United States Environmental Protection Agency Research And Development 21R-1003 (RD-675) April 1991 £EPA Environmental Research Centers Program Annual Report FY 1990 Office Of Exploratory Research Printed on Recycled Paper ------- U. S. ENVIRONMENTAL PROTECTION AGENCY OFFICE OF EXPLORATORY RESEARCH ANNUAL REPORT of the ENVIRONMENTAL RESEARCH CENTERS PROGRAM FISCAL YEAR 1990 ------- TABLE OF CONTENTS History of the Program i Organization of Centers ii Table of Research Centers iii Summary of Outputs iii Contacts iv Chapter 1: Advanced Environmental Control Technology Research Center 1 Chapter 2: Center for Environmental Epidemiology 21 Chapter 3: Ecosystems Research Center 4 1 Chapter 4: Hazardous Waste Research Center 67 Chapter 5: Industrial Waste Elimination Research Center 83 Chapter 6: Marine Sciences Research Center 93 Chapter 7: National Center for Groundwater Research 103 Chapter 8: National Center for Intermedia Transport Research 11 9 ------- U.S. ENVIRONMENTAL PROTECTION AGENCY ANNUAL REPORT OF THE ENVIRONMENTAL RESEARCH CENTERS PROGRAM FOR FISCAL YEAR 1990 History of the Environmental Research Centers Program The primary responsibility of the U.S. Environmental Protection Agency (EPA) is to implement and enforce laws to mitigate or prevent environmental pollution. Central to the execution of this responsibility is the need for reliable scientific information to assist in decision making. EPA also recognizes its responsibility to provide support to the academic environmental research community, as it is this sector which conducts most of the Nation's fundamental research. It is only through the advancement of our understanding of the complex processes involved in environmental pollution and its remediation that significant progress can be made. To ensure the stable and continuing support of long-term, fundamental environmental research, EPA created the Office of Exploratory Research (OER) in 1979. The primary function of OER is to support environmental research grants and centers under which high quality, state-of-the-art scientific studies are performed which may ultimately prove beneficial in our attempts to understand, correct, and prevent environmental pollution. The Environmental Research Centers Program was created in 1979 to provide support to institutions which were willing to dedicate their efforts for several years to addressing especially serious or complex environmental problems of concern to the Agency. Eight university-based centers were established and each conducts research in an area named by EPA as a high priority. The locations of these center's research topics, principal research focuses, and contacts are described in subsequent sections of this report. ------- Organization of the Environmental Research Centers Program Support to each center is provided through a cooperative agreement with EPA. Each center's research program is managed by a center director, in concert with EPA's project officer. The center director is assisted by a Science Advisory Committee which advises the director on the technical progress of ongoing research, and reviews proposals for further research. The Science Advisory Committees (SACs) are composed of scientists and engineers from industry, government, and academic institutions. Each SAC includes at least two members from EPA laboratories. The director of the centers program in OER is responsible for policy matters affecting the centers program and for the review and renewal of individual centers. In 1986, following an intensive evaluation of the Environmental Research Centers Program, it was decided that all of the current eight centers would receive authorization and funding for one more five-year project period. At the end of that time, EPA would determine which of the original eight topics, if any, it would like to continue funding through the centers program or if any new priorities had asserted themselves. The original eight centers would be ineligible to receive additional support under the ERC program unless they successfully won a competition for new centers. In 1990, the Agency issued a solicitation for proposals to establish four new exploratory environmental research centers. The solicitation did not specify research topics. Rather, proposers were asked to design a center around a research theme of their own choosing and to justify in their proposal why the theme they chose is valuable to EPA and to the environmental community in general. Because of this wording, all eight centers were eligible to compete for funds. The seven current centers which elected to participate are competing with 80 other institutions. Peer reviews of all proposals are scheduled to take place in the Summer of 1991 and EPA expects to select winners before the end of the fiscal year. The project period for each of the current centers was extended for one additional year, to provide for an orderly phase-out of operations. The project ending date for each center is shown in Table 1. 11 ------- Table 1: Research Centers University Rice University University of Oklahoma Oklahoma State University University of Illinois, Urbana University of Pittsburgh University of Rhode Island University of California- Los Angeles Illinois Institute of Technology Cornell University Louisiana State University Year Date Center Theme Started Completed Ground Water Research 1979 8/91 Advanced Environmental 1979 11/91 Control Technology Research Environmental Epidemiology 1979 10/91 Marine Science Research 1980 7/91 Intermedia Transport Research 1980 8/92 Industrial Waste Elimination 1980 11/91 Ecosystems Research 1980 12/91 Hazardous Waste Research 1980 1/93 Summary of Center Outputs in FY 1990 The centers are responsible for publishing the results of their work. Though publication in peer-reviewed journals is the preferred approach, other types of publication and presentation are also used to speed information transfer. In Fiscal Year 1990 (FY 1990), which covers the period October 1, 1989 through September 30, 1990, the centers collectively produced a total of 84 refereed journal articles, 24 books or bound proceedings, 55 book chapters, and 63 project reports. In addition, they have sponsored or co-sponsored a total of 25 conferences or seminars. A bibliography containing references for all outputs are listed for each center at the end of its reports. 111 ------- Contacts In the chapters that follow, the activities and plans of each center are described. Additional information about the program generally may be obtained by writing or calling: Karen Morehouse Director Centers and Special Programs Staff (RD-675) U.S. Environmental Protection Agency 401 M Street, Southwest Washington, DC 20460 202/382-5750 Information about specific centers or their programs is available from the individual center directors or project officers. Their addresses and telephone numbers appear at the beginning of each center's chapter. IV ------- CENTER: LOCATION: DIRECTOR: PROJECT OFFICER: Advanced Environmental Control Technology Research Center University of Illinois at Urbana-Champaign Richard S. Engelbrecht Department of Civil Engineering University of Illinois at Urbana-Champaign 205 North Mathews Avenue Urbana, IL 61801 217/333-3822 Fax: 217/333-9464 David G. Stephan Risk Reduction Engineering Laboratory U. S. Environmental Protection Agency 26 West Martin Luther King Drive Cincinnati, OH 45268 513/569-7896 FTS: 684-7896 FUNDS SPENT DURING FY 1990 (10/1/89 - 9/30/90) EPA $573,000 Other Government 6,200 University 52,000 Private Sector 0 Total $631,200 DESCRIPTION OF THE PROGRAM The research effort of the Advanced Environmental Control Technology Research Center (AECTRC) may be described as problem oriented fundamental research or as exploratory research which provides a coupling between fundamental and applied research as it impacts technologies associated with either air or water quality control. Specifically, the research focuses on separation technology, plus contaminant detoxification and destruction. The technologies used in separating contaminants from waste streams, as well as for detoxification and destruction, may be either biological, chemical, or physical in nature. The ultimate objective of the research program is the development of cost- ------- effective technology which can remove specific toxic and hazardous materials found in low concentrations in waste streams. ACCOMPLISHMENTS - FY 1990 Supercritical Fluid Extraction Supercritical fluids (SCFs) are gases compressed to liquid-like densities. In this state, they possess unique solvent characteristics. SCFs have been shown to have extremely valuable properties for separations and reactions in a wide variety of industrial applications. The use of SCFs in environmental control has been the focus of this study, for example, the extraction of low concentrations of highly toxic substances from adsorbents. Water supplies, wastewaters, and leachates, which may contain organic contaminants up to a few hundred milligrams per liter, are frequently treated by adsorbing the contaminants on granular activated carbon (GAC). When the adsorption capacity of the GAC becomes exhausted, the GAC must be replaced or regenerated. SCFs are being investigated for the regeneration of GAC coupled with the separation and concentration of the adsorbed contaminants, making them available for separate detoxification or, in some cases, as valuable products for recycling. Because the economic feasibility of the process appears favorable, a pilot plant was designed and built to study GAC regeneration and to yield the scale-up data needed for the design of mobile GAC treatment facilities. The pilot plant studies have been performed concurrently with computer-aided design studies to determine crucial data needed for reliable designs. Work has been completed on the extraction of model compounds from GAC in the presence and absence of water using pure and cosolvent-modified SCFs. In addition, separation experiments on SCF- contaminant mixtures indicate that the contaminant distributes favorably into the liquid phase for separation. The effect of cosolvent, water, and operating conditions on both extraction efficiency and phase behavior have been used to evaluate and modify the various models needed for design purposes. By using the experimental data to test the thermodynamic models, the ability of the design package to extrapolate to other conditions has been greatly improved. The interaction between the design effort and the pilot plant ------- studies will generate the data and confidence necessary to design a scale mobile unit for SCF regeneration of GAC. full Thermal Regeneration of Activated Carbon: The thermal regeneration of activated carbon has continued to be studied using granular activated carbon (GAC) loaded with methylene blue. The effect of the ratio of the two oxidation gases, steam and carbon dioxide, on the recovery of adsorption capacity has been evaluated. It was found that regeneration with steam and carbon dioxide produced a GAC with an adsorption capacity for p-nitrophenol significantly greater than with steam alone or than that of the virgin material. The possible reasons could be either that more surface area accessible to p-nitrophenol is produced when using carbon dioxide, or that a different surface chemistry which is more amenable to the adsorption of p-nitrophenol is obtained. To determine which of the reasons is valid, nitrogen isotherms were performed on the samples. From the isotherms, BET and Dubinin micropore surface (Smj) areas were calculated. It was found that the iodine number and the methylene blue value correlated well with BET surface area, but that p- nitrophenol capacity correlated with Smj. This led to the conclusion that the mechanism of adsorption for p-nitrophenol is different than that for iodine and methylene blue. In a study of the effect of time of pyrolysis on regeneration, the mass loss due to pyrolysis and regeneration was found to be independent of pyrolysis time. The volume loss after regeneration decreased with increasing pyrolysis time. The reason for the decreasing volume loss could either be that the particles which were pyrolyzed for the longer times swelled during reactivation, or that surface functional groups were formed which did not allow the particles to pack as closely. After further investigation using mercury penetrometry, it was concluded that under certain conditions, surface functional groups can cause apparent GAC volume increases, but that this effect is small and of little practical value. Anaerobic GAC Biological Treatment: The expanded-bed granular activated carbon (GAC) anaerobic bioreactor is a process that combines the biological function of anaerobic treatment with physical adsorption. This process has been shown to be ideally suited for the treatment of wastewaters containing mixtures of biodegradable and refractory organic compounds. This study was designed to assess the effectiveness of the process in treating synthetic wastewaters containing mixtures of RCRA compounds in various background materials. Two reactors were operated on wastewaters designed to simulate the high ------- strength, in-plant process streams prior to dilution with domestic wastewater and rinse/cooling waters. One wastewater contained background materials and six volatile RCRA compounds, while the other contained the same background materials and six semi-volatile RCRA compounds. A third reactor was operated on a 1% mixture of the first two wastewaters prepared in a primary effluent obtained from a domestic wastewater treatment plant. The third wastewater was designed to simulate a more complex and dilute wastewater that may be generated from an industrial complex. All three reactor systems affected excellent removal of all the RCRA constituents. Chloroform, which was added in the feed and was produced within the reactor through the reduction of carbon tetrachloride, was removed to a level of 97%; however, the 3% that persisted in the effluent caused a reduction in the ability of the methanogenic microorganisms to utilize acetic acid and acetone. These compounds persisted in the treated effluent at approximately 60% of their feed concentrations. This study is completed, and shows that the expanded-bed GAC anaerobic bioreactor is an effective technology for removing RCRA compounds from both high-strength and dilute industrial wastewaters. Microbial Selection in Anaerobic GAC Expanded-Bed Biofilms: The objective of this research is to examine factors that influence microbial competition for space and the distribution of the competing species in anaerobic biofilms. Results from this research should explain why certain organic compounds can be removed effectively in attached biofilm treatment systems while other biodegradable compounds may escape treatment. If the microorganisms responsible for the treatment of one compound concentrate on the external surface of a biofilm, they become susceptible to loss by mechanical shear. Such organisms may locate near the outer surface of the biofilm due to either a limited availability of food or to displacement from the more sheltered inner layers of a biofilm by faster growing microorganisms. The study had both an experimental and a theoretical component. The experimental component involved measurements of specific microbial densities in the attached biofilm and in the sheared biomass. This study represented the first time that different shear rates were determined for different groups of microorganisms sharing a common attachment surface. A biofilm model which includes a mathematical description of microbial cultures competing for growth space was developed and calibrated against the experimental data. This model confirmed that differential shear loss of ------- attached microorganisms can occur, and that excessive organic loading rates may indeed lead to the total loss from the bioreactor of certain microbial species responsible for the biodegradation of some contaminants of concern. The results obtained from this study revealed some of the special features of biofilm systems when compared to dispersed growth reactors. Furthermore, this research confirmed the urgent need for a more accurate descriptor of mechanical microbial shear than is available in current models. Most shear models in current use have resulted from attempts to fit first order rate laws to experimental data covering narrow ranges of experimental conditions. Genetic Transfer in Biological Treatment Processes: The transfer of genetic information among different bacteria could alter the capabilities of biological wastewater treatment processes to degrade a range of man-made compounds. Transfer is possible because genes for many degradation reactions and other cell functions (such as resistance to antibiotics) are contained on plasmids, which are small circular strands of DNA that are not essential for routine cell metabolism. The plasmids can be transferred among bacterial cells without affecting the primary genetic make-up contained on the chromosome. A Pseudomonas strain was isolated from a laboratory biofilm reactor and used as a recipient of the RP4 plasmid, which codes for antibiotic resistances and was donated by Rhodabacter capsulatus. Batch kinetic experiments were performed to determine the two plasmid-transfer kinetic coefficients and the plasmid-loss coefficient. Depending on reaction conditions, the plasmid-transfer rates were large enough to allow significant plasmid maintenance in a biological process. The key finding was that the rates of plasmid transfer depend strongly on the energy availability for the donor cell. When energy is made available from consumption of dissolved substrate or storage products, the transfer rates increase dramatically, becoming significant in terms of biological processes. The plasmid loss rate was small, but its low value precluded determination of an exact value. A second set of experiments was initiated with two Pseudomonas strains and the TOL plasmid, which contains genes for the biodegradation of toluene, xylene, and related aromatic compounds. Oligonucleotide probes for the cells' 16S rRNA and the DNA of the TOL plasmid were developed from the sequences of these molecules. Methods to detect each type of probe after it has hybridized to intact cells were developed and tested. ------- A two-part review paper was published as a feature in Environmental Science and Technology [24:23-29 (1990); 24:162-169 (1990); AECTRC Publ. No. 90-2 (1990)]. The paper introduced to the environmental field the concepts of genetic capability in biological processes and how plasmid transfer can affect the capability. The paper provides the first critical review of plasmid-transfer kinetics and a model of plasmid transfer and plasmid content within a biological process. The conclusion of the paper is that plasmid transfer can be a significant mechanism for controlling the capabilities of a biological process, but that much more information is needed concerning the parameters describing transfer kinetics. Ultrafiltration for Removal of Turbidity and Disinfection Byproducts from Water: As drinking water standards in the United States become increasingly stringent, the producers of public water supplies are being forced to consider new technologies for water treatment. Membrane processes are among these new technologies. Because of the extremely small size of the membrane pores, membranes can potentially remove a large number of dissolved and paniculate contaminants from natural water sources. The specific interest of this study has been on the ability of relatively high flux ultrafiltration (UF) membranes to remove pathogenic organisms, turbidity-causing paniculate matter, and compounds resulting from the chlorination of water (disinfection byproducts—DBFs). In this study, a continuous-flow UF pilot plant is being used to treat water from Lake Decatur, Illinois. The pilot plant is located in the laboratory of the South Water Treatment Plant in Decatur. It is equipped for continuous recording of transmembrane pressure, water turbidity, and temperature. The pilot plant uses 100,000 molecular-weight-cutoff, hollow-fiber, membrane cartridges, with internal fiber diameters of approximately a millimeter, and pore diameters of about 100 Angstroms. Quality of treatment is judged by the removal of turbidity, microorganisms, non-purgeable dissolved organic carbon (NPOC), compounds absorbing ultraviolet radiation (UV absorption), and DBFs including the trihalomethanes (THMs). The trihalomethanes consist of a group of four DBFs which may cause cancer in humans; hence, the removal of the THM formation potential is important and is becoming increasingly scrutinized. Other DBFs such as haloaecetic acids, chloral hydrate, and total organic halides also are being measured in samples by EPA in Cincinnati, Ohio. Treatment efficiency of the pilot plant system is evaluated by its ability to prevent irreversible membrane fouling by natural organic matter ------- in the lake water, and on the frequency of UF backflushing required to efficiently remove solid material deposited on the membrane surface. As previously observed with a laboratory-scale batch UF system, it has been found that UF is extremely effective (and dependable) in removing turbidity, consistently resulting in turbidity values less than 0.1 nephelometric turbidity units (NTU). Total heterotrophic plate counts were reduced from about 10,000/mL in the influent to the pilot plant to 10/mL in the UF permeate. Likewise, total coliform bacteria were reduced from about 100/100 mL in the influent to 0/100 mL in the UF permeate. Although UF alone is no more effective than conventional treatment processes for removing NPOC and THM formation potential, it has been found that with powdered activated carbon pretreatment, continuous UF is more effective than conventional processes in removing NPOC and THM formation potential. Further, it has been confirmed that hydrophilic membranes are much less likely than hydrophobic membranes to experience irreversible membrane fouling due to the adsorption of organic materials in the membrane pores. With periods of filtration spanning several days, there is almost negligible loss of membrane permeability. Considerable progress also has been made to improve the pilot plant so as to achieve automatic backflushing at regular periods ranging from 10 to 60 minutes. Sorav Drying for Control of Atmospheric Emissions: Detrimental effects that result from the emission of sulfur dioxide (SO2), nitrogen oxide (NO), and hydrogen chloride (HC1) into the earth's atmosphere have become more evident in recent years. Consequently there is a need for cost-effective SO2, NO, and HC1 emission control technology. Research on the simultaneous separation and removal of these pollutants from waste gas streams with spray drying is being performed. The study focuses on the use of additives that are hygroscopic and can enhance the ability of spray dryers to remove SO2, NO, and HC1 from gas streams. Two laboratory-scale spray dryers have been employed to collect experimental data. In addition, a numerical model has been developed to describe the removal of contaminant gases from gas streams with a spray dryer. Both the experimental and numerically modeled results describe the dependence of SO2, NO, and/or HC1 removal on critical parameters such as the composition of the gas stream and additives, approach to adiabatic saturation temperature of the gas stream at the outlet of the spray dryer, relative amounts of sorbent to contaminant gas used to remove the contaminants of the gas stream, and physical characteristics of the ------- sorbents such as its specific surface area. Overall, there has been close agreement between the experimental and theoretical results. Combined Plasma Photolysis: Detrimental effects that result from the emissions of SC>2 and NO into the atmosphere have become more evident in recent years. Consequently, there is a need to develop more effective methods for the simultaneous removal of SO2 and NO from gas streams. Combined Plasma Photolysis (CPP) is a new method proposed for removal of these gases from gas streams produced by the combustion of coal. CPP consists of select components of existing technology that are currently used for other applications such as carbon dioxide lasers and fluorescent lamps. Simultaneous removal of SO2 and NO from gas streams is hypothesized to occur by the chemical reactions of SO2 and NO with hydroxyl radicals (OH) that are formed in the CPP reactor. This gas phase method of removing gaseous contaminants from gas streams has the potential to replace existing air pollution control technology that is more expensive and less energy efficient. Research over the past year has generated both experimental and numerically modeled results. A laboratory-scale reactor that is interfaced with a flue gas generator and detection system was used to experimentally evaluate the effectiveness of CPP. Experimental results include the removal efficiency dependence of SO2 and NO on concentrations of inlet SO2, H2O, O2, the residence time of the gas in the reactor, and electrical potential difference across the reactor's electrodes. Individual removal efficiencies for SO2 and NO were as high as 80% and 50%, respectively. Results from the numerical modeling portion of the research include SO2 and NO removal efficiency dependence on relevant parameters, such as composition of the gas stream, amount of energy deposited into the gas per unit mass of the gas, temperature of the gas, rate of OH- production, and the use of ultraviolet photolysis to enhance the production of OH- radicals. Numerical results have been in close agreement with experimental results for the SO2 removal efficiency dependence on concentration of O2- Numerical results also have been encouraging for the combined use of the plasma with ultraviolet light. Gas-Particle Interactions: Experimental studies of the interaction between a single particle and its gaseous surroundings are important in investigations such as the acidification of rain droplets, the reduction of atmospheric visibility, and the operation of air pollution control equipment. Studies of single particles have been traditionally performed with the particle held on a supporting surface. Since the physical support can interfere with the measurement, instrumentation has 8 ------- been developed to study single particles suspended without the use of physical supports. One of these devices, the electrodynamic particle balance, uses an electric field to counteract the force of gravity and thus suspends a single particle in a controlled gaseous environment. The voltage needed to suspend the particle is a sensitive measure of the mass of the particle. By recording changes in balancing voltages, changes in particle mass, as the suspended particle grows or shrinks, can be recorded. In FY 1990, an electrodynamic particle balance was constructed using funds provided by the National Science Foundation and the University of Illinois, whereby dry particles can be successfully suspended. A gas generation system was developed to create a gas stream of relative humidities between approximately 5% to 95%. This gas stream is passed through the balance to study the growth or shrinkage of a single particle as changes in relative humidity occur. This study has applications to spray dryers which are air pollution control devices used to remove gaseous contaminants such as SC>2 from gas streams. Since spray dryer efficiency can be improved by increasing the drying time of the liquid droplets used in the device, the growth information gained from the particle balance experiments can be used to understand how droplet drying time can be lengthened and thus, improve the spray dryer efficiency. Activated Carbon Fibers for Removal of Organic Contaminants from Indoor Air: There is interest in removing volatile organic compounds from indoor air because of the health risks posed by prolonged exposure to these gaseous compounds. In this study, the adsorption capacity of activated carbon fibers are being measured to determine how effectively these fibers remove organic gases from an environment that experimentally simulates indoor air. The activated carbon fibers used in this study are in the form of a flexible, woven fabric that has been carbonized and activated. The resulting material has high adsorption capacities and can be regenerated in situ using electrical resistance heating. The adsorption capacities of these fibers, however, have not been quantified for the low concentrations of volatile organic compounds that exist in indoor air. The adsorption capacities of activated carbon fibers are being determined for two organic gases that typically exist in indoor environments: benzene and 1,1,1 trichloroethane. Three main goals were achieved: (1) a gravimetric balance for measurement of adsorption isotherms was obtained and characterized, (2) a permeation tube system has been constructed to produce gas streams with known concentrations of contaminant gas, and (3) a method to calibrate the mass emission rates of ------- the permeation tubes was developed and used to calibrate the permeation tube system. The contaminant gas emitted from the permeation tube is mixed with varying proportions of clean air to produce gas streams of known contaminant concentration. The synthesized contaminated gas stream is then passed through a gravimetric balance and around a sample of the activated carbon fibers. As the fibers adsorb the contaminant, the mass of the fibers increases. The balance system measures this mass change. From the contaminant concentration and fiber weight gain data, the adsorption isotherms can be plotted. The isotherms can then be used with numerical models to predict the efficiency of an air cleaning system containing the activated carbon fibers. General: The Center has continued to be an active partner of the Trilateral Research Agreement between the Japan Sewage Works Agency, the USEPA, and the University of Illinois at Urbana-Champaign, through the exchange of personnel and the sharing of research results. Also, under the Center's Distinguished International Lecturer Program, six engineers or scientists visited the campus during the year to give seminars and to participate in symposia. Although administered through the Center, these two activities do not receive any funding from EPA. RESEARCH GOALS - FY 1991 The design and economic analysis of a process for the regeneration of GAC by supercritical fluid (SCF) extraction will complete this study. Significant experimental accomplishments with the SCF pilot plant have made it possible to develop a model for the SCF regeneration of GAC and the incorporation of this model into a full scale design will be the final product. The design will likely include two basic scales of processing along with economic forecasts based on cost per pound of GAC regenerated. With the incorporation of experimental results, the contingency factors that are an inevitable part of any design will be substantially reduced, giving a much more reliable design and making the SCF process a more viable alternative for hazardous waste processing. Finally, these designs will include consideration of a mobile regeneration unit which can be transported to waste sites on a semi-truck trailer and a large, stationary facility built on-site for more extensive clean-up requirements. To study the effects of oxidizing gases and type of activated carbon* on the thermal regeneration of granular activated carbon (GAC), two types of activated carbon will be loaded with adsorbate and regenerated with several steam and carbon dioxide flow rates at 850_C. This series of 10 ------- experiments will permit the actions of the three factors (type of carbon, steam flow rate, and carbon dioxide flow rate) to be evaluated as well as the interactions between them. In order to study the effects of multiple loading/regeneration cycles on GAC quality, GAC samples will be loaded with methylene blue. All samples will be regenerated at the same temperature, with two each at a steam flow rate to yield proper regeneration, underregeneration, and overregenerated as measured by apparent density. After regeneration, a portion of each sample will be used for analysis and the remainder will be reloaded and regenerated using the same set of conditions. This procedure will be repeated three or four times. The purpose of this final phase of study is to determine if GAC can be restored to near-virgin adsorption capacity in a multiple use system, if volume losses will accelerate as the result of reuse, and what the effect of improper regeneration will be on GAC quality. The transfer of genetic information in biological wastewater treatment processes will be further evaluated by studying the transfer kinetics associated with the TOL plasmid. Special emphasis will be given to the energy availability of the donor and recipient cells. Based upon the experimental results, the current model of plasmid transfer and content will be improved. Finally, the model will be utilized to evaluate the significance of plasmid transfer in actual biological processes and how the processes can be manipulated to enhance the bacteria's degradative capabilities. In studying the treatment of water supplies by ultrafiltration (UF), the existing pilot plant will be further developed for automatic operation and data logging. This will make it possible to operate the pilot plant for longer periods of time. In future studies, the frequency and duration of the backflushing step will be investigated; this is an important consideration in optimizing the overall production of drinking water. At the same time, the effect of various powdered activated carbon (PAC) and coagulant doses on water quality will be evaluated. Finally, upon receipt of the DBF analysis results from EPA, it will be possible to correlate the removal of easily measured NPOC with the removal of the DBPs. Continuation of the research on spray dryers for the control of atmospheric emissions will involve experimental tests to further evaluate the use of high surface area sorbents to remove contaminant gases from gas streams. Experimental research exploring the influence of HC1 on a spray dryer's ability to remove SO2 from gas streams will also be performed. A proposal will be prepared and submitted to the U.S. Department of Energy to continue this research. It is expected that the 1 1 ------- results from the research will be useful in increasing the capability of conventional air pollution control technology to remove SO2, NO, and HC1 from gas streams in a more cost-effective manner. Experimental and theoretical results will be applicable to sources of air pollution such as municipal solid waste incinerators and coal fired power plants. The technology associated with Combined Plasma Photolysis (CPP) will be evaluated experimentally and numerically to determine its ability to simultaneously remove SC>2 and NO from simulated flue gases at a temperature of 160°C. The gases will simulate the composition and temperature of gases produced by the combustion of coal with high and low sulfur content. Experimental and numerical tests will include simultaneous SO2 and NO removal efficiency dependence on gas temperature, concentration of gaseous contaminants, H2O vapor concentration, and electrical energy consumption. Numerical results can then be used to scale up the results to full-scale processes. Proposals also will be prepared and submitted to the US Environmental Protection Agency and US Department of Energy to request support for the continuation of this research. Using the electrodynamic particle balance which is now available to study gas-particle interactions, two phenomena will be investigated during the final months of the study: the growth of dry particles in response to increases in relative humidity and the shrinkage of droplets due to relative humidity decreases. The dry particles to be studied will be the solid sorbents typically used in spray dryers. Proposals to the National Science Foundation and the U.S. Department of Energy are in preparation to continue the research using the particle balance. In continuing the research on the removal of organic contaminants from indoor air by activated carbon fibers, the adsorption isotherms for benzene and 1,1,1 trichloroethane will be constructed. Using the isotherm data, it will be possible to predict the efficiency of an air cleaning system which utilizes the adsorptive capacity of activated carbon fibers. Since activated carbon fibers show promise as an air pollution control technology that can be employed in many situations, research on the fibers should continue. General: Although the current research activities of the Center are scheduled to be phased out over the next six months, it will continue its involvement in the Trilateral Research Agreement between the Japan Sewage Works Agency, the U. S. Environmental Protection Agency, and the 12 ------- University of Illinois at Urbana-Champaign, and organize seminars and symposia under the Distinguished International Lecturer Program. OUTPUTS - FY 1990 Articles in Refereed Journals 8 Articles Submitted or In Press 17 Books and Bound Proceedings 1 Chapters in Other Books 7 Project Reports 8 Conferences and Workshops Held 4 ------- BIBLIOGRAPHY REFEREED JOURNAL ARTICLES Brennecke, J.F., D.L. Tomasko, and C.A. Eckert, "Naphthalene/ Triethylamine Exciplex and Pyrene Excimer Formation in Supercritical Fluid Solutions," Journal of Physical Chemistry. Vol. 94, No. 19, pp. 7692- 7700, 1990; AECTRC Publ. No. 90-9, 1990. Brennecke, J.F., D.L. Tomasko, J. Peshkin, and C.A. Eckert, "Fluorescence Spectroscopy Studies of Dilute Supercritical Solutions," Industrial and Engineering Chemistry Research. Vol. 29, No. 8, pp. 1682- 1690, 1990; AECTRC Publ. No. 90-7, 1990. Fox, P. and M.T. Suidan, "Batch Tests to Determine Activity Distribution and Kinetic Parameters for Acetate Utilization in Expanded- Bed Anaerobic Reactors," Applied and Environmental Microbiology. Vol. 56, No. 4, pp. 887-894, 1990; AECTRC Publ. No. 90-4, 1990. Fox, P., M.T. Suidan, J.T. Pfeffer, and J.T. Bandy, "Hybrid Expanded- Bed GAC Reactor for Treating Inhibitory Wastewaters," Journal of the Environmental Engineering Division (ASCE), Vol. 116, No. 3, pp. 438-453, 1990; AECTRC Publ. No. 90-5, 1990. Laine, J-M., M.M. Clark, and J. Mallevialle, "Filtration of Lake Water: Effect of Pretreatment on Organic Partitioning, THMFP, and Flux," Journal of the American Water Works Association. Vol. 82. No. 12, 1990. Rittmann, B.E., B. Smets, and D.A. Stahl, "The Role of Genes in Biological Processes," Environmental Science & Technology. Vol. 24, pp. 23- 29, 1990; AECTRC Publ. No. 90-2, 1990. Smets, B.F. and B.E. Rittmann, "Sorption Equilibria for Trichloroethene on Algae," Water Research. Vol. 24, No. 3, pp. 355-360, 1990; AECTRC Publ. No. 90-3, 1990. Smets, B., B.E. Rittmann, and D.A. Stahl, "The Role of Genes in Biological Processes," Environmental Science & Technology. Vol. 24, pp. 162-169, 1990; AECTRC Publ. No. 90-2, 1990. 