1990. Walton, C.W., "Material Recovery and Treatment Methods Used in the Chromium Electroplating Process," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. II, pp. 652-672, 1990. Walton, C.W., A.C. Hillier, and G.L. Poppe, "Process Options for Waste Minimization and Metal Recovery for the Metal Finishing Industries," Proceedings of the International Conference on Pollution Prevention: Clean Technologies and Clean Products. U.S. EPA, Washington, D.C., 1990. Walton, C.W., J.R. Quan, and S.S. Bray, "An Analysis of the Use of Ion Permeable Membranes for Waste Metal Recovery," J. Electrochem. Soc.. 215 ------- 1990. Wei, S.M., S.K. Banerji, and R.K. Bajpai, "Pentachlorophenol Interactions with Soil," Water. Air and Soil Pollution Journal. 1990. Wei, S.M., S.K. Banerji, and R.K. Bajpai, "Pentachlorophenol Interactions with Soil," Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, Kansas, Vol. I, pp. 322-346, 1990. BOOKS AND BOUND PROCEEDINGS Characklis, W.G., and K.C. Marshall (eds.) Biofilms. Wiley, New York, 1990 Erickson, L.E. (ed.), Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, KS, May 23-24, 1989. Erickson, L.E. (ed.), Proceedings of the Conference on Hazardous Waste Research. Kansas State University, Manhattan, KS, May 21-22, 1990. Lehr, J.H. (ed.) Ground Water Management: Proceedings of the 1990 Cluster of Conferences. Water Well Publishing Company, Dublin, Ohio, February 20-21, 1990. CHAPTERS IN OTHER BOOKS OR BOUND PROCEEDINGS Berry, N., and J. Schlup, "Initial FTIR Studies of the Adsorption of Polycyclic Aromatic Hydrocarbons onto Soil Constituents," Proceedings of the Conference on Hazardous Waste Research. Erickson, L.E. (ed.), Kansas State University, Manhattan, Kansas, pp. 347-356, 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, pp. 452-466, 1989. Cunningham, A.B., E.J. Bouwer, and W.G. Characklis, "Biofilms in Porous Media," Biofilms. Characklis, W.G. and K.C. Marshall (eds.), John Wiley, New York, pp. 692-732, 1990. 216 ------- Cunningham, A.B., "Hydrodynamics and Solute Transport at the Fluid- Biofilm Interface," Structure and Function of Biofilms. Dahlem Workshop Report 46, John Wiley, New York, pp. 19-31, 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, L.E. (ed.), Kansas State University, Manhattan, Kansas, pp. 1-12, 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, pp. 578-599, 1989. Erickson, L.E., "Waste Minimization and Process Safety in Process Development, Design, Construction, and Start Up," Proceedings of the Conference on Hazardous Waste Research. Erickson, L.E. (ed.), Kansas State University, Manhattan, Kansas, pp. 525-527, 1989. Galitzer, S.J., "Utilization of Waste Exchanges in a Waste Minimization Program," Proceedings of the Conference on Hazardous Waste Research. Erickson, L.E. (ed.), Kansas State University, Manhattan, Kansas, Pages 528- 536, 1989. Gilliland, M.W., W.E. Kelly, and D. 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, pp. 478-481, 1989. Glasgow, L.A., "Some Engineering Considerations in the Venting of Vadose Zone Soils," Proceedings of the Conference on Hazardous Waste Research. Erickson, L.E. (ed.), Kansas State University, Manhattan, Kansas, pp. 600-620, 1989. 217 ------- Huang, Y.L., Y.W, Huang, and L.T. Fan, "An Artificial Intelligence Approach to the Synthesis of a Mass Exchanger Network for Hazardous Waste Minimization and Treatment," Proceedings of the Conference on Hazardous Waste Research. Erickson, L.E. (ed.), Kansas State University, Manhattan, Kansas, pp. 483-499, 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 Waste Research. Erickson, L.E. (ed.), Kansas State University, Manhattan, Kansas, pp. 147-167, 1989. Huang, Y.L., Y.W. Huang, and L.T. Fan, "A Knowledge-Based System for Synthesizing Highly Controllable Heat Exchanger Networks," Proceedings of the 3rd Oklahoma Symposium on Artificial Intelligence. Tulsa, Ok., pp. 270-271, 1989. 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, pp. , 29-43, 1989. Lewandowski, Z., G. Walser, R. Larsen, B. Peyton, and W.G. Characklis, "Biofilm Surface Positioning," Environmental Engineering Proceedings 1990. ASCE, pp. 17-23, 1990. Seybert, R.A., W.P. Walawender, and L.T. Fan, "Preliminary Evaluation of Carbon Tetrachloride Destruction in the KSU Bench-Scale Incinerator," Proceedings of the Conference on Hazardous Waste Research. Erickson, L.E. (ed.), Kansas State University, Manhattan, Kansas, pp. , 426-451, 1989. Wu, J.C., L.T. Fan, and L.E. Erickson, "Modeling and Simulation of In- Situ Neutralization and Bio Remediation Processes," Ground Water Management. Vol. I, pp. 279-293, 1990. 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, pp. 121- 146, 1989. 218 ------- 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. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1990. Characklis, W.G., A.B. Cunningham, W.L. Jones, and Z. Lewandowski, "In-Situ Bioremediation of Organic Groundwater Contaminants," Technical Progress Report, Hazardous Substance Research Center for U.S. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1990. Clevenger, T.E., and EJ. Hinderberger, "Reclamation of Metal and Mining Contaminated Superfund Sites Using Sewage Sludge/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, 1990. Erickson, L.E., and L.T. Fan, "Development of In-Situ Biodegradation Technology," Technical Progress Report, Hazardous Substance Research Center for U.S. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 28, 1990. 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 28, 1990. 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. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 28,1990. Ghosh, S., "Biodetoxification of Hazardous Solid Wastes by Staged Anaerobic Fermentation Conducted at Separate Redox and pH Environments," Technical Progress Report, Hazardous Substance Research Center for U.S. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30,1990. Ghosh, S., "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. EPA Regions 219 ------- 7 and 8, Kansas State University, Manhattan, Kansas, September, 1990. Glasgow, L.A., "Vadose Zone Decontamination by Air Injection," Technical Progress Report, Hazardous Substance Research Center for U.S. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 28, 1990. Hansen, C.L. and D.K. Stevens, "Optimal Bioreactor Design for Biological Removal of Mercury," Technical Progress Report, Hazardous Substance Research Center for U.S. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30,1990. Illangasekare, T.H., "Distribution and Recover of Refinery Waste Products in Groundwater Aquifers: Experimental Study and Model Evaluation," Technical Progress Report, Hazardous Substance Research Center for U.S. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30,1990. Keefer, G.B., and G.J. Thies, "Metal Recovery and Reuse Using an Integrated Vermiculite Ion Exchange-Acid Recovery System," Final Report, Hazardous Substance Research Center for U.S. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1990. Klabunde, K.J., "Nano-Scale Metal Oxide Particles as Reagents for Destruction and Immobilization of Hazardous Substances," Technical Progress Report, Hazardous Substance Research Center for U.S. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1990. 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. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1990. Lewandowski, Z., "Heavy Metals Removal from Dilute Aqueous Solutions Using Biopolymers," Technical Progress Report, Hazardous Substance Research Center for U.S. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1990. Madison, M.F. and L.A. Licht, "Agricultural Ecosystems—The World is Watching," Agricultural Engineering. Vol. 71, No. 1, pp. 12-15, 1990. 220 ------- O'Connor, J.T. and B.J. Brazos, "The Response of Natural Groundwater Bacteria to Groundwater Contamination by Gasoline in a Karst Region", Technical Progress Report, Hazardous Substance Research Center, Kansas State University, Manhattan, Kansas, September 30, 1990. O'Keefe, T.J. and J.L. Watson, "The Characterization and Treatment of Hazardous Materials from Metal/Mineral Processing Wastes," Technical Progress Report, Hazardous Substance Research Center for U.S. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1990. 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. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 29, 1990. Parkin, G.F., and D.T. Gibson, "Feasibility of Using Genetically Engineered Bacteria to Degrade Trichloroethylene in Activated-Sludge Systems," Technical Progress Report, Hazardous Substance Research Center for U.S. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 29, 1990. Peyton, R.L. and S.H. Anderson, "Simulation of Three-Dimensional Transport of Hazardous Chemicals in Heterogeneous Porous Media Using X- Ray Computer Tomography," Technical Progress Report, Hazardous Substance Research Center, Kansas State University, Manhattan, Kansas, September 30,1990. Schlup, J.R., "Adsorption of Hazardous Substances onto Soil Constituents," Technical Progress Report, Hazardous Substance Research Center for U.S. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 28, 1990. Schnoor, J.L. and L.A. Licht, "Deep-Rooted Poplar Trees as an Innovative Treatment Technology for Pesticide and Toxic Organics Removal from Groundwater," Technical Progress Report, Hazardous Substance Research Center for U.S. Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30,1990. 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. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1989. 221 ------- Valentine, R.L., "In-Situ Soil and Aquifer Decontamination Using Hydrogen Peroxide and Fenton's Reagent," Technical Progress Report, Hazardous Substance Research Center for U.S. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1990. Viswanath, D.S., S. Kapila, and T.E. Clevenger, "Development, Characterization and Evaluation of Adsorbent Regeneration Processes for Treatment of Hazardous Waste," Technical Progress Report, Hazardous Substance Research Center for U.S. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1990. Walawender, W.P., L.T. Fan, "Thermochemical Treatment 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, 1990. Walton, C.W., "An Electrochemical Method for Acid Mine Drainage Remediation and Metals Recovery," Technical Progress Report, Hazardous Substance Research Center for U.S. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 28, 1990. Yanders, A.F.and S. Kapila, "Time Dependent Movement of Dioxin and Related Compounds in Soil," Technical Progress Report, Hazardous Substance Research Center for U.S. EPA Regions 7 and 8, Kansas State University, Manhattan, Kansas, September 30, 1990. THESES/DISSERTATIONS Abedeen, F., "Microbial Processes in Porous Media," M.S. Thesis, Department of Civil and Agricultural Engineering, Montana State University, Bozeman, August, 1990. Paterson, K.G., "Fate of Alachlor and Atrazine in Small Plot Field Studies," M.S. Thesis, University of Iowa, Iowa City, May, 1990. Thies, G.T., "Metal Removal and Recovery Using a Vermiculite Ion Exchange System and Acid Extraction," M.S. Thesis, University of Nebraska-Lincoln, August 1990. 222 ------- CONFERENCES AND WORKSHOPS HELD Two-day conference -- Conference on Hazardous Waste Research, Manhattan, Kansas, May 21-22, 1990 -- Engineering Extension, Kansas State University. One-day conference -- Hazardous Waste Minimization, Omaha, Nebraska, January 23, 1990 — Iowa Department of Natural Resources and Nebraska Department of Environmental Control. Two-day cluster of conferences — Agricultural Impacts on Ground Water Quality; Ground Water Geochemistry; Ground Water Management and Wellhead Protection; Environmental Site Assessments: Case Studies and Strategies, Kansas City, Missouri, February 20-21, 1990 — National Water Well Association/Association of Ground Water Scientists and Engineers. Two-day conference -- Controlling Water Contamination, Manhattan, Kansas, March 7-8, 1990 -- Kansas Water Resources Research Institute, Kansas State University. Three-day conference -- Interfacial Microbial Process Engineering, Bozeman, Montana, July 18-20, 1990 -- Center for Interfacial Microbial Process Engineering, Montana State University. Five-day symposium -- Mineral and Hazardous Waste Processing Symposium, September 30-October 5, 1990 -- Advanced Mineral and Hazardous Waste Processing Center of Excellence, Montana College of Mineral Science and Technology and the Northern Rocky Mountain Water Congress. One-day workshop — Minimizing Hazardous Waste: A Workshop for Metal Finishers, Manhattan, Kansas, May 23, 1990 -- Engineering Extension, Kansas State University Three-day workshop -- Introduction to Hazardous Waste Management, Sioux Falls, South Dakota, November 9-11, 1989 -- Engineering Extension, University of Missouri-Columbia. Three-day workshop -- Introduction to Hazardous Waste Management, Lincoln, Nebraska, December 14-16, 1990 -- Engineering Extension, University of Missouri-Columbia. 