REPORT OF THE GREAT LAKES
MASS-BALANCE PLANNING WORKSHOP
Submitted to
U.S. ENVIRONMENTAL PROTECTION AGENCY
ATMOSPHERIC RESEARCH AND
EXPOSURE ASSESSMENT LABORATORY
Compiled Under
Contract Number 68D10111
Compiled by
Research and Evaluation Associates, Inc.
607 14th Street, N.W., Suite 610
Washington, D.C. 20005-2000
(202) 842-2200
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DISCLAIMER
The use of trade names or commercial products in this document does not constitute
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TABLE OF CONTENTS
SECTION PAGE
I. EXECUTIVE SUMMARY OF THE LAKE MICHIGAN MASS-BALANCE
PLANNING WORKSHOP 1
II. INTRODUCTION 3
III. DAY 1 4
A. Objectives 4
B. Preliminary Objectives for Lake Michigan Mass-Balance Model 4
C. Overview of Present Transport/Fate, Food Cham Models
for the Great Lakes 6
D. Estimation of Wet Deposition for Mass-Balance Studies 7
E. Estimation of Dry Deposition for Mass-Balance Studies 9
F. Interface of Atmospheric & Aquatic Models in Design of
Mass-Balance Studies 11
G. Approach to Measuring Urban Contributions to Great Lakes
Toxic Loadings 12
H. Use of Source Apportionment Model Results in Mass-Balance Models 13
I. Great Lakes States' Atmospheric Measurement Objectives &
Data Needs 14
J. Overview of Lakewide Management Planning 15
K. Overview of Air Toxics Data Need for LaMPs 16
L. Great Waters Scientific and Environmental Measurement Needs 16
iV. DAY II 17
A. Availability of Sites 18
B. Group Recommendations 19
APPENDIX A - AGENDA A-1
APPENDIX B - WORKSHOP PARTICIPANTS AND AFFILIATIONS B-1
APPENDIX C - GREAT LAKES STATES1 ATMOSPHERIC MEASUREMENT
OBJECTIVES AND DATA NEEDS -
PRESENTATION - MS. JOANNE FOY C-1
APPENDIX D - GROUP 2'S DISCUSSION SUMMARY D-1
APPENDIX E - OVERVIEW OF LAKEWIDE MANAGEMENT PLANNING -
PRESENTATION - MS. CONSTANCE HUNT E-1
APPENDIX F - LAKE MICHIGAN AIR MONITORING-SITE SUMMARY -
PRESENTATION - DR. CLYDE SWEET F-1
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TABLE OF CONTENTS (Continued)
SECTION PAGE
APPENDIX G - USE OF SOURCE APPORTIONMENT MODEL RESULTS IN
MASS-BALANCE MODELS -
PRESENTATION - DR. ROBERT STEVENS G-1
APPENDIX H - APPROACH TO MEASURING URBAN CONTRIBUTIONS
TO GREAT LAKES TOXIC LOADINGS -
PRESENTATION - DR. JERRY KEELER H-1
APPENDIX I - INTERFACE OF ATMOSPHERIC AND AQUATIC MODELS IN
DESIGN OF MASS-BALANCE STUDIES -
PRESENTATION - DR. WILLIAM BENJEY 1-1
APPENDIX J - INTERFACE OF ATMOSPHERIC AND AQUATIC MODELS IN
DESIGN OF MASS-BALANCE STUDIES -
PRESENTATION (CONTINUED) - MR. TERRY CLARK J-1
APPENDIX K - ESTIMATION OF DRY DEPOSITION FOR MASS-BALANCE STUDIES -
PRESENTATION - DR. THOMAS HOLSEN K-1
APPENDIX L - ESTIMATION OF WET DEPOSITION FOR MASS-BALANCE STUDIES -
PRESENTATION - DR. JOEL BAKER L-1
APPENDIX M - OVERVIEW OF PRESENT TRANSPORT/FATE, FOOD CHAIN
MODELS FOR THE GREAT LAKES -
PRESENTATION - MR. WILLIAM RICHARDSON M-1
APPENDIX N - PRELIMINARY OBJECTIVES FOR LAKE MICHIGAN
MASS-BALANCE MODEL -
PRESENTATION - MR. DAVID DEVAULT N-1
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I. EXECUTIVE SUMMARY OF THE LAKE MICHIGAN
MASS-BALANCE PLANNING WORKSHOP
The Lake Michigan Mass-Balance Planning Workshop, held March 31-April 1, 1992, in
Research Triangle Park, brought together representatives of two communities—scientists and end
users—to discuss capabilities and needs in designing a mass-balance model for Lake Michigan.
Their goals were to identify data collection and quality objectives, propose hypotheses that the
mass-balance study should address, determine measurement protocols, and define key outputs.
After hearing presentations on the current status of monitoring efforts in the Great Lakes
region, the participants divided into two work groups to discuss key elements of the mass-balance
study, which were defined by the first day's presentations and discussions. Those elements were:
1. Data collection objectives (DCOs)
• Pollutants of concern
• Parameters considered essential for modeling
2. Data Quality Objectives (DQOs)
3. Hypotheses
4. Measurement
• Methods and sampling frequency
• Design
Cost, accuracy, other parameters
5. Location of sites
6. Key outputs
Although neither group presented recommendations for every element of the outline, the
outline nonetheless provided a framework for the discussions and elicited new proposals and
considerations that will benefit the design of the mass-balance effort.
Group 1 proposed the following target pollutants for the mass-balance model: PCBs, lead,
atrazme, and trans-nonachlor The group also identified additional parameters as being essential
for modeling:
• determinations of total suspended particles (TSP) in air;
• carbon inputs from air, precipitation, and tributaries; and
• nutrient cycling.
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In addition, Group 1 recommended 7 land sites and 2 ship sites, which are discussed in detail
in the group discussion section of this report.
Group 1 proposed the following hypotheses or issues to be addressed by the mass-balance
study:
• whether measurements over land represent pollutants over water
• event-based sampling vs. monthly sampling
• dry deposition of large particles
• source information
• quality control (QC) issues, particularly regarding new compounds, such as atrazine
• importance of urban vs. regional inputs
The key output proposals for Group 1 were:
• atmospheric loadings to the Lake, plus information for modeling
• calibrated model
Group 2 proposed the following target pollutants for the mass-balance model: PCBs, dieldrin,
lead, nonachlor, mercury, DDT, and PAHs. In addition to identifying these target pollutants,
Group 2 devised a matrix of pollutants and criteria for their inclusion, which is presented in the
detailed summary of the group discussions.
The group identified several additional parameters:
• use Green Bay target pollutant list as minimal base (PCBs at congener level, dieldrin,
TSP, and organic and elemental carbon)
• review list and add parameters as needed
• determine source attribution
• determine air concentration over water and across air/water interface
• characterize precipitation chemistry
• determine phase distribution (vapor and particle)
• determine particle size distribution
Moreover, Group 2 identified the following DQOs:
• use the Green Bay Study as template for process of modeling Lake Michigan
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review and update all Standard Operating Procedures (SOPs) and Quality Assurance
Project Plans (QAPjPs)
establish centralized quality assurance (QA) authority
consider requesting Office of Research and Development (ORD) to provide QA support
offer more than one option to decision-makers, options that require varying levels of
funding
achieve lowest possible analytical detection limits
Group 2 proposed hypotheses that involve determining whether long-range transport has a
significant effect on water quality, whether tributary loadings are significant, and what controls are
required to achieve acceptable concentrations in fish. The proposed outputs were a mass budget
and media contribution; prediction of the effect of control actions on biological/ecological systems;
prediction of benefits from remedial actions; and the relation of benefits to regulatory action.
Although the two group presentations had little redundancy, the clear consensus was that
the desired end product is a calibrated model that can be used to document human health or
ecological effects of pollutants in the Great Lakes region, and thus spur regulatory action.
II. INTRODUCTION
The Lake Michigan Mass-Balance Planning Workshop was held in Research Triangle Park,
NO, on March 31-April 1, 1992. The workshop agenda is given in Appendix A. The names,
affiliations, and addresses of those who attended are listed in Appendix B.
The purpose of the workshop was to assemble two communities—scientists and potential data
users—to discuss the capabilities, needs, and agendas in creating a Lake Michigan mass-balance
program. The two communities are further defined as follows:
Scientists—within the Environmental Protection Agency (EPA), the academic community,
Environment Canada, and others in the Great Lakes region.
Potential users—including those within EPA, representatives of legislative mandates,
environmental groups, and state agencies.