14 ------- ARTICLES SUBMITTED OR IN PRESS Alferi, S.R., D.J. Kaiser, and C.A. Eckert, "Vapor Pressure of Five Heterocyclic Solids," Journal of Chemical and Engineering Data, submitted, 1989. Chang, M.B., M.J. Rood, J.H. Balbach, and MJ. Kushner, "Removal of SO2 Using Dielectric Barrier Discharge in Moist Air and by Combined Plasma Photolysis," Journal of Applied Physics, submitted, 1990. Clark, M.M. and K.S. Heneghan, "Ultrafiltration of Lake Water for Potable Water Production," Desalination, in press, 1990. Eckert, C.A., WJ. Howell, A.M. Karachewski, K.M. Stephenson, J.H. Paik, P.W. Carr, and S.C. Rutan, "An Improved MOSCED Equation for the Prediction and Application of Infinite Dilution Activity Coefficients," Fluid Phase Equilibria, submitted, 1989. Fox, P. and M.T. Suidan, "Determination of Ks for Acetate Utilization in Anaerobic Expanded-Bed with Steady-State Data in Conjunction with Batch Test Results," Applied and Environmental Microbiology, submitted, 1989. Fox, P., M.T. Suidan, and J.T. Bandy, "A Comparison of Media Types in Acetate Fed Expanded-Bed Anaerobic Reactors," Water Research. submitted, 1989. Hansen, A.R. and C.A. Eckert, "A Relationship Between Excess Volumes and Enthalpies," Fluid Phase Equilibria, submitted, 1989. Hansson, H.C., A. Wiedensohler, M.J. Rood, and D.S. Covert, "Experimental Determination of the Hygroscopic Properties of Organically Coated NaCl Aerosol Particles," Journal of Aerosol Science, submitted, 1990. Leman, G.W., H.H. Yang, and C.A. Eckert, "Homogeneous Catalysis for Wet Oxidation: Design and Economic Feasibility of a Mobile Detoxification Unit," Hazardous Materials Control, submitted, 1989. Mayer, M.M., W.J. Howell, D.L. Tomasko, and C.A. Eckert, "Solid-Liquid Equilibria in the Systems Thianthrene + Phenanthrene, Salicylic Acid + Phenanthrene, and 3-Hydroxybenzoic Acid + Phenanthrene," Journal of Chemical and Engineering Data, in press, 1990. 15 ------- Rittmann, B.E., "Reactor Considerations in the Use of Bioaugmentation in Biological Treatment," Bioaugmentation As a Means to Enhance. Waste Treatment. H. Kobayashi (ed.), Lewis Publishers, Ann Arbor, MI, in press, 1989. Rood, M.J. and C.-S. Yuan, "Numerical Modeling and the Experimental Verification of the Simultaneous Collection of SC>2 and NO via Spray Drying," Aerosol Science and Technology, submitted, 1990. Simek, R.E. and MJ. Rood, "Computer Model to Estimate Emissions of Air Contaminants and Power Generation," Journal of the Air and Waste Management Association, submitted, 1990. Sloane, C.S., M.J. Rood, and C.F. Rogers, "Measurement of Aerosol Particle Size: I. Improved Precision by Simultaneous use of Optical Particle Counter and Nephelometer," Aerosol Science and Technology, in press, 1990. Trampe, D.M. and C.A. Eckert, "Calorimetric Measurement of Partial Molar Excess Enthalpies at Infinite Dilution," Journal of Chemical and Engineering Data, submitted, 1989. Trampe, D.M. and C.A. Eckert, "Limiting Activity Coefficients from an Improved Differential Boiler Point Technique," Journal of Chemical and Engineering Data, submitted, 1989. VanAlsten, J.G. and C.A. Eckert, "The Effect of Entrainers and of Solute Size and Polarity in Supercritical Fluid Solutions," Journal of Chemical and Engineering Data, submitted, 1989. BOOKS AND BOUND PROCEEDINGS Sloane, C.S., M.J. Rood, and C.F. Rogers, "Reconciliation of Aerosol Particle Size Measurements," Visibility and Fine Particles. C.V. Mathai (ed.), Transactions of the Air and Waste Management Association, Pittsburgh, PA; pp. 170-176, 1990; AECTRC Publ. No. 90-8, 1990. CHAPTER IN OTHER BOOKS Andrews, E. and S.M. Larson, "Studies of Gas-Particle Interaction Using Electrodynamic Balance," Proceedings. 8th Annual Meeting of th* 16 ------- Midwest Association of Cloud and Aerosol Physics. Urbana, IL, May 17-18, 1990. -Balbach, J., M.J. Rood, and MJ. Kushner, "SO2 Removal Using Combined Plasma Photolysis," Proceedings. Topical Conference of A.P.S.. Gaseous Electronics. Palo Alto, CA, October 1989. Clark, M.M. and K.S. Heneghan, "Ultrafiltration of Lake Water for Potable Water Production," Proceedings. 1990 International Congress on Membranes and Membrane Processes. Chicago, IL, August 20-24, 1990. Rood, M.J. and R.E.H. Contorer, "Influence of Specific Surface Area on SO2 Removal Efficiency in Spray Dryers," Proceedings. American Association for Aerosol Research '90. Philadelphia, PA, June 1990. Rood, M.J. and C.-S. Yuan, "Sulfur Dioxide and Nitrogen Oxides Removal from Flue Gases by Atomized Spray Dryer Sorbents," Proceedings. American Association for Aerosol Research '89. Reno, NV, October 9-13, 1989. Sloane, C.S., M.J. Rood, and C.F. Rogers, "Measurements of Aerosol Particle Size: I. Improved Precision by Simultaneous Use of Optical Particle Counter and Nephelometer," Proceedings. American Association for Aerosol Research '89. Reno, NV, October 9-13, 1989. Yuan, C.-S. and M.J. Rood, "Modeling of Simultaneous SO2 and NOX Collection in a Spray Dryer: Using a Lime Slurry with Inorganic Deliquescent Additives," Proceedings. 83rd Annual Meeting of the Air Pollution Control Association. APCA Paper No. 90-103.5, pp. 1-16, Pittsburgh, PA, June 24-29, 1990. PROJECT REPORTS Ekart, M.P., "Studies of Phase Equilibria in Supercritical Fluids," M.S. Thesis, Department of Chemical Engineering, University of Illinois at Urbana-Champaign, Urbana, IL, 1990. Larson, S.M., M. Shaw, and E. Andrews, "Studies of Gas-Particle Systems Using a Particle Balance," Final Report for Research Planning Study, Advanced Environmental Control Technology Research Center, 17 ------- University of Illinois at Urbana-Champaign, Urbana, IL, 1989; AECTRC Publ. No. 89-12, 1989. MacDonald, J.A., "A New Frontier in Wastewater Treatment: Investigating the Potential for Using Plasmids to Control the Genetic Capabilities of Biological Wastewater Treatment Processes," M.S. Thesis, Department of Civil Engineering, University of Illinois at Urbana- Champaign, Urbana, IL, 1990. Najm, I.N., "Evaluation of the Use of Powdered Activated Carbon for the Control of Organic Compounds During Drinking Water Treatment," Ph.D. Thesis, Department of Civil Engineering, University of Illinois at Urbana- Champaign, Urbana, IL, 1990. Simek, R.E., "Modeling the Combustion of Municipal Solid Waste," M.S. Thesis, Department of Civil Engineering, University of Illinois at Urbana- Champaign, Urbana, IL, 1990. "Summary of Research Activities - 1989," Advanced Environmental Control Technology Research Center, University of Illinois at Urbana- Champaign, Urbana, IL; AECTRC Publ. No. 90-1, 1990. Tomasko, D.L., "A Pilot Plant for the Supercritical Regeneration of Granular Activated Carbon and the Modelling of Solid-Supercritical Fluid Equilibria," M.S. Thesis, Department of Chemical Engineering, University of Illinois at Urbana-Champaign, Urbana, IL, 1990. Yuan, C.S., "Simultaneous Collection of SC«2 and NOX via Spray Drying: Using Sodium Based and Calcium Based Sorbents with Select Additives," Ph.D. Thesis, Department of Civil Engineering, University of Illinois at Urbana-Champaign, Urbana, IL, 1990. CONFERENCES AND WORKSHOPS HELD Distinguished International Lecturer Program Special Seminar -- "Long-Range Transport of Atmospheric Contaminants over the Southwestern United States" — Dr. Edward S. Macias, Provost, Washington University, St. Louis, MO, January 30, 1990. Full-Day Symposium -- "The Removal and Transformation of Organic Matter in Drinking Water" — featuring Dr. Hallvard Odegaard, 18 ------- Norwegian Institute of Technology, University of Trondheim, Trondheim, Norway, April 4, 1990. Also making presentations at the Symposium were Professor Brian Dempsey, University Park, PA, Professor David Reckhow, Amherst, MA, and Mr. Alan Stevens, USEPA, Cincinnati, Ohio. Special Seminar -- "Particle Removal in Wastewater Treatment" -- Dr. Hallvard Odegaard, Norwegian Institute of Technology, University of Trondheim, Trondheim, Norway, April 5, 1990. Kappe Lecture Series -- "Mitigating PCB Contamination in the Hudson River" -- Dr. Paul L. Busch, President, Malcolm Pirnie, Inc., White Plains, NY, September 14, 1990. 19 ------- 20 ------- CENTER: Center for Environmental Epidemiology LOCATION: University of Pittsburgh DIRECTOR: Bruce W. Case, M.D. Graduate School of Public Health University of Pittsburgh 130 DeSoto Street Pittsburgh, PA 15261 412/624-1559 Fax: 412/624-3013 PROJECT OFFICER: Gunther Craun Health Effects Research Laboratory U.S. Environmental Protection Agency 26 West Martin Luther King Drive Cincinnati, Ohio 45268 513/569-7422 FUNDS SPENT DURING FY 1990 (10/1/89 - 9/30/90) EPA $638,000 Other Government 135,000 University 33,000 Private Sector 41,000 Total $847,000 DESCRIPTION OF THE PROGRAM The Center for Environmental Epidemiology is based in the Graduate School of Public Health of the University of Pittsburgh. The Center provides basic health research to characterize and link general environmental exposures and biological outcomes, including disease. The emphasis is on innovative and multidisciplinary approaches, with particular interest in exposure assessment and its input to epidemiology and to risk assessment. Biological monitoring of exposure, including internal dose "biomarkers", receives special attention. Creative approaches are developed using available occupational exposure/disease datasets for environmental chronic disease epidemiology and quantitative risk assessment. Funding is aimed at generating research through feasibility and pilot studies, workshops and symposia on topics of immediate importance to EPA, and 21 ------- EPA mission-related work with local, state, national and international agencies. Collaboration with EPA and other university personnel in identifying the need for planning, and performing epidemiologic studies and related exposure and risk assessment activities is encouraged. FY 1991 is the last year for the cooperative agreement linking this Center with EPA. ACCOMPLISHMENTS Exposure Assessment and Multidisciplinary Activities Fibrous Particulate Lung Content of American Children: There is a great deal of regulatory interest in asbestos in schools, and in potential effects of fibers for lifetime mesothelioma risk in children. Center researchers contacted pathology departments in over 800 pediatric hospitals in seven states. To date almost 300 have responded, and tissue samples (N=141 deceased subjects) have been obtained from 47. As a first test, three groups were constructed of 20 children each, matched for age, sex, and race. Grouping was by community population size (< 5000; 5000-Si 100,000; over 100,000). For each child, paraffin blocks of lung are taken and deparaffinied in heated toluene. The tissue is ashed, then Nucleopore- filtered inorganic residues are examined with a JEOL 100 CX electron microscope (TEM) fitted with a PGT energy dispersive x-ray spectrometer (EDS) for fiber characterization. One aliquot of ashed, resuspended, Millipore-filtered lung was examined at 312X by light microscopy for asbestos bodies (AB): these are almost entirely absent at a detection limit of 0.04 AB/ mg dry lung. In TEM work, researchers examined both longer (> 5 urn) "regulatory" fibers and all fibers (> 0.04 urn length; > 3:1 aspect ratio) at detection limits of .07f/ug dry lung. In total, 11.4% of all fibers counted exceeded 5 um in length. Of these, none were present in more than 25% of children observed to date except "diatoms". A few long chrysotile, glass, and talc fibers were seen in 20% to 25% of subjects, but long amphiboles were entirely absent. The most striking finding among short fibers was the prominence of chrysotile. These fibers were seen in every sample well above background levels, averaging 9 fibers counted per subject or 0.63 fibers/ ug dry lung, accounting for half of all fibers present. No other fiber type was seen in more than half of all subjects. Aluminum silicates, man- made mineral fibers, diatoms and talc were the most common short fibers after chrysotile, with average numbers of 2.2, 1.2, 1.1, and 0.8 fibers/subject respectively. Commercial amphiboles were rare, but total 22 ------- asbestos accounted for 60% of lung fiber burden: a higher proportion than what we have observed in adults. Overall, the mean total concentration for all fibers was 1.33 per ug dry lung per child. As expected, there was a gradient between fiber concentrations in low-population ("rural") areas vs. towns and cities. Median concentrations of all fibers were twice as great for children having lived where population was 5000 or more: 24.5 fibers/ug vs. 12.0 in the "rural" group. There was no difference in fiber concentrations attributable to age, sex, or race. There was, however, a significant relationship between hospital of death and chrysotile fiber concentrations. Children having fiber counts of (> 0.7 fibers/ug or < 0.7 fibers/ug) invariably came from the same hospital subsets (p <.05; Mann-Whitney). Common community exposures (such as schools), exposure while in hospital or post-mortem "exposure" to the same autopsy room environments are possible explanations. This study, performed in cooperation with McGill University laboratory in Montreal, is nearing completion. These observations make it particularly important that widely held views that short chrysotile fibers do not confer risk for mesothelioma be confirmed. Results in the current study have been sufficiently encouraging to prompt applications for further funding of an expanded autopsy database and later phases of the work to NIEHS and to the Health Effects Institute Asbestos Research program (HEI-AR). The preliminary results reported here are to be presented at the Eighth International Symposium on Inhaled Particles in Edinburgh, U.K. in September of 1991. Sputum Asbestos Body Content of School Custodial Workers and Environmentally Exposed Women: This collaborative project takes advantage of the most intensively studied group of school custodial workers: a group in Boston which has been under observation by Center personnel for several years. Radiological abnormalities have been demonstrated which are consistent with asbestos exposure in a high proportion of workers, and during FY 1990 a collection of morning sputum samples was made from a representative group. These are to be analyzed using the dimethylformamide technique for light microscopic counting at McGill University. In related work completed this year, it was shown that women living close to asbestos mines in Quebec demonstrated a high proportion (40%) of positive specimens if exposure could be shown to have occurred prior to 1960 and if sputum was adequate for examination, as determined by alveolar macrophage count. Positive results were related to age, but not to smoking status. 23 ------- Blood Lead Levels in Elderly Women: One Center associate has shown severe effects of lead on children age seven and under, even in amounts resulting in blood levels less than current and proposed standards (e.g. 25 ug dl.; 15 ug/dl. respectively). Measurable, irreversible deficits in cognitive and verbal skills result and continue into adult life. There has been little previous work with older citizens concerning the prevalence and possible effects of lead exposure. To date, Center personnel have measured blood lead in 935 women over age 55. Two laboratories, one having a more sensitive detection limit (2g/ml), were used: interlaboratory agreement has been very high (Kappa 0.623). Distribution of results shows only a very small number of women having levels at or higher than 15g/ml (4/688 completed tests). However, levels below 15 g/ml appear to be log-normally distributed, with medians in the four to five g/ml range. Unlike the situation for fibers in the lungs of children, no rural-urban differences have been observed. Cognitive testing and correlation with blood lead levels has not advanced sufficiently to give conclusive results. Organoarsenate Exposure and Etheno-adduct Formation: This completed project tested exposure of mice via twelve intraperitoneal injections over four weeks of arsenocholine bromide (4.5 mmole/kg), choline bromide (9.0 mmole/kg) and ethyl carbamate (40.0 mmole/kg). The aims were to determine the presence or absence of adduct formation and subsequent adenoma formation; evaluate chromosomal aberrations and sister chromatid exchange (SCE); and to determine cellular processes active in producing the latter. Metabolism of the three chemicals was evaluated in red blood cells and plasma, using a high pressure liquid chromatograph (HPLC). Samples were collected during exposure (after 6th and 12th injections) and at two, four, and six months after treatment. Lung adenomas were evaluated at sacrifice, six months following the final injection. No metabolic changes were detected in this model, suggesting that any metabolism had been completed prior to 24 hours post-injection, the time evaluated which was most proximate to treatment. Adenomas were most common (31%) in the suspect carcinogen group; i.e., arsenocholine bromide. However, choline bromide (21.7%) and even saline control (17.8%) treated animals also developed significant numbers of adenomas, so the difference between groups was not significant. Results suggest further work with shorter post-injection times and perhaps with a vehicle other than saline: these were reported at the Fifth International Conference on Environmental Mutagens, Cleveland, July 1989. 24 ------- Relationship of Water Fluoridation to Bone Density and Fracture: Center personnel initiated a study to determine possible associations between bone density and fractures and fluoridation of water. The study was ancillary to a larger study of osteoporotic fractures in a four-county area, confined to non-Black females over age 65. Water treatment plants/methods were determined for each place of residence for each woman, together with fracture/osteoporosis x-ray data. The working hypothesis is that peak bone mass attained during younger years is increased by fluoride ingestion, resulting in a lower incidence of osteoporosis at a later date. To date, questionnaires have been completed by 1750 respondents of 1976 study participants: 30% will require further follow-up calls. Fluoridation history for each water supply company is being obtained, together with well water samples where applicable. Environmental Influences on Legionella Multiplication and Virulence: Center personnel refined a model for intracellular growth of L. pneumophila in cultured amoebae (H. Vermiformis). A reliable tapwater model was developed. The model is simple to use; amoebic cysts do not need to be washed. Many sero groups and isolates of Legionella SPP. were tested. There was wide variation of results for multiplication in amoebae: highest yields came from L. pneumophila sero group 1, sero group 5, and sero group 6. Studies are in progress to determine the influence of iron on the H. vermiformis-L. pneumophila relationship. To date, concentration of iron greater than 50 mg per liter appears to inhibit growth, suggesting a toxic metal effect. However, lower concentrations of iron (e.g., 5-50 mg/1) appeared to enhance the multiplication by 0.1 to 0.2 log units/ml over the 1.0 to 1.5 log units/ml observed in controlled suspensions. It thus appears that iron significantly influences the multiplication of the amoeba. Additional trials are also needed to better define the survival and multiplication characteristics of Hartmannella and Legionella as influenced by temperature. To date, multiplication has been seen to occur from 15°C to 40° C. At temperatures between 45° C and 50° C degrees, no multiplication was seen, even with transfer to 37°C environments. Pilot Study of Giardia Surveillance: Two Pennsylvania communities have been identified as pilot study target areas by Center personnel. One area has a history of Giardiasis outbreaks; the other, no such history. Treated sewage samples were collected and analyzed from sewage treatment authorities in both areas. Samples were concentrated by simple centrifugation, stained by Lugol's solution and assayed for Giardia cysts using phase contrast microscopy. Cyst concentrations ranged from 2000 to 2170 cysts per liter in the plant supplying the community with a 25 ------- history of giardiasis, while counts were lower (750-1200 cysts/1) in the control community plant. A preliminary investigation of demographic composition of both communities was performed and a stool sampling program developed. To optimize coprodiagnosis of giardiasis, Center personnel visited the laboratories of Drs. Jerva and Sterling at the University of Arizona: enzyme immunoassays and genetic markers are both being developed. In addition, the original protocol was extended to include similar work for cryptosporidium. Additional funds have been obtained from EPA for this purpose. Health Impact of Air Pollution: Center personnel identified five census tracts in close proximity to active coke works. Two census tracts in an area remote from the coke works but having similar demographics were used as control. Two hundred forty-three households were telephoned at random in both exposed and control communities. Questionnaire responses will allow evaluation of medical history, especially as regards lung disease, in addition to risk perception for "pollution problems." Some questionnaire respondents volunteered to have air pollution equipment installed in their homes and/or to have children in fourth through sixth grade evaluated pulmonary function testing. The latter was performed in January and February of 1990. Thirty-nine "exposed" fifth graders and 27 "control" fifth/sixth graders were tested. All results were normal. Hospital admission data for residents for two "exposed" communities are being compared with corresponding control areas. Over 200,000 records are being analyzed for this portion of the study. Actual air monitoring data of PM-10, TSP, and benzo-a-pyrene were collected from the assessed communities for later comparison. Center personnel are also performing analysis for polynuclear aromatic hydrocarbons in PM-10 filter samples obtained by routine means. Finally, houses directly in the path of prevailing winds from the coke plant are being sampled for PM-10 (five 24 hour samples for each site). Indoor air samples from the same houses will also be analyzed. Studies of Total Exposure Assessment Methodology (TEAM) as Applied to Volatile Organic Compounds (VOCs) from Household Water Sources: Activities in this area continued, with this year's focus including development of an indoor model for volatilized chemicals, study of household water use and time behavior patterns, further development of the full-size shower study system, and work on the effects of detergents on the volatilization of trichlorolethylene (TCE). 26 ------- a. Development of Indoor Air Model for Volatilized Chemicals Center personnel further refined the application of an indoor air Model for Analysis of Volatiles and Residential Indoor-Air Quality (MAVRIQ). Residents of a local community used a public ground water supply contaminated with TCE at levels up to 260 (4.g/L. was applied to homes in the community affected to assess inhalation exposures received while showering. Inhalation exposures from a six minute shower in the homes studied were estimated to be about twice those from direct ingestion of one liter of TCE-contaminated water. b. Water Use and Time-Behavior Patterns A literature review was completed for household water consumption in the United States and for relevant behavioral patterns within the households of Americans. Household water consumption patterns were integrated into the indoor-air model for volatilized chemicals. Detailed discussions of the findings and applications of this model were presented at the Indoor Air '90 Conference in Toronto in July 1990, and at the symposium of the American Society of Civil Engineers in Washington, D.C. in July 1990. c. Full Size Shower Studies The shower model used by Center personnel was extended to allow correction of instrumental time lag in the detection of TCE concentrations. Model calibration suggests that higher effective air-exchange rates occur between the shower stall and bathroom than have previously been used in indoor air quality models. Differences in the behavior of various chemicals was also noted. TCE was seen to be most volatile, with chloroform following. Both build up in air concentration in a linear fashion over approximately the first ten minutes of a shower experiment. All three chemicals tested (TCE, chloroform, DBCP) were released from warm shower water (about 40° C) to air in substantial amounts: the overall average volatilization for TCE was about 80%, for chloroform about 60% and for DBCP about 20%. The parameter found to have the biggest impact on the rate and extent of volatilization was K, the Henry's Law Constant. The mass balance model developed was shown to be 27 ------- first-order in nature. The model included shower spray and pooled water around the shower drain as the two principal emission sources. Testing of the model using measured TCE and chloroform demonstrated over-prediction by approximately 50%. Mixtures of TCE and chloroform had no apparent major effect on extent or rate of volatilization. d. Effect of Detergents on Volatilization of TCE Most experiments for studying the effect of agitation and detergent addition on the volatilization of TCE were completed. These indicate that agitation has a substantial and regular impact on increasing the rate, while the addition of detergent is less predictable. The general trend is that detergent (sodium lauryl sulfate) decreases volatilization. e. Sorption of Volatilized Chemicals Onto Fiber Surfaces Research on the sorption of organic vapors to indoor surfaces, such as carpet fiber, has primarily focused on developing the theoretical interpretation of existing data so as to facilitate the design of later experiments. Studies of the interaction of the volatilized species with indoor surface materials yielded new insights concerning sorption. Inconsistencies were found between data acquired from studies using HPLC columns and data obtained using a headspace analysis technique. The data collected in HPLC studies may not yield realistic estimates. Further work will be confined to the gas-headspace technique. Two studies have been performed in this way. In the first, the uptake of chloroform, trichlorolethylene (TCE), tetrachloro- lethylene (PCE), and paradichlorobenzene (PDB) by cotton, nylon, wool, and glass fibers was examined. Cotton and wool fibers were cut from commercially available yarns; both were undyed. Nylon fibers were trimmed from a new carpet. Glass fibers cut from glass wool were used as control. The less volatile organic species partition more strongly to surfaces but partition coefficients for all four chemicals with respect to glass fiber were below the detection limit. Thus, cotton fibers showed the greatest uptake, resulting in a larger decrease from the initial concentration in air and uptake was greatest at lower temperatures. The second study focused on the uptake of TCE vapor by eight surface materials. These included nylon fiber (2 28 ------- diameters), cotton (2 grades), pure carpet latex film, carpet backing (polypropylene), dacron polyester fiber, and glass fiber as control. Results showed that release of TCE to the surface was greatest for the carpet latex, polypropylene, and polyester. This result has practical significance since generally the latex and backing material of a carpet account for approximately 50% of its total weight. If these materials were accessible, they could represent an important reservoir of volatile organic constituents in terms of both their removal and re-emission from fiber surfaces. Additional work will include similar studies of chloroform, PCE, and PDB. Relative humidity, initial gas phase concentration, sorbent mass loading, and system temperature will be varied for each of the experimental fibers. Chronic Disease Epidemiology Arsenic Exposures in Copper Smelting: This project updates and extends a mortality study of 2802 men who worked for one year or more during the period of 1940-1964 at a copper smelter in Tacoma, Washington, where exposure to arsenic and other substances occurred. The study was performed in two phases. In the first of these, the mortality update, determined the vital status of 1690 cohort members known still to be alive as of December 31, 1976 (the date of last followup). A complete list of 1741 names and social security numbers was generated from existing records and checked by Center staff. This listing was submitted to Social Security for tracing purposes. A complete listing was also submitted to the National Death Index (NDI) and to the Pension Benefits Information (PBI) company. NDI reported 450 potential cohort deaths occurring from 1979 to 1987, while PBI returned a total of 657 deaths occurring between 1963 and 1989. Results were collated and death certificate requests have been sent to all states. Three hundred eighty- five death certificates have been received from 21 states; requests on another 129 subjects are still outstanding. Information updates on 254 individuals still actively working for the company are also being obtained for 1) job histories, 2) dates of employee termination, and 3) additional exposure data for the period beginning January 1, 1977. Phase 2 constitutes a nested case control study of the cohort in which 186 matched control subjects have been chosen for 100 respiratory cancer cases using a random selection of two matched controls alive at the time the case died. Matched cases and controls are then traced for lifetime smoking history. Smoking history data is collected through telephone interview with the worker or a knowledgeable informant. In FY 1990, smoking information was collected on eighty analyzable pairs of case and control subjects. Data 29 ------- collection was completed by December 31, 1990, and data analysis is underway. Coke Oven Workers Mortality Studv: This study was completed during FY 1990. It concerned the update of