223 ------- Three-day workshop -- Introduction to Hazardous Waste Management, Denver, Colorado, January 18-20, 1990 -- Engineering Extension, University of Missouri-Columbia. Three-day workshop -- Introduction to Hazardous Waste Management,Overland Park, Kansas, February 15-17, 1990 — Engineering Extension, University of Missouri-Columbia. Three-day workshop -- Introduction to Hazardous Waste Management, Helena, Montana, March 15-17, 1990 -- Engineering Extension, University of Missouri-Columbia. Three-day workshop -- Introduction to Hazardous Waste Management, Kansas City, Missouri, April 18-20, 1990 -- Engineering Extension, University of Missouri-Columbia. Five-day workshop -- Summer Institute on Hazardous Waste Management, Columbia, Missouri, August 6-10, 1990 -- Engineering Extension, University of Missouri-Columbia. Five-day conference -- 1990 Billings Reclamation Symposium, Billings, Montana, March 25-30, — Reclamation Research Unit, Montana State University. One-day teleconference — Ask the Experts: Third Annual Hazardous Materials and Waste Management Update, Manhattan, Kansas, May 11, 1990 - Oklahoma State University. VIDEO PRODUCTIONS Hazardous Waste: What it is: Who is Regulated: Where are the Sources. University of Nebraska-Lincoln, Lincoln, Nebraska, 1990. Hazardous Waste Management Alternatives for Rural Areas. University of Nebraska-Lincoln, Lincoln, Nebraska, 1990. 224 ------- WESTERN REGION HAZARDOUS SUBSTANCE RESEARCH CENTER PARTICIPANTS; DIRECTOR: TECHNOLOGY TRANSFER DIRECTOR: Stanford University Oregon State University Perry L. McCarty, Ph.D. Western Hazardous Substance Research Center Department of Civil Engineering Stanford University Stanford, CA 94305-4020 Phone: 415/723-4131 Fax: 415/725-8662 Kenneth J. Williamson, Ph.D. Training and Technology Transfer Program Western Hazardous Substance Research Program Department of Civil Engineering Oregon State University Corvallis, OR 97331 Phone: 503/737-6836 Fax: 503/737-3462 THE CENTER AT A GLANCE The Western Region Hazardous Substance Research Center (WRHSRC) is a cooperative activity between Stanford University and Oregon State University. It was established to address critical hazardous substances in the nation, as well as those of specific interest in EPA Regions 9 and 10. The Regions include the states of Alaska, Arizona, California, Hawaii, Idaho, Nevada, Oregon, and Washington, and Guam. 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, consultants, and industry. The objectives of the Center are: • 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. 225 ------- 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 hazardous substance usage and disposal. WESTERN HAZARDOUS SUBSTANCE CENTER Research Project Distribution (Number of Projects) Heavy Metals (2) Other (6) 22% Technology Transfer and Training (4) 15% Groundwater/Site Remediation (15) 56% Major Focus: Groundwater cleanup and site remediation, with a strong emphasis on biological approaches, represent the major focus of Center activities. The research and training functions of the Center address the major hazardous substance problems in EPA Regions 9 and 10, including chlorinated and non-chlorinated solvents, petroleum products, pesticides, and toxic inorganic compounds 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. Currently, the Center is overseeing 23 research projects, eight of which are concerned with chlorinated solvents, four involve halogenated aromatic compounds 226 ------- such as pentachlorophenol and PCBs, three address problems with non- halogenated aromatics including petroleum derivatives such as gasoline and ordnance wastes such as TNT, two are directed towards solution of heavy metal problems, and six evaluate factors affecting movement and fate of the above chemicals in the environment or address design and management issues for site cleanup in general. Technology transfer and training activities are broad and include four major activities. They also include sponsorship of sessions at several major conferences, technical workshops directed towards technology transfer, development of a major training program in Oregon, sponsorship of a national meeting of environmental engineering educators to address hazardous substance education, and numerous presentations of research information and technology transfer at conferences, workshops, and seminars for regulators, industry, consulting firms, and university faculty and students. The faculty and staff who are directing the Center's research, training, and technology transfer activities are listed in Table 1. They collectively represent an integrated research team representing four different schools (engineering, earth sciences, medicine, and veterinary medicine), and many different disciplines (microbiology, chemistry, hydrogeology, hydrology, chemical engineering, civil engineering, and medicine). Perry L. McCarty is Director of the overall Center and of the research program. Kenneth J. Williamson serves as Associate Director in charge of training and technology transfer and coordinates the Center's overall activities in Oregon. Lewis Semprini is an Assistant Director who coordinates technology transfer and research activities in California. Martin Reinhard is Assistant Director in charge of the Center's analytical program. Marilyn C. King is the Center's Administrative Assistant. The Center's Science Advisory Committee and Training and Technology Transfer Committee members are listed in Tables 2 and 3, respectively, and represent federal and state governments, industry, consulting firms, and universities. The budgets for the past year and the total since the Center's inception are summarized in Table 4. The number of students supported by the Center are summarized in Table 5. 227 ------- TABLE 1: KEY PERSONNEL IN THE CENTER Stanford University D. L. Freyberg D. G.-Galic S. M. Gorelic L. M. Hildemann M. C. King P. K. Kitanidis J.O. Leckie A. Matin P. L. McCarty M. Reinhard P. V. Roberts L, Semprini Oregon State University A. M. Craig J. D. Istok P. O. Nelson K. J. Williamson S. L. Woods MEMBER John J. Barich John Conomos Frank Deaver John F. Ferguson John Glaser TABLE 2: SCIENCE ADVISORY AFFILIATION US EPA USGS Government Industry University USEPA Ronald Hoeppel Michael C. Kavanaugh* Garrison Sposito James M. Tiedje William A. Wallace John L. Wilson** John T. Wilson John Wise *Chairman **Vice Chairman DOD Government Consulting Engineer University University Consulting Engineer University USEPA USEPA COMMITTEE EXPERTISE Regulations Hydrology Electronics Biological Processes Physical/Chemical Processes Microbiology Physical/Chemical Processes Soil Science Microbiology Design Hydrology Microbiology Planning 228 ------- TABLE 3: TRAINING AND TECHNOLOGY TRANSFER ADVISORY COMMITTEE James T. Allen Kenneth Bigos Robert Courson Ethelwyn Hoffman Margaret Kelly David Kennedy** Jon Kindschy Gregory Peterson David Rozell M. R. Scalf Jack Stanton Kenneth Sutherland* *Chairman **Vice Chairman California Government USEPA USEPA Treatment Technology Air Pollution Planning Washington Government Training USEPA DOD Government University Consulting Engineer Oregon Government USEPA USEPA Industry Training/Technology Transfer Microbiology Hazardous Substances Training Treatment Technology Environmental Quality Groundwater Remediation Training/Technology Transfer Treatment Technology 229 ------- TABLE 4: CENTER FUNDING FUNDING SOURCES FY199Q* FUNDS TO DATE EPA: Centers Program $926,080 $2,926,080 EPA: Other 200,000 200,000 Other Govt: Federal** 450,000 580,000 Other Govt: State 0 0 Consortium 79,620 425,713 Private Sector*** 537.699 724.196 TOTAL $2,193,399 $4,855,989 *Oct. 1, 1989 - Sept. 30, 1990 **Department of Energy; Department of Defense ***Allied Signal Corporation; Brown and Caldwell; CH2M HILL; Electric Power Research Institute; Gas Research Institute; Hewlett-Packard Company; Kennedy/ Jenks/Chilton; Kleinfelder, Inc.; James M. Montgomery Consulting Engineers, Inc.; MBT Environmental Engineering, Ltd.; Orange County Water District; Schlumberger Technologies; Shell Development Corporation TABLE 5: STUDENT SUPPORT STUDENT LEVEL NUMBER* FUNDS TO DATE** Undergraduate 0 0 Graduate 38 $1,075,000 Post Doctoral 2.4 $181,000 TOTAL 40.4 $1,256,000 *Full-Time Equivalents **Includes tuition and travel 230 ------- CENTER DIRECTOR'S REPORT The goal of the Western Region Hazardous Substance Research Center is to develop alternative and advanced processes for treatment of hazardous substance contamination of groundwater and soil. These collectively represents the subsurface environment. The selected subsurface contaminants being addressed are the most prevalent ones throughout the country, and the focus of most national and state cleanup efforts. These include chlorinated solvents and their derivatives, both halogenated and non-halogenated aromatic compounds, and heavy metals. Increasing our understanding of processes governing the movement and fate of these contaminants in groundwater, and the development and evaluation of schemes for groundwater remediation represent the principal emphasis of the Center's research and educational activities. There are several reasons for this focus. One is that groundwater contamination is one of the major and most costly environmental problems both within the western region and the nation as a whole. Also, the faculty team assembled for the Center have a long history of research on groundwater contamination, and so are in an excellent position to address this important problem. This team represents several different disciplines, the combined expertise of which is vital for successfully resolving the complex physical, chemical, biological, geological, and engineering facets of the subsurface contamination problem. During this past year, the Center added four new members to help direct the Center's activities. Dr. Abduhl Matin, a new faculty member from Stanford's Department of Microbiology and Immunology, is evaluating the performance of special microorganisms that have been engineered to degrade trichloroethylene (TCE) under conditions of starvation, which is the usual state of organisms in the environment. Another new member is Dr. Morrie Craig from Oregon State's School of Veterinary Medicine, who discovered a unique degrading ability of microorganisms contained in the rumen of sheep. These natural organisms offer excellent potential for degradating a variety of biologically resistant aromatic compounds including pesticides and ordnance wastes such as TNT. Dr. Lynn Hildemann, a new member of Stanford's Department of Civil Engineering, is a specialist in air pollution, and complements the other faculty who are addressing surface and subsurface environments. She will help insure that in addressing problems of groundwater or soil contamination, we do not simply transfer the problem to another media. Dr. Lewis Semprini, another addition this year, will coordinate some of the Center's administrative functions, and add his expertise as well in process modeling associated with the field studies being conducted. 