Selected participants presented background information on monitoring efforts in the Great
Lakes region This information consisted of:
• preliminary objectives for Lake Michigan Mass-Balance Model,
• an overview of current transport/fate and food-chain models for the Great Lakes;
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• an estimation of wet deposition for mass-balance studies;
• an estimation of dry deposition for mass-balance studies;
• interface of atmospheric and aquatic models in design of mass-balance studies;
• an approach to measuring urban contributions to Great Lakes toxic loadings;
• use of source apportionment model results in mass-balance models;
• Great Lakes states' atmospheric measurement objectives and data needs;
• an overview of Lakewide Management Plan (LaMP)
• an overview of air toxics data need for LaMPs;
• Great Waters scientific and environmental measurement needs; and
• availability of sites.
On the first workshop day, presenters fielded questions and comments from participants. On
the second day, participants divided into two groups to discuss study objectives. Their goals
were to compile independent lists of target pollutants, to identify additional parameters deemed
essential for viable modeling, and to propose central hypotheses that the mass-balance study
should address.
III. DAY1
A. Objectives
Mr. Dale Pahl opened the workshop by informing participants that their objective in the 2-day
workshop was to discuss the capabilities, needs, and agendas in creating a Lake Michigan
mass-balance model. He asked each participant to describe his or her position and work relating
to the Great Lakes monitoring and modeling efforts.
B. Preliminary Objectives for Lake Michigan Mass-Balance Model
Mr. David DeVault of the EPA Great Lakes National Program Office (GLNPO) is responsible
for planning, coordinating, and implementing monitoring programs. He gave an overview of
GLNPO's current objectives for the mass-balance model. The project has received varying levels
of support during the last 2 years, but now it is a priority to GLNPO and EPA. The field year for
data collection is scheduled to be 1993. Sample analyses should be completed by December
1994. Mr. DeVault presented graphics explaining the basic principles of monitoring processes
in the Great Lakes
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Proposed toxic chemicals to be targeted are:
• PCBs
• dieldrin
• trans-nonachlor
• lead
GLNPO plans to study the loading of these compounds to the Lake and their concentrations
in fish identified for their importance to the Lake Michigan sport or commercial fisheries. These
fish are Lake Trout, Coho Salmon, and Bloater Chubs; they also represent differing exposure
routes and histories.
Mr. DeVault stated that GLNPO, Region V, and the Great Lakes states need a mass-balance
plan to determine loadings to Lake Michigan for various toxic chemicals. Once loadings are
determined, building a model will be relatively simple and inexpensive (modeling costs represent
about 10 percent of study costs). Mr. DeVault said a calibrated model is needed to provide
predictability for remedial and regulatory actions and to reduce the amount of necessary
monitoring, thus conserving resources. In addition, GLNPO seeks to establish a framework for
collaboration among 25 or 30 agencies involved in Great Lakes research and regulation.
GLNPO's recommended approach for the mass-balance study is to use the calibrated model
for the Green Bay Study and to focus 1992 data collection on loadings, process rates, and
reactivity. The timeline for the study is being revised. Field work should start in spring 1993, and
a draft study plan is targeted for completion by August 1992.
Lakewide Management Plan committees and Water Quality managers will provide funding for
the study. It will be planned, managed, and coordinated by several technical committees.
Mr. DeVault expressed the hope that, during group discussions scheduled for the second day
of the workshop, participants discard preconceived notions and focus on what is needed to make
the mass-balance study "workable*.
In response to a question about funding, Mr. DeVault said that GLNPO would propose funding
adequate to meet the goals.
Mr. DeVault responded to Ms. Joanne Foy's question about the basis for the pollutants
chosen by saying that the pollutants were shown to bioaccumulate in fish and would eventually
have deleterious health effects to humans and non-humans who ingest the fish—thus, these
pollutants were suitable for mass-balance modeling. Ms. Constance Hunt commented that all the
pollutants mentioned appeared on Region V's critical pollutant list for Lake Michigan, although
lead was listed as a lower-level pollutant.
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Mr. Pahl said that modeling questions are not resolved, and that although management has
given the choices much thought, he understood that the scientific community might not readily
accept the choices.
A general discussion ensued about the choices of pollutants for modeling and about the
importance of integrating atmospheric and aquatic pollutants in a well-designed model. Mr.
DeVault noted that what managers need must be kept in balance with what the chemists believe
is practicable.
C. Overview of Present Transport/Fate, Food Chain Models for the Great Lakes
Mr. William Richardson, Station Chief of the Office of Research and Development's (ORD's)
Large Lakes Research Station, located at Grosse Me, Michigan, has been involved with developing
mathematical models for the Great Lakes for about 20 years. He currently is developing a
management-level model that will assist with Lakewide Management Planning.
Mr. Richardson summarized two decades of modeling efforts in the Great Lakes. Successes
were achieved in relating discharge of nutrients, such as phosphorus, to deficits in dissolved
oxygen in Lake Erie with models developed through studies sponsored by ORD, GLNPO, and the
International Joint Commission (IJC). These studies culminated in the late 1970s with the
development of target loadings for phosphorus and a 10-year surveillance plan in the Great Lakes
to monitor progress in restoring dissolved oxygen levels. The models were successful in relating
loadings to concentrations.
Continued modeling efforts throughout the 1970s focused on determining how toxic chemicals
behave in aquatic systems, using the phosphorus mass-balance model. A minimally funded effort
in modeling at Grosse lie for the Great Lakes was maintained during the 1980s. In 1988, a study
by Lake Ontario Toxic Management Plan and Superfund focused on discharge levels of dioxm into
Lake Ontario at Hyde Park. The Green Bay Mass-Balance Study focused on PCB levels in Lake
Michigan, which remained high after PCBs were banned. The key issues in designing a
mass-balance study are identifying the remaining sources of these toxic substances and the
allocation of regulatory dollars to reduce their discharge.
Mr. Richardson said that the purpose of mass-balance modeling must be clear from the
outset to provide management useful tools. He stressed that the Green Bay Study should be
used as a basis for the Lake Michigan Mass-Balance Study.
Mr. Richardson then expressed the concern that managers do not clearly understand the
need for mass-balance modeling. Ms. Constance Hunt noted that EPA managers see
mass-balance as an academic exercise and are more interested in loadings, a misconception that
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she hoped would be corrected when the results of the Green Bay Study are presented. Mr. Pahl
suggested that •management system" could be substituted for "model" for greater effect, because
a model, in essence, constructs a systematic view of reality. Ms. Hunt commented that the
cost-effectiveness of models must be shown to persuade managers of their usefulness.
Mr. Richardson said that modeling is needed, for example, to predict PCB levels in the lower
Fox River that result from reservoir flow events. Because the Fox River study is manageable, it
can be used to convince management that modeling is valid. Mr. Richardson said that at Grosse
He scientists are attempting to link modeling with GIS databases so that managers have tools they
can use.
To arrive at a cost-effective program, Mr. Richardson said, a system is needed that would
interact with sediments, watersheds, and atmosphere.
Mr. Richardson then presented a series of graphics, including a chemical modeling
schematic; an explanation of chemical and biological processes involved in modeling toxic
substances; bioaccumulation model processes; a food chain chart; PCB loadings; loadings
relative to concentrations in Lake Ontario fish; the source of uncertainty in water concentration
predictions; and the effect of seasonal differences in wind and temperature on volatilization (see
Appendix M)
Mr. Richardson addressed the need for data in the system to compare simulated
concentrations to measurements. He noted that the loading chart was constructed for PCBs
because much historical data were available on PCBs. The graphic of relative loadings to
concentrations in Lake Ontario fish showed an unacceptably large spread. To improve the model
would require more experimental research in process rates and more data collection to calibrate
the model.
Mr. Richardson noted that determining atmospheric loadings is a vital component of
constructing an accurate model, and that the end product is a model that could calculate the
concentration of pollutants over time
Mr. Pahl offered a summary of Mr. Richardson's presentation, stating that available data and
existing models are identifying potential hypotheses that must be considered in the design of a
mass-balance study.
D. Estimation of Wet Deposition for Mass-Balance Studies
Dr. Joel Baker of the Chesapeake Biological Lab, University of Maryland, described issues of
the wet deposition project in Chesapeake Bay. Many of these issues are shared with the Great
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Lakes project, including sampling methods and whether the atmosphere is a source of PCBs to
the Lakes.