cause-specific mortality of coke oven workers and a subset of non-oven workers who were included as members of two large steelworker cohorts, followed for several years by Center personnel. Updated information provided twenty-seven years of work history and vital status followup on 15,818 workers. Findings were consistent with those from earlier studies indicating that occupational exposure to coke oven emissions is associated with significant excess mortality from cancer of the respiratory system and from cancer of the prostate gland. The association with respiratory cancer was particularly strong. Risk for cancer of the lung, trachea, and bronchus varied with type of coke oven job, duration of employment, and cohort. Risk for those who worked five or more years at a coke job were as high as 6.51 times expected in one (Allegheny County) cohort; 4.22 in the out-of-county cohort (P <0.0001 vs. expected). The latter risk is for full- time topside coke oven workers; part-time topside workers showed lesser risk but still a significant risk for respiratory cancer if at least five years of work had been performed (RR >2.0; P <0.01). Side workers also showed highly significant risk for respiratory cancer, at a level of relative risk between 1.7 and 2.2, regardless of duration of work. In summary, the relative risk for those who were employed full-time on top of the coke ovens were two to three times higher than the risk for those not working full-time. These findings provide strong evidence that the association between respiratory cancer and occupational exposure to coke oven emissions is causal. The noted association for prostate cancer is not as convincing. Available data was sparse; only 29 cancers of the prostate were observed in each of the two cohorts. Therefore, cross classification of risks by type of coke oven job, duration of employment, etc., cannot be satisfactorily performed and no sound conclusions could be made regarding trends. Based on age at last followup, the proportion of workers over the age of 74 (that is, those at greatest risk for prostate cancer), was only 16.7% and 10.0% for the Allegheny County and non-Allegheny County cohorts, respectively. A still greater duration of followup is needed in order to accurately assess the possibility of etiological risk for prostate cancer conferred by exposures in coke oven work. 30 ------- Carcinogenic Risk Assessment Enhancement of Methodologies and Application to Cohort Datasets: The overall goal of this long standing research by Center personnel is to develop and refine statistical methodologies used to assess carcinogenic risks from environmental exposures. Research during FY 1990 was a continuation of previous efforts to enhance quantitative risk assessment using the multi-stage model of carcinogenesis, and to initiate similar efforts for the two-stage model proposed by Moolgavkar and colleagues. These methodologies are to be applied to carcinogenic risk assessment of exposure to coke oven emissions and exposure to arsenic using data from the two occupational cohort studies referred to above. Computer software for modeling cohort data from the Allegheny County/non-Allegheny County coke oven emission cohorts has been adapted. Exploratory analysis for modeling of the Allegheny County coke oven workers mortality data with two-stage models of carcinogenesis has been completed. Results were summarized and presented at the Fifteenth International Biometrics Conference in Budapest, Hungary, July 1990. In this paper, models were compared for the prediction of lifetime risk of lung cancer among coke oven workers who were exposed for at least 40 years with exposure initiated at age 20. This multi-stage and a two- mutation model were compared. Local. National and International Activities: The Center continued strengthening ties to local and state health departments. With respect to the latter, Center personnel participated in a school-wide meeting with personnel from the Pennsylvania Department of Environmental Resources for the purposes of developing a systematic response to environmental emergencies and other related problems. It was implied in this meeting that one of the greatest difficulties facing legislators and others concerned with environmental resources and health concerns risk perception. Several steps have been taken to further our understanding of risk perception in Pennsylvania in the context of this Center. First, a new Assistant Director, Dr. Jeannette Trauth was appointed to the Center and to the Department of Health Services Administration in the Graduate School of Public Health, University of Pittsburgh. Dr. Trauth's input will be to address these concerns. A second step was the provision of a general paper on environmental medicine to the State Medical Association Journal (Environmental Medicine in Pennsylvania: Problems, Resources, Solutions. Pennsylvania Medicine. July 1990). Finally, Graduate School of Public Health faculty member, Dr. Gordon MacLeod, has been inducted as President of the Pennsylvania State Medical Society. One of his goals during his tenure will be the increased awareness of physicians and 31 ------- their patients with respect to environmental concerns. It is expected that additional environmental articles of local interest will be provided by Center personnel. At the international level, the major activity in which Center staff were engaged was the Second Annual Meeting of the International Society for Environmental Epidemiology. As in the previous year, Center Assistant Director, Dr. Evelyn Talbott, served as the Secretary-Treasurer for the Society. The Center Director also gave one of the keynote talks on the first morning of the symposium ("Looking for Trouble: A clinical and social perspective for environmental epidemiology"). Additional papers were presented in the area of unusual sources of exposure to lead and a paper putting into historical perspective leukemia risk and electromagnetic radiation. There was a great deal of input into the question of health effects of tremolite at the national level, with the participation of the director in the American Thoracic Society's committee on the health effects of tremolite, and the presentation of a paper on the Health Effects of Tremolite at the "Third Wave of Asbestos Disease" symposium sponsored by the Collegium Ramazzini, in New York City, June 1990. There was ongoing cooperation between Center personnel working in the Total Exposure Assessment Methodology Team and EPA offices, particularly the Atmospheric Research and Exposure Assessment Laboratory. RESEARCH GOALS - FY 1991 FY 1991 will see the completion of the ten year cycle of activities of this exploratory research center. Final reports for all studies indicated under subheadings for FY 1990 will be produced and collated. An overall final report will be generated to deal with the entire output of the Center over its life. Because the Center will be in a phase-out period as concerns EPA funding, very few new activities will be permitted. Those which are currently underway include extensions of some of the work described for FY 1990. One new project for which EPA funds have been obtained separately is to be the writing of a general textbook of environmental epidemiology. This textbook, to be written by Center Project Officer, Gunther Craun, Director, Bruce Case, and Assistant Director, Evelyn Talbott, is aimed at a general audience rather than a group with existing knowledge of the field. It will provide a basic introduction to 32 ------- environmental science in general, and controversial questions of environmental health science in particular. A balanced and comprehensible approach is to be emphasized. Work which is being extended includes that on Giardia and Cryptosporidium, exposure assessment via asbestos-in-sputum for exposed school custodial workers, lung fiber content of children across the United States, and effects of indoor air pollution in a local feasibility study. Continued arrival of new faculty in the Graduate School of Public Health will further emphasize the ongoing trend in the Center towards work involving exposure assessment via the study of direct markers in living systems. In addition, the extensive program using indoor air models and Total Exposure Assessment Methodology will continue well beyond FY 1991. OUTPUTS - FY 1990 Articles in Refeered Journals 16 Articles Submitted or in Press 2 1 Books and Bound Proceedings 1 Chapters in Other Books 3 Project Reports 2 Conferences and Workshops Held 0 33 ------- BIBLIOGRAPHY REFEREED JOURNAL ARTICLES Andelman, J.B., Giardino, N.J., Marshall, J., Esmen, N., Borrazzo, J.E., Davidson, C.I., Small, M. and Wilkes, C., Exposure to Volatile Chemicals from Indoor Water Uses, In: Proceedings of Symposium on Total Exposure Assessment Methodology: A New Horizon, (Las Vegas, Nevada, November 17-30, 1989), Air and Waste Management Association, Pittsburgh, Pa, pp. 300-311, 1990. Andelman, J.B., Hammad, H.R., and Ray, R.C. II, The Impact of Aqueous Surfactants on Air Exposures to Volatile Chemicals from Indoor Water Uses, In: Proceedings, 5th International Conference on Indoor Air Quality and Climate, Ottawa, Vol. 3, pp. 617-622, 1990. Borrazzo, I.E., Davidson, C.I. and Andelman, J.B., The Sorption of Organic Vapors to Indoor Air Surfaces of Synthetic and Natural Fibrous Materials, In: Proceedings, 5th International Conference on Indoor Air Quality and Climate, Ottawa, Vol. 3, pp. 593-598, 1990. Case, B.W., Environmental Medicine in Pennsylvania: Problems, Resources, Solutions, Pennsylvania Medicine. Vol. 93, pp. 52-55, September 1990. Case, B.W., McCaughey, W.T.E., Dufresne, A., Sebastien, P. Exposure Misclassification for Mesothelioma in A Chrysotile Mining District. (Abstract). American Review of Respiratory Disease. Vol. 141, pp. 4, February 2, A242, 1990. Conner, M.K. and Modzelewski, R.A. Etheno-Adduct Production by Carcinogenic and Endogenous Agents. In: Abstracts of the Fifth International Conference on Environmental Mutagens July 1989, Environment and Molecular Mutagenesis. Vol. 14, Supplement 15, 1989. Dong, M.H., Microcomputer Programs for Complex Epidemiologic Procedures: I. Computation of Adjusted Rates, Computing in Biomedical Research. Vol. 22, pp. 349-361, 1989. Dong, M.H., Microcomputer Programs for Complex Epidemiologic Procedures: II. Test for Equality and Trend of Adjusted Rates, Computing in Biomedical Research. Vol. 22, pp. 362-373, 1989. 34 ------- Giardino, N.J., Gumerman, E., Esmen, N.A., Andelman, J.B., Wilkes, C.R. and Small, M.J., Real-time Air Measurements of Trichloroethylene in Domestic Bathrooms Using Contaminated Shower Water, In: Proceedings, 5th International Conference on Indoor Air Quality and Climate, Ottawa, Vol. 2, pp. 707-712, 1990. Marsh, G.M., Callahan, C., Pavlock, D., Leviton, L.C., Talbott, E., Hemstreet, G.: A Protocol for Bladder Cancer Screening and Medical Surveillance Among High Risk Groups: The Drake Health Registry Experience, Journal of Occupational Medicine. Vol. 32, pp. 881-886, 1990. Mazumdar, S., Redmond, C.K., Enterline, P.E., Marsh, G.M., Costantino, J.P., Zhou, S.Y.J., Patwardhan, R.N, Multistage Modeling of Lung Cancer Mortality Among Arsenic-exposed Copper Smelter Workers, Risk Analysis. Vol. 9, pp. 551-563, November 1989. McDonald, J.C., Case, B.W., Enterline, P.E., Henderson, V., McDonald, A.D., Plourde, M., Sebastien, P. Lung Dust Analysis in the Assessment of Past Exposure of Man-made Mineral Fiber Workers, Annals of Occupational Hvgeine. Vol. 34, pp. 427-441, October 1990. Rao, B.R. and Marsh, G.M., Simultaneous Statistical Inference Concerning the SMR's of Several Strata in An Epidemiologic Study, Biometrical Journal. Vol. 32, pp. 107-123, 1990. Small, M.J., Wilkes, C.R., Andelman, J.B., Giardino, N.J. and Marshall, J., Inhalation Exposure from Contaminated Water Uses: A Behavioral Model for People and Pollutants, In: Proceedings of ASCE Environmental Engineering, 1990, Washington, D.C., July 9-11, 1990. Talbott, E.G., Findlay, R.C., Kuller, L.H., et al., Noise Induced Hearing Loss: A Possible Marker for High Blood Pressure in Older Noise-exposed Populations, Journal of Occupational Medicine. Vol. 32, pp. 8, August 1990. Wilkes, C.R., Small, M.J., Andelman, J.B., Giardino, NJ. and Marshall, J., Air Quality Model for Volatile Constituents from Indoor Uses of Water, In: Proceedings, 5th International Conference on Indoor Air Quality and Climate, Ottawa, Vol. 2, pp. 783-788, 1990. 35 ------- ARTICLES SUBMITTED OR IN PRESS Case, B.W. Tremolite "asbestos": Health Effects Now and in the Future, Collegium Ramazzini "Third Wave" Conference, New York, June 1990, Annals of the New York Academy of Sciences. Case, B.W., Armstrong, B., McDonald, J.C., and Sebastien, P., Mesothelioma in the Quebec Chrysotile Mining Region, British Journal of Industrial Medicine. 1990 Case, B.W., Dufresne, A., Siemiatycki, J. and Fraser, R. Decoding Occupational History from Total Lung Paniculate Analysis. II: A Comparative Study, Annals of Occupational Hygiene. 1990. Case, B.W., Monaghan, L.A., Giguere, M. Sputum Asbestos Bodies in Female Residents of Two Chrysotile Mining Towns, American Review of Respiratory Disease. 1990. Case, B.W., Looking for Trouble: Clinical Perspective on Environmental Epidemiology, International Symposium on Environmental Epidemiology, August 1990, Archives of Environmental Health. 1990. Case, B.W., Kuhar, M., Harrigan, M. and Dufresne, A., Lung Fiber Content of American Children Age 8-15: Preliminary Findings, Annals of Occupational Hygiene. 1990. Day, R., Talbott, E.G., Marsh, G.M., A Comparative Ecological Study of Selected Cancers in Kanawha County, WV, American Journal of Industrial Medicine. 1990. DeGuire, L., Cyr, D., Theriault, G., Armstrong, B., Iturra, H., Provencher, S. and Case, B., Malignant Melanoma of the Skin Among Workers of A Large Electrical and Electronics Products Industry: 1976-1983, A Mortality Study, 23rd Occupational Health Symposium, September 1990. Dufresne, A. and Case, B.W. Decoding Occupational History from Total Lung Paniculate Analysis I: A New Comprehensive Methodology, Annals of Occupational Hygiene. 1990. Hourani, G.F. and Underbill, D.W., Long-term Passive Sampling of Environmental Airborne Contaminants, American Industrial Association Journal. 1989. 36 ------- Leviton, L.C., Marsh, G.M., Talbott, E., Callahan, C., et al., "The Drake Chemical Workers Health Registry Study: II. Coping with Community Tension in Health Protection," American Journal of Public Health. 1990. LaPorte, R. and Sweeney, A., "Collecting Early Pregnancy Outcome Data for Risk Assessment," Environmental Health Perspectives. Vol. 90, December 1990. Marsh, G.M., Leviton, L.C., Talbott, E., Callahan, C., Pavlock, D., Hemstreet, G., Logue, J.N., Fox, J. Schulte, P., "The Drake Chemical Workers Health Registry Study: I. Notification and Medical Surveillance of A Group of Workers at High Risk of Developing Bladder Cancer," American Journal of Public Health. 1990. Marsh, G.M. and Day, R., "A Model Standardized Risk Assessment Protocol for Use with Hazardous Waste Sites," Environmental Health Perspectives. Vol. 90, December 1990. Mazumdar, S., Redmond, C.K., Costantino, J.P., Patwardhan, R.N., and Zhou, S.Y.J., "Recent Developments in the Multistage Modeling of Cohort Data for Carcinogenic Risk Assessment," Environmental Health Perspectives. Vol. 90, December 1990. Weill, H.W., Abraham, J., Balmes, J., Case, B.W., Churg, A., Hughes, J., Schenker, M., Sebastien, P., American Thoracic Society Final Report: Health Effects of Tremolite, American Review of Respiratory Disease. December 1990. Patwardhan, R.N. and Mazumdar, S., Confidence Regions in Multistage Models of Carcinogenesis: Application to an Epidemiologic Study and Simulation Results, Biometrics. 1990. Rao, B.R., Day, R., Marsh, G., "Estimation of Relative Risks from Individual and Ecological Correlation Studies," Communications in Statistics-theory and Methods. 1990. Talbott, E.G., Day, R.D., Marsh, G.M., Haile-Cattledge, G.T., McKenna, M., Case, B.W., "Trends in Cancer Mortality in Kanawha County, West Virginia, 1950-1984," Environmental Health Perspectives. 1990. Zhou, S.YJ. and Mazumdar, S., "Investigation of Model Robustness Using the Generalized Linear Model Approach with An Application to 37 ------- Multistage models of Carcinogenesis," Biometrics. Computers and Biomedical Research, 1990. Zhou, S.Y.J., Mazumdar, S., Redmond, C.K., Dong, M.H. and Costantino, J.P., "Computations of Adjusted Rate and Lifetime Risks from Occupational Cohort Data: A Program Package Using FORTRAN and GLIM," Computers and Biomedical Research. 1990. BOOKS AND BOUND PROCEEDIDNGS Seventh Symposium on Environmental Epidemiology: "Methods for Environmental Quantitative Risk Assessment," Environmental Health Perspectives, Vol. 90, December 1990. CHAPTERS IN OTHER BOOKS Andelman, J.B., "Total Exposure to Volatile Organic Compounds in Potable Water," In: Significance and Treatment of Volatile Organic Compounds in Water Supplies, N. Ram. R. Christman and K Cantor, Eds. Chapter 20, pp. 485-504, Lewis Publishers, Inc. Chelsea, Michigan, 1990 States, S.J., Wadowsky, R.M., Kuchta, J.M., Wolford, R.S., Conley, L.F. and Yee, R.B., "Legionella in Drinking Water," In: Drinking Water Microbiology. Ed. G.A. McFeters Chapter 16, pp.340-367., Springer-Verlag, New York, Inc., 1990. Sykora, J.L., "Analysis of Water Samples for Protozoans." In: Methods for the Investigation and Prevention of Waterborne Disease Outbreaks Chapter V, pp. 297-316, EP A/600/l-90/Q05a, September 1990. PROJECT REPORTS Carol K. Redmond, "Cancer Risk Assessment Based on Coke Oven Workers Mortality," Sc.D., Final Report December, 1989. Mary K. Conner, Ph.D., "Do Organoarsenates Form Etheno-Adducts in Nucleotides?" Final Report July, 1990. 38 ------- CONFERENCES AND WORKSHOPS HELD None 39 ------- 40 ------- CENTER: Ecosystems Research Center LOCATION: Cornell University DIRECTOR: Leonard H. Weinstein Ecosystems Research Center Wing Hall Cornell University Ithaca, NY 14853-8101 607/255-3972 Fax: 607/255-5316 PROJECT OFFICER: Michael Slimak Office of Environmental Processes and Effects Research (RD-682) U.S. Environmental Protection Agency 401 M Street SW Washington, D.C. 20460 202/382-5950 FUNDS SPENT DURING FY 1990 (10/1/89 - 9/30/90) EPA $540,000 Cornell 70,860 Private Sector 0 Total $610,860 DESCRIPTION OF THE PROGRAM The Ecosystems Research Center (ERC), founded in 1980, evaluates the potential for improving environmental regulation by switching the level of analysis from that of individual species or particular chemical parameters to that of whole biological communities and ecosystems. The goal of the Center is twofold: (a) to derive basic understanding of what controls the response of entire ecosystems to human-induced stress, and (b) to evaluate the implications of that understanding for the regulation and management of current and emerging environmental problems. The Center's program has been built on analyses of selected environmental problems in particular ecosystems coupled with a comparison of the responses of different ecosystems to stress and disturbance. Operating in tandem with an explicit effort to serve as an 41 ------- interface between ecosystem science and environmental policy, these within-system and across-system analyses keep the program abreast of current thinking and developments in the field of ecosystem science while remaining focused on real-world application to EPA's needs. Since 1987 the Center has also included basic field and laboratory research on the effects of human activities on various ecosystems. This has been accomplished by co-funding research projects of mutual interest to the ERC and other Cornell faculty and by providing seed money for projects with the potential to obtain additional funding from other sources. During the past year, the Center has focused on completing ongoing projects and continuing collaborative projects with Cornell faculty. By establishing collaborative projects with other Cornell faculty, the Center has been able to extend the efforts of its small core staff and the effectiveness of its EPA funding. ACCOMPLISHMENTS - FY 1990 The ERC's major accomplishments during FY 1990 fall into four major areas: (1) ecological risk assessment, including biomonitoring and landfill studies; (2) global change issues, from studies of trace gas production, tropical forests, potential genetic buffers, effects on fisheries and agriculture, to research on the socioeconomic implications of global warming; (3) wetlands research, including studies of soil-stream interactions, watershed liming, factors controlling the occurrence of rare and uncommon wetland habitats, and gas fluxes in wetland plants; and (4) scale and modeling issues. A brief description of projects in each area follows. Ecological Risk Assessment Ecological risk assessment (ERA) has been a focal area for the ERC for several years. ERC staff have been continuously involved in the development of concepts and methods appropriate to ecological risk assessment. Current work focuses on developing biomonitoring techniques and on the ecological effects of coal fly ash landfills. Use of Plants for Biomonitoring Near Municipal Waste Incinerators: Continual monitoring of incineration sites is essential to ensure that health and safety standards are maintained in the face of airborne and potentially toxic emissions. Monitoring equipment, however, can be both cumbersome and expensive. The use of plants as bio- 42 ------- indicators of pollution may provide a relatively inexpensive alternative, since plant tissue often accumulates airborne toxins and can be analyzed at relatively low cost for trace concentrations of these toxins. ERC staff are collaborating with scientists at the Boyce Thompson Institute for Plant Research and Cornell's Waste Management Institute to develop, test, and implement a method for collecting and quantifying emissions from solid waste incinerators using plants as bio-indicators of pollution using a combination of biological monitoring, deposition modeling, and statistical analysis. The final product will be a manual that describes the different systems developed to be used to monitor emissions in the areas near facilities. Several plants have been identified which possess the necessary qualities of hardiness, ease of cultivation, the ability to accumulate toxins, and susceptibility to specific toxins. Among the plants chosen are: curly kale, curly parsley, rye grass cultures, gladiolas, and mosses. Different plants will be required to monitor different pollutants such as fluoride, sulfur oxides, heavy metals, particulates and volatile organic compounds. In conjunction with this project, the ERC co-funded a visit to Cornell by Drs. Uwe Arndt, Hohenheim University, Stuttgart and Willfried Nobel TUV, Stuttgart, two scientists prominent in plant biological monitoring in Germany, where monitoring is mandated by law. Terrestrial Ecology of a Closed Flv Ash Landfill: Coal fly ash is the residue collected by mechanical collectors or electrostatic precipitators on coal combustion incinerators. The major disposal method for this material is burial in a plastic- or clay-lined landfill that is then capped with soil. Run-off from the landfill is collected in a lagoon. Landfill sites are naturally inhabited by a variety of terrestrial and aquatic fauna and support the growth of a number of indigenous grasses, forbs, shrubs, and small trees. ERC staff have worked with scientists at the Boyce Thompson Institute (BTI) and the Departments of Natural Resources and Entomology at Cornell in studies of several landfills in central New York State that have been repositories for coal fly ash. The overall goal of the studies is to provide information on future utilization of these closed landfill sites. Measurements of the uptake of chemical elements by cultivated and indigenous plants grown on a soil-capped fly ash landfill showed that Selenium (Se) accumulated in some species 50-fold more than in plants grown on control sites. Other elements, such as molybdenum (Mo) and 43 ------- boron (B), were often higher than controls, but the degree of accumulation was usually less than two-fold. Specifically, rutabaga (Cruciferae) and alfalfa (Leguminosae) accumulated more Se than species such as carrot (Umbelliferae), corn, timothy, or bromegrass (Gramineae), red clover (Leguminosae), or milkweed (Asclepiadaceae). Leaves arising from the upper stem of wild carrot and bitter weed (Compositae) accumulated more Se than older rosette leaves. In sweet and field corn cultivars, greater amounts of Se were found in leaves and kernels than in stems, cobs, or roots. Field corn grown under no-till cultivation had 50 to 75% more Se in leaves, stalks, and seeds than corn grown under conventional tillage. This may be due to the greater moisture conservation in the soil from no-till cultivation, allowing more favorable conditions for Se absorption. The use of gypsum in limiting Se uptake by plants offers a possible management tool to control cycling of Se through plants to other biota. Researchers found that Se uptake in rutabaga and carrot shoots and roots could be reduced by about 60% by applying gypsum (CaSC>4) at a rate of 2.0 tons per hectare. This reduction is related to the competition between sulfur and selenium in the metabolism of xthe plant, and the capacity of selenium to substitute for sulfur in some of the sulfur-containing amino acids and peptides. Global Change Over the past three years, the ERC has enhanced significantly its capabilities in the area of global environmental problems. The program has continued to build rapidly because of its longterm work in the areas of ecosystem modeling and attention to the conceptual and methodological problems of scale inherent in ecosystem analysis; the programmatic decision to complement the Center's synthesis and modeling work with a stronger experimental program in field and laboratory research on globally important trace gases; an organizational decision to emphasize collaborations with Cornell faculty through commitment of core funds to seed projects proposed by faculty; and close collaboration with Cornell's Global Environment Program (GEP), headed by Mark Harwell, who has continued as a senior staff member within the ERC. As part of its strategy to leverage core funds from EPA, the Center has committed some of those funds to seed projects proposed by Cornell 44 ------- faculty that are relevant to global environmental issues, basing funding decisions on an open competition. The Center's efforts during FY 1990 focused on basic research into factors controlling production in natural systems of methane, trace greenhouse gases, and dimethylsulfide, an "anti-greenhouse" gas; dormant stages as buffers against global climate change, the basic nutrient dynamics determining the characteristics of lowland tropical forests, the potential impact of global warming on agriculture and fisheries, and socioeconomic implications of global warming. Each of these projects is described below. Methane Production by Beaver Ponds: The Center's research reveals that beaver impoundments are a large and often overlooked source of atmospheric methane. One hundred years ago beavers were trapped nearly to extinction, but since that time their population has exploded to the point that beaver ponds may comprise up to 10% of the landscape in some areas. These shallow ponds, unlike lakes, maintain high temperatures conducive to methane generation because they do not undergo turnover. Beavers stir up the bottom sediments, making the water appear nearly black. On a day when the ambient temperature is 22° C, the temperature of the water can measure as high as 30°C. Researchers at the Center have found that beaver ponds are point sources for huge amounts of methane, and represent the single largest flux rate per unit area, producing 1000 mg methane/m^/day, or five times the normal rate. Controls of DMS Production by Phytoplankton in Marine Ecosystems: ERC staff have initiated studies of the controls of dimethylsulfide (DMS) production by phytoplankton in marine ecosystems. DMS is the principal volatile sulfur compound emitted from the oceans, with total oceanic fluxes constituting about 20% of the total (anthropogenic + biogenic) sulfur input to the global atmosphere. These gaseous fluxes are a critical factor in the control of global climate because DMS is a precursor in the formation of cloud condensation nuclei. The abundance of these nuclei influences the reflectivity of marine clouds and thus the albedo of the earth; increasing DMS may lead to global cooling or less rapid warming than would be expected from increasing concentrations of "greenhouse" 45 ------- gases. While phytoplankton are known to be the main natural source of DMS, the mechanisms and controls of DMS production are unknown. The objective of the Center's research this year has been to develop methods suitable for testing the hypotheses in laboratory and field experiments and to run preliminary experiments that test the linkage of molybdenum availability, nitrogen assimilation, and DMS production by phytoplankton (Mo is an essential element in the enzymes used for nitrate reduction and nitrogen fixation). In addition to adapting existing methods from the literature to measure accurately DMS concentrations in seawater and DMSP (the biochemical precursor of DMS) in phytoplankton cells, the Center has developed a new method that efficiently traps DMS in an organic solvent compatible with a scintillation cocktail. Recovery of standards exceeds 95%. This method allows direct measurement of the rates of DMS production and consumption in situ, using 35s. Using this radioisotopic assay, it is possible to run experiments in the field as well as in the laboratory. While Center researchers have encountered difficulties in culturing marine phytoplankton in a manner suitable for their experiments on the role of molybdenum and nitrogen in controlling DMS production, one experiment has been conducted using a natural assemblage of freshwater phytoplankton that was dominated by cyanobacteria (blue-green "algae"). This is the only freshwater phytoplankton group that produces significant quantities of DMS. The hypothesis was that if DMS production is related to the uptake of molybdenum for nitrogen assimilation, then cyanobacteria that are fixing nitrogen will produce more DMSP than cyanobacteria that use reduced N (as ammonium). Results that were consistent with this hypothesis were obtained during the first two days of a batch experiment with two treatments: (1) additions of phosphate and ammonium, and (2) additions of just phosphate. With phosphate alone cyanobacteria rapidly fixed N and nearly doubled the concentration of DMSP, while with the addition of both phosphate and ammonium no change occurred in the DMSP concentration of non-fixing cultures. After these initial days, however, the batch cultures grew very dense and DMSP concentrations dropped rapidly in both treatments. This experiment is currently being repeated. During the past year, Center researchers have presented their hypotheses and perspectives on current DMS research and global climate change at a Cornell University symposium, a Cornell short course on global 46 ------- climate change, and in an invited presentation at a symposium of the Ecological Society of America (ESA). A report on the Center's ESA presentation was to be published in the November 1990 issue of Bioscience. Finally, with ERC support, a proposal was approved by the U.S. EPA Environmental Biology Research Program to sustain this study of the controls of DMS production. Dormant Stages as Buffers Against Environmental Change: Marked changes in global climate will alter lake environments, with the possibility that lake depths may be reduced. The effects of such change on planktonic communities will in part depend upon the amount of genetic variation present in populations. Scientists at the Center have been testing the hypothesis that dormant eggs, stored in lake sediments of deeper reaches, represent a reservoir of genetic variation that may act as a buffer against environmental change if lower water levels release them. Dormant eggs from the copepod Diaptomus sanguineus are abundant in lake sediments and remain viable for decades. The present study aims to compare levels of genetic variation found in D. sanguineus dormant eggs, sampled and hatched from sediment cores, to those of active individuals. A cellulose acetate enzyme electrophoresis system was developed to assay genetic variation in Diaptomus sanguineus. Using this system, researchers have established the level of variation in natural populations of this species. In anticipation of extending dormant stage analyses into larger lakes, genetic variation for a similar array of enzymes was also examined in two additional copepod species (D. minutus and D oregonensis) and 2 other crustacean species (Daphnia pulicaria and D galeata) from Oneida Lake, N.Y. Genetic variation was assayed in dormant eggs from D. sanguineus collected from live adult females. Because of the microscopic size of the eggs, which are only lOOfim, this work has extended the analysis capability of the electrophoretic system beyond anything previously attempted. The Agronomic and Economic Consequences of Gradual Climate Change: A Preliminary Investigation of Midwestern Crop Farming: If the global climate is in fact changing as rapidly as many experts believe, agriculture will have to respond accordingly. Climate change will affect the agricultural ecosystem: the course of growth and the yield of field crops will change, as will the periods of time available for field operations. These changes will be reflected in the decisions made by farmers. 