231 ------- The Center's primary emphasis on groundwater and soil contamination complements the focus of the other four EPA hazardous substance research centers. By carefully focusing on a small set of the several hazardous substance problems, there is a greater possibility of solving important, but complex problems. The Center's studies on groundwater are helping to define new processes that have potential for application in surface treatment systems as well. For example, studies on groundwater processes have led to the finding of naturally occurring microorganisms with the capability to destroy man-made organic chemicals that were previously believed to persist in the natural environment. Several laboratory and field studies are underway to take advantage of the potential of these organisms for in-situ bioremediation. In addition, because of the great potential, efforts are being made to capture this natural ability in above-ground engineered systems where the reaction rates can be greatly increased and the overall process can be better controlled. Such research on surface processes is a natural extension of the Center's subsurface research since most approaches to resolving subsurface contamination involve some form of surface treatment. The development of both in-situ and surface advanced treatment systems (to handle the problem compounds being researched) by the Center requires new engineering concepts and increased knowledge about the physical, chemical, and biological processes involved. The team approach of the Center is essential to address the various difficult issues inherent in such complex technology development. In addition to research, the Center supports training and technology transfer activities, both by Center personnel and others. Through Dr. Kenneth Williamson, Associate Director of the Center and head of this program, training and technology transfer needs throughout the region- pair were determined and updated from input by the Center's Training and Technology Advisory Committee and through many discussions with state and federal regulatory agencies. One need is for the development of a university-based continuing- education hazardous substance training program, and another is the development of an annual hazardous substance conference in the Northwest region, for practitioners and regulators similar to programs presently in operation in California and elsewhere. Another is a series of seminars and workshops to present results of research that has direct application in the field. Finally, presentations by all Center faculty of research findings at international, national, and regional conferences and publication in widely-read and peer-reviewed journals is essential for the dissemination of results to potential academic users. The Center has been highly active in all these 232 ------- areas. These various training and technology transfer initiatives are vital to the rapid dissemination and implementation of research findings. This outreach effort is of great importance today because of the newness and complexity of the hazardous substance problems. The Center was initiated in the Spring of 1989 with 14 separate research projects. An additional 12 research projects have since been added, and three have been completed. While most projects are funded by the EPA Center's program, five of them have been supported by industry, two are supported by the U.S. Department of Navy, two are financed by the U.S. Department of Energy, and one is jointly supported by EPA and industry. In addition, gift support from industry, consulting engineering firms, and municipalities has helped expand the overall efforts of the Center greatly, and at the same time has helped insure that we are addressing environmental problems of significance to the country. HIGHLIGHTS FOR 1990 This second year of Center activity has seen significant growth in the number of research projects being conducted, ranging from basic to applied. As well as the education of practitioners in hazardous substance cleanup and in transfer of research findings. Among the new projects funded this year are four that are concerned with bioremediation of chlorinated solvents, the major groundwater contaminants in the country. These range from basic studies in genetic engineering to design for application of bioremediation at a Superfund site. This increases the number of projects being conducted in this area to eight. Another major focus has been anaerobic processes for biotransformation of both halogenated and nonhalogenated aromatic compounds. In the past these compounds were believed to be resistant to biotransformation in the absence of oxygen, but field observations just a few years ago suggested this was not the case. The aromatic compounds were found to be transformed under natural conditions in the absence of oxygen. This has important implications for site remediation. These studies are being extended into a third class of aromatic compounds that contain nitro groups through a new Center project. Heavy metal contamination of soils and groundwaters is growing in significance in the western region of the country, and so a new project has been added here. This is an area that we would like to see increase within the Center, both because of its importance and because we have experienced researchers at both Center universities to carry out the needed studies. 233 ------- Training and technology transfer activities have increased significantly this past year, and range from numerous presentations at seminars, workshops, and conferences for industry, the consulting profession, and regulators. Sponsorship of two major conferences and several sessions in the western region this year, and another in the coming year, have contributed to the technology transfer activities. In addition, the initiation of a hazardous substance training program in Oregon has been undertaken. More detailed information of these activities follows: Biodegradation of Chlorinated Solvents: Chlorinated solvents and their transformation products (chloroaliphatics) are the most prevalent priority contaminants found in groundwater in the United States. They include trichloroethylene (TCE), dichloroethylene (DCE), 1,1,1-trichloroethane (TCA), dichloroethane (DCA), and vinyl chloride (VC). These chemicals are characterized by their relatively high mobility in groundwater and their resistance to biological degradation. However, in recent years transformation both in the presence and absence of molecular oxygen has been found possible. Here, microorganisms are fed a primary substrate for energy and growth such as methane during which they produce enzymes or coenzymes that fortuitously transform the chlorinated compounds. This process termed cometabolism has not been used in the past, but it now offers new possibilities for environmental restoration. Most of the Center's biotransformation studies with chloroaliphatic compounds involve cometabolism by methanotrophs, or microorganisms that consume methane. Methane monooxygenase (MMO) is the enzyme used by methanotrophs for the initial step in methane oxidation, and this enzyme fortuitously oxidizes the chloroaliphatics. Through previous studies in the laboratory and at the Moffett Naval Air Station field site in Mountain View, California, a team of Center researchers demonstrated that native methanotrophic bacteria would indeed degrade TCE, DCE, and VC when methane and oxygen were dissolved in water and injected into the ground. Compounds such as VC with less chlorine atoms per molecule were much more rapidly degraded than ones with more chlorine atoms per molecule such as TCE. Technology Application at Superfund Site: A Superfund site at St. Joseph, Michigan, has now been found that appears ideal for the first application of this technology at full scale, and an initial feasibility study was conducted this past year through support from the Allied Signal Corporation and EPA. Here, a relatively uniform fine-sand unconfined aquifer about 10 meters below ground surface has been contaminated with 234 ------- mg/1 concentrations of TCE. In addition, both DCE and VC are present at similar concentrations, and were perhaps formed from TCE by anaerobic biological reductive processes in the groundwater. Because of the promise indicated by the feasibility study, funds have been received from EPA to initiate the design of a full scale system. Cooperating in this study is the Gas Research Institute which is providing additional funds for evaluating an alternative method for subsurface mixing of methane and oxygen with groundwater so that the groundwater need not be brought to the surface for this purpose. The St. Joseph site will allow an evaluation of the methanotrophic process at full scale, and also provides an opportunity to explore alternative technologies for introduction and mixing of required bacterial substrates and nutrients with contaminants. This mixing is one of the more difficult unresolved problems with in-situ bioremediation. The St. Joseph project is a cooperative venture between the federal government, industry, consultants and the the Center to bring innovative technology to practice. We believe there is a great need for such activity and hope that more such opportunities can develop in the future. While in-situ treatment by methanotrophs is attractive, it is likely that groundwater at most sites will be pumped to the surface and treated there. Two other Center projects are concerned with the development of technology for biological treatment of chloroaliphatic compounds in surface reactors where the process can be better controlled. These studies are being jointly sponsored by EPA and the Gas Research Institute. Considerable progress has been achieved this past year in understanding the basic mechanisms involved in cometabolism. Appropriate reaction rate models have been developed, and a two-stage bioreactor for treatment is currently under evaluation. Most Center studies on biotransformation of chloroaliphatics have involved methanotrophs, but other researchers have found other microorganisms that oxidize propane, ethylene, toluene, or ammonia also produce oxygenases that can cometabolize chloroaliphatic compounds. Particularly promising here are organisms with toluene monooxygenase (TMO), which is a better understood enzyme than MMO. TMO has been genetically characterized and is available for evaluation through genetic engineering. One new current project with Drs. Abduhl Matin and Dunja Grbic-Galic as principal investigators is concerned with incorporation of TMO genes into E. coli in such a way that the enzyme can be produced only when the microorganism is growing under starvation conditions, which is the normal state of microorganisms in the environment. In addition, the Department of Energy is helping to support a comparitive 235 ------- evaluation between the MMO and TMO enzyme systems at the Moffett field site so that the relative advantages and disadvantages of these two systems under natural conditions with native organisms can be determined. Aromatic Compounds: The Center is also studying the second most prevalant groundwater contaminants, the soluble components of gasoline, which include the aromatic hydrocarbons: benzene, ethylbenzene, toluene, and xylene (BETX). In addition, the Center is evaluating several other aromatic compounds, some of which sorb strongly to soil and thus tend to be more associated with surface contamination. These include polynuclear aromatics (PAHs), and halogenated aromatic compounds such as the wood preservative pentachlorophenol (PCP), and polychlorinated byphenols (PCBs). Research activities at Stanford University are focused primarily on BETX and PAHs, while Oregon State University's primary focus is PCP and PCBs. A new Center project with Dr. A. Morrie Craig of the Oregon State Department of Veternary Medicine as principal investigator, is exploring the potential of the microflora associated with sheep rumen to degrade ordnance hazardous compounds such as trinitrotoluene (TNT). Considerable knowledge is available on the degradation of aromatic compounds in the presence of oxygen (aerobic), and applications of biodegradation here is common. However, aromatic compounds have recently been found to be degraded in the absence of oxygen (anaerobic) conditions as well. The Center faculty at both Stanford and Oregon State have been instrumental in the development of knowledge of anaerobic aromatic biodegradation, and so continue to study this important area through support from the Center. Anaerobic conditions often occur in the subsurface environment where the availability of oxygen is limited. For this reason, better understanding of the conditions required, the organisms involved, and the additional compounds formed from degradation are of great significance. During this past year at Oregon State faculty Dr. Sandra Woods and her students have explored the different pathways by which PCPs are degraded under anaerobic conditions. They are working with a consortium of bacteria that convert organic compounds into methane (methanogenesis). And have found that of the five chlorine atoms on the PCB molecule, those in the number one and three positions on the ring generally are removed first, with some preference for the former. While chlorine atoms in the number two position are less favored, they too are sometimes removed initially. Because these different pathways are all 236 ------- operative to some degree leads to the formation of mixtures of intermediate compounds of great complexity and susceptibility to further transformation. However, they all lead to the formation of less halogenated compounds which can then be more readily destroyed by aerobic activity. The development of a combined anaerobic-aerobic treatment system in which the overall destruction of these compounds is favored is also under study at Oregon State University. An additional area of research support by the Center is on the movement, fate, and treatment for heavy metals. Of particular concern in the region pair is chromium (CrVI), which is a major groundwater contaminant. Research at both Stanford University under Dr. James Leckie and Oregon State University under Dr. Peter Nelson is addressing this issue. During this past year the research group working with Dr. James Leckie has developed a data base that will permit development of a model for describing mass transport limited adsorption in porous metal oxide particles. The experimental