The necessary objectives of wet-deposition measurements must be clearly defined. If only
gross loadings are needed, then that straightforward requirement can be met with moderate site
density and monthly, integrated sampling. If exploring scavenging mechanisms, source
attribution, or speciation of chemicals are high priorities, then event-based sampling and high-site
density would become a priority. The latter study would require more money.
Or. Baker described the need for, and difficulty of, studying scavenging mechanisms, source
attribution, and speciation. It is not known precisely how and how much of the PCBs are
scavenged from the atmosphere in wet deposition. To build a predictive model that starts with
concentrations in the air, the mass-transfer processes must be understood to calculate the
wet-deposition loadings. The distribution between the vapor phase and the aerosol phase also
is extremely important and is a strong function of the ambient air temperature.
Data from Chesapeake Bay indicated that equilibrium partitioning with the ambient vapor
phase accounts for only 2-3 percent of dissolved-phase PCBs in ram: The rain seems to be
supersaturated with these compounds. Many additional mechanisms contribute, including:
• aerosol wash-out by precipitation
• temperature-driven disequilibrium
• rate of absorption at the air-water interface
Modeling pollutant scavenging is not as simple as scientists had hoped. Other mechanisms
that are difficult to characterize are the exchange across air-water interfaces, volatilization, and
meteorological influences on exchange rates. Temperature influences in particular are extremely
important to vapor-aerosol distribution and the mass-transfer coefficient.
Speciation is important, Dr. Baker said, because the fate of a material is determined largely
by its form at deposition. The varying effects of weather require data collection throughout the
year.
Dr. Baker recommended that wet-deposition sampling for the Lake Michigan mass-balance
study be characterized by:
• monthly sampling
• 2-3 remote sites
• event-based sampling in urban areas
• short-term intensive field work, coupled with meteorology
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• study of speciation in precipitation and scavenging
Mr. Pahl asked whether Dr. Baker called for a study of microlayer measurements. Dr. Baker
replied that he could not answer that question because the uncertainty in the mass-transfer
coefficient is large. A general discussion ensued about the feasibility of event-based sampling.
E. Estimation of Dry Deposition for Mass-Balance Studies
Dr. Thomas Holsen, of the Illinois-Institute of Technology's Environmental Engineering
Department, studies dry deposition measurement and modeling. He opened his discussion of
dry-deposition estimation by stating that:
Realistic estimates of dry deposition can be made with existing models if complete
mass-size distributions are obtained.
Model predictions compare favorably with dry deposition measurements using surrogate
surfaces.
Dr. Holsen presented various graphics illustrating sampling techniques to complete size
distributions and deposition plates that directly measure dry-deposition flux He also presented
slides of devices used to collect samples and described particle sizes monitored by each.
Dr. Holsen then described the method of calculating flux from atmospheric size distribution
through mass-transfer coefficients, or deposition velocities: Size distributions multiplied by
deposition velocities equal flux. Dr. Holsen presented three models to obtain deposition velocity.
Showing results of samples taken in Chicago, Dr. Holsen pointed out that although different
mass-size distributions were found, flux distributions were similar Most of the flux in Chicago is
attributable to large particles. If the mass-size distribution is divided into three sections (0.1-1 pm,
1-1 Opm, and 10-100pm), and if each concentration is multiplied by the appropriate deposition
velocity and then summed, the result is cumulative flux. Data indicated that particles less than
1 pm are responsible in all cases for less than 1 percent of total flux; particles less than 10 pm
are responsible for 10 percent of flux; and particles 10-100 pm are responsible for 90 percent of
flux.
The significance of these findings is that the samplers typically used to estimate dry
deposition collect small particles (i.e., < 10pm), which in fact do not account for most flux. The
same is true for metals and other compounds
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The accuracy of the model was tested using PCBs, for which no complete mass-size
distributions are available. Samples were analyzed under a microscope to determine size and
group particles, and the models accurately matched counts on the plate.
Using nine Chicago dry-deposition samples with fairly equal distribution of fine and coarse
particles, Dr. Holsen applied three different models and compared flux measure and atmospheric
sizes. The three types of models used were:
• product model
• 1-step methods
• 9-step methods
The product model and one-step models accounted for only the fine-particle phase. The
nine-step models accounted for coarse- and fine-particle phases and were most stable. The
models that called for partitioning concentration by particle size and applying the appropriate
deposition velocity for each size particle yielded results that matched plate counts. Dr. Holsen
presented data from Chicago supporting the hypothesis that coarse particles are responsible for
most flux.
Using the equation that total flux is the sum of flux for fine-particle phase and coarse-particle
phase, scientists calculated flux by multiple regression for every element represented. The results
agreed with model predictions.
Models also accurately predicted deposition velocities for gas-phase compounds in a study
of PCB and PAH samples collected in a 30-day period. Dr. Holsen noted that the data were more
scattered for PCBs than for metals.
Dr. Holsen summarized research findings by repeating his introductory statements that
dry-deposition estimates can be made if complete mass-size distributions are obtained and that
model predictions compare well with measured dry deposition. He added that coarse particles
are responsible for most dry-deposition flux.
Dr. Holsen then discussed the implications of these findings for the mass-balance study. Two
methods are available to quantify dry deposition:
• measuring complete size distribution and applying deposition velocity models
• estimating dry deposition directly using flux models
Dr. Holsen stressed that using partial size distribution has little physical meaning because this
method does not measure the particles responsible for deposition.
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Using complete size distributions offers two advantages: an easy link with meteorological
models and the application of deposition velocity models.
Coarse-particle samplers are short-term, making complete mass-size distributions difficult and
expensive, and they do not provide direct measurement of flux.
The automated flux plate is simple and easy to use, provides direct measurement of flux,
compares well to model data, and operates for long and short terms. A disadvantage, however,
is that collected particles need to be counted to calculate mass-size distribution.
Dr. Holsen pointed out differences in samplers used in taking urban and non-urban samples.
Dr. Holsen and Dr. Robert Stevens discussed various particle sampling methods, and Dr. Stevens
questioned the validity of the Noll rotary sampler.
F. Interface of Atmospheric & Aquatic Models in Design of Mass-Balance Studies
Dr. William Benjey, with EPA in Research Triangle Park, NC, began discussing the interface
of atmospheric and aquatic models by reviewing the Atmospheric Research and Exposure
Assessment Laboratory's (AREAL's) toxic emission inventory compilations for regional dispersion
and deposition modeling Because a detailed inventory is not available, compilations were
derived from other databases, particularly the National Acid Precipitation Assessment Program
(NAPAP) database. Results are compared with the Toxic Release Inventory System, which was
conducted under the Clean Air Act Amendments (CAAA), Section 313. Dr. Benjey acknowledged
that both databases are limited.
The purpose of the Interim Toxic Emissions Inventory is to make an initial, general
assessment. Currently, QC procedures are being conducted, and emissions data are being
merged from regional and local sources. The modeling application procedures being applied are
geographic distribution and analysis by source type and category. Dr. Benjey then presented
results of data gathered thus far on various pollutants (see Appendix I).
Dr. Benjey presented graphics that included a GIS-generated distribution map of mercury
emissions and charts of various pollutant distributions in the Lake Michigan area and Detroit.
Dr. Benjey conceded that the data are by no means complete, especially data concerning
volatilization. In addition, a model is needed to link these data with aquatic data. The data
currently do not include banned pesticides, and no reliable method of reporting PCBs is available.
EPA potentially could add any number of pollutants to the inventory, but knowledge of emissions
and speciation factors is a limiting factor A research program initiated by the Office of Air Quality
Planning and Standards (OAQPS) and AREAL will account for non-point source emissions.
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Mr. Terry Clark, of AREAL in Research Triangle Park, has studied atmospheric modeling of
toxic movements in the Great Lakes on a regional scale and has worked with Ms. Pamela Blakely
of Region V in calculating atmospheric deposition of several toxins to Lake Michigan.
Mr. Clark presented modeling work being conducted, examples of how models can aid
mass-balance efforts, and output for lead deposition in Lake Michigan.
Two models are in use in this work:
Regional Lagrangian Model for Assessment of Pollutants (RELMAP)—which creates
emission puffs that transport and disperse the pollutant, then dry- and wet-deposit the
mass as it is transported downwind; and
Regional Acid Deposition Model (RADM)—a comprehensive model that incorporates all
known processes, operates in an episodic mode, and is very sophisticated, having
undergone extensive peer review.