47 ------- In response to these problems, Center researchers wanted to develop an interdisciplinary protocol which could be used to model the effects of climate change on farm operations and profitability and to apply this protocol to a case study with important policy implications. A complete experimental protocol has been developed and put in written form. This protocol is unique in attempting to track the effects of climate through a mechanistic atmosphere-soil-crop model to a model of farm-level decision making. It combines models from the fields of climatology, soil science, crop physiology, and agricultural economics in a unified framework to predict the effect of gradual climate change on farm operations and profitability. The model is composed of several integrated parts, including a FORTRAN subroutine to generate daily climates under different scenarios, a complete restructuring of a previous crop model, inclusion of the ability to compute and record field hours, and construction of a composite soil profile. It is unusual in its emphasis on soils, and its investigation of the effects of gradual climate change. Preliminary simulation results show, for example, that maize yields could be maintained in a period of warming through the introduction of later maturing varieties, i.e., varieties that under present conditions would be considered "super late". Several experimental runs have been made on the economic component of the model as well. When complete, the model will predict the decisions which would be made by midwestern grain farmers in the face of changing climate, and through the decisions, the levels of production of various grain crops, and the profitability of farms. Further efforts on this project will be supported by funds from the U.S. Department of Agriculture. Potential Effects of Global Climate Change on Fisheries: Initial research on this project involved a study of published material to define how lentic (still water) freshwater and marine fish yields varied as a factor of large scale climate differences. Two very different patterns were found for oceanic and inland waters. The latter exhibit yields that are high in the tropics and one to two orders of magnitude lower at temperate and subarctic latitudes. In contrast, marine fishery yields show much less relation to latitude. Marine and freshwater systems were compared and suggest that the hypothesis that fish yields bear a strong positive relation to temperature is 48 ------- not correct. Center scientists are pursuing the alternative hypothesis that mixing is the key determinant of fish yield. Surrogates are being sought, such as, average wind velocity (with effects modified by water depth), that adequately represent mixing as a determinant of fish yield. A model of yield as a function of mixing and, as appropriate, other variables, is being developed. Once this is accomplished, researchers will couple this model with global climate model-generated climate change scenarios. This work was presented at the Annual Meeting of the American Society of Limnology and Oceanography held in Williamsburg, Virginia, June 11-14, 1990. Control of Fine Root Growth in Tropical Forests: The consequences of deforestation of the tropics are of tremendous concern both locally and globally. An understanding of basic ecosystem properties within tropical forests is necessary for effective management, and also for predicting and compensating for the climatic changes that may occur as a result of global warming and/or deforestation. With funding from the Smithsonian Institution, ERC staff are examining the control of fine root growth within the tropical moist forest on Barro Colorado Island, Republic of Panama. Because temperature and photoperiod are relatively constant within tropical forests, the seasonal changes in rainfall are thought to be the ultimate cause of seasonality. Thus the global changes in precipitation patterns that are expected to accompany global climate warming may affect the growth and productivity of tropical forests. In particular, researchers are investigating how water and soil nutrient resources act in concert to control rates and timing of fine root growth. Current research demonstrates that biological processes are much more important than physical processes in maintaining nutrients in the soil. In other words, soil microbes and fine roots play a tremendous role in nutrient conservation. For example, 50% of the phosphorus in this system is found within microbes, as compared to 5% in other systems. The ramifications of these findings are substantial. Microbes and fine roots, the natural conservers of nutrients, are destroyed when tropical forests are cut down and used for field crops or pasture. This explains why these soils lose their fertility within a few growing seasons after deforestation. 49 ------- Socioeconomic Implications of Global Warming: The purpose of this project was to reassess the approaches taken by social scientists to global change-related phenomena, particularly global warming and sustainable development. The study produced four major findings. First, virtually all social science literature on global change and global warming is based on an assumption that global warming scenarios are very likely; social scientists appear to accept the likelihood of global warming more than most climate researchers. Most of the social science literature has therefore been devoted to understanding the social factors that contribute to global warming and the social mechanisms that might enable policy changes that can respond to the global warming threat. Clearly both the social and environmental science communities need to be aware of the social implications of the extraordinary growth of extra- scientific consensus that has developed over global warming. Second, many popularized notions from modern environmental science now have a complicated, and sometimes contradictory, status of serving simultaneously as scientific concepts and as social movement ideology. A very rapid shift was observed in the stance of most major environmental organizations over the past few years toward basing their goals and rationales for policy changes on the concepts of global change and global warming. Global change has thus, in a sense, become the predominant ideological form of the international environmental movement. The interrelations of environmentalists and environmental scientists are thus very important to an understanding of the development of environmental science knowledge and the role this knowledge plays in policy formulation. Third, a key component of the diffusion of global change and global warming knowledge to the public is that it must be packaged in a way that can build popular awareness and support. Center staff focused on a comparison between the current milieu of global change and global warming, on one hand, and the experience 15 years ago with "the limits to growth", on the other. There are many factors that apparently have led to greater popular concern about global change/warming than was the case with the limits to growth. One of them is that there has been a tendency to frame discussions of global change/warming in relatively benign terms with respect to societal sacrifices, as compared to the relatively draconian implications (zero economic growth, stringent population control, etc.) that were part of the limits to growth notion. Despite the fact that global change/warming would imply the need for some very significant and rapid changes in energy policy, this has not been given major emphasis in the 50 ------- popularized literature on global warming. In fact, there is a tendency for the need for new and/or alternative energy sources, often including nuclear power, to be stressed over the need for very strict conservation. Finally, many of the prominently-discussed policies for addressing global change and related problems suggest either the possibility of future dissension or potentially negative implications for particular social groups and countries. The current framing of global change/warming issues tends not to stress energy conservation, and often is limited to discussing alternatives to coal and other fossil fuels for producing as much energy as is now consumed. This will increase the likelihood of a significant renaissance of nuclear power. Among other implications, this may ultimately split the environmental community into anti-nuclear and relatively pro-nuclear factions. In addition, many Third World states are beginning to react against some of the concerns expressed by environmental groups and public entities on tropical deforestation as it relates to global change issues. Wetlands Research Wetland regulation under Section 404 of the Clean Water Act and the current federal policy of "no net loss" of wetlands is based in part on scientific understanding of the value of wetlands as habitats for particular species and on their capacity to modify the chemistry of water moving through them. ERC staff continue to conduct fundamental studies on the factors controlling: (a) wetland modification of surface and ground water moving through them, and (b) maintenance of fen communities as habitats for rare plant species. The applied aspect of the Center's work continues to focus on the development of cumulative impact assessment for wetland landscapes and regions. Investigation of Soil—Stream Interactions in Natural and Man-Manipulated Watersheds: Typically within forested watersheds of the Northeast, headwater streams are associated with small wetland areas. Although the extent of these areas is small, their functional role may be large. For example, it is thought that a large portion of the water draining the upland portions of these watersheds passes through the wetlands before entering the stream. Therefore the chemistry of the stream water appears to be altered substantially by biological and physicochemical processes occurring within the wetland areas. With support from the National Science Foundation, ERC staff have monitored water and soil chemistry of two small wetland areas within the Bear Brook 51 ------- watershed of the Hubbard Brook Experimental Forest, located in the White Mountains of New Hampshire. The results of this study have important implications for the logging industry, which does not take special precautions to prevent erosional damage of wetlands when wetlands comprise so small a portion of the landscape. As a result, logging may damage wetland areas irreparably. Transport of Gases Between the Shoots and Roots of Wetland Plants: The ability of wetland plants to transport oxygen through their shoots to roots and the zone immediately around their roots has been of longstanding interest among plant scientists as an explanation for survival in flooded soils. Current interest in this plant mediated transfer of oxygen between the atmosphere and root zone extends beyond flooding tolerance to the capacity of wetland plants to influence biogeochemical cycles through effects on sediment oxidation-reduction processes in the bulk sediment. Results of previous studies, however, have not been conclusive. Some studies report no net release of oxygen; others report high rates or variable rates of release. Few studies have been done on freshwater wetland species and the methods used in some of these studies are questionable with regard to their applicability to whole, mature wetland plants growing over extended periods of time. The Center developed an experimental system and procedures for testing mature wetland plants over periods of several weeks. The results for five different species show that the net effect of wetland plants is not to oxygenate their root environment. This finding is controversial and has serious implications for the design of constructed wetlands for waste water treatment, the carbon budgets of wetlands, and methane production within wetlands. The results of this study have been submitted for publication in the peer-reviewed literature and were presented as a poster at the Ecological Society of America's Annual Meeting, 31 July 1990. Mitigation of Acidified Water Through Soil Liming: As part of the Experimental Watershed Liming Study funded by the Electric Power Research Institute (EPRI) and Living Lakes, Inc., ERC staff have monitored water and soil chemistry of several different small wetland areas within a limed watershed and have quantitatively described the pattern of lime distribution. These wetland areas are home to a wide variety of plant species. It was expected that liming in the wetlands would lead to degradation of these areas, but thus far this is not the case. On the 52 ------- contrary, it was found that the wetlands sustained minor damage only in hollow areas, while hummocks were not disturbed; plants that died in the hollows were quickly replaced by other, more pH tolerant species. Lime washed out of the wetlands and into the lake, and thus the pH of the wetlands was not affected in any significant manner. Vegetation and Water Chemistry of New York Fens: In New York State, fens are uncommon peatland communities that include several rare species. With the goals of refining a classification of fen communities, establishing permanent plots for monitoring, and determining relationships between vegetation and surface water chemistry, ERC staff sampled 19 lOOrn^ plots at fen sites in 13 counties throughout New York State. The sites .represent seven types of fen communities currently recognized by the NY Natural Heritage Program: inland poor fen, Coastal Plain poor fen, medium fen, rich graminoid fen, rich sloping fen, rich shrub fen, and marl fen. These fens occur at elevations ranging from 8m on Long Island to 640m in the Adirondack Mountains. It was found that species richness tends to be positively correlated with surface water pH, conductivity, and concentration of calcium, as well as with soil pH. Species composition appears to be related to low nutrient water feeding these sites. These sites, therefore, are threatened by nutrient rich run-off from agriculture. These results were presented in a poster session of the Annual Meeting of the Ecological Society of America, Snowbird, Utah, 31 July 1990. Great Lakes Wetlands: A Cumulative Impact Assessment: A paper on this topic was presented at the International Symposium on Great Lakes Wetlands, and will be published in the proceedings of the symposium. When Great Lakes wetlands are analyzed at the level of the entire Great Lakes Basin, it is evident that the cumulative impact of human activities on the total wetland resource base has been extremely severe. Most wetlands within the basin have been lost, and of those that remain, most are degraded. Only a relatively small number and acreage of high quality, undisturbed sites remain. These should be given high priority for protection. Degraded sites should be evaluated for restoration. The Center has proposed a framework for cumulative impact assessment for the entire Great Lakes basin. Ecotones Workshop; In collaboration with the ERC, Oak Ridge National Laboratories (ORNL) conducted a workshop to facilitate the testing of theories about the role of wetland and riparian ecotones (zones of 53 ------- transition between ecosystems) in landscape dynamics. As the scale of environmental problems expands from the local to the regional and global, various scientific and policy groups have begun to focus on theories and methods for addressing issues at these larger scales. Several promising conceptual and methodological advances have been made in characterizing spatial-temporal patterns of entire landscapes and in quantifying exchanges across ecosystem boundaries within those landscapes. One general theory that has emerged from these advances is that ecotones — zones of transition between ecosystems — are particularly susceptible to environmental changes. The policy implication is that they therefore should be monitored as early indicators of human impacts on landscape dynamics. The present need is for data with which to test specific hypotheses about ecotones and to guide future monitoring efforts. This workshop, funded by the U.S. Man and the Biosphere Program, the EPA, and the U.S. Department of Energy, focused on applying theory, identifying existing date and needed data, and developing methods. A report for the peer-reviewed literature is in preparation. Scale and Modeling Issues ERC staff continue to address the conceptual and methodological problems associated with modeling total ecosystem response to stress. Efforts have focused on four areas: (1) considerations of scale in modeling ecosystems, (2) modeling plant responses to interactive stresses, (3) landscape modeling, and (4) theoretical models of the spread of agricultural pests in fragmented landscapes. Problems of Scale in Ecosystem Modeling: ERC staff are involved in an ongoing set of projects to understand the relationship between scale and ecosystem dynamics. These projects are currently funded by the ERC Center, the National Science Foundation (NSF), the National Aeronautics and Space Administration (NASA), and the National Oceanic and Atmospheric Administration (NO A A). The issues of scale are among the most fundamental of those facing ecosystem modelers and policymakers. The relationship of properties across different scales is central to addressing questions of global climate change and determining the ecological significance of different types of environmental stress. These problems include merging temporal and spatial scales, and extrapolating data collected on one scale to phenomena occurring at another. With the advent of high speed computers, it is now possible to take a comprehensive approach to understanding the relationship of pattern to scale in varied ecosystems, thus enabling 54 ------- scientists to explore the dependence of species and community patterns on underlying dynamic processes within the ecosystem. Disturbances to ecosystems come in many varieties, and these and other events introduce complicated patterns of spatial and temporal correlation into natural systems. To address these issues, and to develop a method for the analysis of such disturbance controlled systems, the Center is examining a variety of descriptors of spatial and temporal pattern, and is applying them to systems in which localized disturbance is a critical determinant of landscape pattern. The properties of the pattern descriptors are being investigated, using several approaches: analysis of computer simulations of simple systems, analysis of spatial data sets, and finally integration of experimental and modeling studies of serpentine grassland located at Jasper Ridge in California and Northeastern temperate forests. Among the advantages of the latter approach is that it is possible to compare model predictions and experimental results over a range of scales. Integration of experimental studies with modeling allows scientists to improve the model using information gained through experimentation and to design experiments suggested by model predictions. A further advantage of a modeling approach is that extrapolation is possible across scales of space and time in a way that cannot be accomplished using experimental studies alone. Center personnel have developed a theory extending the use of spectral analysis and autocorrelation analysis to determine the critical scales driving ecosystem dynamics. The underlying motivation for this project is to develop approaches to interpret empirical results from a variety of studies on different ecosystems including, for example, information obtained from remote sensing, since such information is typically available only for a limited range of spatial and temporal scales. In a closely related project funded by the Department of Energy and NASA, the Center is in the initial phase of developing, empirically calibrating, and testing a theory of forest dynamics that encompasses a broad range of spatial and temporal scales. The research consists of an integrated program of computer and mathematical modeling, analysis of remotely sensed images of pattern in forested systems, and empirical studies of twelve forest tree species that are canopy dominants in transition oak—northern hardwood forests. The work involves investigators from three institutions: Cornell, the University of Connecticut, and the Institute of Ecosystem Studies. The principal objective of the work is to understand the factors controlling forest community dynamics and structure and, specifically, to identify the 55 ------- ecological processes responsible for observed spatial and temporal patterns across a broad range of scales and determine how these processes become represented in a scale-dependent pattern. ROPIS: Response of Plants to Tnteractive Stresses: Ecosystems and the plants and animals they contain are being exposed to more than one pollutant simultaneously. For example, mountain regions in the Northeastern U.S. that are receiving large amounts of acidic precipitation are also being exposed to periodic high concentrations of ozone. Further, organisms under stress from natural agents, such as drought or nutrient limitation, can have increased susceptibility to pollutant damage. However, most regulatory efforts to protect ecosystems from damage have treated each pollutant independently. It is therefore critical to understand how an array of co-occurring stresses can exacerbate or alter the growth patterns of organisms. The simulation model, TREGRO, was developed by ERC staff to analyze the response of red spruce trees to multiple stresses, in particular exposure to ozone and acidic deposition. The most important function of the model is to examine the mechanisms by which different stresses cause responses in plants, including alterations in the processes of photosynthesis, allocation, and damage repair. The model can aid in evaluating the long term effect of pollution upon resource availability, the potential for gradual deterioration of tree health under long periods of pollution exposure, and imbalances in growth accompanying shifts in carbon allocation. Because of these capabilities, TREGRO was used as part of the 1989 NAPAP assessment to provide insight into factors that increase the probability of significant pollution damage to trees. Center personnel predicted a decrease in growth and shifting pattern of carbon allocation expected for an isolated tree exposed to ozone and decreased nutrient availability due to acidic deposition. Researchers have identified some of the conditions under which a tree is likely to be able to alter its growth or resource allocation pattern to mitigate against long term damage. As a bookkeeping device, identifying small changes in pools of carbon resources within the tree, the model has suggested trends in the deterioration of tree health under pollutant exposure that may become measurable only after many years of exposure. Policy makers must be able to have hands-on experience with assessment tools such as TREGRO in order to sort through the complexities involved in setting standards for pollutants under real-world conditions. 56 ------- The goal is to provide an educational software package that can be used by a wide range of people, from managers to scientists, to further their understanding of plant responses to stress. The model structure which was developed provides a tool for the user to explore easily the variables that affect plant response to pollutants. New types of displays are being added, including animations of growing trees, that will demonstrate visually the predicted responses of a tree to different types of stress. In the future, this software will be developed further by adding systems structures that will lead users to a better understanding of the ramifications of model results. Finally, Center researchers are beginning to work with scientists at the EPA laboratory in Corvallis, Oregon to test the ability of the model to communicate these important concepts. Landscape Modeling: In addition to other modeling activities, ERC staff have begun to develop the conceptual basis for creating a new type of ecological simulation model. The concept is to distribute ecosystem and agricultural simulation models across a spatial grid that could represent the landscape at the regional level. One of the aims of this new model is to increase the spatial scale of ecological models in order to match the minimum scales of climate models. The approach is to use highly parallel computing systems, with a central processor dedicated to a geographic information system (GIS) platform through which the landscape is illustrated and through which information is exchanged among the individual ecosystem cells of the landscape. Each individual ecosystem type (e.g., deciduous forest, grassland, maize crop, etc.) will be simulated by a process-based simulation model implemented on a single processor of the parallel computer. Thus, all cells in the landscape that are of a particular ecosystem type will be simulated by a particular processor, at the same time that all the cells of another ecosystem type are simulated by another processor. The initial scheme is to use the Cornell Theory Center's HyperCube computer, consisting of 32 386-equivalent processors, but new purchases by the Theory Center may provide greater computing capabilities. The overall structure of the landscape model has been developed, acquired committed time and space on the HyperCube, and prepared a research proposal for funding the actual model development. Modeling the Spread of Agricultural Pests: In a modeling project supported by Hatch funds from the Department of Agriculture, Center researchers are studying theoretical models of the spread of agricultural pests in fragmented landscapes. Center researchers are considering the dynamics of spread of insect pests and weeds using models 57 ------- ranging from classical diffusion models to more recently developed models involving interacting particle systems and percolation theory. From these building blocks, more complex simulation models will be developed to run on the supercomputer at the Cornell National Supercomputer facility. Technical Support to EPA; ERC continues to provide technical support to EPA through participation in meetings and workshops, review panels and working groups, individual meetings with EPA staff, and the review of proposals. As part of the EPA Science Advisory Board Environmental Risk Reduction Project, ERC staff served on the ecological welfare risk subcommittee of the Relative Risk Reduction Strategies Committee (RRRSC), and developed the methodology that was used to establish the relative risk rankings for environmental problems affecting ecological systems and human welfare. In conjunction with participation in this subcommittee, ERC staff gave briefings to EPA personnel and NSF program officers, wrote substantial parts of the subcommittee report, and drafted a manuscript for publication in Environmental Management entitled, "Prioritizing ecological and Human Welfare Risks from Environmental Stresses." The RRRSC report, "Reducing Risk: Setting Priorities and Strategies for Environmental Protection," was released by EPA Administrator William Reilly on September 25, 1990. ERC staff participated in the EPA's Ecological Risk Assessment Forum by preparing input that described the process of characterizing how ecosystems are exposed to, respond to, recover from and adapt to stress. Each of these areas requires understanding a full set of issues concerning ecological endpoints and ecological indicators, subjects studied in depth by ERC staff over the past few years. That input is being incorporated into a series of colloquia proceedings presently in preparation by the Forum. In addition, ERC staff assisted the Forum in its development of ecological risk assessment guidelines, and will continue into next year as a primary scientific adviser for preparation of Forum documents on risk assessment. ERC staff continued to participate in various EPA Science Advisory Board Subcommittee meetings reviewing EPA's reports to Congress on global climate change scientific issues, policy issues, and strategic options. They also participated in the scientific review of studies performed by EPA's Office of Policy, Planning, and Evaluation on the agricultural effects 58 ------- of climate change, served as reviewer of the science study and summary reports for the Intergovernmental Panel on Climate Change, and contributed to chapters by the effects study group on ecological and agricultural effects. RESEARCH GOALS — FY 1991 During the Center's final year, the primary goals are to achieve a smooth shut-down of ERC operations, and to complete papers for submission and dissemination of information about recent accomplishments. Research efforts will continue on biomonitoring, the terrestrial ecology of closed fly ash landfills, DMS and other trace gas production, tropical forest nutrient analysis, soil-stream interactions, and liming of watersheds. The study of New York fens will be extended to focus on the threat to these areas from nutrient rich run-off from agriculture. In addition, research will continue on into the relationship between scale and ecosystem dynamics by adding extensions to the Jasper Ridge simulation model, and further refinements will be made to TREGRO model. As many ERC-sponsored projects now receive substantial portions of their financial support from agencies other than the EPA, these projects will continue to evolve beyond the end of the ERC program as a whole. OUTPUTS — FY 1990 Number of Articles in Refereed Journals 9 Number of Articles Submitted or In Press 18 Books and Bound Proceedings 2 Chapters in Other Books 16 Project Reports 0 Conferences and Workshops Held 1 59 ------- BIBLIOGRAPHY REFEREED JOURNAL ARTICLES Andow, D.A., P.M. Kareiva, S.A. Levin, and A. Okubo, "Spread of Invading Organisms," Landscape Ecology. Vol. 4, No. 2/3, pp. 177-188, 1990. Ford, J., "A 10,000 Year History of Natural Ecosystem Acidification," Ecological Monographs. Vol. 60, No. 1, pp. 57-89, 1990. Kelly, J.R., D.T. Rudnick, R.D. Morton, L. Buttel, S.N. Levine, and K.A. Carr, "Tributyltin and Invertebrates of A Seagrass Ecosystem: Exposure and Response of Different Species," Marine Environmental Research. Vol. 29, pp. 245-276, 1990. Limburg, K.E. and R.E. Schmidt, "Patterns of Fish Spawning in the Hudson River Watershed: Biological Response to An Urban Gradient," Ecology. Vol. 71, pp. 1238-1245, 1990. Stoewsand, G.S., J.L. Anderson, L.H. Weinstein, J.F. Osmeloski, W.H. Gutenmann, and D.J. Lisk, "Selenium in Tissues of Rats Fed Rutabagas Grown on Soil Covering A Coal Fly Ash Landfill," Bulletin of Environmental Contaminant Toxicology. Vol. 44, pp. 681-685, 1990. Weinstein, L.H., J.F. Osmeloski, J.B. McCahan, C.A. Bache, A.O. Beers, and D.J. Lisk, "Uptake of Chemical Elements by Grasses and Legumes Growing on Soil Covering Coal Fly Ash Landfill Sites," Journal of Food Safety. Vol. 9, pp. 291-300, 1989. Wieder, R.K., J.B. Yavitt, and G.E. Lang, "Methane Production and Sulfate Reduction in Two Appalachian Peatlands," Biogeochemistry. Vol. 10, pp. 81-104, 1990. Yavitt, J.B., D.M. Downey, E. Lancaster, and G.E. Lang, "Methane Consumption in Decomposing Sphagnum-derived Peat," Soil Biology and Biochemistry. Vol. 22, No. 4, pp. 441-447, 1990. Yavitt, J.B., D.M. Downey, A.J. Sexstone, and G.E. Lang, "Methane Consumption in Two Temperate Forest Soils," Biogeochemistrv. Vol. 9, pp. 39-52, 1990. 60 ------- ARTICLES SUBMITTED OR IN PRESS Bedford, B.L., D.R. Bouldin, and B.D. Beliveau, "Net Oxygen and Carbon Dioxide Balances in Solutions Bathing Roots of Wetland Plants," Journal of Ecology, submitted, 1990. Dwyer, G., S.A. Levin, and L. Buttel, "A Simulation Model of the Population Dynamics and Evolution of Myxomatosis," Ecological Monographs, in press, 1990. Frithsen, J.B., D.T. Rudnick, and C.A. Oviatt, "Long-term Patterns of Macrobenthic Community Response to Nutrient Enrichment," Journal of Marine Science, submitted, 1989. Gore, J.A., J.R. Kelly, and J.D. Yount, "Application of Ecological Theory to Determining the Recovery Potential of Disturbed Lotic Ecosystems: Research Needs and Priorities," Environmental Management, in press, 1990. Hambright, K.D., R.W. Drenner, S.R. McLomas, and N.G. Hairston, Jr., "Gape-limited Piscivores, Prey Size Refuges, and the Trophic Cascade," Limnologica 21. in press, 1990. Kelly, J. R., "Consumer and Supplier Roles of the Benthos Relative to Phytoplankton Production: A Simple Classification Diagram," Journal of Marine Research, submitted, 1990. Kelly, J.R., "Experimental Studies on Benthic-pelagic Nutrient and Carbon Dynamics with Nutrient Enrichment of Shallow Coastal Ecosystems," Journal of Marine Research, submitted, 1990. Kelly, J.R., "Paradigms of Benthic-pelagic Coupling of Carbon and Nutrients in Coastal Ecosystems as Derived from Annual Field Studies," Journal of Marine Research, submitted, 1990. Kelly, J.R., L. Buttel, S.N. Levine, K.A. Carr, D.T. Rudnick, and R.D. Morton, "Tributyltin Effects Within A Thalassia Seagrass Ecosystem," Estuaries, in press, 1990. Kelly, J.R. and M.A. Harwell, "Indicators of Ecosystem Recovery," Environmental Management, in press, 1990. 61 ------- Levine, S.N., D.T. Rudnick, J.R. Kelly, R.D. Morton, L. Buttel, and K.A. Carr, "Pollutant Dynamics as Influenced by Seagrass Beds: Experiments with Tributyltin in Thalassia Microcosms," Marine Environmental Research. in press, 1990. Moloney, K.A., "Shifting Demographic Control of A Perennial Bunchgrass Along A Natural Habitat Gradient," Ecology, in press, 1990. Moloney, K.A., S.A. Levin, N. R. Chiariello, L. Buttel, "Pattern and Scale in A Serpentine Grassland," Theoretical Population Biology, submitted, 1990. Morin, A., K.D. Hambright, N.G. Hairston, Jr., D.M. Sherman, and R.W. Howarth, "Consumer Control of Gross Primary Production in Replocate Freshwater Ponds," Internationale Vereinigung for Theoretische und Angewandte Limnologie 24. in press, 1990. Rudnick, D.T., G.T. Banta, A.E. Giblin, J.E. Hobbie, and R.W. Howarth, "Controls of Carbon Cycling in Marine Sediments: Are Anoxia and Porewater Metabolites Important?" Science, submitted, 1990. Yavitt, J.B. and G.E. Lang, "Methane Production in Contrasting Peatland Sites: Responses to Substrate Quality and to Sulfate Reduction," Geomicrobiology Journal, in press, 1990. Yavitt, J.B., G.E. Lang, and A.J. Sexstone, "Methane Fluxes in Wetland and Forest Soils, Beaver Ponds, and Low-order Streams of A Temperate Forest Ecosytem," Journal of Geophysical Research, in press, 1990. Yavitt, J.B. and R.M. Newton, "Liming Effects on Some Chemical and Biological Parameters of Soils (Spodosols and Histosols) in A Hardwood- Forest Watershed," Water. Air, and Soil Pollution, in press, 1990. BOOKS AND BOUND PROCEEDINGS Castillo-Chavez, C., S.A. Levin, and C. Shoemaker, eds., "Mathematical Approaches to Problems in Resource Management and Epidemiology," Lecture Notes in Biomathematics. Vol. 81, Springer-Verlag, Heidelberg, 1989. Levin, S.A., T.G. Hallam, and LJ. Gross, eds., "Applied Mathematical Ecology," Biomathematics. Vol. 18, Springer-Verlag, Heidelberg, 1989. 