work indicated that porous particles can be designed with the physical size and strength appropriate for engineered processes and with a pore size distribution to allow a large adsorption capacity (internal) and a time dependency appropriate for engineered systems (uptake and regeneration within 1-2 hours). Thus it now appears feasible to consider applications where it is practical to reuse trace metals and the adsorbent oxide particles. Concentration ratios of 1000 or greater may be possible for dilute waste streams where the adsorbed metals can be eluted off in concentrated form. Potential users of such an engineered system are the electronics industry (rare earth metals), metal finishing industries (toxic trace metals), power industry waste streams (fly ash pond waters), and agricultural areas with elevated concentrations of metalloids such as selenium and arsenic. TRAINING AND TECHNOLOGY TRANSFER During the first year of Center activity, a survey was made of hazardous substance training and technology transfer needs in EPA Regions 9 and 10. California was found to have an excellent training program in place at the nine campuses of the University of California, but this did not exist in of the other eight states in the region pair. Also a need for better transfer of research findings to regulators and consulting engineers existed, especially in California. A cooperative venture was established between the Center and the California University Extension program to extend their experience and materials in training courses to 237 ------- other states in the region pair, and to initiate seminars and workshops for technology transfer. In addition, several conferences within the region have been co-sponsored by the Center, and programs for individual workshops and sessions have been developed in order to foster better transfer of technology. These activities are in addition to the numerous presentations by Center researchers on findings of their studies at local, state, and national conferences, seminars, and workshops. A program in hazardous waste training has now been established in Portland, Oregon, to be operated by the Portland Community College System. Last year, the Center was a joint sponsor of an International conference on processes affecting the movement and fate of contaminants in the subsurface environment. This, year, the Center co-sponsored with Idaho State University and the Idaho Association of Commerce and Industry the 1990 Regional Conference on Hazardous Materials and Wastes in Pocatello, Idaho. The Center also co-sponsored the 1990 Responsible Hazardous Materials Management Conference in Portland, and organized six seminars on subjects ranging from methodology for groundwater monitoring to remediation of heavy metal contamination in groundwater and bioremediation of chlorinated solvents. Each seminar was attended by 30 to 60 individuals. Two one-day workshops were conducted in northern and southern California on chlorinated solvents in groundwater, and co-sponsored with the University of California extension service. There were over 160 in attendance at the northern California meeting, and a full 110 individuals at the southern California workshop. Because of the success of this workshop, plans are underway to present it elsewhere in California, and perhaps other region states as well. Other similar workshops are also being planned. This cooperative venture with the University of California Extension service is working well The Center is also a co-sponsor of an International Conference on In-Situ and On-Site Bioreclamation that was initiated by Battelle, March, 1991 in San Diego, California. This meeting has attracted much interest and a number of foreign participants. The Center has been responsible for organizing a session on chlorinated aliphatic compounds. A final but important activity that the Center is sponsoring August, 1991 is a meeting of the Association of Environmental Engineering Professors (AEEP) to evaluate educational issues. AEEP represents about 100 universities that educate environmental engineers and scientists 238 ------- throughout the country. AEEP has educational meetings about once every four to five years. One of the three main topics at this meeting will be how best to incorporate hazardous substance issues into the curriculum. Environmental education at the undergraduate level will also be a major theme at this meeting. Oregon State University was selected as the site for this important conference because of the focus of the WRHSRC and its relevance to the topics of the Conference. TABLE 6 WESTERN REGION HAZARDOUS SUBSTANCE RESEARCH CENTER PROGRAM SUMMARY PRINCIPAL INVESTIGATOR PROJECT CHEMICAL MOVEMENT/FATE/TREATMENT END DATE CURRENT BUDGET TOTAL BUDGET Reinhard/ Treatment of Complex Grbic-Galic/ Mixtures Leckie/McCarty/ Roberts 1992 $96,000 $285,000 Gorelick Reinhard/ Roberts Kitanidis Kitanidis/ Freyberg Hildemann/ Roberts Design of Reliable and Cost-Effective Mitigation Schemes Gaseous Stripping of Non-aqueous Liquids from the Vadose Zone 1992 1992 Detection and Assessment 1991 of Subsurface Contamination FASTCHEM© Applications and Sensitivity Analysis 1991 Dispersion Modeling of 1992 Volative Organic Emmission from Ground-Level Treatment Systems $60,000 $72,000 $66,000 $53,000 $76,000 $181,000 $205,000 $195,000 $53,000 $159,000 239 ------- PRINCIPAL INVESTIGATOR Roberts END DATE 1992 PROJECT Determining and Modeling Defusion-limited Sorption and Desorption rates of Organic Contaminants in Heterogeneous soils BIOREMEDIATION/CHLORINATED SOLVENTS McCarty/ Oxidation of Chlorinated 1991 Roberts Solvents by Methanotrophs McCarty/ Effects of Sorption on 1992 Roberts Biodegradation of Halo- genated Organics Reinhard/ Long-Term Chemical 1991 McCarty Transformation of 1,1,1- Trichloroethane (TCA) and Freon 113 Under Acquifer Conditions Matin/ Use of Starvation and Stress 1992 Grbic-Galic Promoters for Biodegradation of Hazardous Wastes McCarty/ Subsurface Mixing of 1991 Kitanidis/ Nutrients and Groundwater Roberts/ for In-Situ Bioremediation Semprini McCarty/ Test-Bed Evaluation of In- 1992 Roberts/ Situ Bioremediation of Semprini Chlorinated Aliphatic Compounds by Toluene McCarty/ Demonstration of In-Situ 1991 Roberts/ Bioremediation of Chlori- Gorelick/ nated Aliphatics by Kitanidis/ Methanotrophs at Semprini St. Joseph CURRENT BUDGET TOTAL BUDGET BIOREMEDIATION/AROMATIC COMPOUNDS Woods Interactions between Electron Acceptors in the Treatmet of Wastewaters Containing Sulfate, Chlorophenols and Acetate 1992 $80,000 $70,000 $15,000 $76,000 $90,000 $185,000 $200,000 $47,000 $260,000 $211,000 $50,000 $156,000 $90,000 $384,000 $200,000 $139,000 240 ------- PRINCIPAL INVESTIGATOR Williamson/ Nelson PROJECT END DATE Enhancing Biodegradation 1992 with Sorption with Alternating Aerobic/Anaerobic Environments CURRENT BUDGET $56,000 TOTAL BUDGET $168,000 Istok/ Woods Grbic-Galic Reinhard/ McCarty Craig/ Woods Reinhard/ McCarty Development and Verifica- 1992 tion of a Numerical Model to Predict the Fate and Transport of Chlorinated Phenols in Groundwater Anaerobic Microbial Trans- 1992 formation of Homocyclic and Heterocyclic Polynuclear Aromatic Hydrocarbons $58,000 $166,000 In-Situ Biological Treat- ment of Aromatics in Groundwater Biotransformation of Ordnance Wastes Using Unique Consortia of Anaerobic Bacteria The Effect of Surfactants on Biiodegradation of Chlorinated Biphenyls in the Presence of Soils HEAVY METALS Leckie Nelson/ Istok Trace Metal Removal Processes Hexavalent Chromium Sorption and Desorption in Natural Soils and Subsoils Semprini Williamson Williamson/ Semprini Continuing Education Program 1992 1992 1990 1992 1992 TRAINING AND TECHNOLOGY TRANSFER Williamson Hazardous Waste Training 1992 Advanced Topic Workshops 1992 1992 Conference Sponsorship 1992 $64,000 $130,000 $193,000 $28,000 $72,000 $48,000 $15,000 $20,000 $15,000 $10,000 $190,000 $260,000 $438,000 $86,000 $212,000 $100,000 $45,000 $60,000 $45,000 $30,000 241 ------- RESEARCH PROJECT DESCRIPTIONS CHEMICAL MOVEMENT, FATE, AND TREATMENT Treatment of Complex Mixtures: Martin Reinhard, Dunja Grbic-Galic, J. 0. Leckie, P. L. McCarty, and P. V. Roberts, Stanford University. Goal: The goal of this project is to apply a computer-aided information system to the problems of hazardous waste treatment. Rationale: When designing treatment processes and assessing the risk of complex hazardous wastes, numerous complex and interrelated factors must be considered. Foremost are the biodegradability and the physico- chemical characteristics of the contaminants. However, such data are not available except for the most common contaminants. Using computer- based property estimation techniques and process simulation, pilot studies can be designed with considerable cost savings. Approach: An information system is being used to analyze in detail the performance of single and multi-step treatment plants for which the removal efficiencies of a broad range of contaminants have been characterized. In these cases, substance properties relevant to treatment of contaminated waters, such as aqueous solubility and n-octanol/water partition coefficients as a function of treatment conditions, are being correlated with observed removal rates during air-stripping, activated carbon and reverse osmosis. Biological properties will also be considered. Status: Detailed analysis of air-stripping and activated carbon treatment should be complete by March 1991. Analysis of multi-process treatment trains including reverse osmosis and biological process is about to begin with completion expected in March 1992. Client/Users: Consultants, educators and regulators interested in treatment plant design for complex mixtures, and researchers studying the relationship between properties and environmental fate of contaminants. 242 ------- Design of Reliable and Cost-Effective Mitigation Schemes: Steven M. Gorelick, Stanford University Goal: 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 ensure capture of contaminant plumes. Reliable designs must be based on reliable predictive models. Quantifying both model parameter uncertainty and consequent prediction uncertainty is a major research goal. 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. Given this uncertainty, any pump-and-treat system must be over designed. 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, and focuses on the Gloucester Special Waste Compound in Ontario, Canada. In 1989 design began for pump-and-treat remediation to remove hazardous organic solvents. The best remediation design requires optimal well selection and the determination of optimal pumping rates. The problem is being approached by developing stochastic simulation models based upon available field data. Then these models are combined with nonlinear optimization methods in order to identify reliable design strategies. Model parameter uncertainty is considered to be a key indicator of design reliability. In this approach, model parameters are first described statistically. This quantification of uncertainty in model input is then translated into confidence bounds on model predictions of contaminant transport. The reliability indicated by the predictive model is then used to over design the remediation system to the extent necessary to insure success. Status: Analysis of the hydraulic and chemical field data for the Gloucester site has been completed. Geologic characterization and hydrogeologic conceptualization are also complete. A large scale two- dimensional finite- element simulation model was developed which simulates the hydraulic head distribution and solute migration. Using a coupled-process approach, both the hydraulic head and solute concentration data were jointly used to estimate parameter values and 243 ------- their uncertainties. This simulation- regression model proved to be a powerful tool to reduce parameter uncertainty and consequent prediction uncertainty. Currently, a stochastic optimization formulation, based on the parameter estimates, is being used to establish reliable remediation design alternatives. Completion is expected by March 92. Client/Users: Engineers and hydrogeologists involved in aquifer remediation design. Groundwater modelers interested in parameter estimation methods. Gaseous Stripping of Nonaqueous Liquids from the Vadose Zone: Martin Reinhard and Paul V. Roberts, Stanford University Goal: The objective of this study is to gain a better understanding of the factors which control the efficiency of vapor phase stripping of volatile contaminants from the vadose (unsaturated) zone. Rationale: Vapor stripping is becoming an increasingly popular method of removing nonaqueous liquids from the unsaturated zone. However, there is no basis for assessing when conditions are favorable for this process, nor is there any way of predicting the rate and extent of removals. Approach: This investigation is divided into three areas. The first is the measurement of organic vapor sorption isotherms for trichloroethylene on a range of different solids. The second involves measuring the rate at which the organic solvents desorb from the soils under vapor stripping conditions. The third encompasses computer modeling of the stripping process using the isotherm and kinetic data obtained in the other two phases of the project. Status: A novel methodology has been developed to measure adsorption isotherms under conditions of the unsaturated subsurface environment. Three aquifer materials have been characterized, and adsorption isotherms have been measured for TCE. Desorption rates have been measured and models are being evaluated to rationalize the observed removal rates. Client/Users: Consultants and educators interested in groundwater and soil remediation technology. 