Mr. Clark noted that a version of the RADM is planned for use as a toxic deposition model in
the future. Nevertheless, Mr. Clark focused on RELMAP, which uses emissions inventories and
creates 3-hour puffs of pollutants in 40-km grid cells. The model was used to calculate wet
removal based on wash-out ratios that are specific for each toxic pollutant. Dry deposition to land
surfaces was calculated, as well as water surfaces within grid cells, and results were spatially
integrated over the water-only portion of cells to determine total lake loading. Planned
improvements to the model include adding processes that account for volatilization from
land/water surfaces and resuspension from particles, as well as volatilization and possible
deposition downwind from the water surface itself.
Mr. Clark then presented ways in which the model can assist in the mass-balance study; input
requirements for atmospheric deposition models; and data on lead deposition to Lake Michigan
(see Appendix J).
G. Approach to Measuring Urban Contributions to Great Lakes Toxic Loadings
Dr. Jerry Keeler presented research activities conducted at the University of Michigan at Ann
Arbor. The University of Michigan has worked with EPA on the Lake Michigan Urban Air Toxics
Study, and, in conjunction with the State of Michigan, has been studying toxics transport and
deposition (especially for ambient mercury and lead) throughout the state.
Dr. Keeler stated that before site and pollutant discussions can begin, the scale of the
management problem must be considered. Sources of pollutants may not be in the Great Lakes
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Basin itself, which mandates a larger perspective. Historical evidence indicates that urban areas
are important to deposition to lake surfaces.
The objectives of the Lake Michigan Urban Air Toxics Study are:
• to quantify levels of air toxics species
• to identify categories of sources
• to identify deposition to Lake Michigan
• to differentiate between urban sources around the Lake and those upwind
Dr. Keeler presented data from monitoring sites (see Appendix H) operated during the
summer of 1991 in the lower Lake Michigan area. Four sites were used to sample for PCBs,
PAHs, and metals. Three sites collected samples for mercury.
To characterize urban atmospheric loadings, Dr. Keeler recommended an emissions inventory
and meteorology dispersion modeling. In addition, he recommended monitoring wet/dry
deposition from samples in source areas, and upwind and downwind of urban areas.
Coarse-particle loading should be considered, too.
Dr. Keeler stressed the importance of meteorological data and year-round measurement, and
he noted that the following issues should be part of the design of a mass-balance study:
• overall goals
• perspective or scale
• pollutant list
Once those issues are resolved, determinations can be made regarding site selection, sampling
frequency, analysis techniques, and surrogate/tracer compounds.
H. Use of Source Apportionment Model Results in Mass-Balance Models
Dr. Robert Stevens from EPA presented the attributes of various source apportionment
methods. He began by discussing the effect of air toxics on the Great Lakes and presented a
graphic describing the dispersion model and receptor model.
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Dr. Stevens warned against taking a narrow view of sampling methods. He particularly spoke
against using solely PM10 samplers because they include both acid and alkaline particles. He
provided seven recommendations for improving sampling methodology:
1. Collect and analyze fine and coarse particles separately.
2. Use filters appropriate to the analysis.
3. Use denuders for collection and analysis of semi-volatile organic compounds (SVOCs).
4. Collect and analyze samples for VOCs.
5. Incorporate SEM analysis methods.
6. Use hybrid models.
7. Perform deposition experiments at the receptor site.
Dr. Stevens also advocated a dry-deposition program that would incorporate gas and
particles to improve deposition estimates.
I. Great Lakes States' Atmospheric Measurement Objectives & Data Needs
Ms. Joanne Foy represents the State of Michigan Department of Natural Resources as the
Great Lakes Air Program Coordinator. She serves as liaison for the other Great Lakes states in
initiatives such as the Lake Michigan Mass-Balance Study.
Ms. Foy assured participants that the Great Lakes states' goals for controlling pollutants
complement those outlined in the CAAA of 1990. The end result desired is the answer to the
question "Are additional regulatory efforts required?' To achieve this, significant additional
research should be done to evaluate both wet and dry deposition, air/water exchange flux
dynamics, seasonal, and spatial variations, over lake vs. over land issues, standardized sampling
and analytical protocols, and QA/QC concerns.
Michigan and other states have conducted toxics monitoring programs and have data to
share. Also available will be VOC and meteorological data and transport analysis from the Lake
Michigan ozone study Ms. Foy showed graphics depicting sites potentially available for
sampling, which appear in Appendix C.
The Great Lakes Protection Fund provided the Michigan Department of Natural Resources
a grant to conduct a baseline toxics monitoring study for compounds of concern in the Great
Lakes, which tracked seasonal trends through monthly ambient air samples for PCB congeners,
VOCs, pesticides and metals at 3 sites in Michigan. The data reviewed to date indicates seasonal
and spatial differences. Ms. Foy vouched for the representativeness of the data by pointing out
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that the findings matched levels and trends identified by other researchers. This network is being
enhanced and expanded to include sampling every 6 days for at least 1 year, with back-trajectory
analysis to be conducted by the University of Michigan.
Mr. Pahl asked whether the Great Lakes states were interested less in bioaccumulation than
in regulating pollutants through the CAAA. Ms. Foy replied that the states certainly consider
bioaccumulation a criteria in selecting pollutants of concern, but that the states are not able to
effect much change for some pollutants, such as pesticides that were banned years ago. From
a regulatory perspective, compounds of concern, such as benzo(a)pyrene and mercury, which
have known air point sources, are of highest priority.
Ms. Melissa McCullough said that, whereas bioaccumulation (of any toxic chemical) is a
concern, chemicals should be chosen for study that have deleterious effects to both ecosystems
and human health and which can be controlled through air quality management techniques to
optimize resources. Mr. Pahl replied that identifying compounds for study could be approached
in two manners: relating bioaccumulation to human health; or taking a proactive role in choosing
new compounds that may pose a problem in 5 to 10 years.
A general discussion ensued on the assessment, human health effects, and regulatory issues
of PCBs. Ms. Foy said that the Great Lakes states have identified critical pollutants, including
benzo(a)pyrene, alkylated lead compounds, and dioxins, but she noted that any critical pollutant
would be of concern (critical in terms of listing in the Great Lakes Water Quality Agreement
[GLWQA]).
J. Overview of Lakewide Management Planning
Ms. Constance Hunt, program Manager for LaMP in Region V of EPA in the Water Division,
stated that the goals of LaMP are to.
• determine the critical pollutants in each of the Great Lakes and their sources;
• develop a plan to reduce loads of persistent, toxic compounds, and/or bioaccumulation
of toxics; and
• prevent further release of those pollutants.
In pursuing these goals, Region V hopes to build a relationship with other organizations to avoid
duplication of effort.
15
-------
Ms. Hunt gave an overview of LaMP's history. The GLWQA, Annex II, identified critical
pollutants as compounds that impair beneficial use of the Lakes, including conventional pollutants.
Section 118 of the Clean Water Act (CWA) required EPA to lead GLWQA initiatives.
Identifying critical pollutants is a main concern to the LaMP program. Ms. Hunt noted that,
ideally, the mass-balance study should be a reiterative process, evolving from new information
as well as drawing on historical evidence.
Identifying pollutant sources will require an emissions inventory to estimate load reduction
targets and to plan risk-based remediation action.
In response to Mr. David Cowgill's question regarding parameter criteria, Ms. Hunt said that
LaMP will take whatever action is feasible based on two opportunities: regulation and voluntary
pollution prevention. Ms. Hunt pointed out that the largest sources of pollutants may be non-point
sources.
Ms. McCullough commented that another pitfall in decision-making is that the political climate
may have changed by the time regulations are imposed. Mr. Richardson responded that science
should not vacillate with politics. Ms. McCullough agreed that science always must be validated
and advanced, but said that issues such as chemical targeting and defining effects as "adverse"
typically are left to policy-makers.
Ms. Hunt then presented a graphic explaining LaMP's tiering concept for pollutants (see
Appendix E). Level I pollutants are in violation of a numerical criteria such as water quality
standards and fish consumption advisories. Level II pollutants have a strong association with
beneficial use impairment. Level III pollutants have a moderate association with beneficial use
impairment, and Level IV polutants have a possible association based on presence in the Lake
and ability to impair uses. Pollutants may be shuffled among levels. For example, mercury was
moved to Level I because of the concentration found in fish tissue in Upper Michigan. A
screening process is ongoing to determine the top candidates for a mass-balance model.