62 ------- CHAPTERS IN BOOKS AND BOUND PROCEEDINGS Andow, D.A., P.M. Karieva, S.A. Levin, and A. Okubo, "Spread of Invading Organisms: Patterns of Spread," Evolution of Insect Pests: The Pattern of Variations. (K.C. Kim, ed.) John Wiley and Sons, New York, in press, 1990. Bedford, B.L., "Assessing Impacts on Peatland Ecosystems: Feedbacks Between Vegetation and Environment," Proceedings of the British Ecological Society International Symposium on Peatland Ecosystems: An Impact Assessment, in press, 1990. Bedford, B.L., "Increasing the Scale of Analysis: The Challenge of Cumulative Impact Assessment for Great Lakes wetlands," Proceedings of the International Symposium on Wetlands of the Great Lakes, submitted, 1990. Castillo-Chavez, C., K. Cooke, and S.A. Levin, "On the Modeling of Epidemics," Proceedings of European Symposium on High Performance Computing. March. 1989. Montpellier, France, pp. 389-402, (J.-L. Delhaye and E. Gelenbe, eds.) Elsevier Science Publishers B.V., North Holland, 1989. Harwell, M.A., C.C. Harwell, D.A. Weinstein, and J.R. Kelly, "Characterizing Ecosystem Responses to Stress," Ecological Risks: Perspectives from Poland and the United States, pp. 91-115, (W. Grodzinski et al., eds.) National Academy Press, Washington, D.C., 1990. Levin, S.A., "An Ecological Perspective," Proceedings of a Conference on The Genetic Revolution: Scientific Prospects and Public Perceptions. American Academy of Arts and Sciences, Cambridge, Massachusetts, May 19-20, 1989, in press, 1990. Levin, S.A., "Models in Ecotoxicology: Methodological Aspects," Applied Mathematical Ecology. Biomathematics. Vol. 18, pp. 315-321, (S.A. Levin, T.G. Hallam, and L.J. Gross, eds.) Springer-Verlag, Heidelberg, 1989. Levin, S.A., "Physical and Biological Scales, and the Modeling of Predator-prey Interactions in Large Marine Ecosystems," Patterns. Processes, and Yields of Large Marine Ecosystems. AAAS Selected Symposium. (K. Sherman and L.M. Alexander, eds.) American Association for the Advancement of Science, in press, 1990. 63 ------- Levin, S.A., "The Mathematics of Complex Systems," Ecosystem Experiments. Proceedings of the SCOPE Ecosystem Experiments Workshop. June 13-15, 1988, Mitwitz, Germany, in press, 1990. McGlathery, K.J., R. Howarth, and R. Marino, "Nutrient Limitation of the Rhizoid Macroalga, Penicillus Capitatus, in Bermuda," Proceedings of Factors Regulating Primary Production in Coastal Environments Symposium, submitted, Estuaries, 1989. Weinstein, D.A., "Use of Simulation Models to Evaluate the Alteration of Ecotones by Global Carbon Dioxide Increases," Proceedings of the Scientific Committee on Problems of the Environment (SCOPE') Conference. December, 1988, (F. DiCastri and A. Hansen, eds.) Paris, France, in review, 1990. Weinstein, D.A., and R. Beloin, "Evaluating Effects of Pollutants on Integrated Tree Processes: A Model of Carbon, Water, and Nutrient Balances," Forest Growth: Process Modeling of Forest Growth Responses to Environmental Stress, pp. 313-323, (R.K. Dixon, R.S. Meldahl, G.A. Ruark, and W.G. Warren, eds.) Timber Press, Portland, Oregon, 1990. Weinstein, D.A. and R. Beloin, "TREGRO, a Model of Carbon, Water, and Nutrient Balances to Predict Response of Plants to Interacting Stresses," National Acid Precipitation Assessment Program: State of Science and State of Technology Report No. 28: The Development and Use of Tree and Forest Response Models. (R. Kiester et al., eds.) in press, 1990. Weinstein, L. H., M. Richmond, E.W. Wischusen, R.E. Schneider, J.A. Laurence, A.O. Beers, and G. Rubin, "Uptake and Accumulation of Chemical Elements by Terrestrial Plants Growing on A Coal Fly Ash Landfill," Proceedings of International Conference on Metals in Soils. Waters. Plants and Animals. Symposium on Coal Combustion Products, in review, 1990. Wieder, R.K., J.B. Yavitt, and G.E. Lang, "Sulfur Cycling in A Freshwater Sphagnum-dominated Wetland: A Case Study," Proceedings of Sulphur Cycling in Terrestrial Systems and Wetlands. SCOPE. (R.W. Howarth and J.W.B. Stewart, eds.t Paris, in review, 1989. Yavitt, J.B., "Methane, Biogeochemical Cycle of," Encyclopedia of Earth System Science. (W.A. Nierenberg. ed.) Academic Press. San Diego, California, in press, 1990. 64 ------- CONFERENCES AND WORKSHOPS HELD "Wetlands and Riparian Ecotones in Landscape Dynamics: A Workshop on Applying Theory, Data, and Methods," held in Oak Ridge, Tenn., September 18-21, 1990, in collaboration with Oak Ridge National Laboratory. 65 ------- 66 ------- CENTER: Hazardous Waste Research Center LOCATION: Louisiana State University DIRECTOR: Louis J. Thibodeaux Hazardous Waste Research Center 3418 CEBA Building Baton Rouge, LA 70803 504/388-6770 FAX: 504/388-5990 PROJECT OFFICER: David G. Stephan U.S. Environmental Protection Agency Risk Reduction Engineering Laboratory 26 Martin Luther King Drive Cincinnati, OH 45268 513/569-7896 FTS: 684-7896 FUNDS SPENT DURING FY 1990 (10/1/80 - 9/30/90) EPA $540,000 Other Government 543,359 University 64,616 Private Sector 143,000 Total $1,290,975 DESCRIPTION OF THE PROGRAM The Hazardous Waste Research Center (HWRC) conducts research on fundamental and applied aspects of hazardous waste treatment and disposal. The purpose of this research is to provide better options for waste management by contributing to the development of advanced technologies for the destruction, detoxification, recovery, or containment of hazardous wastes. The Center has three research priorities. These are: (1) incineration, (2) alternate methods of treatment/destruction, and (3) interaction of waste constituents and natural media. The incineration research program seeks to develop a basic understanding of the underlying chemical and physical mechanisms of kiln incineration, including how waste volatility 67 ------- and bed composition affect system performance and the relative extent to which volatilized wastes are destroyed in the flame region of the kiln and afterburner. The focus of the alternative waste treatment methods research is on destruction of hazardous organic wastes by biological treatment and electrokinetic soil processing. Research on waste interaction with natural media includes a study of reactions occurring during cement hydration in the presence of added soluble silicates and added inorganic and organic wastes, as well as a modeling effort directed toward the development of fundamentally valid descriptions of the subsurface movement and mass transfer properties which must be taken into account in evaluating in situ soil recovery/extraction technologies. In addition to the fundamental research activities of the Center, active applied research and technology transfer programs are being carried out. The applied research program fosters university-industry research, and is currently comprised of three projects. These include the fate of wastes injected underground, single cell cascade cross-flow air stripping of volatile organics from groundwater, and development of a simulation model of Chemical Waste Management's portable, low temperature thermal desorber. The technology transfer program provides an effective means of communicating research results, both fundamental and applied, and conducting short courses, conferences, and seminars on subjects involving hazardous waste. ACCOMPLISHMENTS - FY 1990 Fundamental Research Program The Hazardous Waste Research Center funded seven fundamental research projects and three applied research projects during Fiscal Year 1990. Of the seven basic research endeavors, five were fully funded and two received close-out funding. Research activities have contributed significantly to the solution of some key hazardous waste management, treatment and/or destruction problems. Specific accomplishments of these projects are described for each research area. Incineration: An In-depth Study of Rotary Kiln Incineration; A comprehensive study aimed at understanding rotary kiln performance is underway and represents a cooperative effort among university, industry, and government. The unique part of this program lies in the ability to sample in situ from the Louisiana Division rotary kiln facility of Dow Chemical U.S.A., located in Plaquemine, Louisiana. Access to a kiln-simulator and other bench-scale facilities at the University of Utah 68 ------- has contributed further to an understanding of the processes that occur during desorption of contaminants from solid materials, thus adding to an understanding of the scaling behavior that is present between field and pilot scale units. The modeling effort to date has concentrated on development of scaling criteria and verification of numerical codes using data collected from all scales of the experimental program. The objective of this multifaceted approach is the development of a predictive capability for the destruction of hazardous wastes in the kiln environment. The consequences of such a capability in the design of rotary kiln incinerators are far reaching. Research in FY 1990 focused on the development of scaling criteria between the field scale (Dow kiln results) and the pilot scale (University of Utah results). Field scale work has focused on obtaining an understanding of which process parameters impose first order influence on the ultimate destruction levels attainable in rotary kilns. While the thrust of earlier years' efforts has been to obtain the temperatures, stable species concentrations, and, if applicable, their transient responses in both the kiln and afterburner as well as the stack, more recent efforts have focused on evaluating the comparison of contaminant evolution rates between similar, but not identical, operating conditions in the field and in the laboratory. Using scaling criteria that account for temperature, rotation rate, and percent fill in the kiln, good correspondence has been obtained between rates inferred from experimental measurements at field scale with those obtained in the laboratory. Alternate Methods of Treatment/Destruction: Biological Treatment of Petrochemical Sludges: The use of online biological treatment as a method of treating petroleum and petrochemical sludges is being investigated. A heterogeneous microbial population acclimated to such wastes has been used to monitor the biodegradation pathways of one of the most bioresistant polynuclear aromatic constituents present in such sludges, benzo(a)pyrene (BaP), in closed continuous suspended growth systems. The ultimate scope of the research is development of engineering parameters for design of pilot plant systems which will be more effective than existing alternative technologies in reducing accumulations of persistent polynuclear aromatic compounds at Superfund sites. The key independent variables studied during FY 1990 were feed sludge dosage rate, waste sludge recycle, microbial population growth, volumetric loading rates, and mean cell residence time. Performance criteria in terms of BaP removal and partitioning between the vapor, liquid, and solid phases in the reactors were measured. Results indicated 69 ------- that removal rates for the BaP exceeded 90 percent and the balance partitioned into the settleable solids fraction except for a small percentage which was measured in the reactor scums and above-surface wall accumulations. Correlations between changes in input variables and performance of the continuous growth systems were observed. Alternate Methods of Treatment/Destruction: Liquids/Solids Contact Reactor Methodology: Research was conducted on the feasibility of biologically degrading pentachlorophenol ground waters/rinsates and pentachlorophenol/creosote sludge materials using a contact reactor method incorporating the use of acclimated biomass in a highly aerated stirred-tank reactor system. The overall objective of this investigation has been to identify those mechanisms associated with removal of dioxins, primarily the major contaminant, octachlorodibenzo-p- dioxin (OCDD), from contaminated soils and sludges. In addition to the evaluation of the abiotic and biotic degradative pathways for OCDD and related polynuclear aromatic creosote contaminants, investigations during FY 1990 were initiated to identify process variables which optimize photolytic decomposition and, simultaneously, optimize microbial biotransformation. Results to date indicate that three criteria must be met in order for dioxin photolysis to be practical: the wavelengths of incident light must correspond to appreciable absorption by the dioxins, the light must penetrate the medium to contact the dioxin component, and a source of extractable hydrocarbons must be present. The liquids/solids contact reactors provided situations in which these criteria have been met. Results also suggest that in the presence of elevated concentrations of dioxins and furans, microbial attack may be indicated under aerobic conditions. Alternate Methods of Treatment/Destruction: Electrokinetic Soil Processing: Electrokinetic soil processing is an emerging technology in waste remediation and treatment. Coupling between electrical, chemical, and hydraulic gradients is responsible for different types of electrokinetic phenomena in soils. However, studies investigating removal of ions from soils by the electrokinetic phenomena are limited, possibly due to insufficient understanding of the electrochemistry associated with the process. Recent studies at Louisiana State University provided a better understanding of the electrochemistry and demonstrated that the acid front generated by electrolysis reactions at the anode advances and eventually flushes across the specimen by advection, migration, and diffusion. It has been demonstrated that the factors influencing the acid/base profiles across the porous medium would significantly affect the 70 ------- flow, the flow efficiency, and the extent of ion migration and removal in electrokinetic soil processing. During FY 1990, the applicability of electro-osmosis soil processing in removing organic contaminants was investigated. For example, phenol removal from saturated kaolinite was found to be 85% to 95% complete. It was found that electrokinetic processing did not result in any retardation due to desorption mechanisms, thus implying that removal only by advection and dispersion is involved. Chemicals/Materials Interaction and Stabilization: Transport of Nonaqueous Phase Liquids: It is hypothesized that soil heterogeneities play a significant role in the transport and entrapment of nonaqueous phase liquid (NAPL) contaminants of the subsurface. Research is currently in progress at the University of Colorado and Louisiana State University to address this and certain other issues related to the behavior, modeling, direct recovery, and ultimate cleanup of NAPLs in groundwater systems. The objectives of this research are: (1) to obtain a fundamental understanding of the processes associated with the entrapment and movement of nonaqueous phase liquid wastes in heterogeneous soil-water systems, (2) to evaluate different techniques for direct recovery and extractive recovery of these waste products, and (3) to evaluate the adequacy of existing numerical modeling tools to simulate the processes associated with movement and recovery of these waste products in naturally heterogeneous aquifers. Results of research during FY 1990 indicate that the heterogeneities of the soil below the spill in both the unsaturated and saturated zones play a significant role in the movement and distribution of a NAPL, and that entrapment of the NAPL is controlled by both pore scale processes and larger scale heterogeneities. A finite element model for the simulation of multiphase flow in porous media has been developed. A sharp front model capable of addressing aspects of the multiphase subsurface flow phenomena has also been developed. Chemicals/Materials Interaction and Stabilization: Capping Contaminated Bed Sediments In Situ: The existence of contaminated bed sediment in a natural aquatic system usually results in the overlying water column receiving some contamination from this source. Therefore, a bed sediment source of contamination can lead to multimedia environmental exposures. Research at the Center has shown that capping contaminated sediment with clean sediment is a technically feasible in- place stabilization technique, and is stable under normal tidal and wave 71 ------- conditions. However, field studies have been inconclusive regarding the efficiency of capping to prevent contaminant uptake by water column and organisms. Of particular concern is the efficiency of the method in retarding the movement of toxic chemicals within the sediment to water and to pelagic and benthic biota. During FY 1990, a capping simulator cell was developed to investigate the transport of a hydrophobic organic chemical, 2,4,6- trichlorophenol (TCP), through clean cap layers placed over a contaminated sediment. Four capping materials with different organic carbon contents and textures (two sediments and two sands) were tested and TCP flux measurements obtained. The flux data were used to obtain chemical breakthrough time, time to achieve a steady-state rate, and the steady- state rate. The times to achieve breakthrough and steady-state were found to be directly dependent on the equilibrium partition coefficient, Kp. The larger the Kp, the longer the time required for chemical emergence from the cap. The steady-state flux of TCP through the four cap materials was found to be independent of Kp. Cap porosity and depth are the dominant parameters at steady-state. A conceptual model, which describes TCP fate due to the combination of molecular diffusion in interstitial pore water and partitioning onto fresh sediment, was evaluated. Chemicals/Materials Interaction and Stabilization; Immobilization Mechanisms in Solidification/Stabilization: Solidification/stabilization (S/S) is a valuable technology, but significant questions remain about the range of its applicability. Cement chemistry, for instance, is very complex and relatively poorly understood, and the possibility that contaminants could adversely affect the durability and permeability of the matrix is very real. The aim of the present project is to obtain detailed information about waste-matrix interactions, particularly using cement binders and organic-inorganic mixed wastes. Both leaching tests and sophisticated characterization methods for solid samples have been applied, including microscopy and solid-state nuclear magnetic resonance (NMR) spectroscopy, to samples containing arsenic, chromium, and lead, three species which are known to give problems in S/S practice, combined with phenols. Both phenols and certain metals, such as lead, are significant set retarders for Portland cement. However, the combination of the two can result in a much more dramatic effect than either contaminant alone. For instance, p-bromophenol combined with lead (II) and solidified with cement results in a setting reaction, but hydration of the silicate phase of the cement, which is primarily responsible for strength development, is almost completely retarded 72 ------- through 28 days of cure. The matrix effects are being correlated with teachability. Two specific goals are: (1) to determine the extent to which the alterations in the matrix are cumulative when contaminants are mixed, and (2) the extent to which effects of one contaminant result in enhanced leachability of a second. Applied Research Program Simulation of the Effects of Shale Heterogeneities o n Effective Permeability in Deep Well Injection Disposal Systems: Among the many factors which determine the efficiency of containment of waste materials which have been injected into the subsurface, the effective permeability of the confinement zone under steady-state, uniform flow conditions is of great importance. The current research uses Monte Carlo methods to estimate the expectation value of the effective permeability of the confinement zone with two permeability values, Ksd and Ksh, in sand and shale respectively. For isotropic formations the expectation values of the effective permeability agree very well with the analytical and numerical results obtained by other researchers. For anisotropic formations the expectation values of the effective permeability are not strongly dependent on shale size and anisotropic ratio. Simulation of the Chemical Waste Management X*TRAX Soil Decontamination System: The development of a steady-state simulation model of a portable, low temperature thermal desorber (the X*TRAX process) developed by Chemical Waste Management is the goal of this research effort. The simulation model will use the ASPEN process simulation program, and the overall model will be developed in phases, so that different ASPEN models of increasing complexity will evolve during the course of the project. Each model will be tuned using data obtained during operation of Chemical Waste Management's pilot scale units. Crisscross Flow Air Stripping of Moderately Volatile Compounds: The separation of a waste into its hazardous and non- hazardous components is an important aspect of a hazardous waste management program. Through separation, pollutants are removed and concentrated, allowing recovery of reusable materials and more effective and economical treatment or destruction of the unwanted hazardous waste component(s). One applied research project addresses air stripping in crossflow cascades involving moderately volatile compounds such as 1,2- dichloroethane, naphthalene, chloroethyl ether, acetone, and phenol. The effects of baffle spacing and liquid loading rates upon the liquid phase mass transfer coefficients and steady-state removal efficiencies were 73 ------- investigated. Results indicate stable operation of the column even beyond conditions that are considered traditionally inoperable for conventional countercurrent columns. RESEARCH GOALS - FY 1991 Research efforts of the Hazardous Waste Research Center will continue in the areas of incineration, chemicals/materials interactions, and alternate methods of treatment. The five projects fully funded in FY 1990 will continue to be funded in FY 1991 with emphasis on bringing all projects to completion so that significant conclusions can be drawn. Information gained from these studies will contribute further understanding and new technologies applicable to hazardous waste site cleanup projects and to hazardous waste management strategies. OUTPUTS - FY 1990 Articles in Refereed Journals 5 Articles Submitted or In Press 17 Books and Bound Proceedings 18 Chapters in Other Books 9 Project Reports 2 Conferences and Workshops Held 1 74 ------- BIBLIOGRAPHY REFEREED JOURNAL ARTICLES Cartledge, F., Butler, L., Chalasani, D., Eaton, H., Frey, F., Tittlebaum, M., and Yang, S., "Immobilization Mechanisms in Solidification/Stabilization Using Portland Cement Fixing Agents," Environmental Science and Technology. Vol. 24, No. 6, 1990. Lighty, J., Silcox, G., Pershing, D., Cundy, V., and Linz, D., "Fundamentals for the Thermal Remediation of Contaminated Soils- Particle and Bed Desorption Models," Environmental Science and Technology. Vol. 24, No. 5, pp. 750-757, May, 1990. Valsaraj, K. and Thibodeaux, L., "On the Estimations of Micelle-Water Partition Constants for Solutes From Their Octanol-Water Partition Constants, Normal Boiling Points, Aqueous Solubilite Bond and Group Contribution Schemes," Separation Science and Technology. Vol. 25, No. 4, pp. 369-395, 1990. Valsaraj, K. and Thibodeaux, L., "Studies in Batch and Continuous Solvent Sublation, I. A Complete Model and Mechanisms of Sublation of Neutral and Ionic Species from Aqueous Solutions," Separation Science and Technology. Vol. 26, pp. 1275-1296, 1990. Wood, D., Locicero, L., Valsaraj, K., Harrison, D., and Thibodeaux, L., "Air Stripping of Volatile Hydrophobic Compounds Using Packed Crisscrossflow Cascades," Environmental Progress. Vol. 9, No. 1, pp. 24-29, 1990. ARTICLES SUBMITTED OR IN PRESS Chitgopekar, N., Reible, D., and Thibodeaux, L., "A Model for Describing Short Range Dispersion near Area Sources of Toxics," Journal of the Air and Waste Management Association, in press, 1990. Cundy, V., Lester, T., Jakway, A., Leger, C., Lu, C., Montestruc, A., Conway, R., and Sterling, A., "Incineration of Xylene/Sorbent Packs- A Study of Conditions at the Exit of a Full-Scale Industrial Incinerator," Environmental Science and Technology, in press, 1990. 75 ------- Doshi, D., Reible, D., and Ulangasekare, T., "The Influence of Mass Transfer Limitations on the Effectiveness of In Situ Contaminant Extraction," Journal of Hazardous Materials, submitted, 1990. Faschan, A., Tittlebaum, M., Cartledge, F., and Eaton, H., "Effect of Additives on Solidification of API Separator Sludge," Environmental Monitoring and Assessment, accepted for publication, 1990. Lester, T., Cundy, V., Sterling, A., Montestruc, A., Jakway, A., Lu, C., Leger, C., Pershing, D., Lighty, J., Silcox, G., and Owens, W., "Rotary Kiln Incineration: Comparison of Field and Pilot Scale Measurements of Contaminant Evolution Rates from Sorbent Beds," Environmental Science and Technology, in review, 1990. Lester, T., Cundy, V., Montestruc, A., Leger, C., Acharya, S., and Sterling, A., "Dynamics of Rotary Kiln Incineration of Toluene/Sorbent Packs", Combustion Science and Technology, in press, 1990. Owens, W., Silcox, G., Lighty, J., Deng, X., Pershing, D., Cundy, V., Leger, C., and Jakway, A., "Thermal Analysis of Rotary Kiln Incineration: Comparison of Theory and Experiment," Combustion and Flame, in review, 1990. Reible, D., Ulangasekare, T., Doshi, D., and Malhiet, M., "Infiltration of Immiscible Contaminants in the Unsaturated Zone," Ground Water, in press, 1990. Reible, D., Malhiet, M., and Ulangasekare, T., "Modeling Gasoline Fate and Transport in the Unsaturated Zone," Journal of Hazardous Materials, in press, 1990. Roy, A., Eaton, H., Cartledge, F., and Tittlebaum, M., "Microstructural and Microchemical Characterization of Cementitious Binders Containing a Heavy Metal Sludge and Various Interfering Compounds," Environmental Science and Technology, in review, 1990. Roy, A., Eaton, H., Cartledge, F., and Tittlebaum, M., "Solidification/Stabilization of a Heavy Metal Sludge by a Portland Cement/Fly Ash Binding Mixture," Hazardous Waste and Hazardous Materials, accepted for publication, 1990. Thibodeaux, L., Nadler, K., Valsaraj, K., and Reible, D., "The Effect of Moisture on Volatile Organic Chemical Vapor-to-Particle Partitioning with 76 ------- Atmosphere Aerosol- Competitive Adsorption Theory Predictions," Atmospheric Environment, in press, 1990. Valsaraj, K., Lu, X., and Thibodeaux, L., "Studies in Batch and Continuous Solvent Sublation IV. Continuous Countercurrent Solvent Sublation and Bubble Fractionation of Hydrophobic Compounds from Water," Separation Science and Technology, in press, 1990. Valsaraj, K. and Thibodeaux, L., "Studies in Batch and Continuous Solvent Sublation II. Countercurrent Continuous Solvent Sublation of Neutral and Ionic Species from Aqueous Solutions," Separation Science and Technology, in press, 1990. Valsaraj, K., Thibodeaux, L., and Lu, X., "Studies in Batch and Continuous Solvent Sublation III. Solubility of Pentachlorophenol in Alcohol-Water Mixtures and Its Effects on Solvent Sublation," Separation Science and Technology, in press, 1990. Wang, X-Q., Thibodeaux, L., Valsaraj, K., and Reible, D., "The Efficiency of Capping Contaminated Bed Sediments In Situ I. Lab-Scale Experiments on Diffusion/Adsorption in the Capping Layer," Environmental Science and Technology, submitted, 1990. Znidarcic, D., Illangasekare, T., and Manna, M., "Laboratory Testing and Parameter Estimation for Two-phase Flow Problems," American Society of Civil Engineering, submitted, 1990. BOOKS AND BOUND PROCEEDINGS Acar, Y. and Gale, R., "The State-of-the-Art in Electrokinetic Soil Processing," Proceedings of the Fourth Annual Symposium on Hazardous Waste Research. Louisiana State University, Baton Rouge, Louisiana, October 23-24, 1990. Cundy, V., Lester, T., Conway, R., Cook, C., Jakway, A., Leger, C., Lu, C, Montestruc, A., Acharya, S., Sterling, A., Walker, D., Larson, F., Moore, J., Eian-Xue, D., Lighty, J., and Owens, W., "An Indepth Study of Rotary Kiln Incineration," Proceedings of the Fourth Annual Symposium on Hazardous Waste Research. Louisiana State University, Baton Rouge, Louisiana, October 23-24, 1990. 77 ------- Doshi, D., Reible, D., and Illangasekare, T., "Numerical and Laboratory Modeling of the Behavior of Nonaqueous Phase Liquids," Summer National Meeting of the American Institute of Chemical Engineering, San Diego, California, August 19-22, 1990. Field, S., Wojtanowicz, A., and Marks, R., "Advanced Biological Treatment and Separation of Hazardous Constituents from Petrochemical Sludges," Proceedings of the Fourth Annual Symposium on Hazardous Waste Research. Louisiana State University, October 23-24, 1990. Illangasekare, T., Armbruster, E., and Reible, D., "Experimental Study of Effect of Heterogeneities on Transport and Entrapment of Nonaqueous Phase Liquids," Spring Meeting of the American Geophysical Union, Baltimore, Maryland, 1990. Illangasekare, T., Armbruster, E., Szlag, D., and Reible, D., "Effect of Heterogeneity on Transport and Entrapment of Nonaqueous Phase Waste Products in Aquifers," Proceedings of the 3rd Symposium on Hazardous Substances. Kansas State University, Manhattan, Kansas, 1990. Illangasekare, T., Armbruster, E., Yates, D., Szlag, D., Reible, D., Doshi, D., and Smith, J., "Experimental Study on Unsaturated Flow Processes," Invited Presentation at Nordic Workshop, Copenhagen, Denmark, 1990. Koulermos, A., Valsaraj, K., Reible, D., and Thibodeaux, LM "The Effects of Porewater Colloids on the Transport of Hydrophobic Compounds from Bed Sediments," Symposium on Organic Substances and Sediments in Water, ACS National Meeting, Boston, Massachusetts, April, 1990. McKay, D., Shiu, W., Valsaraj, K., and Thibodeaux, L., "Air-Water Transfer: The Role of Partitioning," Proceedings of Second International Symposium on Gas Transfer at Water Surfaces. University of Minnesota, September 10-11, 1990. Owens, W., Silcox, G., Lighty, J., Deng, X., Pershing, D., Lester, T., Cundy, V., Leger, C., and Jakway, A., "Hydrocarbon Evolution from Contaminated Solids: Effects of Moisture and Operating Parameters in a Rotary Kiln Environment," 23rd Symposium (International^ on Combustion. Orleans, France, July, 1990. Owens, W., Silcox, G., Lighty, J., Deng, X., Pershing, D., Lester, T., Cundy, V., Leger, C., and Jakway, A., "Thermal Analysis of Rotary Kiln Incineration: 78 ------- Comparison of Theory and Experiment," 23rd Symposium (International) on Combustion. Orleans, France, July, 1990. Portier, R., Fujisaki, K., and Henry, C., "Mineralization of Chlorinated Dioxin Photolytic Products by an Autochthonous Microbial Population in a Liquids/Solids Contact Reactor," Proceedings of the Fourth Annual Symposium on Hazardous Waste Research. Louisiana State University, Baton Rouge, Louisiana, October 23-24, 1990. Reible, D., "Subsurface Processes: Implications for In Situ Remediation," Ground Water Symposium, Baton Rouge, Louisiana, 1990. Reible, D., Illangasekare, T., Doshi, D., Smith, J., Armbruster, E., Yates, D., and Szlag, D., "Transport and Entrapment of Nonaqueous Phase Liquids in Heterogeneous Media," Proceedings of the Fourth Annual Symposium on Hazardous Waste Research. Louisiana State University, Baton Rouge, Louisiana, October 23-24, 1990. Silcox, G., Pershing, D., Keyes, B., Owens, W., Lighty, J., Deng, X., Cundy, V., Leger, C., and Jakway, A., "Heat Transfer, Mass Transfer, Vaporization, and Combustion in Rotary Kilns," American Institute of Chemical Engineering National Meeting, San Diego, California, August 19-22, 1990. Sterling, A., Cundy, V., Lester, T., Montestruc, A., Jakway, A., Leger, C., Lu, C., and Conway, R., "Fundamental Kiln Processes," Fourth Annual National Symposium- Incineration of Industrial Wastes (Toxcon Engineering Company, Inc.), Houston, Texas, February, 1990. Sterling A., Cundy, V., Lester, T., Montestruc, A., Jakway, A., Leger C., Lu, C., and Conway, R., "Rotary Kiln Incineration-The LSU In Situ Field Testing Program," Proceedings of the 83rd Annual Meeting of the Air and Waste Management Association. Pittsburgh, Pennsylvania, June 24-29, 1990. Wang, X-Q., Thibodeaux, L., Valsaraj, K., and Reible, D., "The Efficiency of Capping Contaminated Bed Sediments In Situ I. Lab-Scale Experiments on Diffusion/Adsorption in the Capping Layer," Proceedings of the Fourth Annual Symposium on Hazardous Waste Research. Louisiana State University, Baton Rouge, Louisiana, October 23-24, 1990. 79 ------- CHAPTERS IN OTHER BOOKS Portier, R., "Applications of Adapted Microorganisms for Site Remediation of Contaminated Soil and Water," In Biological Treatment of Solid Wastes. A.M. Martin, ed., Elsevier Science Publishers, Inc., in press, 1990. Portier, R., Fugisaki, K., and Henry, C., "Detoxification of Contaminated Sludges Using Combined Microbiological and Photolytic Degradative Approaches," In Bioreactor Systems. Vol. 3, H. Freeman, ed., Lewis Publishing, in press, 1990. Portier, R., Roy, M., and Achee, J., "Design of the In Situ Biodegradation Systems for Persistent Pesticide Remediation", In Pesticide Remediation Approaches, an American Chemical Society environmental publication series, Lewis Publishing, in press, 1990. Reible, D. and Illangasekare, T., "Subsurface Processes of Nonaqueous Phase Liquids," In Intermedia Pollutant Transport: Modeling and Field Measurements. D.T. Allen, Y. Cohen, and I.R. Kaplan, eds., in press, 1990. Silcox, G., Lighty, J., Owens, W., Pershing, D., and Cundy, V., "Thermal Effects and Heat Transfer in the Rotary Kiln Incinerator of Contaminated Soils and Sorbents," In Emissions from Combustion Processes. R.E. Clement and R.O. Kagel, eds., CRC Press, Inc., in press, 1990. Sterling, A., Lester, T., Cundy, V., Leger, C., Acharya, S., Montestruc, A., and Morse, J., "In Situ Sampling from an Industrial Scale Rotary Kiln," In Emissions from Combustion Processes. R.E. Clement and R.O. Kagel, eds., CRC Press, Inc., in press, 1990. Thibodeaux, L., Valsaraj, K., and Reible, D., "Chemodynamic Models for Transport of Chemicals from Bed Sediments," In Handbook of Environmental Chemistry. Vol. 2, O. Hutzinger, ed., in press, 1990. Thoma, G., Koulermos, A., Valsaraj, K., Reible, D., and Thibodeaux, L., "The Effects of Porewater Colloids on the Transport of Hydrophobic Compounds from Bed Sediments," In Organic Substances and Sediments in Water. S. Boyd and C. Chiou, eds., in press, 1990. Valsaraj, K., Thibodeaux, L., and Reible, D., "The Effects of Porewater Colloids on the Transport of Hydrophobic Contaminants from Bed 80 ------- Sediments," In Soils and Sediments in Water. C.T. Chion and S. Boyd, eds., Lewis Publishers, 1990. PROJECT REPORTS Armbruster, E., "Study of Transport and Distribution of Lighter than Water Organic Contaminants in Ground Water," M.S. Thesis, Department of Civil, Environmental, and Architechtural Engineering, University of Colorado, Boulder, 1990. Yates, D., "Transport and Distribution of Nonaqueous Organics in Ground-water Aquifers: Experimental Investigation and Numerical Model Development," M.S. Thesis, Department of Civil, Environmental, and Architectural Engineering, University of Colorado, Boulder, 1990. CONFERENCES AND WORKSHOPS HELD "Fourth Annual Symposium on Hazardous Waste Research", Louisiana State University, Baton Rouge, Louisiana, October 23-24, 1990. 