244 ------- Detection and Assessment of Subsurface Contamination: Peter K. Kitanidis, Stanford University Goal: The thrust is the development of better techniques for characterizing contaminated sites. Objectives include the development of better computational 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 at field scales. Rationale: There is seldom enough information to determine with certainty the precise values of all parameters for characterizing a contaminated site, especially at the local scale. Measurements of some critical transport parameters, such as hydraulic conductivity, indicate variability over orders of magnitude over short distances. Other parameters, such as thermodynamic constants and rate coefficients, are quite variable too. In many cases, however, determination of the "effective" parameters of the heterogeneous formation, i.e., those which govern the net or "macroscopic" rate of advection, dispersion, and chemical attenuation, rather than the highly variable local rates, is sufficient and is what is sought by this study. Approach: The approach combines measurements, mechanistic models describing the transport and fate of pollutants, and statistical methods. Because of spatial variability and incomplete knowledge, the parameters which determine the 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 (such as geological) information using geostatistical techniques. Then, through the governing flow and mass transport equations, the statistics of solute concentration are determined. 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 measurements. Status: Initial efforts focused on the determination of 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. The second year produced a numerical spectral method for carrying out computations of interest. 245 ------- Client/Users: Groundwater modelers; engineers working in the characterization of hazardous-waste sites; regulators; and policy makers interested in evaluating the worth of data. FASTCHEM Applications and Sensitivity Analysis: Peter K. Kitanidis and David L. Freyberg, Stanford University Goal: 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: 1) quantifying the sensitivity and uncertainty of predicted chemical distributions (in time and space) to variations in input parameters; 2) developing a set of computer programs which apply state-of-the art estimation methods for the interpolation of parameters from sparse measurements; and 3) evaluating the literature and developing new techniques for optimal decontamination strategies at utility hazardous waste sites under uncertainty. Rationale: 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. In response 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. There is a need now to determine the applicability of the model and for incorporating subroutines for the utilization of data. Approach: The model's sensitivity and uncertainty is evaluated through application to specific case studies. Methods for incorporating available measurements are being based on linear estimation methods. Status: The computer codes have been installed and tested and recommendations for model improvement have been made. The model is currently being applied to six case studies representing typical problems of ash disposal from coal-fired plants. The sensitivity of the results to the input parameters is being evaluated. Clients/Users: The electric utility industry; regulators; policy makers. 246 ------- Dispersion Modeling of Volatile Organic Emissions from Ground- Level Treatment Systems: Lynn M. Hildemann and Paul V. Roberts, Stanford University Goal: Treatment to remove organic substances present in contaminated groundwater can result in the emission of hazardous volatile organics into the atmosphere. This project will develop a detailed model for the dispersal of emissions from a ground-level area source into the atmosphere, with the goal of accurately predicting concentration levels near the source as well as further away. Rationale: The potential toxicity of air emissions from waste treatment processes has been the focus of increasing concern over the past decade. However, published attempts at estimating the potential impact of such treatment processes on the local atmosphere have utilized simple dispersion models which are only reliable at significant distances downwind over long averaging times for an elevated source. A more accurate approach is needed to evaluate the risk posed in the near vicinity of a ground-level treatment process due to atmospheric emissions. Approach: A detailed model capable of predicting the near-source dispersion of emissions from a ground-level area source will be developed. Accurate theoretical expressions for the variation of wind speed and eddy diffusivity with vertical height will be incorporated in order to accurately model dispersion in the surface layer regime. This model will be linked to an already-developed model predicting emission rates resulting from aerobic biological treatment of wastewaters. The model predictions then will be compared with published measurements of concentrations downwind of treatment sites. Status: Since the project began in October 1990, a review of the literature to identify recent work dealing with the characterization of fluid mechanical behavior in the surface layer of the atmosphere has been undertaken. The next step will be to begin development of the atmospheric diffusion model. Client/Users: Industries and regulators involved in the treatment of contaminated groundwater, and researchers concerned with risk assessment with such treatment. 247 ------- Determining and Modeling Diffusion-limited Sorption and Desorption Rates of Organic Contaminants in Heterogeneous Soils: Paul V. Roberts, Stanford University Goal: The overall goal of this project is to advance the understanding of the basic processes governing the uptake and release of aqueous phase organic contaminants in a heterogeneous porous medium. Rationale: Aquifer remediation strategies, such as pump-and-treat or biorestoration, can be greatly prolonged by the diffusion limitations on sorption and desorption from the soil matrix. Equilibrium models, which are the most commonly used solute transport models, do not account for these effects. There is presently little basis for assessing when mass transfer conditions are favorable for pump-and-treat and/or biorestoration strategies, nor is there an accepted method for predicting the required duration of remediation efforts. Approach: Long-term batch experiments for measuring the uptake and release rates of several contaminants from solids obtained from an experimental aquifer restoration site are being conducted. The data will be used to evaluate and parameterize existing transport models. Status: Batch sorption rate data have been used to study the breakthrough of several compounds in the experimental aquifer. A purge- and-trap method for studying desorption rates is being developed. The completion of sorption/desorption studies, and related modeling efforts, is expected March 92. Client/Users: Researchers interested in mass transfer limitations on the transport or biodegradation of organic contaminants; state and EPA regulators, industry, and consultants concerned with site remediation. CHLORINATED SOLVENTS Chlorinated Solvents and Oxidation of Chlorinated Solvents by Methanotrophs: Perry L. McCarty and Paul V. Roberts, Stanford University Goal: Methanotrophic bacteria, which oxidize methane for energy, can also oxidize chlorinated solvents such as TCE by co-metabolism. The goals of this project are: 1) to evaluate competitive inhibition effects between 248 ------- methane and chlorinated compounds; 2) to assess mass transfer limitations to treatment-reactor design; and 3) to optimize the design for an above ground treatment system. Rationale: There have been several studies of treatment systems for degrading chlorinated solvents and related compounds by cometabolism. However, knowledge of reaction kinetics are poorly understood so that little scientific basis currently exists for optimizing treatment reactor design. In addition, since the substrates and contaminants of concern are all poorly soluble in water, mass transfer is of great significance and must be considered. Approach: It is hypothesized that oxidation rates for methane and chlorinated contaminants can be described by a competitive inhibition model. 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 are then being predicted and measured in order to test the hypothesis. In mass transfer studies, model calculations that consider mass transfer effects and biological reaction kinetics are being made for a variety of reactor configurations. The model results will guide reactor design and will help to determine important knowledge gaps for further research. Status: Preliminary laboratory studies have indicated basic reaction coefficients for methane and trichloroethylene utilization alone by methanotrophs. Model calculations have been carried out for a suspended growth reactor, and results are being evaluated to determine where knowledge gaps exist. Client/Users: Researchers interested in co-metabolism, and industry, consulting engineers, and state and EPA regulators who are evaluating treatment options for chlorinated solvents. Effects of Sorption on Biodegradation of Halogenated Organics: Perry L. McCarty and Paul V. Roberts, Stanford University (funded by EPA) Goal: The goal is to determine how compound sorption onto solid surfaces affects the rates of degradation of chlorinated solvents by methanotrophic bacteria. 249 ------- Rationale: Rates of biodegradation of organic compounds are 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 is needed in order to better predict fate of chemicals, and to devise treatment schemes where sorption is involved. Approach: The availability of sorbed trichloroethylene (TCE) to biological degradation by methanotrophic bacteria which use methane as primary substrate for growth is being evaluated. Biotransformation kinetics for TCE by non-fed (resting) methanotrophic bacteria, and parameters associated with sorption kinetics of TCE on a well-defined synthetic media (silicalite) are being determined. A numerical model for experimental evaluation is being developed to relate desorption and biotransformation kinetics, using the hypothesis that transformation rates are directly related to solution concentration of TCE. Status: Studies of TCE transformation by resting cells have been completed. Experiments on the effect of sorption onto silicalite on reaction rates have been completed. Progress is on schedule. Client/Users: Researchers interested in co-metabolism, and industry, consulting engineers, and state and EPA regulators who are evaluating treatment options for chlorinated solvents. Long-Term Chemical Transformation of 1,1,1-Trichloroethane (TCA) and Freon 113 Under Aquifer Conditions: Martin Reinhard, Stanford University Goal: The goals of this project are: 1) to determine the rates and pathways of chemical transformation of 1,1,1-trichloroethane (TCA) and Freon 113 under conditions representative of those encountered in an aerobic aquifer; and 2) to determine the extent to which sorbing aquifer materials and different solution composition may influence transformation rates and pathways. Rationale: Previous data obtained at high temperature has demonstrated that TCA undergoes abiotic dehalogenation in aqueous solution. However, extrapolation to groundwater temperature is fraught with uncertainty, and the influences exerted by the presence of aquifer solids and ground water solutes are not well understood. 