K. Overview of Air Toxics Data Need for LaMPs
Ms. Pamela Blakely of EPA summarized Region V's need to understand the mass-balance
theory and how it would affect the regulatory framework for pollutants. She addressed LaMP's
air toxics data needs by stating a general goal of identifying and quantifying loadings for load
reduction. She distinguished two phases of this goal. The short-term phase involves identifying
source categories emitting critical pollutants to develop an action plan to reduce loads. The
long-term phase involves determining a plan that will meet regulatory requirements within the
various groups concerned with pollution in the Great Lakes.
16
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Ms. Blakely stated that the mass-balance program is critical to achieving water quality
standards. She then noted that there are three methods of controlling pollutants. Voluntary
reduction provides an effective means of control, as does implementation of state programs
outlined in CAAA 112 (I). Recommendations from the Great Waters Study also may provide
means of controlling pollutants.
Ms. Blakely added that she supported the addition of mercury to the critical pollutant list
because utilities appear to be primary sources of mercury and Title III may be the only means of
utilities regulation.
Dr. Stevens stated that, whereas the purpose of a mass-balance study is to determine the
distribution of pollutants from air and water, an emissions inventory would not allow an
understanding of the major sources of air toxics. Mr. Pahl responded that if source category
information is important, it will have profound implications for the study.
Ms. Foy said that the Great Lakes states have expressed a need for emissions inventories,
monitoring, and modeling. Dr. Stevens said that sources can be identified through receptor
modeling, particularly the hybrid model that combines dispersion and receptor modeling. Dr.
Stevens emphasized that the hybrid receptor model was the tool of choice for quantitative
analysis
L Great Waters Scientific and Environmental Measurement Needs
Ms. Melissa McCullough of the EPA OAQPS, the leader of the Great Waters program,
presented the mandates for the Great Waters Study set forth in Section 112(m) of the CAAA. She
noted specifically that the CAAA require EPA to report to Congress in 1993 and every 2 years
thereafter. Reports are to include an analysis of the relative atmospheric contribution of
hazardous air pollutants (HAPs); and an identification of HAPs-caused effects. They also are to
identify sources of HAPs and whether HAPs cause water violations. Finally, reports are to offer
recommendations for regulatory revisions.
Ms. McCullough said the Great Waters Study will focus on those issues and will collect
data that will support a logical and credible case for any recommended action.
The Great Waters program will consist of emissions inventory, monitoring, modeling, and
effects assessment activities. Ms. McCullough stated that, whereas all groups associated with the
Great Lakes have common goals, the Great Waters Study will rely on the scientific community to
recommend a research strategy that will be endorsed by peer review.
17
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The following have been defined as high-priority tasks for the Great Waters Study:
• compiling background information
• evaluating methodology for determining deposition/flux of toxic pollutants
• characterizing urban influences
• characterizing processes and parameters
Mr. Pahl asked what strategies the Great Waters Study planned to employ for interstate
transport, given that Section 112(m) is a federal program allowing for state involvement. Ms.
McCullough replied that recommendations will be included in the Great Waters Report, but by the
time the report is submitted to Congress, the source category regulation schedule will be set.
The two mam sources of funding for the Great Waters Study would be the OAQPS and the
ORD Air Toxics Research Committee.
IV. DAY II
Mr. Dale Pahl opened the second day of the workshop session by announcing that the
participants would divide into two groups, both charged with addressing the following issues
defined by the first day's discussions and articulated by Mr. Pahl:
1. Data collection objectives (DCOs)
Pollutants of concern
• Parameters considered essential for modeling
2. Data Quality Objectives (DQOs)
3. Hypotheses
4. Measurement
• Methods and sampling frequency
Design
• Cost, accuracy, other parameters
5. Location of sites
6. Key outputs
After a brief discussion, participants agreed that Dr. Clyde Sweet and Ms. Joanne Foy should
present information on available sites before the group sessions.
18
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A. Availability of Sites
Ms. Joanne Foy generally described available state sites around Lake Michigan. She stated
that much time and money have been spent by the states on site searches for toxics and ozone
monitors and that additional sites may be evaluated as monitoring funding becomes available.
Ms. Foy said that Great Lakes states are receptive to input on siting on states' monitors from
the groups represented at this workshop and could assist EPA in finding appropriate sites for
additional CAA monitors. Even though the Great Lakes air regulatory agencies have proceeded
on their own in the past to establish air toxics monitoring sites in light of little or no previous
federal funding or guidance, some of these sites may be appropriate to use for CAA
implementation. Since these sites were established independently for various purposes, some
might need to be relocated or enhanced in their monitoring capabilities to be compatible. Other
sites considered comparable to EPA efforts may be appropriate to factor into EPA's sponsored
programs as they exist.
The Great Lakes air regulatory agencies have formed an air monitoring coalition committed
to monitoring planning and coordination, which includes states, local organizations, and Canadian
organizations. This relatively informal coalition can serve as the coordination mechanism with the
various organizations represented at the workshop if desired.
Dr. Clyde Sweet of the Illinois State Water Survey, which is associated with the University of
Illinois in Champaign-Urbana, has worked under contract with GLNPO on various Great Lakes
issues, including the air monitoring component of the Green Bay Mass-Balance Study. He
currently manages the air sampling, chemical analysis, and data analysis for the Integrated
Atmospheric Deposition Network's (lADN's) U.S. sites.
Dr. Sweet gave a historical overview of lADN's integrated monitoring program in the Great
Lakes (including Lake Michigan area), a joint effort with Canada. He said that the pollutant list
consists of selected toxic compounds found in fish in the Great Lakes area that can be monitored
on a routine basis. The list includes PCBs, some pesticides (including dieldnn), PAHs, and lead.
Mercury was rejected because the methods available for study would be difficult to implement for
routine monitoring.
Sites chosen represented a compromise of the ideal and the economically feasible. Three
or 4 sites—1 master and 2 or 3 satellite sites-on each of the Great Lakes are planned, although
currently only the master sites are in place. Master sites are designed to support routine
monitoring and research projects, and satellite sites are designed strictly for monitoring to
supplement the master sites.
19
-------
Dr. Sweet pointed out a need for quantifying urban input to the Lakes and said that three
sites per Lake are not adequate to measure urban input. Because of this, IADN has focused on
regional sites that reflect the atmosphere over the Lake as a whole. The mass-balance study is
an opportunity to test urban influence on the Lakes by characterizing input in a 1 -year study and
extrapolating those results to other areas
IADN has been struggling to find a method of monitoring over the Lakes. Monitoring from a
platform over the Lake or from a ship is expensive. Island sites may be feasible in some cases,
but they do pose logistical problems. IADN has opted for shoreline sites, but new evidence
suggests that these sites may reflect neither the land nor the water environment. The need for
meteorological data at each site is becoming increasingly important.
Dr. Sweet presented slides of sites (see Appendix F) and reviewed issues associated with
each, including proximity to major sources, staffing at stations, nearby use of pesticides, and
relations with private land owners. In the process, he summarized IADN operational, available,
and potential sites.
Dr. Sweet then presented data from air samples of total suspended particulates (TSP) at three
Green Bay Study sites that indicate that urban pollutants may be transported by regional air
masses.
B. Group Recommendations
The two groups discussed the issues outlined by Mr. Pahl and reconvened to share their
recommendations. The groups used the elements defined by Mr. Pahl as a basis for discussion.
Dr. Sweet gave a brief overview of Group 1 's discussion before presenting recommendations.
Limiting the list of pollutants and obtaining a well-characterized and well-calibrated model were
issues that were of prime concern.
The target compounds identified by Dr. Sweet's group were:
• PCBs
• lead
• atrazine
• trans-nonachlor
PCBs and lead were chosen because they were components of the Green Bay Study.
Atrazine was chosen because it is a current-use pesticide, it has been identified as a potential
problem and because it has a variety of ways in which to enter the Lake. In addition, it is reactive.
Dr. Sweet expressed Group 1's hope that including atrazine would increase the model's
20
-------
sophistication. Trans-nonachlor was chosen because it bioaccumulates and does not pose a
significant analytical problem.
Additional parameters recommended were:
• TSP in air
• carbon inputs from air, precipitation, tributaries
• nutrient cycling
Site recommendations were:
• 7 land sites (1 in the north, 2 mid-Lake, and 4 around the South Basin)
• 2 ship sites (operational only part of the year)
The group recommended the high-volume (hi-vol) sampler with a filter and XAD vapor trap
for monitoring air pollutants on a 12-day schedule for the 3 upper Lake sites and a 3-day
schedule for lower Lake sites. For dry deposition, Group 1 recommended the Noll sampler. For
precipitation, the group recommended a monthly composite and large-area sampler for event
sampling. A denuder was suggested to help evaluate information from the standard hi-vol
sampler.
