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
------- |