250 ------- Approach: This work involves a long-term (5-year) study of the rates and pathways of reaction of TCA and Freon 113 in aqueous solution in the presence, as well as the absence of aquifer material. Because under ambient conditions, the half-life of TCA is on the order of a year and several different products may form, substrate disappearance and product formation will be monitored over several years in order to make obtain mass balances. Status: The test systems have been in operation for 10 months, and several products of TCE transformation are now being detected and quantified. The study is expected to be completed in 1994. Client/Users: Consultants, regulators, and researchers interested in natural processes affecting the long-term fate of TCA and Freon 113 in the subsurface environment. Use of Starvation and Stress Promoters for Biodegradation of Hazardous Wastes: Abdul Matin, Dunja Grbic-Galic, Stanford University Goal: The goal of this project is to use bacterial starvation and stress promoters to create recombinant strains that maintain high biodegradation activity under typical environmental stress conditions. Rationale: Biodegradation activity in the environment is typically limited by nutrient deficiencies or other stresses, including carbon, nitrogen, or phosphorus starvation. Bacterial strains that maintain high degradation activity in the face of typical environmental stresses would be very useful in treatment of hazardous waste sites. Approach: Bacterial stress promoters are genetic elements that turn on in response to specific stress conditions. Our laboratory has isolated and characterized genetic promoters that turn on under carbon starvation conditions. We have also obtained other stress promoters that respond to more general stress conditions. Our approach is to splice the toluene monooxygenase (TMO) gene (responsible for trichloroethylene (TCE) degradation) under control of these stress promoters, and to characterize the degradation activities of these recombinant strains. Status: The TMO gene has been cloned under control of two carbon starvation promoters and a stress promoter in E.coli, which has permitted the organism to maintain TCE degradation activity for several hours after 251 ------- the onset of starvation. The degradation ability under a variety of stress conditions is now being evaluated. Client/Users: Researchers, consultants, and regulators interested in understanding environmental factors affecting biotransformation, and potential methods for improving biotransformation rates. Subsurface Mixing of Nutrients and Groundwater for In-Situ Bioremediation: P. L. McCarty, P. K. Kitanidis, P. V. Roberts, and L. Semprini, Stanford University Goal: A scheme by which gases such as methane and oxygen are introduced directly into groundwater for mixing with contaminants is proposed for evaluation in order to avoid bringing contaminants to the surface for this purpose. Rationale: In-situ bioremediation of chlorinated solvents in groundwater with methanotrophic bacteria requires that the primary substrate, methane, and oxygen for its oxidation be introduced into the groundwater and mixed with the contaminants. This is difficult to accomplish, especially when the contaminants do not sorb strongly to the soil. Bringing contaminated groundwater to the surface for this purpose poses a health hazard, and so a method for accomplishing the introduction and mixing of gases without removing groundwater is desirable. Approach: A subsurface mixing system is proposed which consists of a series of submerged wells with intake screens at the bottom and top. A pump permits drawing groundwater into the well through the bottom screen and pumping it back into the aquifer through the top screen, or vice versa. In the well, oxygen and methane are introduced and mixed with the groundwater. Model analysis is being conducted to determine the effect of design parameters on the degree of mixing of dissolved gases with contaminated groundwater, and to predict the effect of these operating parameters on the degree of in-situ bioremediation that can be achieved. Alternative methods for introduction of gases into the submerged wells are also being evaluated. Status: Funds to begin this one-year study were received in October 1990, and the proposed analysis has begun. 252 ------- Client/Users: Researchers studying in-situ bioremediation, and State and EPA regulators, industries, and consulting engineers with interests in biotreatment systems for organically-contaminated ground waters. Test-Bed Evaluation of In-Situ Bioremediation of Chlorinated Aliphatic Compounds by Toluene: P. L. McCarty, P. V. Roberts, L. Semprini, and G. Hopkins, Stanford University Goal: The goal is to evaluate in the field the rate and extent of degradation of chlorinated aliphatic compounds through cometabolism using phenol as a primary substrate. Rationale: Recent research has indicated that microorganisms containing the toluene monooxygenase (TMO) or toluene dioxygenase (TDO) enzyme can oxidize chlorinated aliphatic compounds such as trichloroethylene (TCE) by cometabolism, similar to biodegradation by methanotrophs with methane monooxygenase (MMO). In order to obtain a comparison between the relative advantages and disadvantages of the TMO or TDO and the MMO enzyme system, an evaluation will be conducted at the Moffett Naval Air Station field site in Mountain View, California, where a four-year evaluation of the MMO system has been completed. Approach: The field study with TMO- or TDO-producing bacteria will be conducted similar to the previous study in which methane was used as a primary substrate so that the results can be directly compared. Here, phenol and oxygen will be dissolved in recycled groundwater along with TCE, dichloroethylene (DCE), and vinyl chloride (VC) for introduction into a confined aquifer about four meters below the surface that is about 1.2 meters deep and 6 meters long. The growth of a native phenol degrading population, and the rate and extent to which the introduced chlorinated compounds are removed will be monitored. The extent of transformation will be evaluated through comparison of concentration decreases using conservative tracers for reference. Status: Funds to begin this study were received in October 1990, and preparation of the test-bed for beginning of this evaluation has just begun. Client/Users: State and EPA regulators, industries, and consulting engineers concerned with chlorinated solvents and related compounds present in groundwaters. 253 ------- Demonstration of In-Situ Bioremediation of Chlorinated Aliphatics by Methanotrophs at St. Joseph, Michigan: P. L. McCarty, P. V. Roberts, S. M. Gorelick, P. K. Kitanidis, and L. Semprini, Stanford University Goal: This project will evaluate alternative technologies leading to the design of a full-scale system for in-situ cometabolic biodegradation of chlorinated solvents and related compounds by methanotrophic bacteria. Rationale: Bioremediation of groundwaters offers great promise because it results in destruction of contaminants. However, application of promising techniques requires research and demonstration at full scale. Field and laboratory studies at Stanford University have helped develop a basic understanding of the processes involved in methanotrophic treatment of chlorinated aliphatic compounds. The next step towards application is an evaluation of potential technologies for the process through research and demonstration at full scale. Approach: The Superfund site at St. Joseph, Michigan, is underlain with a relatively homogeneous fine-sand aquifer. It is contaminated with mg/1 concentrations of trichloroethylene, dichloroethylene, and vinyl chloride. Laboratory, field, and modeling studies conducted by the WRHSRC indicated that conditions were ideal for evaluating in-situ bioremediation at this site. In order to develop an appropriate treatment system design, additional site characterization is required. Alternative technologies need to be researched, and modeling studies for alternatives need to be evaluated. Further, a system design needs to be developed for evaluation by the responsible industries, their engineers, and state and EPA regulators. These tasks will be carried out by a team of researchers at Stanford University in cooperation with the interested parties. Status: Funding for this study was received in September 1990. The team of researchers has agreed on a division of tasks, and evaluations have been started, with the expected design recommendation scheduled for summer 1991. Client/Users: State and EPA regulators, industries, and consulting engineers interested in the removal and degradation of chlorinated solvents and related compounds present in groundwaters. 254 ------- AROMATIC COMPOUNDS Interactions between Electron Acceptors in the Treatment of Wastewaters Containing Sulfate, Chlorophenols and Acetate: Sandra L. Woods, Oregon State University Goal: The goal is to develop and verify a mathematical model for anaerobic biotransformations in the presence of competing electron acceptors, and to measure process kinetic constants. Electron acceptor interactions between chlorophenols and their dechlorinated metabolites and interactions between chlorophenols and sulfate are examined. Rationale: Reductive dechlorination of chlorinated aromatic compounds appears to progress such that parent compounds are almost completely removed before degradation of metabolic products begins. To evaluate this hypothesis, the kinetics of pentachlorophenol biotransformation is evaluated in the presence of varying quantities of alternate electron acceptors (metabolic products and sulfate). Approach: Organisms acclimated to pentachlorophenol or pentachlorophenol and sulfate are grown in continuous flow anaerobic reactors. The reactors are allowed to reach steady-state and then used as a source of organisms for subsequent batch experiments. Progress curves for chlorophenol, sulfate and acetate degradation are generated from the batch experiments. From the results the effect of alternate electron acceptors on the rate of chlorophenol biotransformation are determined. Status: Several batch experiments have been conducted that indicate acclimated cultures carry out transformations by several routes compared to a single route by unacclimated cultures. Biotransformation rates have been measured individually for each chlorophenol congener, and in the future will be used to measure chlorophenol transformation rates under varying initial conditions. Clients/Users: Consultants and regulators concerned with site characterization for bioremediation or above-ground biological treatment of pentachlorophenol, and researchers interested in biotransformation reaction kinetics in a complex system. 255 ------- Enhancing Biodegradation with Sorption and Alternating Aerobic/Anaerobic Environments: Kenneth J. Williamson, Peter O. Nelson, Oregon State University Goal: The goal is to develop and verify a mass transport and biokinetics model of the sorption and biological degradation of pentachlorophenol and its degradative products by an anaerobic and aerobic biofilms on activated carbon. Rationale: Granular activated carbon (GAC) has been shown useful for enhancing biological treatment of toxic organic compounds by adsorption, resulting in reduced aqueous concentrations to below inhibitory levels. This enables biological degradation to occur of toxic compounds by the attached biofilms. Haloaromatic compounds undergo different biodegradation pathways under anaerobic and aerobic conditions. Anaerobic pathways typically result in metabolic products that cannot undergo further metabolism in that environment. By sorbing these compounds to GAC and then moving the GAC to an aerobic environment, complete and rapid degradation may be possible. Approach: Anaerobic and aerobic biofilms will be developed on GAC maintained in upflow expanded beds with recycle with acetate as the primary substrate. Pentachlorophenol will be fed as a secondary substrate to the anaerobic column, and should rapidly dechlorinate to a series of tri- and di-chlorophenols which are primarily sorbed to the GAC. The GAC will be moved from the anaerobic column to the aerobic column with a solid retention time of 30 days. The tri- and di-chlorophenols slowly desorb in the aerobic reactor and should undergo degradation by the aerobic biofilms. Status: Experiments have been conducted to determine substrate removal rates for pentachlorophenol and its metabolic products under aerobic and anaerobic conditions. Adsorption isotherms have been conducted on GAC. The column reactors have nearly achieved steady-state and data collection is underway. The project began in February 1989 and is expected to be completed in January 1992. Client/Users: Researchers and consulting engineers interested in developing treatment technologies for chlorinated aromatic and aliphatic compounds. 