Group 1 proposed the following hypotheses for the mass-balance study:
i
• whether measurements over land reflect pollutants over water
• event-based vs. monthly sampling
• dry deposition of large particles
• source information
• quality control issues, particularly regarding new compounds, such as atrazme
• importance of urban vs. regional inputs
Recommended outputs for the mass-balance study were1
• atmosphere loadings to the Lake, plus information for modeling
• calibrated model
Dr. Sweet stated that the calibrated model was the real goal of the study. A calibrated model
is necessary to be able to predict the fate of pollutants entering the Lake from the atmosphere
21
-------
and can be applied to new chemicals not included in the mass-balance study. The model will
also predict the effects of controlling a particular source and will help determine which controls
will have the most positive effect.
Mr. David Cowgill summarized Group 2's discussions, which focused on initiatives that would
meet managers' needs and would win funding approval. Generally, the group advocated building
on the Green Bay Study and choosing parameters that have transferability to other water bodies.
Group 2 identified the following pollutants of concern:
• PCBs
• dieldrin
• lead
• nonachlor
• mercury
• DDT
• PAHs
Mr. Cowgill presented his group's matrix, which listed identified pollutants on one axis and
reasons for their selection on the other axis. A pollutant must meet one or more of these criteria
to be useful to the mass-balance study (however, satisfaction of one or more criteria does not
mandate a pollutant's inclusion in the study):
• has ecological significance to the Great Lakes
• is bioaccumulative
• can be measured in air and water
• has known modeling method
• can be regulated
• acts as a surrogate
• has known atmospheric source
• is a potential new pollutant that identifies an emerging problem
Group 2 provided several modeling parameters. The group suggested using the Green Bay
Study target pollutant list as a minimal base and reviewing the list and adding parameters as
needed. In addition, source attribution should be determined and precipitation chemistry, and
the air concentrations over water and across air/water interface should be characterized. Finally,
both phase distribution (air and precipitation) and particle size distribution should be determined.
22
-------
Group 2's DQOs were:
• use Green Bay Study as template for Lake Michigan QA program
• review and update all SOPs and QAPjPs
• establish centralized QA authority
• consider requesting ORD to provide QA support
• offer more than one option to decision-makers, options that require varying levels of
funding
• achieve lowest possible analytical detection limits
Group 2 formulated several hypotheses that the study should address-
Long-range transport has a significant effect on the water quality of the Lakes (sources
outside the Basin are contributing to loadings).
Tributary loadings are significant.
Once load reduction "y" is achieved, concentration in fish reaches acceptable levels in "x1
number of years.
Sign of air/water flux changes through seasons
Saturated microlayer can form a barrier to limit atmospheric flux to the water.
The key outputs deemed significant by Mr. Cowgill's group were:
• mass budget and media contribution
• prediction of impact of control actions on biological/ecological systems
• prediction of benefits from remedial actions and relation of benefits to regulatory action
Mr. DeVault questioned the group's list of pollutants, pointing out that, although they are
pollutants of concern, some are not good candidates for modeling, particularly mercury. Dr.
Swackhamer asked to see the pollutant list/criteria for selection matrix again and reiterated Mr.
DeVault's point, saying that pollutants that cannot be measured cannot be used to develop or
validate a model. Mr. Cowgill replied that his group was aware of the problems in measuring
mercury, but that it was important to start research on mercury because of public interest in this
pollutant. Dr. Swackhamer replied that analytical research is being conducted on mercury, but
it was nevertheless a poor choice for the validation of this mass-balance model. In a
mass-balance model, she said, chemicals are the tools that make the model work A good data
set is needed to calibrate the model.
23
-------
Ms. McCullough said that the group's intent in including mercury was to present a
well-supported case for regulatory action of a chemical that has a documented, validated human
health or ecological impact. Dr. Swackhamer replied that many other chemicals would fill that
need—atrazine, for example.
Dr. Swackhamer suggested prioritizing the selection criteria and completing the matrix for
various pollutants, thus achieving a valid parameter list. The ability to measure and model
pollutants would be the most significant selection criterion.
Mr. Pahl ended the workshop by observing that the group discussions were productive and
spurred new ideas that would affect design of the mass-balance study. Mr. DeVault said that the
next step for Region V was to complete the mass-balance study plan in 2-3 months and to start
measurement work in spring 1993.
Mr. Pahl stated that this was the first of a series of mass-balance studies and that it would
have a significant effect on all air and water quality plans.
24
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APPENDIX A
MEETING AGENDA
A-1
-------
LAKE MICHIGAN MASS BALANCE PLANNING WORKSHOP
FINAL AGENDA
GUEST QUARTERS SUITES
2515 MERIDIAN PARKWAY
RESEARCH TRIANGLE PARK, N.C.
TUESDAY MARCH 31,1992
10:30
10:40
11:10
11:40
12:15
1:30
2:10
2:45
3:15
3:30
4:00
4:15
4:30
4:45
5:00
Introduction
Preliminary Objectives for Lake
Michigan Mass Balance Model
Overview of present transport/
fate, food chain models for the
Great Lakes
Estimation of Wet Deposition
for Mass Balance Studies
LUNCH
D. Pahl
D. DeVault
B. Richardson
J. Baker
Estimation of Dry Deposition for T. Holsen
Mass Balance Studies
Interface of atmospheric & aquatic T. Clark/
models in design of Mass Balance B. Benjey
Studies.
Approach to measuring urban contributions
to Great Lakes toxic loadings J. Keeler
BREAK
Use of Source Apportionment Model
Results in Mass Balance Models R. Stevens
Great Lakes States' atmospheric J. Foy
measurement objectives & data needs
Overview of Lakewide Management
Planning
Overview of air toxics data need
for LaMP's
C. Hunt
P. Blakely
Great Waters scientific and
environmental measurement needs
M. McCullough
Adjourn /Social Hour/Raleigh Room
A-2
-------
WEDNESDAY, APRIL 1,1992
8:15 GROUP DISCUSSION: Identification of air data needs
for Lake Michigan mass balance study and modelling
(Pollutants, parameters, sampling frequency,
analytic objectives, DQO's, Q.A.)