81 ------- 82 ------- CENTER: Industrial Waste Elimination Research Center LOCATION: Illinois Institute of Technology DIRECTOR: Kenneth E. Noll Pritzker Department of Environmental Engineering Illinois Institute of Technology Chicago, IL 60616 312/567-3535 Fax: 312/567-3548 PROJECT OFFICER: Albert Klee Risk Reduction Engineering Laboratory U.S. Environmental Protection Agency 26 West Martin Luther King Drive Cincinnati, OH 45268 513/569-7493 FUNDS SPENT DURING FY 1990 (10/1/89 - 9/30/90) EPA $482,000 Other Government 0 University 52,000 Private Sector 0 Total $534,000 DESCRIPTION OF THE PROGRAM The Industrial Waste Elimination Research Center (IWERC) conducts research on fundamental and applied aspects of industrial waste management associated with in-plant recovery, as well as containment, avoidance, and minimization of pollutant discharges. The research focus is multi-media, including air and water pollutants and hazardous wastes, and is primarily concerned with waste reduction in industrial manufacturing processes and the development of recycle/recovery strategies for the constituents of selected industrial wastestreams. 83 ------- IWERC is a problem-oriented exploratory research center utilizing the tools of basic science and engineering to perform research directed at industrial waste elimination. Principal areas of research include: • Metal Speciation and Separation • Sorption/Desorption Phenomena • Particle Size and Shape Control • Process Catalysis and Control ACCOMPLISHMENTS - FY 1990 Six research projects funded by IWERC were conducted in FY 1990. The major features and accomplishments of these projects are described briefly below. Metals Speciation. Separation, and Recovery: As noted in previous reports and as widely recognized, heavy metals found in industrial wastewaters present a serious pollution control problem for many sectors of industry. The metals are often highly toxic, and most are subject to strict regulatory requirements. However, such contaminants can be viewed as resources to be recovered from industrial waste streams — by developing appropriate technical approaches and techniques for removal and recovery that are economically attractive. Work in this area has been a consistent priority for the IWERC. The traditional treatment technique for the removal of metals from industrial wastewaters is alkaline precipitation. When a sufficient amount of hydroxide ion is added to a metal salt solution, a metal hydroxide precipitate is formed. This initial solid phase typically is highly disordered, and is not in the thermodynamically stable final form of the solid. In time, the initial solids will pass through an aging and rearrangement process into a more stable form. Although widely applied throughout industry, the mechanisms of the precipitation process are not well understood. Historically, this has not been a problem because treatment based on empirical evidence was adequate prior to the recent promulgation of restrictive sludge disposal regulations. However, with the new regulatory framework there is a need to optimize precipitation processes. Information is needed on nucleation and particle growth rates, as well as a better description of the physicochemical characteristics of the precipitate solids. The ability to 84 ------- influence and accurately predict the precipitation process has major implications for residual metals management practices. Research in FY 1990 dealt with the alkaline precipitation of copper in the presence of nitrate. Principal sources of copper in industrial waste streams are metal cleaning and plating baths and rinses. Other potential sources are jewelry manufacturing, mining wastes and acid mine drainage, nonferrous metalworks and foundries, motor vehicles and aircraft plating and finishing, wood preserving, pulp and paper mills, fertilizer manufacturing, and petroleum refining. Nitrate is one of several anions that can induce precipitation of basic cupric salts. It is a common anion in industrial wastewater, and may affect both the thermodynamics and kinetics of copper precipitation through adsorption, occlusion, or coprecipitation reactions. The precipitation process is traditionally divided into three stages, nucleation, particle growth, and aging. Future work consists of completion of three projects, which are in varying stages of development that have evolved from earlier work. The most advanced of these is exploring the aging phenomena associated with copper precipitates. A second project which is directly related to the current cupric-hydroxy-nitrate work, is exploring the dewatering characteristics of the various copper precipitates. Finally, problem definition is just beginning for a project dealing with nickel precipitation. Removal and Recovery of Non-Ionic Hydrocarbons from Aqueous Solutions: Removal of non-ionic organics (NOCs) from waste is traditionally done with activated carbon. Once the sorption capacity of the activated carbon is exhausted, the carbon must be disposed of, typically in a hazardous waste landfill. As an alternative, the carbon may be regenerated, by driving the sorbed NOCs off the activated carbon with heat. This process is expensive and is not easily amenable to the recovery and reuse of the NOCs. This research takes a fundamentally different approach. The overall goal of this project is to determine if NOCs can be sorbed and subsequently desorbed by surfactant coated ferrihydrite in a manner in which the ferrihydrite, surfactant, and NOC can be recovered and reused. During FY 1990, research showed that anionic surfactants can be adsorbed by ferrihydrite at low pH and desorbed at high pH. This adsorption process makes the ferrihydrite hydrophobic and enables it to remove NOCs from solution. As expected, the amount of NOC removed 85 ------- from solution increased at higher surfactant coatings. NOCs having lower water solubilities (higher hydrophobicities) were removed from solution better than NOCs having higher water solubilities. A simple model was developed relating the amount of NOCs removed to the amount of surfactant on the ferrihydrite and the NOCs water solubility. Future research will determine whether the modified iron oxide can remove a mixture of NOCs, and if so, whether they would be differently sorbed and if this differential sorption can be predicted from known NOC properties. It may also determine if anions commonly found in wastewater streams will interfere with surfactant sorption, determine if different types of surfactants preferentially sorb different classes of NOCs. For example, a surfactant containing a benzene ring may preferentially sorb aromatic compounds. Equilibrium of Mixed Solid Phases: It is well known that wastewater precipitation processes generally result in mixed solid phases containing a number of metal hydroxides and/or carbonates, sulfides, nitrates and sulfates. In the past, it has been shown that mixed solid solutions generally have different solubilities than pure solid phases, and precipitation processes do not generally obey simple equilibrium relationships. Attempts to describe this deviation from ideality have included studies on kinetics and surface adsorption. However, no studies on mixed solid phase non-idealities have been proposed or extensively researched. Although solid phase non-idealities have been shown to exist in several mixed solid solutions at trace concentrations, no data is currently available on the metal hydroxide systems of interest in metal precipitation processes frequently used in wastewater treatment. The practical significance of non-idealities in metal precipitation processes is that there is potential for a change in the point of minimum solubility of all the components in the solid mixture. The existence of such phenomena may make new separation processes possible, which is based upon exploitation of non-ideal behavior among the components. The primary objective of this research project is to investigate the possible existence of non-ideal behavior with respect to ideal solution theory in the hydroxide system composed of mixtures of cupric and cadmium hydroxide. In general, results obtained from the pure solid systems are in close agreement with established values, and results obtained from the mixed 86 ------- solid systems consistently indicate that substantial non-idealities exist. Work during the next quarter of this project period will focus on data reduction and evaluation. Development of Oxides of Iron as Sorbents for the Control. Separation. and Recovery of Inorganic Hazardous Waste Components: This project, which complements related work on the evaluation and development of iron oxides as a potential technique for dealing with contaminated industrial wastewaters, is conducted at Clarkson University, with cooperation of the Aluminum Company of America (ALCOA) Technical Center, and the use of the Cornell University Theory Center's supercomputer. During the past year, particularly the last quarter, progress was achieved in two areas. First, dynamic column experiments using the granular iron oxide adsorbent were completed. Experimental data for adsorption and desorption of the chromate ion revealed acceptable mass balance closure, averaging 93% recovery during sorption cycles. These data are currently undergoing further analysis to determine relevant sorption parameters. The second area is that of sorbent modeling studies using a fractal characterization of the pore structure. This work is necessarily computationally oriented, making use of parallel and vector processors where possible. During this quarter, both theoretical and computational approaches to the problem have been explored. Conversion of Chlorinated Hydrocarbon Containing Wastes into Useful Products: The objectives of this program, which has been supported by IWERC for several years, are to develop practical high- temperature chemical processes to dehalogenate chlorine-containing organic hazardous wastes and convert them into valuable gaseous hydrocarbon products, such as acetylene, ethylene, and synthesis gas (CO+H2). These objectives are being reached by undertaking a systematic program of experimental and numerical modeling studies. In the experimental program, high-temperature pyrolysis and oxidative pyrolysis reactions of representative, model chlorinated hydrocarbons are studied in flow reactors and flames coupled with on-line mass spectrometry and gas chromatography. In parallel, modeling studies involve the development of predictive detailed chemical kinetic mechanisms describing the high temperature reactions of these model chlorinated hydrocarbons. To date, studies with chloromethane have been the most productive, resulting in the development of the Chlorine-Catalyzed Oxidative-Pyrolysis (CCOP) process to convert methane into acetylene and ethylene, which are 87 ------- two of the major building blocks of the organic chemical industry. The process has been patented (US Patent 3,714,796). In FY 1990, studies began on the oxidative pyrolysis of C6H5C1 (monochlorobenzene) to extend earlier research to aromatics and to better simulate some of the high priority hazardous waste streams. Because CgHsCl is a liquid at ambient conditions, modifications had to be made to the experimental system, which was designed primarily to study gaseous feed streams. The modifications in the injection and sampling systems allowed samples containing high molecular weight species to be obtained. Thus, species such as benzene, chlorobenzene, and naphthalene, etc., were detected. This poses a new challenge in modeling the reaction pathways that are responsible for the formation of these compounds. Also, since such compounds are observed during pyrolysis of lower molecular weight chlorinated chemicals, the development of this modified experimental system is necessary. Design and Testing of a Moving Bed Volatile Organic Carbon (VOC) Adsorption System: This project takes advantage of the previous adsorption/desorption studies funded by IWERC. Its purpose is to investigate methods to reduce the size of VOC control equipment applied to low concentration gas streams (less than 200 ppm), and to determine if the new adsorption system can be applied to provide a concentrated VOC stream. The major objective will be to investigate the economics of recovering the concentrated VOC material from the adsorption section. The pilot plant will allow the identification of potential problems due to the adsorption/desorption process, and difficulties that can be expected to be encountered in applying such a process to actual installations. By using a pilot plant which incorporates both a moving adsorption bed and a continuous desorption of VOC and recycling of the adsorbent, the potential advantages when applied to actual emission streams can be examined. RESEARCH GOALS - FY 1991 Since IWERC is in the final year of full funding, new projects were not sought, and therefore, the November Annual Program Review Meeting was not scheduled. Instead, energy is being directed into the formation and preparation of a research symposium which will formally acknowledge and celebrate the accomplishments of the Industrial Waste Elimination 88 ------- Research Center. Even more, this symposium will ensure that the research projects have been successfully concluded. The symposium will also include the participation of past and present Scientific Advisory Committee (SAC) and Industry Advisory Council (IAC) members. Following the symposium, a meeting with the IAC and SAC is planned, to recap, discuss and suggest future focus and direction. OUTPUTS - FY 1990 Articles in Refereed Journals 2 Articles Submitted or In Press 5 Books and Bound Proceedings 1 Chapters in Other Books 0 Project Reports 18 Conferences and Workshops Held 0 89 ------- BIBLIOGRAPHY REFEREED JOURNAL ARTICLES Senkan, S.M., M.K. Abdelaal, and M. Qun, "The Chemical Structure of Fuel-Rich l,2-C2H4Cl2/CH4/O2/Ar Flames: The Effects of Microprobe Cooling," Combustion Science and Technology. 67, pp. 147-157, 1989. Senkan, S.M. and M. Qun, "The Chemical Structure of Atmospheric Pressure, Fuel-Rich, Flat Flames of CH2Cl2/CH4/O2/Ar," Hazardous Waste and Hazardous Materials Journal. 7, pp. 55-71, 1990. ARTICLES SUBMITTED OR IN PRESS Kassem, M., and S. M. Senkan, "Chemical Structures of Fuel-Rich Premixed, Laminar Flames of l,2-C2H4Cl2 and Glfy," Combustion and Flame, in press, 1990. Yildirim, R. and S. M. Senkan, "An Experimental Study of the Pyrolysis and Oxidative Pyrolysis of C2H5C1," Submitted to Industrial Engineering Chemical Research, in press, 1990. Sethuraman, S. and S. M. Senkan, "An Experimental Study of C6H5C1 Oxidation in a Flow Reactor," Submitted to Environmental Science Tech. in press, 1990. Yildirim, R. and S. M. Senkan, "Detailed Chemical Kinetic Modeling of the Oxidation and Pyrolysis of C2H5C1," Submitted to Industrial Engineering Chemistry Research, in press, 1990. Gasca, E. and P. R. Anderson, "Surface Chemical Characteristics of Iron Oxides," Submitted to the Journal of Soil Science, in press, 1990. BOOKS AND BOUND PROCEEDINGS Noll, K. E., V- Gounaris, and W-S. Hou. Adsorption Technology for Arr and Water Pollution Control." Lewis Publishers, Chelsea, Michigan (in press), 1990. 90 ------- CHAPTERS IN OTHER BOOKS None PROJECT REPORTS Patterson, J. W., Anderson, P. R. "Metals Speciation, Separation and Recovery," 3 Quarter Reports, IWERC Project 9001 (1990). Holsen, T. M. "Removal and Recovery of Non-Ionic Hydrocarbons from Aqueous Solutions," 3 Quarter Reports, IWERC Project 9002 (1990). Haas, C. N. "Equilibrium of Mixed Solid Phases," 3 Quarter Reports, IWERC Project 9003 (1990). Theis, T. L. "Development of Oxides of Iron as Sorbents for the Control, Separation, and Recovery of Inorganic Hazardous Waste Components," 3 Quarter Reports, IWERC Project 9004. (1990). Senkan, S. M. "Conversion of Chlorinated Hydrocarbon Containing Wastes into Useful Products," 3 Quarter Reports, IWERC Project 9005 (1990). Noll, K. E. "Design and Testing of a Moving Bed VOC Adsorption System," 1 Quarter Report, IWERC Project 9006 (1990). Luo, B. "Kinetics of Cadmium Hydroxide Precipitation in a Continuous Stirred Tank Reactor," Ph.D. Thesis, Pritzker Department of Environmental Engineering, Illinois Institute of Technology (May, 1990). Chen, W-Y. "Evaluation of a Magnetite-Based Adsorption Process," M.S. Thesis, Pritzker Department of Environmental Engineering, Illinois Institute of Technology (August, 1990). Katsimbalis, G. "Alkaline Precipitation of Cu(II) in the Presence of Nitrate," M.S. Thesis, Pritzker Department of Environmental Engineering, Illinois Institute of Technology (May, 1990). Madgal, S. "A Study of Cationic and Anionic Sorption Equilibrium on a Granular Iron Oxide Adsorbent," M.S. Thesis, Report No. 90-12, 91 ------- Department of Civil and Environmental Engineering, Rowley Laboratories, Clarkson University, Potsdam, N.Y. 13699 (May, 1990). CONFERENCES AND WORKSHOPS HELD None 92 ------- CENTER: Marine Science Research Center LOCATION: University of Rhode Island DIRECTOR: Michael E.Q. Pilson Graduate School of Oceanography University of Rhode Island Narragansett, RI 02882-1197 401/792-6104 Fax: 401/792-6160 PROJECT OFFICER: Jan Prager U.S. Environmental Protection Agency South Ferry Road Narragansett, RI 02882 401/782-3133 FTS 838-3133 FUNDS SPENT DURING FY 1990 (10/1/89 - 9/30/90) EPA $612,974 Other Government 41,177 State 136,085 University 168,662 Private Sector 18,466 Total $977,364 DESCRIPTION OF THE PROGRAM The Marine Science Research Center (MSRC) derives from an EPA- supported initiative in 1975 to develop the capacity for experimentation on complex enclosed ecosystems. Such experimentation requires both a successfully functioning facility and an interdisciplinary group of scientists to carry out the necessary experiments and observations. Thus the MSRC (also called the Marine Ecosystems Research Laboratory, or MERL) is composed of people largely interested in experimental marine biogeochemistry and ecology. The focus is mainly on work in mesocosm enclosures, along with some comparison field work in Narragansett Bay. In comparison with other such attempts to work with experimental marine ecosystems, the mesocosms maintained at MSRC are the most well defined, have operated continuously over the longest time, and most faithfully capture the functional properties of the coastal marine ecosystem. During 93 ------- the last 14 years, over 70 investigators from the University of Rhode Island and at least 25 institutions in the United States, Canada, and Europe have carried out studies in these mesocosms. In addition to numerous technical reports, some 170 papers dealing with work in the mesocosms and related field work have appeared in the peer-reviewed professional literature. The MSRC has been effective in training students in the field, and some 30 people have received advanced degrees for work done entirely or in part at MSRC. At the present time about four students are carrying out pollution related thesis research at MSRC. Two more recently applied and have been admitted to the University of Rhode Island with the intention of carrying out thesis research at MSRC. One visiting professor from another country is also here with the intention of participating in mesocosm research. The MSRC facility consists of a laboratory and office building with an outside experimental mesocosm farm. Fourteen mesocosms, each containing 13 cubic meters (3500 U.S. gal.) of water and 37cm depth of sediment, are maintained under natural sunlight, mixing, flushing, and temperature regimes. These living models fill a gap between laboratory experiments and field observations and can be used for both fundamental and practical investigations. Information from all three approaches provides a basis for regulation of pollutant discharges. Experimentation in the mesocosms has considerably increased the basic understanding of the functioning of coastal marine ecosystems, especially in those aspects that are relevant to the impact of human activities. Direct quantitative studies of the effects and fates of numerous pollutants have been carried out, including extensive studies of No. 2 fuel oil and other petroleum hydrocarbons and some halocarbons, studies of the fates of about 15 trace metals, examination of the fate and effects of sewage sludge and sewage effluent, and several extensive studies of nutrients alone and in combination with regard to the complex effects of eutrophication. Support for research at MSRC has come largely from the U.S. Environmental Protection Agency, but additional support has from time to time been received from the National Oceanographic and Atmospheric Administration, the U.S. National Science Foundation, the Department of Energy, the University of Rhode Island, and the Andrew W. Mellon Foundation. Indirect support has come from other sources in the form of additional support of investigators at other institutions. 94 ------- ACCOMPLISHMENTS - FY 1990 Model of a Salt Wedge Estuary: Models representing estuaries with freshwater flowing in at the surface and saltwater flowing in at the bottom have been established in the summer of 1990. One of the models was well mixed and the other was stratified. These models permit the controlled examination of transformations along salinity, light, and temperature gradients. Most pollutants enter estuaries from freshwater streams and rivers. Many processes which occur along these gradients act to trap or transform these materials. In the center's latest experiment, well mixed and stratified salt wedge models were established. Nutrient uptake rates and primary production were studied by Sea Grant researchers from East Carolina University. Limiting nutrients were examined for phytoplankton growth along the gradients. For nutrient mass balances and speciation, measurements were made of inflows, outflows, water column and benthic remineralization, benthic denitrification, standing stocks, and uptake by primary production. Investigators found that phosphorus and light were limiting to plant growth at the fresh ends of the gradients and nitrogen was limiting at the saltwater end. Even though the systems were not nutrient enriched, low oxygen concentrations developed in the bottom waters of the stratified systems. The Cretaceous Ocean: The National Science Foundation has provided funding to M. Arthur (Graduate School of Oceanography), M.E.Q. Pilson (Director MSRC), and K. Hinga (MSRC marine scientist) to study the fate of elevated carbon dioxide levels in the water column. This experiment simulates the Cretaceous period when atmospheric levels of carbon dioxide were elevated compared to present day levels. This experiment tests basic assumptions on carbon fate and isotope ratios used by paleoecologists. The experiment began in mid summer 1989 and ended in December 1990. Four mesocosms were devoted to this experiment. The design for introducing and maintaining elevated carbon dioxide concentrations (maximum is 10 time saturation concentration) has worked satisfactorily. Final results will be available for the next annual report. Synthesis Reports for the EPA Narragansett Bay Project: Five reports have been prepared for Narragansett Bay including a Toxics report, a Sediment Toxicity report, a Fisheries Management report and a status report on East Greenwich Bay. A status report on the Blacks tone River will 95 ------- be forthcoming. Four of the reports have been peer reviewed and are being revised. Monitoring Plan for Narragansett Bay: The Narragansett Bay Project necessitated the development of a monitoring plan for Narragansett Bay. The purpose of the plan is to measure the effectiveness of water quality management in reducing pollutant inputs and restoring environmental quality. Task One of four tasks in the plan have been completed. EPA Region II Bays Program: Researchers at the Center have compiled nutrient data sets for the New York Bight Apex and Harbor to document the nature and extent of environmental problems in the area caused by low dissolved oxygen conditions. With the help of statistics and available information investigators have examined the relationships between organic carbon inputs, nutrient concentrations, phytoplankton production and biomass and hypoxia/anoxia. Additional funds have been awarded to continue this project. Acute and chronic hypoxic and toxic effects will be assessed, as will tolerances for key estuarine species in the New York New Jersey Harbor. The toxic effects will include hydrogen sulfide, ammonia and chlorine. Approaches ranging from physiology to community structure will be considered. RESEARCH GOALS FOR 1991 Stratification acts as a lid on bottom waters preventing atmospheric recreation. Normal respiration rates in these waters results in hypoxia even when carbon inputs from primary production in the overlying water are not excessive. While bottom water never went anoxic during the 1990 experiment, values of 0.5, 1.5, and 2.0 ppm were present for weeks at a time. In the coming year, center personnel will explore the combinations of nutrient level, stratification and flushing that result in hypoxic conditions. These results will be used to assess "what if" scenarios for the Chesapeake Bay Model. For example, what if nutrients are reduced by IX, 2X and 4X and thus anoxic oxygen conditions improve to 0.5, 1.5, and 2.0 ppm? How will the flora and fauna change? Over the winter, Dr. Ted Durbin of GSO will be examining the growth and survival of winter flounder larvae under different temperature regimes, different zooplankton food regimes and different mixing regimes. 96 ------- This project has received funding from Sea Grant, Millstone Atomic Power and some support from the university. In the coming year, MSRC scientist Dr. Ken Hinga will be conducting interviews and workshops to assess the status of eutrophication in our nations estuaries. This project has been funded by the National Oceanic and Atmospheric Administration. OUTPUTS IN FY 1990 Articles in Refereed Journals 11 Articles Submitted or In Press 10 Books and Bound Proceedings 1 Chapters in Other Books 2 Project Reports 1 0 Conferences and Workshops Held 0 97 ------- BIBLIOGRAPHY ARTICLES IN REFEREED JOURNALS Adelman, D., K.R. Hinga and M.E.Q. Pilson, "Biogeochemistry of Butyltins in an Enclosed Marine Ecosystem," Environmental Monitoring and Assessment. Vol. 24, pp. 1027-1032, 1990. Hinga, K.R., and J.A. Knauss, "Ocean Disposal: Some Aspects of the Debate," Maritimes. Vol. 33, No. 2 pp. 8-9, 1989. Hinga, K. R., "Alteration of Phosphorus Dynamics During Experimental Eutrophication of Enclosed Marine Ecosystems," Marine Pollution Bulletin. Vol. 21, pp. 275-280, 1990. Jeffries, H.P., A.A. Keller, and S. Hale, "Predicting Winter Flounder (Pseudopleuronectes Americanus) Catches by Time Series Analysis," Canadian Journal of Fish and Aquatic Sciences. Vol. 46, pp. 650-659, 1989. Keller, A. A. and R. L. Ric, "Effects of Nutrient Enrichment on Natural Populations of the Brown Tide Phytoplankton Aureococcus Anophagefferens (Chrysophyceae)," Journal of Phvcologv. Vol. 25, pp. 636-646, 1989. Keller, A.A. and U. Riebesell, "Phytoplankton Carbon Dynamics During a Winter-Spring Diatom Bloom in an Enclosed Marine Ecosystem: Primary Production, Biomass and Loss Rates, Marine Biology. Vol. 103, pp. 131-142, 1989. Keller, A.A., "Modeling the Effect of Temperature, Light and Nutrients on Primary Productivity: A Comparison of Two Approaches, Mechanistic Versus Empirical," Limnology and Oceanography. Vol. 34, pp. 82-95, 1989. Keller, A. A. and R. L. Rice, "Variation in DCMU-Enhanced Fluorescence Relative to Chlorophyll A: Correlation with the Brown Tide Bloom," Journal of Phvcologv. Vol. 26, pp. 202-205, 1990. Keller, A.A., P.H. Doering, S.P. Kelly and B.K. Sullivan, "Growth of Juvenile Atlantic Menhaden, Brevoortia Tyrannus (Pisces: Clupeidae) in MERL Mesocosms: Effects of Eutrophication," Limnology and Oceanography. Vol. 35, No. 1, pp. 109-122, 1990. 98 ------- Keller, A.A., L.L. Beatty, L.E. Weber and C.A. Heil, "Soluble Fluorescence: Effects on Chlorophyll Determination at Different Salinities," Canadian Journal of Fish and Aquatic Sciences. Vol. 47, No. 9, pp. 1700- 1709, 1990. Nowicki, B.L. and C.A. Oviatt, "Are Estuaries Traps for Anthropogenic Nutrients? Evidence from Estuarine Mesocosms," Marine Ecology Progress Series. Vol. 66, No. 1-2, pp. 131-146. ARTICLES SUBMITTED OR IN PRESS Adelman, D., K. R. Hinga and M. E. Q. Pilson. "Fractionation of Butyltin Species During Sample Extraction and Preparation for Analysis," Environmental Monitoring Assessment. Vol. 13, in press. Doering, P.H., L.W. Reed, C.A. Oviatt and J.H. McKenna. "The Behavior of Dissolved Organic Carbon During Simulated Estuarine Mixing," Limnology and Oceanography, submitted. Doering, P.H., C.A. Oviatt and M.E.Q. Pilson, "Control of Nutrient Concentrations in the Seekonk-Providence River Region of Narragansett Bay, Rhode Island," Estuaries. Vol. 13, in press. Hinga, K.R., A.A. Keller, and C.A. Oviatt, "Atmospheric Deposition and Nitrogen Inputs to Coastal Waters," Ambio. in press. Jaworski, N.J., P. Groffman, A. Keller and J. Prager, "A Water-Scale Analysis of Nitrogen Loading: The Upper Potomac River," Estuaries. submitted. Keller, A.A., C.A. Oviatt and R. Rice, "Phytoplankton Community Response to Nutrient Enrichment and the Benthos in Shallow, Coastal Ecosystems," Marine Ecology Progress Series (in prep). Lane, P. A., "Receiving Water Responses to Wastewater Discharges to the Marine Environment - Biological Effects and Risk Analysis," Chapter to appear in "Wastewater Discharges to Marine Environment", D. Waller, ed. T.U.N.S. Symposium, in press. Selligman, P.P., RJ. Maguire, R.F. Lee, A.O. Vakirs, P.M. Stang and K.R. Hinga, "Persistence and Fate of Tributyltin in Aquatic Ecosystems. Chapter 99 ------- 18 in Tributyltin: Environmental Fate and Effects. M.A. Champ and P.P. Selyman (eds). Elsevier Applied Science Publishers Ltd.. in press. Sullivan, B.K. and P.V. Banzon, "Food Limitation and Benthic Regulation of Populations of the Copepod Acartia Hudsonica Pinhey in Nutrient-Limited and Nutrient-Enriched Systems," Limnology and Oceanography, in press. Widbom, B. and C.A. Oviatt, "The World Prodigy Oil Spill in Narragansett Bay, Rhode Island: Acute Effects on Macrobenthic Crustacean Populations," Marine Environmental Research, submitted. BOOKS AND BOUND PROCEEDINGS Jackson, Susan K., "Suspended Paniculate Trace Metal Concentrations in a Control and Nutrient Enhanced Coastal Marine Ecosystem: A Mesocosm Study," Thesis for M.S., University of Rhode Island. CHAPTERS IN OTHER BOOKS Frithsen, J. B., D. Nacci, C. Oviatt, C. J. Strobel, and R. Walsh, "Using Single-Species and Whole Ecosystem Tests to Characterize the Toxicity of a Sewage Treatment Plant Effluent," G. W. Suter II and M. A. Lewis (Eds.), Aquatic Toxicology and Environmental Fate: Eleventh Volume. American Society for Testing and Materials, STP 1007, pp. 231-250, 1989. Hinga, K.R., "Subseabed Disposal of High-Level Radioactive Wastes: Transition from Hare-Brained Idea to a Feasible Technology," L.M. Alexander, S. Allen and L.C. Hanson (eds), Marine Science and Technology: Economic. Legal, and Political Aspects of Change. Law of the Sea Institute, pp. 245-270, 1989. PROJECT REPORTS Doering, P.H., C.A. Oviatt and B.L. Welsh, "Characterizing Late Summer Water Quality in the Seekonk, Providence River and Upper Narragansett Bay," Final Report, Rhode Island Department of Environmental Management, Narragansett Bay Project, pp. 23. 