256 ------- Development and Verification of a Numerical Model to Predict the Fate and Transport of Chlorinated Phenols in Groundwater: Jonathan D. Istok and Sandra L. Woods, Oregon State University Goal: The objectives are to develop a numerical model to predict the fate and transport of pentachlorophenol and its primary anaerobic degradation products in field soils and ground water aquifers. And to verify the model using laboratory and field experiments. Rationale: Predictive models of pollutant transport are needed for site characterization and to design effective biological remediation strategies. Approach: A mathematical model was developed based on the processes of advection, dispersion, diffusion, sorption, and anaerobic degradation for pentachlorophenol and its metabolites, an electron donor (acetate), and biomass. Monod kinetics and a "macroscopic bulk concentration" concept are used to describe degradation and 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 (2 m wide x 4 m long x 20 cm deep) supported by a steel framework. Dispersion coefficients and sorption parameters were measured in miscible displacement experiments in packed soil columns (30.0 cm long by 5.38 cm in diameter). Comparisons between predicted and measured effluent concentrations will be made during miscible displacement experiments in inoculated soil columns. Status: Batch experiments to measure equilibrium sorption coefficients and degradation rates have been completed. Model verification in the soil tanks will be completed by February 1992. Clients/Users: Consultants and regulatory agencies concerned with site characterization for bioremediation and understanding of pentachlorophenol fate and transport. Anaerobic Microbial Transformation of Homocyclic and Heterocyclic Polynuclear Aromatic Hydrocarbons: Dunja Grbic- Galic, Stanford University Goal: While monoaromatic hydrocarbons such as benzene have been shown to undergo anaerobic microbial degradation, information on anaerobic biodegradability of polynuclear aromatic hydrocarbons (PAH) is scarce. The goal of this project is to seek anaerobic microbial activity 257 ------- towards PAH and complex nitrogen, sulfur, and oxygen heterocycles (NSO) under sulfate-reducing and methanogenic conditions. Once such activity is found the transformation routes will be evaluated. Rationale: Environmental contamination by PAH and NSO compounds, which are chemically stable and potential carcinogens, is widespread. Frequently, oxygen is not present so that anaerobic transformation is the only possibility for destruction of PAH and NSO. Thus, it is important to know whether such transformation can occur. And if so, what are the microorganisms involved, what is the degree of transformation (partial chemical change versus mineralization), what intermediates and products are formed, and what interactions occur in mixtures of PAH and NSO. Approach: Saturated batch microcosms with aquifer solids from several contaminated sites in the country and with prereduced defined mineral medium are being amended with single PAH (indene, naphthalene, acenaphthene) or NSO compounds (indole, quinoline, benzothiophene, benzofuran), or with mixtures of these chemicals. In some cases, benzoate or lactate are added to examine the possibility of cometabolic transformation. Additionally, sulfate is being added as an alternative electron acceptor. Once transformation is observed, enrichments will be developed for isolation of individual strains with the ability to transform aromatic hydrocarbons. In an alternate approach, mixed methanogenic cultures (originally obtained from sewage sludge), shown to degrade toluene, benzene, naphthalene, and acenaphthene, are being evaluated. Status: To date, only aquifer solids from the contaminated site in Pensacola, Florida, have exhibited activity towards PAH (indene, naphthalene) and NS compounds. Ongoing studies are evaluating the adaptation times required, pathways, and environmental factors affecting transformation rates. Attempts are being made to isolate pure cultures of bacteria from naphthalene- and acenaphthene-degrading methanogenic consortia. Client/Users: EPA regulators, industries, and consultants concerned with clean-up of sites contaminated by petroleum or creosote. In-Situ Biological Treatment of Aromatics in Groundwater: Martin Reinhard and Perry L. McCarty, Stanford University Goal: The objective of this study is to develop and characterize microbial consortia capable of transforming aromatic hydrocarbon compounds under 258 ------- anaerobic conditions with emphasis on methanogenic, sulfate- and nitrate- reducing conditions. And to understand the effect of environmental factors on the transformation processes. Rationale: Although most gasoline constituents are readily degraded in aerobic surface water systems, the groundwater environment associated with hydrocarbon spills is typically anaerobic, thus precluding aerobic degradation pathways. In the absence of oxygen, degradation of gasoline components can take place only with the utilization of alternate electron acceptors such as nitrate, sulfate, carbon dioxide, and possibly ferric iron or some other metal oxides. Neither the potential for transformation of these compounds under field conditions using alternate electron acceptors, nor the rate of such transformations has yet been assessed. Approach: Microbial consortia from aquifer solids and other sources are being enriched for anaerobic biotransformation of benzene and selected alkyl-substituted monoaromatic compounds. The different media for the enrichments are formulated to favor consortia that use selected electron acceptors (nitrate, sulfate, and carbon dioxide), and mixtures of aromatic compounds are being used to ascertain multicomponent effects on acclimation. Fundamental kinetic constants of the individual microbial consortia will be determined using substrate utilization and biological growth experiments. Results of laboratory studies will be compared with degradation rates determined in bioreactors placed into a gasoline contaminated aquifer at site in Southern California (Seal Beach.) The field research is being developed and carried out in cooperation with research staff of the Orange County Water District (Dr. Harry F. Ridgway and Don Phipps). Status: The hydrodynamic characteristics of the three in-situ bioreactors at Seal Beach have been determined and experiments are underway to assess biotransformation rates under prevailing anaerobic conditions. Beginning in 1991, different redox regimes will be induced at the field site, and contaminant removal will be assessed. Client/Users: Researchers interested in anaerobic biotransformation of hydrocarbons and aquifer bioremediation; state and EPA regulators and industry concerned with gasoline and hydrocarbon remediation. 259 ------- Biotransformation of Ordnance Wastes Using Unique Consortia of Anaerobic Bacteria: A. Morrie Craig and Sandra Woods, Oregon State University Goal: The objectives are to determine trinitrotoluene (TNT) degradation rates and transformation products with anaerobic metabolism by sheep ruminal microorganisms utilizing 14C radiolabel. Rationale: Pilot trials have shown that a new source of bacteria capable of degrading aromatic compounds have been found in sheep's rumen. The uniqueness of these microorganisms is the time rate in which total degradation of the toxic molecules occur. Few anaerobes from sediments can degrade TNT. However, preliminary evidence has shown that sheep microorganisms can degrade lOOmg/ml within 96 hours. Commercializations of these bacteria in bioremediation of munitions sites for the Navy and other branches of the armed forces would be highly desirable. Approach: A three-fold approach will be used: 1) the ruminal microorganisms will be enriched for TNT degradation, and a partially purified bacterial consortia will be defined; 2) degradation of radiolabelled TNT will be used to identify the metabolic transition and end products of TNT metabolism; and 3) optimum growth parameters and degradation rates utilizing this consortia will be determined. Status: The grant was initiated October 1, 1990. Sheep have been fistulated to obtain ruminal fluid. Anaerobic hoods have been calibrated and checked for optimum efficiency. Primary cultures are currently degrading TNT at a 96 hour rate. Different select media are being tried to enhance growth of detoxifying organisms and degradation rates. Client/Users: The U. S. Navy and other DOD units, their consultants, and regulatory agencies who are interested in the biotransformation of munitions; and researchers who are exploring new microbial consortia for aromatic compound degradation. The Effect of Surfactants on Biodegradation of Chlorinated Biphenyls in Soils: Martin Reinhard, Stanford University Goal: The goal of this project is to explore the effect of surfactants on the aerobic biodegradation of strongly sorbing compounds, such as polychlorinated biphenyls (PCBs), in the presence of soils. Solubilization 260 ------- using surfactants has been proposed as a means of facilitating biodegradation of these compounds which are recalcitrant due to strong sorption onto soils and sediments. Rationale: Sorption is thought to be one of the primary factors limiting the biotransformation of PCBs in soils and sediments. By increasing the bioavailability through the addition of solubilizing agents, biotransformation of PCBs could be enhanced and soil and sludge decontamination by microbial processes could be accelerated. Approach: This feasibility investigation includes the following: 1) a test of 4-chlorobiphenyl desorption using several commercial surfactants; 2) a test of surfactant toxicity to 4-chlorobiphenyl degrading organisms; 3) determination of the solubilizing effect of surfactants in soils; and 4) a test of the rate of 4-chlorobiphenyl degradation in the presence of solids and surfactant at various concentrations. Status: The experimental work using a 4-chlorobiphenyl desorbing surfactant is underway, with completion expected by December 31, 1990. Client/Users: Researchers interested in PCB degradation; regulators concerned with controlling levels of toxic/carcinogenic compounds in the environment, and industry with contaminated sites to remediate . HEAVY METALS Trace Metal Removal Processes: James O. Leckie, Stanford University Goal: The goal is development of an experimental data base and mathematical model for mass transfer limited adsorption of trace metals in porous particles. Experimental results and the mathematical model will facilitate the design of removal process utilizing porous metal oxide particles. Rationale: Previous experimental work with porous, high-surface-area oxide particles has demonstrated a dramatic increase in adsorption capacity of the porous material relative to non-porous particles. From an engineering perspective, porous particles with high internal surface area are appropriate for treating large volumes of dilute metal bearing wastewaters and allowing regeneration and recycling of the adsorbent. Reactions within porous particles can be severely limited by intraparticle 261 ------- diffusion. Investigation of diffusional limitations is an objective of this project. Choice of particles with a suitable pore size distribution will provide the high surface area desired without imposing severe pore diffusion limitations. Approach: The approach involves the design and implementation of a parametric study of adsorption of an oxyanion (selenite) and a cation (cadmium) on porous, amorphous alumina particles. Samples of three different porous aluminum oxide particles were obtained from ALCOA for the study. The first phase of the experimental work involved the physical- chemical characterization of the adsorbent (particle morphology, particle size distribution, pore size distribution, surface area, solid structure, surface site density, acidity constants, electrolyte binding constants, and trace element binding constants). The second and main phase of the experimental work explores the role of mass transfer on trace element adsorption/desorption in the porous alumina particles. The parametric study includes experiments at variable pH values, solid and trace element concentrations, solid/solution ratios, and ionic strengths. Based on particle characterization and data developed in the second experimental phase, a time-dependent mathematical model will be developed coupling diffusion processes with adsorption. The modeling task is difficult because of the inability to measure experimental parameters directly associated with trace metal adsorption inside the particles Status: The physical characterization of the adsorbent has been completed and chemical characterization is being carried out. Equilibrium experiments with selenite have confirmed the high adsorptive capacity of the porous alumina. Rate experiments indicate that the approach to equilibrium depends on the solid-to-liquid ratio, as expected for diffusion limited adsorption, and desorption rates were found comparable to adsorption rates. The next phases will involve modeling of equilibrium and rate experiments. Client/Users: Researchers interested in trace metal removal processes; electronics, electroplating, and power industries; areas with high trace metal concentration problems (e.g., Kesterson reservoir). 