10:30 BREAK
10:45 Availability of sites C. Sweet, J. Foy
11:15 Break into two teams to formulate preliminary
monitoring plan
12:00 Lunch
1:00 Work group deliberations (continued)
2:30 Work Group Presentations
3:00 Wrap-up and summary D. Devault/
A. Hoffman
3:30 Adj ourn
A-3
-------
APPENDIX B
WORKSHOP PARTICIPANTS AND AFFILIATIONS
B-1
-------
LIST OF PARTICIPANTS
LAKE MICHIGAN MASS BALANCE PLANNING WORKSHOP
Guest Quarters Suite Hotel
March 31-April 1,1992
Dr. Joel Baker
Chesapeake Biological Lab
P.O. Box 38
University of Maryland
Solomons, MD 20688
(301) 326-4281
(301) 326-6342 (FAX)
Dr. William Benjey
U.S. Environmental Protection Agency
MD-80
Research Triangle Park, NC 27711
(919) 541-0821
Ms. Pamela Blakely
U.S. Environmental Protection Agency
GLNPO/Region V
77 W. Jackson Boulevard
Chicago, IL 60604
(312)886-6054
Mr. Terry Clark
U.S. Environmental Protection Agency
MD-80
Research Triangle Park, NC 27711
(919) 541-3372
Dr. Larry Cupitt
U.S. Environmental Protection Agency
MD-78A
Research Triangle Park, NC 27711
(919) 541-2454
Mr. David DeVault
U.S. Environmental Protection Agency
GLNPO/Rgion V
77 W. Jackson Boulevard
Chicago, IL 60604
(312) 353-1375
(312) 353-2018 (FAX)
Ms. Gerri Dorosz
U.S. Environmental Protection Agency
MD-14
Research Triangle Park, NC 27711
(919)541-5492
Mr. Gary Evans
U.S. Environmental Protection Agency
MD-56
Research Triangle Park, NC 27711
(919) 541-3124
Ms. Joanne Foy
Michigan Department of Natural Resources
Box 30028
Lansing, Ml 48909
(517)373-7039
(517) 373-1265 (FAX)
Mr. Alan Hoffman
U.S. Environmental Protection Agency
MD-76
Research Triangle Park, NC 27711
(919) 541-1929
(919) 541-4609 (FAX)
Dr. Thomas Holsen
Environmental Engineering
Illinois Institute of Technology
3201 South State Street
Chicago, IL 60616
(312) 567-3559
(312) 567-3548 (FAX)
Ms. Connie Hunt
U.S. Environmental Protection Agency
GLNPO/Region V
77 W. Jackson Boulevard
Chicago, IL 60604
(312) 886-0271
B-2
-------
Dr. Jerry Keeler
Department of Environmental &
Industrial Health
University of Michigan
109 Observatory Street
Ann Arbor, Ml 48109-2029
(313)936-1836
(313) 764-9424 (FAX)
Ms. Melissa McCullough
U.S. Environmental Protection Agency
MD-13
Research Triangle Park, NC 27711
(919)541-5646
(919) 541-5661 (FAX)
Ms. Anne McMillan
Environment Canada (AES)
4905 Dufferin Street
Downsview, Ontario
CANADA M3H 5T4
(416) 739-4867
(416) 739-4288 (FAX)
Mr. Dale Pahl
U.S. Environmental Protection Agency
MD-56
Research Triangle Park, NC 27711
(919)541-1851
(919) 541-1486 (FAX)
Mr. Michael Papp
U.S. Environmental Protection Agency
GLNPO/Region V
77 W. Jackson Boulevard
Chicago, IL 60604
(312) 886-4063
(312) 353-2018 (FAX)
Ms. Anne Pope
U.S. Environmental Protection Agency
MD-15
Research Triangle Park, NC 27711
(919) 541-5373
Dr. William Richardson
U.S. Environmental Protection Agency
Large Lakes Research Station
9311 Groh Road
Grosselle, Ml 48138
(313)692-7611
(313) 692-7603 (FAX)
Mr. Paul Ringold
U.S. Environmental Protection Agency
OEPER (RD-690)
401 M Street, SW
Washington, DC 20460
(202) 260-5609
Dr. Robert Stevens
U.S. Environmental Protection Agency
MD-47
Research Triangle Park, NC 27711
(919)541-3156
(919) 541-4609 (FAX)
Dr. Deborah Swackhamer
School of Public Health
Box 197 - Mayo Building
University of Minnesota
420 Delaware Street, SE
Minneapolis, MN 55455
(612) 626-0435
Dr. Clyde Sweet
Illinois State Water Survey
2204 Griffith Drive
Champaign, IL61820
(217) 333-7191
(217) 333-6540 (FAX)
B-3
-------
APPENDIX C
GREAT LAKES STATES' ATMOSPHERIC MEASUREMENT OBJECTIVES AND DATA NEEDS
PRESENTATION
MS. JOANNE FOY
C-1
-------
Great Lakes Toxics Monitoring
Total RGBs
o
*> CO
E
11/9012/90 1/91 2/91 3/91 4/91 5/91 6/91 7/91 8/91 9/91
GTB
SAG
] SOO
-------
Great Lakes Toxics Monitoring
g-HCH
0.35
O
co
11/9012/901/91 2/91 3/91 4/91 5/91 6/91 7/91 8/91 9/91
GTB
SAG
SOO
-------
Great Lakes Toxics Monitoring
Dieldrin
o
CO
0.4
0.35
0.3
0.25
0.2-
0.15-
0.1-
0.05-
o-
11/9012/901/91 2/91 3/91 4/91 5/91 6/91 7/91 8/91 9/91
GTB
SAG
SOO
-------
Great Lakes Toxics Monitoring
HCB
o
en CO
Z
0.6-
0.5-
0.4-
0.3
0.2-
0.1H
11/9012/90 1/91 2/91 3/91 4/91 5/91 6/91 7/91 8/91 9/91
GTB
SAG
1SOO
-------
Great Lakes Toxics Monitoring
a-HCH
o
D)
C
0.3-
0.25-
0.2-
0.15
0.1-
0.05
11/9012/901/91 2/91 3/91 4/91 5/91 6/91 7/91 8/91 9/91
GTB
SAG
SOO
-------
APPENDIX D
GROUP 2 DISCUSSION
SUMMARY
D-1
-------
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D-7
-------
D-8
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D-9
-------
APPENDIX E
OVERVIEW OF LAKEWIDE MANAGEMENT PLANNING
PRESENTATION
MS. CONNIE HUNT
E-1
-------
LAKE MICHIGAN LAKEWIDE MANAGEMENT PLAN
m
'IVJ
Goal: To reduce loads of persistent, toxic, and/or
bioaccumulative pollutants in order to restore
beneficial uses to the Lake Michigan basin through
an ecosystem-based, multi-media approach
-------
Lake Michigan Lakewide Management Plan
Background
m
1. Great Lakes Water Quality Agreement Annex II
a. provided mandate for Lakewide Management Plans for the
Great Lakes
2. Critical Programs Act
a. mandates a proposed Lakewide Management Plan for Lake
Michigan be published in January 1992
b. mandates s final Lakewide Management Plan for Lake
Michigan be published in January 1994
-------
LAKE MICHIGAN LAKEWIDE MANAGEMENT PLAN
Participating Agencies
U.S. EPA Illinois EPA
U.S. Fish and Wildlife Service Indiana DEM
U.S. Geological Survey Michigan DNR
U.S. Department of Agriculture Wisconsin DNR
U.S. Army Corps of Engineers
Ohippewa/Ottawa Treaty Fishery Management Authority
-------
Proposed Critical Pollutants for Lake Michigan
Level I
Level
Total PCBs
Dieldrin
Chlordane
DDT and Metabollties
Mercury
Level II
Dioxins
Furans
Level IV
Hexachlorobenzene
Toxaphene
PAHs
Cadmium, Chromium,
Copper, Load, Zinc
-------
m
6>
Critical Pollutants
Tiering Concept
LEVEL I: Numerical Standard « » LaMP Focus; Enforce Standards;
Violated Reduce Loads
LEVEL II: Strong Association LaMP Focus; Reduce Loads
with Use Impairments
t t t CRITICAL POLLUTANTS tit
LEVEL III: Moderate Association , Develop Information Base;
with Use Impairments * Encourage Load Reductions
LEVEL IV: Possible Association « » Develop Information Base;
with Use Impairments Encourage Pollution Prevention
-------
Monitor Source
Reductions
Implement Activities
Identify Prevention.
Reduction, and
Remediation Activities
Establish Load
Reduction Targets
Monitor Ecosystem
Response
EcologicaJ Stability
impaired or
Threatened?
Declare
Success)
Determine Critical
Pollutants
Identify Sources
i
Quantify Loads
E-7
-------
APPENDIX F
LAKE MICHIGAN AIR MONfTORING-SITE SUMMARY
PRESENTATION
DR. CLYDE SWEET
F-1
-------
LAKE MICHIGAN AIR MONITORING - BITE SUMMARY
4-1-92
OPERATIONAL SITES*
Sleeping Bear Dunes (IADN Master Site)
Indiana Dunes (IADN Satellite Site)
Chicago 68th St. Crib (Offshore urban plume site)
AVAILABLE SITES*
Chicago (3 GLAD sites, IIT, urban sites)
Milwaukee UW (GLAD, urban site)
Green Bay UW (used in GBMB, PCB source area)
Sturgeon Bay Coast Guard Sta. (ship traffic, topography)
Beaver Is. (GLAD site, other potential sites on MDNR land)
Muskegon NOAA (paper mill, public beach nearby)
Benton Harbor (GLAD site, some industry nearby)
Manitowoc UW (GLAD site)
POTENTIAL SITES*
Peninsula State Park, WI (used in GBMB, tree cover)
Fayette State Park, MI (LMOS used a private site nearby)
Zion State Park, IL
Cana Light USCG
Mission School (MDNR Air Toxics Site, Traverse City)
Grant Twp. (1991 LMOS site)
Holland (1991 LMOS Site)
j*
Whirlpool Corporation
Warren Dunes State Park, MI
* OPERATIONAL = Now in operation or operations planned for 1992
AVAILABLE = Written or verbal approval has been obtained.
POTENTIAL = No approval has yet been obtained.