100 ------- Hinga, K.R., N.F. Lewis, R. Rice, K. Dadey and A. Keller, "A Review of Narragansett Bay Phytoplankton Data: Status and Trends," Narragansett Bay Project, Report #NBP-89-21, pp. 251, March 1989. Hinga, K.R., "Monitoring Tributyltin in Narragansett Bay," Contract report to the Rhode Island Department of Environmental Management, Division of Agriculture, 1990. Hinga, K.R., A.A. Keller and C.A. Oviatt, "Atmospheric Deposition and Nitrogen Inputs to Coastal Waters," Final Report to the Environmental Protection Agency Environmental Research Laboratory - Narragansett (CR- 8124-87-03), August 1990. Jeon, H. and C.A. Oviatt, "A Review of Biological Effects of Toxic Pollutants on Organisms in Narragansett Bay," Report to Narragansett Bay Project, September 1990. Keller, A.A. and K.R. Hinga, "New York - New Jersey Harbor Estuary Program Module 4: Nutrient and Organic Enrichment," 2nd Quarterly Report - Long Term Trend Analyses, April 1990. Keller, A.A. and K.R. Hinga, "New York - New Jersey Harbor Estuary Program Module 4: Nutrient and Organic Enrichment," 3rd Quarterly Report and Preliminary Data Report, July 1990. Keller, A.A., K.R. Hinga and C.A. Oviatt, "New York New Jersey Harbor Estuary Program Module 4: Nutrient and Organic Enrichment," Draft Final Report, November 1990. Nowicki, B.L. and J.H. McKenna, "A Preliminary Assessment of Environmental Quality in Greenwich Bay, Rhode Island," Report to the Narragansett Bay Project, Providence, RI, pp. 35, 1990. Saila, S.B. and A. Keller, "Suggestions Regarding Management Planning for Some Vertebrate and Invertebrate Resources of Narragansett Bay," Report to Narragansett Bay Project, November 1990. CONFERENCES AND WORKSHOPS HELD None 101 ------- 102 ------- CENTER: LOCATION: DIRECTOR: National Center for Ground Water Research Consortium: Rice University University of Oklahoma Oklahoma State University Dr. C. H. Ward Department of Environmental Science and Engineering Rice University P. O. Box 1892 Houston, TX 77251 713/527-4086 Fax: 713/285-5203 Mr. M. R. Scalf Robert S. Kerr Environmental Research Laboratory U. S. Environmental Protection Agency P. O. Box 1198 Ada, OK 74820 405/332-8800 FTS: 743-2308 FUNDS SPENT DURING FY 1990 (10/1/80 - 9/30/90) PROJECT OFFICER: EPA Other Government University Private Sector Total $845,000 180,000 305,000 825,000 $2,155,000 DESCRIPTION OF THE PROGRAM The objective of the National Center for Ground Water Research (NCGWR) is to improve the understanding of the subsurface environment and its interaction with pollutants. To meet this objective, research is conducted in three major areas: transport and fate of ground water contaminants, study of subsurface and pollutant characteristics which affect the transport and fate of pollutants, and development of methods to assess and protect ground water quality. This research program provides information on the behavior of subsurface pollutants in order to: (1) evaluate options for control of specific sources, (2) assess the impact of 103 ------- contamination events, (3) determine the likelihood that a chemical will persist underground, (4) take remedial action in the restoration of ground water quality, and (5) develop criteria for disposal site selection or rejection. Research sponsored by the NCGWR is oriented toward studies required to explain and predict the transport and fate of synthetic organic compounds in the subsurface, especially in ground waters associated with hazardous waste sites. ACCOMPLISHMENTS - FY 1990 Stimulation of indigenous subsurface microorganisms to degrade synthetic and petroleum derived organic compounds present in ground water is termed in situ biorestoration. In the last five years, the Center has played a major role, in cooperation with the U. S. EPA and especially the Robert S. Kerr Environmental Research Laboratory, in developing the quantitative data needed for design and optimization of in situ biorestoration processes. In addition to mechanistic studies by research groups led by individual investigations, the Center has contributed substantively to an EPA-sponsored field demonstration of the Raymond Process for in situ biorestoration of petroleum contaminated ground water at the U. S. Coast Guard Air Station in Traverse City, Michigan. Coordination and interaction of basic laboratory studies with complementary field investigations has proven to be one of the most productive of the Center's strategies for advancing the state-of-the-art in chemical transport and fate research and in the application of basic science to the solution of ground water problems. The lack of mechanistic research on the behavior and interaction of contaminants and microbes in the subsurface inspired the use of an empirical approach to in situ bioprocess development and application. Research at Rice University has addressed three factors considered important in optimization of in situ biorestoration technology. Studies on the use and behavior of hydrogen peroxide (H202) for delivery of electron acceptors to support biodegradation has clearly demonstrated microbial adaptation (increased catalase activity) to increasing H2^2 concentrations and increased resistance to deleterious effects due to specific, commonly used application regimes. Experiments to determine the effects of flow rate and hydraulic conductivity on microbial movement in the subsurface indicate that microbial transport may be the factor most limiting to the use of specially adapted and/or genetically engineered organisms in the subsurface. In other experiments on populations of subsurface microorganisms from clean and contaminated sites, it has been clearly 104 ------- demonstrated that exposure to contaminants results in the selection and preferential growth of microbes that produce surface active agents that may enhance the bioavailability (and degradation) of contaminants in aquifers. A study at the University of Oklahoma has used microcosms to probe the anaerobic biodegradability of several aromatic compounds and pesticides known to contaminate aquifers. The biodegradation of these materials largely depended upon the terminal electron acceptors available in the aquifer; this, in turn, determined the fate and route of substrate decomposition. m-Cresol and phenol anaerobically degraded via a carboxylation reaction while p-hydroxybenzoate degraded through a decarboxylation step. Carboxylation and decarboxylation steps appear to be slightly reversible during phenol metabolism. Among pesticides, propanil was anaerobically metabolized through hydrolysis and linuron by demethoxylation, while 2,4,5-T, 2,4-D, and bromocil degraded through reductive dehalogenation. Toluene and xylene were also rapidly degraded in defined aquifer slurries, but their metabolic pathways are as yet unknown. Benzene proved highly recalcitrant under anaerobic conditions. An automated data-acquisition device has been invented and is now in practical use to measure the production or consumption of gaseous endproducts or substrates of anaerobic metabolism. Such a device will allow for the automated testing of numerous compounds for their anaerobic biodegradation potential. Progress was made on a field study of the spatial and temporal variability of aquifer methanogenesis. Results suggest that high spatial and temporal variability in methane production rates existed at both methanogenic and sulfate-reducing sites. Statistical analysis of the field and laboratory data suggest that pH, temperature, and sulfate levels are the major, but not the only, environmental variables influencing the mineralization of organic matter in anoxic aquifers. For deeper subsurface environments, a method was developed to assess the microbial integrity of collected samples. Coliform bacteria were used as tracer organisms and acted as efficient tools in evaluating the degree of microbial contamination accidentally encountered from drilling fluids. The fate of halo-organic compounds belonging to different chemical classes was examined in anoxic aquifer samples. A variety of these compounds were biotransformed by reductive dechlorination reactions. The rate of dehalogenation was stimulated by the addition of low molecular weight fatty acids and alcohols and inhibited by the addition of sulfate. Reductive dehalogenation was also demonstrated for a nitrogen 105 ------- heterocyclic compound. A dehalogenating pure culture anaerobic bacterium was characterized and was found to be able to grow either autotrophically or heterotrophically. The 16S rRNA sequence analysis indicated that the organism belongs to a new genus of sulfate-reducing bacterium. The organism is now formally classified as Desulfomonile tiedjei gen. nov. and sp. nov. The biochemistry of dehalogenation activity was studied with this organism. The activity was membrane associated and shown to occur in cell-free extracts. This is a prerequisite to the first isolation of an aryl dehalogenase. Other research at Rice University during the past year included the development of a conceptual understanding of source effects from residual oil residing above the water table as well as experimentation in the laboratory and field to investigate such release mechanisms by observation. This included a field test at Traverse City, Michigan in October, 1989 which verified the importance of residual oil contribution to waste loading of unconfined aquifers. Water was infiltrated from the surface and past a layer of residual oil near the water table. Cone penetrometers were used for sampling of BTEX in the unsaturated and saturated zones. Results clearly showed a water quality release from the residual oil near the water table. The hydrology group at Rice also developed a numerical model to simulate the fate and transport of an oily waste and its dissolved constituents in the subsurface. A multiphase unsaturated zone contaminant transport model, MUCT, was developed to describe the fate of an oily waste, with contaminants contained within the waste, spilled at the surface. MUCT was developed to simulate the simultaneous vertical flow of water and a second immiscible phase fluid through porous media. The model was based upon solving three-phase flow equations using semi- analytical techniques. The model was linked with OILENS and a horizontal plane source model. Research at Oklahoma State University has centered on the cometabolic metabolism of the ground water pollutant trichloroethylene (TCE). Previous research has demonstrated that growth of the bacterium Alcaligenes eutrophus IMP 134 on phenol or 2,4-D allowed the concurrent removal of TCE. Researchers have cloned the genes which encode the enzymes of the 2,4-D pathway and have demonstrated that the 2,4- dichlorophenol hydroxylase is oxidizing TCE. By inference, it can be" assumed that the phenol hydroxylase is likewise involved, but these chromasomally encoded genes have resisted isolation. The tfdB gene which encodes the dichlorophenol hydroxylase is positively regulated in its 106 ------- wildtype configuration and therefore expresses only a fraction of its normal activity when cloned. Slow release of contaminants is a result of desorption occurring more slowly than expected. Sorption and desorption had been assumed to have the same rates. Recent studies at Rice University have shown that this slow release of contaminant is temperature dependent. The release process is slowed by lower temperatures. The effect of ground water flow rate on the extent of adsorption and absorption (i.e., retardation) of methylated benzenes was evaluated with soil columns for three different soils. The ground water velocity was varied from 0.25 to 30 ft/day. For compounds with octanol/water partition coefficients of 1,000 or greater, the retardation factor was inversely proportional to velocity, below about 3 ft/day. The release of residual aviation gasoline saturation from field contaminated sandy aquifer material was investigated using soil columns. Flushing with water produced constant low (<200 ppb) effluent concentrations of methylated alkanes. Addition of a biodegradable non- ionic surfactant (Triton X-100) to the flushing solution produced an immediate increase in concentration to several ppm, which declined over 20 pore volumes to initial levels. Use of three times the influent concentration of surfactant (15 g/1) resulted in an increase in effluent concentration to more than 10 times that of the 5 g/1 experiment, which decreased to initial levels in one-third of the volume. Soil analysis showed that more than 95% of the residual saturation in the columns had been removed. Isopropyl alcohol added to the flushing solution at 50% by volume caused a rapid and dramatic increase and subsequent decrease in effluent concentration over less than two pore volumes. Once again, soil analysis indicated that more than 95% of the oil had been removed from the column. Significantly, at 20% by volume, the alcohol did not appear to enhance the release of residual oil saturation. The Center's experimental and modeling studies are being integrated into a conceptual framework of the bioremediation process. If this effort is successful, it will result in the first engineering process design manual for microbially enhanced restoration of contaminated ground water. The Center's information transfer activities were highlighted by numerous presentations on subsurface chemical transport and fate and 107 ------- aquifer remediation at local, national, and international symposia and disciplinary scientific meetings and to EPA and industrial technical personnel. Another highlight of the Center's FY 1990 technology transfer program was initiation of training activities of the Superfund University Training Institute (SUTI) in cooperation with the R. S. Kerr Environmental Research Laboratory. Also significant was the Center's seminar (in cooperation with RSKERL and the University of Texas) on "Methods to Estimate the Migration Potential of Chemicals at Superfund Sites," which was used by the Agency's Science Advisory Board (Environmental Engineering Committee, Leachability Subcommittee) as a resource for a SAB self-study on subsurface leaching phenomena. Technology transfer projects completed in FY 1990 include: C. H. Ward Superfund University Training Institute Rice Univ. "Transport and Fate of Contaminants in Houston, TX the Subsurface" • April 9-10, 1990, R. S. Kerr Environmental Research Laboratory, Ada, OK • September 18-20, 1990, Rice University, Houston, TX R. C. Loehr "Superfund Site Remediation Analyses — Univ. of Texas Application and Limitations of Austin, TX Leaching Tests" J. J. Lund "Indirect Methods for Estimating the Hydraulic U of Calif. Properties of Unsaturated Soils" Riverside, CA RESEARCH GOALS - FY 1991 Four major areas will provide focal points for the Center's research program: (1) transport and fate of pollutants, (2) subsurface characterization, (3) methods development, and (4) information transfer. The Center will support active programs in all four areas; however, major emphasis will continue to be placed on the development of biotechnology for aquifer and subsurface restoration. Work on four important issues related to enhancement of aerobic in situ biorestoration will continue: (1) the factors limiting the use of 108 ------- hydrogen peroxide (H2O2) in the subsurface to provide oxygen for microbial metabolism, (2) the influence of subsurface characteristics on the rates of microbial degradation, (3) the transport, colonization, and metabolism of surface microorganisms introduced into the subsurface, and (4) the role of biosurfactant production by in situ microorganisms in biodegradation of ground water contamination. Studies at Rice University will determine the biochemistry involved in microbial adaptation to highly oxidizing conditions resulting from injection of high concentrations of ^2^2 into the subsurface. Laboratory and field studies on the transport and fate of marker organisms injected into the subsurface will continue. A series of potentially important controlling parameters such as subsurface structure and chemistry and microbial morphology will be evaluated. The diversity and factors controlling microbial biosurfactant production in the subsurface will be investigated. The mechanisms governing the slow release of contaminants from aquifer materials will continue to be a major focus of research in contaminant fate and transport. Understanding the effect of naturally fluctuating environmental parameters on desorption rates will assist in the optimization of remediation technologies. Modeling goals at Rice University for 1990-91 include further testing of models with data from controlled soil columns and further analysis of data from the Traverse City, Michigan test. The source module will then be inserted into the Bioplume II model to better represent the residual source leaching from BTEX spills. In further research at Oklahoma State University, a series of Pseudomonas expression vectors obtained from Michigan State University will allow the tfdB gene to be cloned under the control of either a very active inducible or constitutive promoter. This should yield high level expression of the tfdB gene product and increase the rates of TCE removal by the recombinant organism. A library of chromosomal DNA has been prepared and will be transferred into a Pseudomonas putida strain in which the normal phenol hydroxylase has been disabled. This should allow the isolation of the unregulated phenol hydroxylase gene from the chromosome. This gene will in turn be cloned into the Pseudomonas expression vector system. Research at the University of Oklahoma will continue to probe the limits of anaerobic biodegradation of xenobiotic compounds which are important contaminants in aquifers. Radiotracer techniques will be used to 109 ------- probe the prevalent metabolic pathways for substrates like m-cresol, phenol, and benzene. This task will be facilitated by the enrichment and isolation of the requisite microorganisms. Purification of the dehalogenase from Desulfomonile tiedjei will be pursued. The fundamental mechanism of the dehalogenation reaction will be pursued with this enzyme. Dehalogenation of chloroethenes will also be pursued with these enzyme preparations. It may be that such preparations have properties that make them desirable for field use. The metabolic fate of 26 heterocyclic compounds under anaerobic conditions will also be examined. The field study on quantitative estimates of the degree of spatial and temporal variability on biodegradation rates will continue. It may be necessary to redesign the gas collection wells. The data acquisition system will be used to monitor a variety of biodegradation experiments and to probe the consumption of gaseous substrates by defined cultures. Collectively this research centers on (1) identifying the types of substrates subject to anaerobic decay and the prevalent metabolic pathways, (2) providing quantitative descriptions of anaerobic biodegradation kinetics, (3) confirming the metabolic pathway by isolation of the enzymes responsible for promising bioconversions and (4) suggesting biological strategies for the restoration of contaminated areas and/or the prevention of problems through desirable waste disposal procedures. Technology transfer projects underway in FY 1991 include: Superfund University Training Institute (SUTD Course Schedule: • Ground Water Investigations, 4 offerings (2 unscheduled, based on requests) • Transport and Fate of Contaminants in the Subsurface, 2 offerings - Rice and Denver (January 22-24, 1991) • Remediation of Contaminated Soils, 2 offerings, Seattle and Atlanta • Solute Transport Modeling at Hazardous Waste Sites, 2 offerings - Rice and RSKERL • Bioremediation of Subsurface Environments, 2 offerings - University of Texas and Rice 110 ------- • Pump and Treat Technology for Aquifer Remediation, 2 offerings - University of Oklahoma and Rice Workshops/Conferences C. H. Ward "Soil Venting Workshop," Houston, Texas, Rice Univ. April 28-30, 1991; Co-sponsored by the R. S. Houston, TX Kerr Environmental Research Laboratory and the National Center for Ground Water Research C. H. Ward "Biological Processes for Subsurface Restoration," Rice Univ. International Conference, 1992 Houston, TX OUTPUTS - FY 1990 Articles in Refereed Journals 17 Articles Submitted or In Press 7 Books and Bound Proceedings 0 Chapters in Other Books 13 Project Reports 1 5 Conferences and Workshops Held 2 111 ------- BIBLIOGRAPHY REFEREED JOURNAL ARTICLES Adrian, N.R. and J.M. Suflita, Reductive Dehalogenation of a Nitrogen Heterocyclic Herbicide in Anoxic Aquifer Slurries, Applied Environmental Microbiology. Vol. 56, pp. 292-294, 1990. Beeman, R.E. and J.M. Suflita, "Evaluation of Deep Subsurface Drilling Procedures Using Serendipitous Microbial Contaminants as Tracer Organisms," Geomicrobiology Journal. Vol. 7, pp. 223-233, 1989. Beeman, R.E. and J.M. Suflita, "Environmental Factors Influencing Methano-genesis in a Shallow Anoxic Aquifer: A Field and Laboratory Study," Journal of Industrial Microbiology. Vol. 5, pp. 45-58, 1990. DeWeer, K.A., L. Mandelco, R.S. Tanner, C.R. Woese, and J.M. Suflita, "Desulfomonile tiediei Gen. Nov. and Sp. Nov., A Novel Anaerobic, Dehalogenating, Sulfate-Reducing Bacterium," Archives of Microbiology. Vol. 154, pp. 23-30, 1990. DeWeer, K.A. and J.M. Suflita, "Aryl Reductive Dehalogenlation of 3- Chlorobenzoate and Other Halobenzoates by Extracts of Desulfomonile tiedjei." Applied Environmental Microbiology. Vol. 56, pp. 2999-3005, 1990. Gibson, S.A. and J.M. Suflita, "Anaerobic Biodegradation of 2,4,5- Trichloro-phenoxyacetic Acid in Samples from a Methanogenic Aquifer: Stimulation by Short Chain Organic Acids and Alcohols," Applied Environmental Microbiology. Vol. 56, pp. 1825-1832, 1990. Marker, A.R., and Y. Kim, "Trichloroethylene Degradation by Two Independent Aromatic-Degrading Pathways in Alcaligenes eutrophus JMP134," Applied Environmental Microbiology. Vol. 56, pp. 1179-1180, 1990. Kan, A.T. and M.B. Tomson, "Effect of pH Concentration on the Transport of Naphthalene in Saturated Aquifer Media," Journal of Contaminant Hydrology. Vol. 5, pp. 235-251, 1990. 112 ------- Kan, A.T. and M.B. Tomson, "Ground Water Transport of Hydrophobia Organic Compounds in the Presence of Dissolved Organic Matter," Environmental Toxicology and Chemistry. Vol. 9, pp. 253-263, 1990. Kuhn, E.P. and J.M. Suflita, "The Biodegradation of Nitrogen, Oxygen and Sulfur Heterocyclic Compounds under Anaerobic Conditions: Results with Aquifer Microorganisms," Environmental Toxicology and Chemistry. Vol. 8, pp. 1149-1158, 1989. Kuhn, E.P., G.T. Townsend, and J.M. Suflita, "Effect of Sulfate and Organic Carbon Supplements on Reductive Dehalogenation of Chloroanilines in Anaerobic Aquifer Slurries," Applied Environmental Microbiology. Vol. 56, pp. 2630-2637, 1990. Linkfield, T.G., J.M. Suflita, and J.M. Tiedje, "Characterization of the Acclimation Period Prior to the Anaerobic Biodegradation of Haloaromatic Compounds," Applied Environmental Microbiology. Vol. 55, pp. 2273-2778, 1989. Newell, C.J., J.F. Haasbeek, and P.B. Bedient, "OASIS: A Graphical Decision Support System for Ground Water Contaminant Modeling," Ground Water. Vol. 28, pp. 224-234, 1990. Newell, C.J., L.P. Hopkins, and P.B. Bedient, "A Hydrogeologic Database for Ground-Water Monitoring," Ground Water. Vol. 28, pp. 703-714, 1990. Rifai, H.S. and P.B. Bedient, "Comparison of Biodegradation Kinetics with an Instantaneous Reaction Model for Groundwater," Water Resources Research. Vol. 26, pp. 637-645, 1990. Sims, J.L., J.M. Suflita, and H. Russell, "Reductive Dehalogenation: A Subsurface Bioremediation Process," Remediation. Vol. 1, pp. 75-93, 1990. Thomas, J.M., V.R. Gordy, S. Fiorenza and C.H. Ward, "Biodegradation of BTEX in Subsurface Materials Contaminated with Gasoline: Granger, Indiana," Water Science and Technology. Vol. 22, pp. 53-62, 1990. ARTICLES SUBMITTED OR IN PRESS Delphon, J.K., C.P. Yang, W.W. Clarkson, and A.R. Harker, "Stability and Integrity of a Single-Species Biofilm within an Expanded Bed Reactor," . submitted, 1990. 113 ------- Ramanand, K., and J.M. Suflita, "Anaerobic Degradation of m-Cresol in Anoxic Aquifer Slurries: Carboxylation and Decarboxylation Reactions in a Sulfate-Reducing Bacterial Enrichment," Applied Environmental Microbiology, submitted, 1990. Rifai, H.S. and P.B. Bedient, "Modeling Contaminant Transport and Biodegradation in Ground Water," Advances in Environmental Science Groundwater Contamination. Vol. 1: Methodology and Modeling. McGraw- Hill, in press, 1990. Suflita, J.M., K. Ramanand, and N. Adrian, "The Anaerobic Biotransformation of Selected Pesticides in Aquifer Sediments," Organic Substances and Sediments in Water. Robert Baker, ed., Lewis Publishers, Chelsea, MI, accepted, 1990. Suflita, J.M., L-.N. Liang, and S. Liu, "The Anaerobic Metabolism of 2- Hydroxybiphenyl by Sulfate-Reducing Bacterial Enrichments," Current Microbiology, accepted, 1990. Wise, W.R., C.C. Chang, R.A. Klopp, and P.B. Bedient, "Impact of Rainfall Upon the Sampling of Ground Water Quality Below Residual Oil," Ground Water Monitoring Review, submitted, 1990. Yang, C.P., J.K. Delphon, A.R. Marker, and W.W. Clarkson, "Limitations within a Single-Species Expanded Bed Biofilm Reactor which Affect the Removal of 2,4-Dichlorophenoxyacetic Acid," Biodegradation. submitted, 1990. BOOKS AND BOUND PROCEEDINGS None CHAPTERS IN OTHER BOOKS (INCLUDING PROCEEDINGS) Alder-Schaller, S.E. and P.B. Bedient, "Evaluation of the Hydraulic Effect of Injection and Pumping Wells on In Situ Bioremediation," Proceedings. National Water Works Association/American Petroleum Institute Conference on Petroleum Hydrocarbons and Organic Chemicals in Ground Water. Houston, TX, pp. 191-201, November 1989. 114 ------- Bedient, P.B., L.A. Vance, and H.S. Rifai, "Implementation of Wellhead Protection Programs Utilizing Geographical Information Systems," Proceedings. 8th National Conference on Microcomputers in Civil Engineering. Orlando, FL, pp. 87-90, 1990. Bedient, P.B., F.W. Schwarz, and H.S. Rifai, "Hydrologic Design for Groundwater Pollution Control," Handbook of Hydrology. Chapter 29, McGraw-Hill, in press, 1990. Chang, C.C., W.R. Wise, R.A. Klopp and P.B. Bedient, "In Situ Source Release Mechanism Study at an Aviation Gasoline Spill Site: Traverse City, Michigan," Proceedings. 4th National Outdoor Action Conference on Aquifer Restoration. Ground Water Monitoring and Geophysical Methods. Las Vegas, NV, pp. 459-473, 1990. Hopkins, L.P., CJ. Newell, and P.B. Bedient, "A Hydrogeologic Database for the EPACML Regulatory Model," Proceedings. National Water Works Association/American Petroleum Institute Conference on Petroleum Hydrocarbons and Organic Chemicals in Ground Water. Houston, TX, pp. 265-279, November 1989. Rifai, H.S. and P.B. Bedient, "A TC Model Alternative for Production Waste Scenarios," Proceedings. First International Symposium on Oil and Gas Exploration and Production Waste Management Practices. U.S. Environmental Protection Agency, New Orleans, LA, pp. 955-965, September 1990. Rifai, H.S., P.B. Bedient, and CJ. Newell, "Review and Analysis of the Toxicity Characteristics Composite Landfill Model," Proceedings. National Water Works Association/American Petroleum Institute Conference on Petroleum Hydrocarbons and Organic Chemicals in Ground Water. Houston, TX, pp. 143-157, 1990. Suflita, J.M. "Microbiological Principles Influencing the Biorestoration of Aquifers," Transport and Fate of Contaminants in the Subsurface. EPA/625/4-89/019, Center for Environmental Research Information and R.S. Kerr Environmental Research Laboratory, Ada, OK, pp. 85-99, 1989. Suflita, J.M., "Microbial Ecology and Pollutant Biodegradation in Terrestrial Subsurface Ecosystems," In Transport and Fate of Contaminants in thp. Subsurface. EPA/625/4-89/019, Center for Environmental Research Information and R. S. Kerr Environmental Research Laboratory, Ada, OK, pp. 67-84, 1989. 115 ------- Thomas, J.M. and C.H. Ward, "Bioremediation of Contaminated Aquifers," Proceedings. 3rd Annual Hazardous Materials (HAZMAT^O) Management Conference/Central. Rosemont, IL, pp. 388-393, 1990. Ward, C.H. and J.M. Thomas, "In Situ Ground Water Bioremediation," Proceedings. Prevention and Treatment of Groundwater and Soil Contamination in Petroleum Exploration and Production. Calgary, Ontario, pp. 28.0-28.15, 1989. Ward, C.H. and J.M. Thomas, "In Situ Biodegradation of Organic Pollutants in Ground Water," Proceedings. Bioremediation of Wood Treating Waste Forum. Mississippi State University, pp. 125-131, 1989. Wise, W.R. and P.B. Bedient, "Infiltration Past Residual Oil: Advective Transport of a Partially Soluble Organic Compound to an Underlying Aquifer," Proceedings. National Water Works Association/American Petroleum Institute Conference on Petroleum Hydrocarbons and Organic Chemicals in Ground Water. Houston, TX, pp. 271-280, November 1990. PROJECT REPORTS Bedient, P.B. and H.S. Rifai, "Effects of Various Pumping and Injection Schemes and Variable Source Loading in Biorestoratin," Yr XI Quarterly Reports I, II, HI. Bedient, P.B., W. R. Wise, S.E. Alder-Schaller, and C.C. Chang, "Effects of Various Pumping and Injection Schemes and Variable Source Loading in Biorestoration," Yr X Annual Report, National Center for Ground Water Research, October 1989. Beeman, R.E., "The Microbial Ecology of a Shallow Anoxic Aquifer Polluted by Landfill Leachate: Field and Laboratory Investigations," Ph.D., University of Oklahoma, Norman, OK, 1990. Canter, L.W., V.V. Mandlekar, and A. Tameshy, "Ground Water Implications of Aircraft Paint Stripping Wastewater Sludges: Treatment and Sludge Disposal Considerations," Yr X Annual Report, National Center for Ground Water Research, October 1989. 116 ------- Clark, Gary L., "Flow Rate Effects on the Sorption of Methyhlated Benzenes in Saturated Aquifer Materials," Ph.D., Rice University, Houston, TX, 1990. Francy, D.S., J.M. Thomas, V.R. Gordy, S. Fiorenza, HJ. Marlow, and C.H. Ward, "Optimization of In Situ Biorestoration of Contaminated Subsurface and Aquifer Materials," Yr XI Quarterly Report III. Gibson, S.A., "The Reductive Dehalogenation of Aromatic Pollutant Chemicals by Microorganisms from Diverse Anaerobic Habitats," Ph.D., University of Oklahoma, Norman, OK, 1989. Haasbeek, J.F., "Application of Numerical Models to the Design of In Situ Ground Water Restoration Systems Under Variability of Hydrogeologic Conditions," M.S., Rice University, Houston, TX, 1990. Harker, A.R., "A Recombinant Approach to the Isolation and Characterization of a Primary Degrader of Trichloroethylene, Yr XI Quarterly Reports I, II, III; Yr X Annual Report, National Center for Ground Water Research, October 1989. Ongley, L.K., A.T. Kan, T.A. McRae, G.L. Clark, and M.B. Tomson, "Factors Influencing the Slow Release of Hydrocarbons from Aquifer Materials," Yr X Annual Report, National Center for Ground Water Research, October 1989. Ongley, L.K, T.A. McRae, G. L. Clark, and M.B. Tomson, "Factors Influencing the Slow Release of Hydrocarbons from Aquifer Materials," Yr XI Quarterly Reports, I, II, III. Nofziger, D.L., "Simulation Models for the Transport and Fate of Contaminants in Unsaturated Porous Media as Decision-Making Tools," Yr X Annual Report, National Center for Ground Water Research, October 1989. Suflita, J.M., "Microbial Metabolism of Xenobiotic Chemicals in Anoxic Aquifers," Yr XI Quarterly Reports I, II, III; Yr X Annual Report, National Center for Ground Water Research, October 1989. Ward, C.H., J.M. Thomas, V.R. Gordy, S. Firoenza, HJ. Marlow, and D.S. Francy, "Optimization of In Situ Biorestoration of Contaminated Subsurface and Aquifer Materials," Yr XI Quarterly Reports I, II; Yr X Annual Report, National Center for Ground Water Research, October 1989. 117 ------- Wise, W.R., C.C. Chang, and P.B. Bedient, "Effects of Various Pumping and Injection Schemes and Variable Source Loading on Biorestoration," Yr XI Final Report, National Center for Ground Water Research, October 1990. CONFERENCES AND WORKSHOPS HELD Methods to Estimate the Migration Potential of Chemicals at Superfund Sites, Rice University, Houston, TX, 14-15 December, 1989 Ground Water Research Seminar, Oklahoma City, OK, April 2-4, 1990; Co-sponsored by the R. S. Kerr Environmental Research Laboratory and the National Center for Ground Water Research. 118 ------- CENTER: National Center for Intermedia Transport Research LOCATION: University of California, Los Angeles DIRECTOR: Yoram Cohen Department of Chemical Engineering University of California, Los Angeles Los Angeles, CA 90024-1592 213/825-8766 Fax: 213/825-9741 PROJECT OFFICER: Joseph V. Behar U. S. Environmental Protection Agency ESML-LV P. O. Box 15027 Las Vegas, NV 89114 702/798-2216 FTS: 545-2216 FUNDS SPENT DURING FY 1990 (10/1/89 - 9/30/90) EPA $540,000 Other Government 485,193 University 49,714 Private Sector 52,409 Total 1,127,316 DESCRIPTION OF THE PROGRAM The National Center for Intermedia Transport Research (NCITR) focuses its research activities on the physical and chemical processes associated with the transport of particle or gaseous environmental pollutants from one medium, such as air, land, vegetation and water, to another. The NCITR also supports and participates in the application of intermedia and multimedia tools developed by the Center to identify and evaluate pollutant sources, to assess pollution prevention strategies, and to evaluate the regional impact of pollutants. The goals of the NCITR are: (1) to conduct fundamental research on intermedia transport, (2) to develop new methods of dealing with multimedia transport processes involving a variety of separate but interacting environmental compartments, such as soil, air, water, etc., (3) to 119 ------- conduct these studies for certain chemical species, primarily organic about which less is known, which are expected to be of special importance in the future, (4) to disseminate information pertaining to the preceding goals through seminars, conferences and workshops, and (5) to promote the use of intermedia and multimedia tools in environmental studies and environmental education through a technology transfer program. The Center has research activities in the following areas: multimedia transport modeling, mechanisms and rate of dry deposition, rain scavenging, organic and inorganic compounds in wet deposition, atmospheric chemistry/microphysics aerosol modeling, air/vegetation and multiphase soil transport and transformation processes, and multimedia evaluation of source emissions. The Center addresses a variety of intermedia transport questions such as: • What are the levels of multimedia distribution of chemicals emitted from mobile and stationary sources? • Are there chemicals accumulating in the atmosphere, water, and soil environments which have not yet been detected? • What are the fundamental processes determining dry and wet deposition? • How do temperature, humidity, vegetation growth, and other factors influence the pollutant deposition process? • What are the factors affecting the transport of non-aqueous phase liquids in the multiphase soil matrix? • What are the effects of moisture and temperature variations on contaminant transport in the soil matrix? How do bio-transformations affect contaminant transport in the soil environment? At UCLA, the NCITR collaborates with the State of California Risk and System Analysis for the Control of Toxics (RSACT). Investigators from* NCITR and the RSACT program interact in a complementary manner to make it possible to treat the entire environmental system from industrial sources to exposure of human and ecological receptors. 120 ------- ACCOMPLISHMENTS - FY 1990 Over the last year, there have been significant accomplishments. The research conducted at the NCITR over the last year continued to focus on the various aspects of pollutant transport across environmental phase boundaries. The NCITR programs contain both experimental and theoretical components with the NCITR developed transport models providing the focal point for the interpretation and guidance of fundamental intermedia transport studies. The NCITR multimedia fate and transport software is now in use by about 300 users nationwide. This model, the spatial-multimedia- compartmental model (SMCM Version 3.0), is being employed by universities, EPA and state offices, various private companies, and non- profit environmental organizations. A new technique for source allocation of reactive organics is under development, and the dual-tracer technique for field determination of dry deposition velocities has been demonstrated for polycyclic aromatic hydrocarbons (PAHs). In a related study, the Low Pressure Impactor/Fourier Transform Infrared (LPI/FTIR) method for determining the composition of aerosols is being evaluated. As a consequence of the NCITR work on atmospheric hydrogen peroxide, the factors controlling the formation of hydrogen peroxide and its effect on air quality are now better understood. A new regional chemistry/aerosol transport (CAT) modeling effort that relies on intermedia predictions developed at the NCITR and meteorological and topological data is in the advanced development stage. A new front-tracking model to predict migration of a non-aqueous phase liquid (NAPL) through the unsaturated soil zone was developed. Also, the transport of volatile organics in the unsaturated soil zone was found to be affected by temperature and moisture variations. Biotransformations may be important in affecting the fate of contaminants in the soil matrix. In this regard, NCITR scientists have been working towards identifying the conditions that may trigger the biotransformation of various chemicals of concern. Finally, the NCITR publishes an environmental newsletter - The Multimedia Environment. This newsletter keeps various governmental agencies and the academic and industrial communities informed of the NCITR activities and scientific advances made at the NCITR. Specific details of the NCITR's accomplishments in its eight research areas are given below. 