262 ------- Hexavalent Chromium Sorption and Desorption in Natural Soils and Subsoils: Peter O. Nelson and Jonathan D. Istok, Oregon State University Goal: The intent of this research is to gain a better understanding of the chemical behavior of hexavalent chromium, Cr(VI), in natural soils. Emphasis will be placed on determination of reaction kinetics and the effects of competing solute anions on Cr(VI) sorption and desorption. Results will be used to improve transport modeling of the fate of Cr(VI) and to better design remediation schemes for chromium-contaminated soils. Rationale: Remediation schemes for chromium contaminated sites give strong consideration to soil flushing, or pump-and-treat technology. Pump-and-treat has been selected for at least one Region 10 site (United Chrome Products), and is being considered for many others around the country. The efficacy of pump-and-treat is highly dependent on chromium sorption and desorption kinetics and on the influence of competing solute anions. Models to predict the transport of Cr(VI) in soils must therefore incorporate these effects. Approach: A controlled laboratory investigation is proposed in which Cr(VI) sorption and desorption reactions with natural soils and subsoils are studied. Batch reactor experiments will be used to determine equilibrium sorption parameters for chromate and sorbing co-solutes on soil and to study sorption and desorption kinetics over extended time periods (weeks to months) that are relevant to soil contamination sites. Soil column studies will be used to more closely simulate field conditions of porous media flow for investigation of diffusion-limited sorption and desorption kinetics. This latter is necessary for transport modeling and the preliminary design of in-situ chemical extraction- remediation processes. Status: This two-year project began on March 1, 1990. Design of laboratory experiments for batch and soil column reactors has been completed, and experimental work is in progress. Expected project completion date is February 28, 1992. Client/Users: Practitioners selecting remediation processes for sites with hexavalent chromium contamination will benefit from the methodology developed in this research. 263 ------- TRAINING AND TECHNOLOGY TRANSFER Hazardous Waste Training: Kenneth J. Williamson, Oregon State University and Gilbert Albelo, Mt. Hood Community College Goal: The goal is to develop a comprehensive and coordinated program of hazardous substance training in the State of Oregon involving the community colleges and Oregon State University. Rationale: A coordinated education program in Oregon was not available, but was found to be necessary to train and educate individuals for careers in the hazardous substance field. Approach: A consortium of higher education, regulatory, and industrial representatives was developed to plan a multiple-level curriculum for hazardous substance management. The University of California extension program was used as a model. The curriculum would be implemented by the Oregon community college and university system. Status: A curriculum has been developed and is being adopted at four community colleges and at Oregon State University. A proposal has been developed to the Oregon Legislature to adopt statutory requirements of certification for all employees with hazardous substance responsibilities. The levels in the certification are tied directly to various educational levels in the developed curriculum. The project began in January 1990 and is expected to be complete in June 1991. Advanced Topic Workshops: Lewis Semprini, Stanford University Goal: The goal is to give advanced topic workshops to transfer results of basic and applied research being performed at the Center to regulators, consultants, industry, and researchers, illustrating how the research findings pertain to problems encountered in practice. Rationale: There is an expressed need among the community working on hazardous substance problems for the most recent available research findings in the field together with a theoretical foundation on which the research findings are based. Approach: The Center is presenting these workshops primarily in California where the expressed need has been the greatest. They are being 264 ------- provided in conjunction with the University of California Extension Program in Environmental Hazard Management to complement the basic training program which they already provide. The one to two day workshops are presented by a group of Center researchers to provide a broad range of expertise on central contaminant problems of concern in EPA Regions 9 and 10. Status: Two workshops entitled "Biological Transformations of Chlorinated Solvents in Subsurface Systems - Natural Processes and In-situ Bioremediation" were given on June 22, 1990, at Stanford University, and on June 28, 1990, at the University of California Irvine. They were attended by over 200 professionals from industry, governmental agencies, and consulting firms. This workshop may be given again this coming year. A new workshop on "Biological Transformations of Chlorinated and Non- Chlorinated Aromatic Compounds is also being planned for the coming year. Continuing Education Program: Kenneth J. Williamson, Oregon State University Goal: The goal of this activity is to provide continuing education courses for professionals in the hazardous substance field. Rationale: There is a need by regulators, consultants, and industrial personnel who are working in the hazardous substance field to obtain greater knowledge about hazardous chemical management and treatment, and to keep abreast of current developments. Extension courses provide greater breadth and depth of knowledge in given areas than can be obtained from conferences, seminars, or workshops alone. A need for such courses existed in Oregon. Approach: A series of extension courses is being given by the Oregon State University Center faculty at the Tektronix Learning Center, Beaverton, Oregon, which is near the Portland area, where the need is large. Status: This past year three courses were given entitled: Hazardous Substance Management, Hazardous Substance Legislation, and Hazardous Substance Minimization. For this coming year, two courses are currently being planned: Groundwater Contaminant Transport, and Hazardous Substance Legislation. 265 ------- Conference Sponsorship: Kenneth J. Williamson, Oregon State University, and Lewis Semprini, Stanford University Goal: The goal is for the Center to actively participate in the cosponsorship of conferences held in EPA Regions 9 and 10 that address technical aspects of hazardous substance problems. Rationale: Conferences are a highly efficient and cost-effective way to achieve the transfer of technology from research, and thus the Center should be active in sponsoring them, and organizing and participating in sessions, seminars, and workshops associated with them. Status: This year the Center cosponsored, organized sessions, and participated in two conferences: the 1990 Idaho Regional Conference on Hazardous Materials and Wastes in Pocatello, Idaho, and the 1990 Responsible Hazardous Materials Management Conference in Portland. In addition to these conferences next year, the Center is also cosponsoring the International Symposium on In-Situ and On-Site Bioreclamation, San Diego, and the Association of Environmental Engineering Professors Educational Conference at Oregon State University. 266 ------- BIBLIOGRAPHY REFEREED JOURNAL ARTICLES Gorelick, S.M; "Large Scale Nonlinear Deterministic and Stochastic Optimization: Formulations Involving Simulation of Subsurface Contamination", Mathematical Programming, Vol. 48, pp. 19-39, 1990. Kitanidis, P. K., Effective Hydraulic Conductivity for Gradually Varying Flow, Water Resources Research, Vol, 26, No. 6, pp. 1197-1208, 1990. Chrysikopoulos, C. V., P. K. Kitanidis, and P. V. Roberts, "Analysis of One-Dimensional Solute Transport through Porous Media with Spatially Variable Retardation Factor", Water Resources Research, Vol. 26, No. 3, pp. 437-446, 1990. ARTICLES SUBMITTED OR IN PRESS Alvarez, L. M. and P. L. McCarty, "TCE Transformation by a Mixed Methanotrophic Culture: Effects of Toxicity, Aeration, and Reductant Supply," Applied and Environmental Microbiology, (accepted 1990). Alvarez-Cohen, L. and P. L. McCarty, "A Cometabolic Bi©transformation Model for Halogenated Aliphatic Compounds by Resting Microbial Cells," (submitted 1990). Alvarez-Cohen, L. and P. L. McCarty, "Two-Stage Dispersed-Growth- Treatment of Halogenated Aliphatic Compounds by Cometabolism," (submitted 1990). Chrysikopoulos, C. V., P. K. Kitanidis, and P. V. Roberts, "Macrodispersion of Sorbing Solutes in Heterogeneous Porous Formations in Spatially-Periodic Retardation and Velocity Field," (submitted 1990). Chrysikopoulos, C. V., P. K. Kitanidis, and P. V. Roberts, "Generalized Taylor-Aris Moment Analysis of the Transport of Sorbing Solutes through Porous Media with Spatially Periodic Retardation Factor," (submitted 1990). Dykaar, C. B., and P. K. Kitanidis, "Determination of Effective Hydraulic Conductivity in Heterogeneous Porous Media," (submitted 1990). 267 ------- Grbic-Galic, D., S.M. Henry, E. M. Godsy, E. Edwards, and K.P. Mayer, "Anaerobic Degradation of Aromatic Hydrocarbons and Aerobic Degradation of Trichloroethylene by Subsurface Microorganisms," (submitted 1990). Grbic-Galic, D., "Degradation of Aromatic Hydrocarbons and Phenols in Methanogenic Environments," (submitted 1990). Harmon, T.C., L. Semprini, and P.V. Roberts; "Simulating Groundwater Solute Transport Using Independently Determined Sorption Parameters," (submitted 1990). Henry, S.M., and D. Grbic-Galic, "Trichloroethylene (TCE) Oxidation by Methanotrophic Cultures from a Ground Water Aquifer: Endogenous and Exogenous Electron Donors and TCE Oxidation Toxicity, Appl. Environ. Microbiol., (accepted 1990). Istok, J. D., S.B. Lee, and S.L. Woods, "A Numerical Model for Interpreting Results of Column Transport Experiments with Nonlinear, Nonequilibrium Sorption," (submitted 1990). BOOKS AND BOUND PROCEEDINGS K.J. Dawson and J.D. Istok, Aquifer Testing: A Manual for the Design and Analysis of Pumping Tests, Lewis Publishers, Inc, Chelsea, Michigan (accepted, 1990). McCarty, P. L. and P. V. Roberts, editors, "Contaminants in the Subsurface Environment," Water Science and Technology, Vol. 22, No. 6, pp. 110, 1990. CHAPTERS IN OTHER BOOKS OR BOUND PROCEEDINGS Grbic-Galic, D., "Anaerobic Microbial Degradation of Aromatic Hydrocarbons," Proceedings, Conference on Microbially Enhanced Oil Recovery, Norman, Oklahoma, (submitted 1990). Gailey, R.M. and S.M. Gorelick, "Coupled Process Parameter Estimation: The Combined Worth of Concentration and Head Data", International Conference on Calibration and Reliability in Groundwater Modelling, The Hague, The Netherlands, (submitted 1990). 268 ------- PROJECT REPORTS McCarty, P. L., L. Semprini, M. E. Dolan, T. C. Harmon, S. Just, C. Tiedeman, S. M. Gorelick, and P. V. Roberts, "Evaluation of In-Situ Methanotrophic Bioremediation for Contaminated Groundwater, St. Joseph, Michigan," Technical Report No. WR-1, WRHSRC, Department of Civil Engineering, Stanford University, Stanford, CA (1990). THESES/DISSERTATIONS S.B. Lee, A Numerical Model for the Fate and Transport of Chlorinated Phenols in Groundwater, Ph.D. thesis, Department of Civil Engineering, Oregon State University, Corvallis, Oregon (1990). K.J. Dawson, Aquifer Testing: A Manual for the Design and Analysis of Pumping Tests, M.S. thesis, Department of Civil Engineering, Oregon State University, Corvallis, Oregon (1990). CONFERENCES AND WORKSHOPS HELD McCarty, P. L. P. V. Roberts, D. Grbic-Galic, and L. Semprini, "Biological Transformations of Chlorinated Solvents in Subsurface Systems - Natural Processes and In-situ Bioremediation," One day workshops held June 22, Stanford University, and June 28, 1990, University of California Irvine, California. Western Region Hazardous Substance Research Center, Idaho State University, and the Idaho Association of Commerce and Industry, "Regional Conference on Hazardous Materials and Wastes," Pocatello, Idaho, Western Region Hazardous Substance Research Center, Associated Oregon Industries, Department of Environmental Quality, Oregon Council, American Electronics Association, and Semiconductor Safety Association, "Responsible Hazardous Materials Management Conference," Portland, Oregon, October 9 and 10, 1990. 269, U S GOVERNMENT PRINTING OFFICE 1991-517-003 >t 7 0 1 5 ------- |