121 ------- Multimedia Transport of Chemical Pollutants: During FY 1990, the multimedia transport program has improved the SMCM model version 3.0, based on feedback from users, and has extended the model to include the transport of particle-bound pollutants, and on a number of multimedia case studies. Several intermedia transport processes were included in the revised comprehensive-spatial-multimedia-compartmental model (COSMCM). These processes include rain scavenging, dry deposition, wind resuspension, air-particle partitioning, runoff, infiltration, colloidal transport, sedimentation, and resuspension of particles in the water column. A rain scavenging module was developed and tested, and the infiltration and runoff modules have also been revised and tested. In another project, a detailed multimedia exposure model that was designed to interface with the SMCM model was completed. The model will provide the necessary link between multimedia fate and transport and risk assessment. In an important case study, the first phase assessment of multimedia distribution of pollutants associated with emissions from an oil refinery was conducted in collaboration with the AMOCO corporation. The investigated pollutants include benzene, toluene, butadiene, ethylene, propylene, ethylbenzene, trimethylbenzene, xylene, methanol, methyl tert- butyl ether, and naphthalene. Phase I of the study was designed to identify the significant and insignificant pathways for multimedia transport and exposure. Phase II will focus on a refined transport and exposure pathway analysis that has been classified as significant. The results of Phase I indicate that even volatile chemicals which are emitted only to the atmosphere can be found in detectable amounts in the water and soil compartments. Characterization of Complex Atmospheric Aerosols: In aerosol sampling and analysis, investigators are able to account for most of the mass in an atmospheric aerosol in terms of the measured concentrations of sulfates, nitrates, ammonium ion, metal oxides, and organics. The majority of the inorganic mass can be attributed to individual chemical species; however, the organic fraction is not well resolved. The organic components of atmospheric aerosols are complex mixtures of hundreds of species and identification of individual species is extremely difficult. Most methods for identifying organic species require large sample quantities and long analysis times, and can identify only a small fraction of the organics. In order to address these constraints, recent NCITR work on 122 ------- analysis of aerosol organics has focused on functional group and compound class characterization. The method developed in this project is a new technique for the analysis of paniculate matter which allows size segregated samples to be analyzed. The size segregated samples are collected on zinc selenide using a Low Pressure Cascade Impactor. Samples are analyzed directly, without extraction, using transmission FTIR. Detection limits are in the picogram range. The spectra of the aerosol size fractions result in a series of functional group fingerprints for particular size fractions. Functional group profiles as a function of particle size have been determined by using the FTIR method during the Southern California Air Quality Study. The infrared spectra collected show strong inorganic and organic absorbances that have been attributed to ammonium, inorganic nitrate, organic nitrate, sulfate, aliphatic carbon, and carbonyl functionalities. All of the absorbances have been quantified and converted to mass loadings. The compound class size distributions measured in this work have revealed interesting features of ambient Los Angeles aerosol which were not apparent before this study. The most significant result is that secondary aerosol organics (products of gas phase photochemical reactions) occur in two particle size fractions which have different deposition velocities, atmospheric lifetimes, and chemical composition. They may be due to different gas phase precursors. Thus, the finding suggests the prospect of tracking the eventual chemical fate of classes of air pollutants via the combination of gas and aerosol sampling. Dry Deposition Processes: Size distributions for ten PAHs have been obtained from the data generated during the field study completed last year. Data for the vehicular source, obtained from particles sampled in two traffic tunnels, show a unimodal size distribution with about 80% of PAH mass occurring in particles less than 0.12 micron in diameter. The ambient PAH size distributions are bimodal in nature with an additional mode in the 0.5-1.0 micron size range. These distributions resemble carbon size distributions seen in previous studies because the organics are absorbed on the surfaces of the emitted particles. PAH decay factors were calculated using carbon monoxide as a conserved gaseous tracer. These show that the more reactive PAHs are depleted to greater extents because of photochemical decay and that this decay is greater in the summer months due to the higher photochemical reaction rates. In another part of this program, size distributions have been determined for copper, nickel, lead, manganese, zinc, and iron for both ambient aerosols in Los Angeles and automobiles. Approximate size 123 ------- distributions were obtained for aluminum, silicon, titanium, vanadium, potassium, and sulfur. Analysis and interpretation of the size distribution data are ongoing. Work is also continuing on the determination of the size distributions of elemental carbon, barium, cerium, samarium, and lanthanum. Source Allocation Studies: This year, a new research effort has been initiated to link the ongoing work on dry deposition processes to source allocation studies. Source allocation is used to determine the sources of air pollution as well as the percentages of specific pollutant levels in the atmosphere which can be attributed to those sources. An important goal of the Center's work is to develop a method which would allow changes in pollutant levels, resulting from chemical reactions and dry deposition, to be directly included in source studies. Currently, these processes are generally ignored in source allocation studies. Including the effects of dry deposition and chemical reactions in receptor modeling would improve the accuracy of existing models. Additional benefits would accrue. First, procedures would be developed to quantify the mass of specific pollutants being deposited as well as to determine the important sources of deposited material. Also, source allocation models would be extended to reactive species which cannot at present be accurately treated. The first step in this work has been the development of a method to apportion emissions of PAHs using stable PAH compounds as tracers. The method has been used to determine the contribution of automobiles to PAH levels in Los Angeles as well as the relative contributions of diesel and gasoline-powered vehicles. Vehicles were found to be the primary source of PAH emissions in Los Angeles. Newer catalyst equipped gasoline vehicles and older noncatalyst equipped gasoline vehicles were each responsible for approximately 45% of vehicular PAH emissions while diesel vehicles accounted for the remaining 10% of vehicular emissions. Organic Compounds in Wet Deposition: During the present funding period, efforts were concentrated on two programs in this area. The first was the continuation of measurements of hydrogen peroxide in atmospheric samples. The sampling occurred during 1989 and 1990 in the San Bernardino Mountains at the South Coast Air Quality Monitoring District (SCAQMD) station at Lake Gregory. The rationale for doing these measurements is to determine the relative content of oxidants in the area of conifer tree growth, where damage to the canopy had previously been observed as early as the 1950s. Unlike the distribution of hydrogen peroxide (H2O2) in the Los Angeles Basin, which reaches a maximum 124 ------- around mid-day, H2O2 peaks at Lake Gregory were frequently measured at night. Gas phase concentrations of H2O2 are generally higher in the mountain region than in the basin. The data were assembled and assessed and a manuscript has been prepared. In conjunction with the project, a laboratory experiment is being conducted for determining the harmful effects of atmospheric H2O2 on pine trees (see Ecosystem Transport Processes). The second component of the project concerns the measurement of aldehydes, oxidants (H2O2), organic acids, pH, conductivity, and the major anions and cations in acid rain at Westwood (UCLA), Los Angeles. This now represents the fifth year for collection of such a data base, and it is one of the largest data bases on organics in rain. Collection of rain for the above measurements will be performed also for the 1990-1991 season. Rain Scavenging: Below-cloud rain scavenging of semi-volatile organics (RASVO) was investigated by a model that accounts for the dynamic partitioning of atmospheric organics in gas/particle/rain phases during a rain event. Case studies for pyrene and fluoranthene rain scavenging in Los Angeles for two rain events (3/11/82 and 11/9-10/82) indicated that pollutant rain concentrations at ground level depend on pollutant emission rates, cloud base height and wind direction. High emission rates of pollutants, low cloud base and easterly wind direction (e.g., wind blowing from downtown Los Angeles towards the UCLA sampling site) lead to high pollutant rain concentrations at ground level. In contrast, low pollutant emission rates, high cloud base and westerly wind direction (e.g., wind blowing from the Pacific Ocean to UCLA) are responsible for lower pollutant rain concentration at ground level. Simulations revealed that variation of particle size distributions below- cloud due to rain scavenging, has a significant effect on the concentration in both the air and rain phases during a rain event. The simulations also demonstrated that washout ratios for semi-volatile organics may vary by an order of magnitude during a rain event. This implies that the application of the commonly reported average washout ratios for semi- volatile organics from field studies is questionable. Finally, the RASVO model, which can be used as a stand-alone model to assist in the design and interpretation of rain-scavenging field studies is currently being incorporated into a new multimedia transport model for aerosol-bound organics. Chemistry anfl Dispersion Modeling: Advances in the Chemistry/Aerosol Transport (CAT) modeling project have been made in 125 ------- three principal research areas during this funding period: (1) pollution source characterization, (2) objective wind analysis, and (3) aerosol chemistry/microphysics/transport modeling. In the area of pollution source characterization, using the carbon monoxide and paniculate lead emissions data from the NCITR "Dry Deposition Processes" project, an analysis of the synoptic behavior of smog events in the Los Angeles basin was initiated. One purpose of this work was to identify case studies to test model accuracy in the tracer dispersion calculations. It also provides a means to determine the patterns of tracer transport in the basin for interpreting the NCITR data. These studies will lead to an empirical characterization of the mixed layer in the Los Angeles basin as a function of time of day and regional meteorological state. A component of the project focused on the development of an objective wind analysis for the Los Angeles basin using the SCAQMD surface wind measurements. The optimization technique produces gridded surface winds over the domain of interest from the distributed set of observational sites by interpolation. Several methods of interpolation were considered, including the use of polynomials and the correction method. The correction method proved to be simpler, involved smaller extrapolation error, and was more accurate when used on data taken near data sites. The surface wind data are sparse in regions where terrain variation is large, and extrapolated winds may be unrealistic in these regions. A one-level mesoscale model was constructed to obtain a more reasonable and consistent wind field. The NASA Ames/UCLA chemical transport model has been established on the atmospheric sciences computer system, and has been adapted to the Los Angeles Basin. The model solves the continuity equations for any number of specified compounds that are advected by winds and subject to chemical and physical transformation according to a prescribed set of processes. Any emission source, including natural biogenic sources, for example, can be treated in the model. Considerable progress has been made in installing Carbon-Bond-IV photochemical smog mechanisms in the model utilizing about 80 chemical tracers. Preliminary transport simulations have been carried out to test the algorithms for mass conservation and to establish appropriate regional boundary conditions for the simulations. Ecosystems Transport Processes and Interactions- Investigations of the physiological and biochemical implications of hydrogen peroxide for plant growth response and photosynthesis capacity 126 ------- have been initiated. The model system used in these studies is Pinus ponderosa which grows naturally in areas where NCITR studies have documented relatively high ambient levels of hydrogen peroxide. Greenhouse experiments are using four concentrations of hydrogen peroxide administered in an aerosol mist. Plant response to this treatment is being monitored through time using a range of biochemical assays for antioxidant activity and physiological measurements of photosynthetic and stomatal response in comparison to control plants. Field studies of the natural inter- and intrapopulational variability in antioxidant resin production by Larrea tridentata (creosote bush) in the Mojave Desert have been completed. The final data set is from an elevational gradient of sites extending northward from Las Vegas into the relatively unpopulated areas of the Nevada Test Site. Concentrations of both total resin and NDGA are as variable within and between populations, and no influence of the Las Vegas urban area on antioxidant activity is apparent. Bio-transformation Processes: The goal of this program is to evaluate rate-limiting steps involved in the microbial bio-decomposition process. The major focus in the past year was on examining how one group of microorganisms in the anaerobic food chain, the methanogens, responds to variations of substrate, osmolarity and salt stress in a cell environment. Just as nutrient availability can severely limit bio-transformation processes in nature, so can rapid and extreme changes in osmolarity affect microbe viability and bio-transformation performance. Studies were conducted to determine how representative methanogenic microbes with different nutritional requirements and varying ecological habitats cope with changes in substrate and with saline stress. For example, osmotic stress may be encountered in a variety of man-made and natural habitats. The major man-made habitats being studied are industrial and domestic sewage digestion systems. Desiccated soils and saline estuaries are the natural habitats under investigation. A significant finding was that one class of the methanogens was able to adapt over a considerable range of osmotic stress conditions, and they synthesized a previously unknown group of compounds to aid this adaption process. The compounds were identified to be N-acetyl-B-lysine, B-glutamine, and B-glutamate. Structure determinations were performed using high pressure liquid chromatograph (HPLC) and nuclear magnetic resonance (NMR). The levels of each compound in the different species of methanogenic microorganisms were then evaluated in cells grown under different stress conditions. These B-amino acids apparently function in an osmoprotection process and allow 127 ------- the organisms to survive and carry out functions necessary for byconversion processes during varying ionic conditions. RESEARCH GOALS - FY 1991 Multimedia Transport of Chemical Pollutants: The multimedia transport program will continue to focus on contaminant transport in the multimedia environment. Future work with the SMCM model will include the extension of the model to incorporate the transport of particle-bound pollutants. Additionally, a parameterized model, based on the Center's multiphase model of solute transport in the soil matrix will be incorporated into the SMCM model. The Center also plans to interface its multimedia exposure module to the SMCM software in order to broaden its applicability. Finally, the below-cloud model for rain scavenging of organic particles developed in the wet scavenging project, which is not considered in the current version (3.0) of the SMCM software, will be incorporated in a new version of the SMCM software. Characterization of Complex Atmospheric Aerosols: The low pressure cascade impactor/Fourier transform infrared (LPI/FTIR) analytical method developed in this project provides a unique tool for examining the composition of atmospheric aerosol or the reaction of gases with atmospheric particles. The rates of oxidation of gas-phase hydrocarbons and subsequent paniculate formation are currently being studied in smog chamber experiments using the LPI/FTIR method as an aerosol analysis tool. In addition, pure hydrocarbons particles and atmospheric aerosols will be deposited on both filters and zinc selenide plates. The particles will be exposed to air streams containing ozone, oxides of nitrogen, and other oxidants at typical ambient concentrations. Infrared microscopy will be used to follow reaction rates in real time. Dry Deposition Processes: • Particle Size Distribution Studies. Dry deposition velocities will be estimated for these organics by the dual tracer method previously developed using lead and carbon monoxide concentrations measured at ambient sites and in roadway tunnels. Similar calculations will be performed for elemental carbon and metal species emitted primarily by automotive sources. An additional term to account for PAH reactivity will be included in the mass balance of the impactor stages to estimate dry deposition velocities. These data will allow the residence time distribution for the aerosol to be determined. 128 ------- The measurements of barium, cerium, lanthanum, samarium will be analyzed to determine the usefulness of these elements as tracers for automotive emissions. This work is vital, as lead will be completely eliminated from gasoline sold in California over the next few years. Source Allocation Studies. The work initiated this in FY 1990 will be expanded using the data obtained during the 1989 field study, results from the literature and by new studies. Organic Compounds in Wet Deposition: In the next year, the project will continue to focus on the harmful effects of hydrogen peroxide and organic compounds on pine trees. Both field studies in the San Bernardino Mountains and laboratory experiments at UCLA will be conducted to understand how hydrogen peroxide and organic compounds damage plant cells. Also the collection of rain-, fog-, and dew-waters will be continued in the Los Angeles Basin and the San Bernardino Mountains in order to determine annual wet deposition rates of major acids (e.g. sulfate, nitrate and organic acids) and oxidants (e.g. hydrogen peroxide) in these regions. Rain Scavenging: The rain scavenging project will continue its focus on the development of a wet scavenging model. Specifically, the testing of a below-cloud model for semi-volatile organics will be continued, and an aqueous-chemistry submodel will be developed to deal with the generation of sulfate and organic acids in the aqueous phase. The rain scavenging model, in combination with gas-phase chemistry, aqueous- phase chemistry and below-cloud rain scavenging submodels, will be used to interpret the available field data. Atmospheric Chemistry and Dispersion Modeling: By Spring, 1991, preliminary simulations of air pollutant formation and dispersion in the Los Angeles Basin will be carried out. At that time, appropriate validation and case studies will be initiated. A regional mesoscale dynamics model to drive the CAT model in a more sophisticated prognosis analysis will be developed. A six-level mesoscale model has been constructed for regional weather prediction, and it will initially be adapted to the Southwest United States for the CAT modeling project. In later work, the use of a state-of-the-art mesoscale model such as the Penn State MM4, which is available to the project through the NASA Ames Research Center, is envisioned. 129 ------- Ecosystems Transport Processes and Interactions: During FY 1991, hydrogen peroxide studies will be expanded to utilize cotton as a pollutant-sensitive species whose physiology is well known. Researchers hope to be able to apply new physiological techniques of guard cell extraction in cotton to be able to investigate in detail the mechanistic impacts of oxidant pollution damage to stomatal function. Using these innovative techniques developed at UCLA, it will be possible to measure individual biochemical responses such as ATPase activity levels, proton pump activity, red and blue light response, and other photosynthesis parameters. The Center will also investigate the significance of the induction of natural antioxidant defenses at the cellular level. Bio-transformation Processes: The NCITR is continuing to examine how microorganisms adapt to environmental stress and to determine what biological limits exist for their participation in bioconversion processes in nature. These factors directly affect the potential for and rates of microbial action. The Center's efforts will focus on oxygen availability on microbial metabolism and biodegradation. The effect of limiting oxygen on alternative metabolic reactions in the cell will be examined using chemostat methods and continuous culture. We will attempt to establish what concentrations of this substrate must be present to permit induction and normal functioning of aerobic pathways for cell survival and growth. As the oxygen response may also vary with exposure to certain environmental toxins, this will also be tested. Studies will continue on evaluating how known genera of methanogens respond to saline stress. Strains will be screened for growth and production of unique B-amino acids at varying saline conditions. The occupance of these organisms in natural habitats will allow a prediction regarding the ability of an existing microbial population to participate in desirable biotransformation reactions versus the need to populate that habitat with different microbial populations. OUTPUTS - FY 1990 Articles in Refereed Journals 16 Articles Submitted or in Press 9 Books and Bound Proceedings 0 Chapters in Other Books 5 Progress Reports 8 Conferences and Workshops Held 17 130 ------- BIBLIOGRAPHY REFEREED JOURNAL ARTICLES Cohen, Y. and P. A. Ryan, "Chemical Transport in the Top Soil Zone - The Role of Moisture and Temperature Gradients", Journal of Hazardous Materials. Vol. 22, pp. 283-304, 1989. Cohen, Y., W. Tsai and S. L. Chetty, "An Undergraduate Course on Multimedia Environmental Transport, Exposure and Risk Assessment", Chemical Engineering Education, in press. Cohen, Y., W. Tsai and S. L. Chetty, "Partitioning of Pollutants in the Multimedia Environment: The SMCM Software", CACHE News. Vol. 30, pp. 18-26, 1990. Cohen, Y., W. Tsai, S. L. Chetty and G. Mayer, "Dynamic Partitioning of Organic Chemicals in Regional Environments: A Multimedia Screening- Level Modeling Approach", Environmental Science and Technology. Vol. 24, pp. 1549-1558, 1990. Cotter, P. A. and R. P. Gunsalus, "Oxygen, Nitrate and Molybdenum Regulation of dmsABC Gene Expression in Escherichia coli," Journal of Bacteriology. Vol. 171, pp. 3817-3823, 1989. Dangler, M., S. Buker, S. V. Bering and D. T. Allen, "Direct FTIR Analysis of Size Segregated Aerosols: Results from the Carbonaceous Species Methods Intercomparison Study", Aerosol Science and Technology. Vol. 12, No. 1, pp. 172-181, 1990. Gonzalez-Coloma, A., C. Wisdom and P. Rundel, "Compound Interactions and Effects of Plant Antioxidants in Combination with Carbaryl on Performance of Trichoplusia ni (cabbage looper)", Journal of Chemical Ecology. Vol. 16, pp. 887-899, 1990. Kalman, L. V. and R. P. Gunsalus, "Identification of a Second Gene Involved in Global Regulation of Fumarate Reductase and other Nitrate Controlled Anaerobic Respiratory Genes in Escherichia coli", Journal of Bacteriology. Vol. 171, pp. 3810-3816, 1989. 131 ------- Main, H. and S. K. Friedlander, "Dry Deposition of Atmospheric Aerosols by Dual Tracer Method. Part I: Area Source", Atmospheric Environment. Vol. 24a, pp. 103-108, 1990. Pickle, T., D. T. Allen and Pratsinis, "The Sources and Size Distributions of Aliphatic and Carbonyl Carbon in Los Angeles Aerosol", Atmospheric Environment. Vol. 24a, No. 8, pp. 2221-2228, 1990. Ryan, P. and Yoram Cohen, "Diffusion of Sorbed Solutes in Gas and Liquid Phases of Low-Moisture Soils", Soil Science Society of American Journal. Vol. 54, pp. 341-345, 1990. Sakugawa, H. and I. Kaplan, "H2O2 and 03 in the Atmosphere of Los Angeles and its Vicinity: Factors Controlling their Formation and their Role as Oxidants of SC>2", Journal of Geophysical Research. Vol. 94, pp. 12957- 12974, 1989. Sakugawa, H. and I. Kaplan, "Observation of the Diurnal Variations of Gaseous H2O2 in Los Angeles Air Using a Cryogenic Collection Method", Aerosol Science and Technology. Vol. 12, pp. 77-85, 1990. Sakugawa, H., I. R. Kaplan, W. Tsai and Y. Cohen, "Atmospheric Hydrogen Peroxide", Environmental Science and Technology. Vol. 24, pp. 1452-1462, 1990. Sakugawa, H., W. Tsai, I. R. Kaplan and Y. Cohen, "Historic Trend of the Levels of Atmospheric H2C>2 during 1960's-1980's in Los Angeles", Geophysical Research Letters. Vol. 17, pp. 937-940, 1990. Sakugawa, H., W. Tsai, I. R. Kaplan and Y. Cohen, "Factors Controlling the Photochemical Generation of Gaseous H2O2 in Los Angeles Atmosphere", Geophysical Research Letters. Vol. 17, pp. 93-96, 1990. ARTICLES SUBMITTED OR IN PRESS Cotter, P. A., V. Chepuri, R. B. Gennis and R. P. Gunsalus, "Cytochrome o (cvoABCDE') and d (cv_dAB_) Oxidase Gene Expression in Escherichia coli is Regulated by Oxygen, pH and fnr Gene Product", Journal of Bacteriology, in press, 1990. 132 ------- Kawamura, K. and I. R. Kaplan, "Stabilities of Carboxylic Acids and Phenols in Los Angeles Rainwaters During Storage", Water Research, in press, 1990. Meinzer, F. C, C. S. Wisdom, A. Gonzalez-Coloma, P. W. Rundel and L. M. Shultz, "Effects of Leaf Resin on Stomatal Behavior and Gas Exchange of Larrea tridentata", Functional Ecology, in press, 1990. Ryan, P. A. and Y. Cohen, "One-Dimensional Immiscible Phase Transport of NAPL (Non-Aqueous Phase Liquids) Containing Sparingly Water Soluble Organics in the Unsaturated Soil Zone", Water Research, in press, 1990. Sakugawa, H. and I. R. Kaplan, "The Chemistry of Atmospheric Hydrogen Peroxide in Southern California", Advances in Environmental Sciences and Technology, submitted, 1990. Sakugawa, H., "The Chemistry of Acid Rain - The Relationship between SC«2 Emission and Sulphate Wet Deposition", Nihon-Kagakukaishi (in Japanese), submitted, 1990. Sowers, K. R., D. E. Robertson, D. Knoll, R. P. Gunsalus, and M. F. Roberts, "NE-acety-fi-lysine: A Compatible Osmolyte Synthesized by Methanogenic Archaebacteria", Proceedings of the National Academy of Sciences. 87. in press, 1990. Tsai, W., Y. Cohen, H. Sakugawa and I. R. Kaplan, "Hydrogen Peroxide Levels in Los Angeles: A Screening-level Evaluation", Atmospheric Environment, in press, 1990. Tsai, W., Y. Cohen, H. Sakugawa and I. R. Kaplan, "Dynamic Partitioning of Semi-Volatile Organics in Gas/Particle/Rain Phases During Precipitation Scavenging", Environmental Science and Technology submitted, 1990. BOOKS AND BOUND PROCEEDINGS None 133 ------- CHAPTERS IN OTHER BOOKS Cecchini, G., D. J. Westenberg, B. A. C. Ackrell and R. P. Gunsalus, "Mutants of Escherichia coli Fumarate Reductase Anchor Peptides Which Effect Electron Transfer with Quinones", in Biochemistry. Bioenergetics and Clinical Applications of Ubiquinone. G. Lenaz (ed.), Taylor & Francis, Ltd., London, pp. 150-153, 1990. Cotter, P. A. , S. Melville and R. P. Gunsalus, "Regulation of Aerobic and Anaerobic Electron Transport Pathways in Escherichia coli", in Proceedings for the 6th European Bioenergetics Conference. August 26-31, Elsevier, Amsterdam, 1990. Kawamura, K. and I. R. Kaplan, "Organic Compounds in Rainwater", in Organic Chemistry of the Atmosphere. D. J. Eatough and L. D. Hansen, The Telford Press, in press, 1990. Onishi, Y., L. Shuyler and Y. Cohen, "Multimedia Modeling of Toxic Chemicals", in Proceedings of the International Symposium on Water Quality Modeling of Agricultural Non-Point Sources. Part 2. pp. 479-502, 1990. Rundel, P. W., "Shrubs", in Interpreted Response to Stress in Plants. W. Winner, H. A. Mooney, and E. Pell (eds.), Academic Press, San Diego, 1990. PROJECT REPORTS Palen, EM "Infrared Spectroscopy of Size Resolved Fine Aerosol", Ph.D. Thesis, UCLA Chemical Engineering Department, May 1990. Sakugawa, H. and I. R. Kaplan, "Measurement of Atmospheric ^2^2 in Forest Regions of the San Bernardino Mountains", Report to the South Coast Air Quality Management District, El Monte, California, 1989. The Multimedia Environment Newsletter, Volume III, No. 1, February, 1990. The Multimedia Environment Newsletter, Volume III, No. 2, September, 1990. 134 ------- User Manual, "The Spatial-Multimedia-Compartmental (SMCM) Model: A User Friendly, Screening Level Pollutant Transport Model (Version 3.0)" Cohen, Y., "Evaluation of Environmental Risks", Paper presented at the Seminari "La Gestio i Control Ambientals en L'Europa de L'Any 2000: Aspectes Technics, Legislatus i Administratius", Divisio de Centre Universitaris del Camp de Tarragon, Spain, October 1-5, 1990. Cohen, Y., "Partitioning of Organic Pollutants in the Environment", Paper presented at the Seminari "La Gestio i Control Ambientals en L'Europa de L'Any 2000: Aspectes Technics, Legislatus i Administratius", Divisio de Centre Universitaris del Camp de Tarragon, Spain, October 1-5, 1990. Cohen, Y. and P. A. Ryan, "Contaminant Migration in the Unsaturated Soil Zone", Paper presented at the Seminari "La Gestio i Control Ambientals en L'Europa de L'Any 2000: Aspectes Technics, Legislatus i Administratius", Divisio de Centre Universitaris del Camp de Tarragon, Spain, October 1-5, 1990. CONFERENCES AND WORKSHOPS HELD Science Advisory Committee Program Review, UCLA Faculty Center, University of California, Los Angeles, January 18-19, 1990, Los Angeles, California. Seminar, "Air Quality Modeling/Rain Scavenging", Wangteng Tsai, Post-Graduate Fellow, January 26, 1990, 5513 Boelter Hall, University of California, Los Angeles. Seminar, "Alcohol-Fuel Related Atmospheric Chemistry Issues in Brazil", Professor Antonio H. Miguel, Visiting Professor, University of Sao Paolo, Brazil, February 16, 1990, 5513 Boelter Hall, University of California, Los Angeles. Seminar, "The Addition of an Exposure Module to a User-Friendly SMCM Model", Steven L. Chetty, Graduate Student, 5513 Boelter Hall, University of California, Los Angeles. 135 ------- Seminar, "Objective Wind Analysis for the Chemistry/Microphysics Aerosol Transport (CAT) Model", David Waymire, Graduate Student, March 8, 1990, 5513 Boelter Hall, University of California, Los Angeles. Seminar, "Multimedia Transport of Particle-Bound Pollutants", Robert Clay, Graduate Student, March 9, 1990, 5513 Boelter Hall, University of California, Los Angeles. Seminar, "Microscale Hydrogeochemistry", Mordeckai Magaritz, Professor at the Weizmann Institute, Israel, and Visiting Professor at Caltech, April 17, 1990, 7608 Math Sciences, University of California, Los Angeles. Seminar, "Rain Scavenging", Wangteng Tsai, Post-Doctoral Fellow, April 27, 1990, 5513 Boelter Hall, University of California, Los Angeles. Seminar, "Adaption of Methane Bacteria to Osmotic Stress", Kevin Sowers, Graduate Student, May 3, 1990, 7608 Math Sciences, University of California, Los Angeles. Seminar, "Human Exposure Resulting from the Distribution of Pollutants in the Environment", Steven L. Chetty, Graduate Student, May 18, 1990, 5513 Boelter Hall, University of California, Los Angeles. Seminar, "Multimedia Transport of Particle-Bound Pollutants", Robert Clay, Graduate Student, June 22, 1990, 5513 Boelter Hall, University of California, Los Angeles. Seminar, "Formulation of a Multimedia Transport Equations for Particle-Bound Organics", Wangteng Tsai, Post-Doctoral Fellow, September 21, 1990, 5531 Boelter Hall, University of California, Los Angeles. Seminar, "Multimedia Exposure Analysis: Progress Report", Steven L. Chetty, Graduate Student, October 5, 1990, 5513 Boelter Hall, University of California, Los Angeles. Seminar, "Chemical Characterization of Sub-Micron Aerosol in the Los Angeles Basin: PAH Size Distribution", Chandra Venkataraman, Graduate Student, November 8, 1990, 5513 Boelter Hall, University of California, Los Angeles. 136 ------- Seminar, "Rain Scavenging of Semi-Volatile Organics", Wangteng Tsai, Post-Doctoral Fellow, November 15, 1990, 5513 Boelter Hall, University of California, Los Angeles. Seminar, "Human Exposure Resulting from the Distribution of Pollutants in the Environment", Steven L. Chetty, Graduate Student, November 29, 1990, 5513 Boelter Hall, University of California, Los Angeles. Seminar, "Acid Rain Study in Southern California", Hiroshi Sakugawa, Post-Doctoral Fellow, December 12, 1990, 5513 Boelter Hall, University of California, Los Angeles. 137 ------- |