F-2
-------
Fayette'
Beaver Is
Cana
Sleeping
Bear Dunes
Sturgeon
Bay
Milwaukee
CHICAGO
Mission
School
Grant
Muskegon
Holland
Whirlpool
•I Benton Harbor
Warren Dunes
Indiana Dunes
F-3
-------
GREEN BAY PROJECT TSP VALUES 1988-1989
m
E
o»
•""
"
I I I I I I I I I M I I I I I I I I \ \ I I I I 1 I I I I I I I II I I I I I M I I II I I M I I I I I | I I | H | | i | | | |
AMMJ J J J J J J JAAAAASSSSOONTi-INNDDCODJ J J J J FFFFFMMMMAAAAMMMMJ J J J J A55S55CQOCTO
GREEN BAY
MONTH
FAYETTE
PENINSULA
-------
GREEN BAY PROJECT TSP VALUES 1988-1989
130
n
E
a
c/i
1111111ii111111 M 1111 11111 n 111111
AMMJ J J J J J J JAAAAA5553OTNNNNNDDDDDJ J J J J FFFFFMMMMAAAAMMMMJ J J J J ASSS55COOOOO
GREEN BAT
MONTH
FAYETTE
PENIN5UA
-------
Fayette State Park
(MI
Peninsula State Park (WI)
/ U.W.—Green Bay
F-6
-------
BEAVER ISLAND (GLAD)
F-7
-------
MUSKEGON (NOAA)
F-8
-------
BENTON HARBOR(GLAD)
F-9
-------
MISSION SCHOOL (MDNR)
WHIRLPOOL CORP
F-10
-------
HOLLAND (LMOS)
GRANT TWP. (LMOS)
F-11
-------
INDIANA DUNES NATIONAL LAKESHORE (NADP)
F-12
-------
LOW TSP
9/13/89
7/15/89
3/29/89
-------
HIGH TSP
10/25/89
7/ 3/89
3/11/89
-------
APPENDIX G
USE OF SOURCE APPORTIONMENT MODEL RESULTS IN MASS-BALANCE MODELS
PRESENTATION
DR. ROBERT STEVENS
G-1
-------
GREAT WATERS AIR TOXIC DEPOSITION
RESEARCH PROGRAM
Recommendations for Sampling and Analysis
Collect and Analyze Fine & Coarse Particles
Separately
Use Filters Appropriate for Analysis
Use Denuders for Collection and Analysis of
SVOCs
Collect and Analyze VOCs
Incorporate SEM Analysis Methods
Use Hybrid Models
Perform Deposition Experiments at Receptor
Sites
G-2
-------
HYBRID RECEPTOR MODEL
ANY PROCEDURE FOR ESTIMATING
THE SOURCES OF AMBIENT AIR
POLLUTANTS AT A RECEPTOR (AMBIENT)
SITE, WHICH COMBINES ELEMENTS OF
BOTH RECEPTOR AND DISPERSION
MODELING APPROACHES.
G-3
-------
Source Apportionment Methods
Emissions
Inventory
Meteorology
Dispersion
Model
Ambient
Concentration
Due to Source J
Ambient
Concentrations
of Chemical Species
Some Source
Information
Receptor
Model
Ambient
Concentration
Due to Source J
-------
APPENDIX H
APPROACH TO MEASURING URBAN CONTRIBUTIONS TO GREAT LAKES TOXIC LOADINGS
PRESENTATION
DR. JERRY KEELER
H-1
-------
43e30'
Overlake
Transport
MILWAUKEE*
West
Shore
SOURC
LAKE
MICHIGAN
May 16.20;
June 6-10;
August 14-19;
Septembar 26-30.
1977 Location of
R/VSImona
Chicago/
Gary
S.E. Shore
May-Dacambar. 1978
oeatlon of Sampling
ram 68th Street Crib
CHICAGO* \*
I0 20 30 40 SO
FIGURE 1. Location of Source Regions and Sampling Data.
H-2
-------
H-3
-------
URBAN AIR TOXICS COMPONENT
DESIGN CONSIDERATIONS:
ioei
1M
land lake
OFFSHORE MIXING ZONE-VERTICAL PROFILE
-------
URBAN AIR TOXICS COMPONENT
DESIGN CONSIDERATIONS
SUMMERTIME EPISODIC WIND PROFILE:
SHADED AREA ON WESTERN SHORE-MAX O3
-------
S04 CencMiiratlen (mf/U
NADP only
Figure 8(a). Spatial distribution of volume-weighted SOA
concentrations in the Great Lakes region,
using NADP data for 1982-83.
S04 Cenecntntion (m^L)
GLAD * NADP
2.50
Figure 8(b). Sue as (a), but using the coabined GLAD /NADP
data set.
H-6
-------
C* Concentration (mg/L)
NAOP only
Figure 9(a). Spatial distribution of volume-weighted Ca
concentrations in the Great Lakes region,
using NADP data for 1982-83.
C* Conctntntion (mg/L)
GLAD + NAOP
Figure 9(b). Same as (a), but using the combined CLAD/NADP
data set.
H-7
-------
Figure 10(a). Spatial distribution of volume-weighted N03
concentrations in the Great Lakes region.
using NADP data for 1982-83.
NO3 Concentration (mg/L)
GLAD* NADP
Figure 10(b).
-------
PM-10
Konkakee
E
\
cr>
100 -i
80 -
60 -
40 -
20 -
0
Fine
Coarse
T
T
100 -,
80 -
'E 60 -
\
¥ 40 -
20 -
0
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
III
100 -i
80 -
"> 60 -
I? 40 H
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
R/V Laurentian
I I I I I I I I I I I I I I I I [ 1 \I I I I \ \ I I I I
1112 23 24 25 26 27 567
100 -i South Haven
80 -
"> 60 -
I? 40 H
20 H
0
i I I I I I I I I I I I I I I I I . I IT I
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
July
H-9
Date
August
-------
GAS PHASE MERCURY RESULTS:
TOTAL VAPOR PHASE MERCURY COLLECTED ON GOLD-COATED SAND TRAPS
VALUES REPORTED IN UNITS OF NG MERCURY/M3
SITE N 25& 5Q& 90% MEAN STD DEV MAX
SHA 38 1.5 1.8 2.9 2.0 0.6 4.3
IIT 58 2.9 4.5 14.9 8.7 12.0 62.7
LAU* 25 1.8 2.2 2.9 2.3 0.7 4.9
*DATES: 7/11-7/12, 7/25-7/27, 8/5-8/8
-------
100 -,
10 -
E
\
c
0.1
III
Vapor Phase Mercury
1 2 Hour Average
n—i—r
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
100 -i
R/V Laurehtian
10 -
cr>
c
1 -
0.1
' ' I T"T I I I
11 12
| | | | | | j I I I I I I | | ri"T"T I
23 24 25 26 27 5678
100 -,
South Haven
10 -
CT>
c
1 -
0.1
I I I I I I I I I I" T T T T"l
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
July
H-11
August
Date
-------
Vapor Phase Mercury
100 -i
10 -
III
01
c
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
a>
c
100 -,
10 -
1 -
0.1
R/V Lourenfian
i I I I I I I TTT'l l l I I l I I I l l l l I l I I I I I I iTTTT l TTT'l I I I I I I I I I i i iTTTTTl I I I I
11 12 23 24 25 26 27 5678
100 -n
South Haven
10 -
en
c
1 -
0.1
i i i T i T i T i T i T i TTn T i n Fi Ti Fi Fi r\ ~\ Ti Fi Fi i i fi Fi Fi T\ T\ T\ T\ T\ T\ T\ T\ T\ TTi
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
July
H-12
Dote
August
-------
Pb - Coarse
E
\
Ql
25 -H
20 -
15 -
10 -
5 -
Kankakee
l.l.ll.llllll .llll..l.l. .1 ..I
r i i i i i i i. i i i i i in r~i i i i i i i i—i—i—i—i—i—i—i—rr—i
7 8 9 10 11 12 13 U 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
25 -,
20 -
15 -
r 10 H
5 -
81
I IT
.In.Ml
I T T T
7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
25 -
i
c
5
0
E
\
en
I.I
11 12
25 -i
20 -
15 -
10 -
5 -
South Haven
-f I ff T'MI IT" Mrl 1i
i i i i i i i i i i i i i i n i i r i i i ~n rn i i i i i i i i i
7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
July
Date
H-13
August
-------
Pb - Fine
en
c
40 -,
30 -
20 -
10 -
Kankokee
iliilll.lin
~T~l—I I I I I I I I I I I I I I I I I—rTTTTTTl I I I | | | i
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 2B 29 30 31 1 2 3 4 5 6 7 8 9 10
40 -i
30 -
\ 20 -
62
NT
62
en
c
10 -
4-t-
4-r-
40 -,
30 -
20 -
10 -
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
R/V Laurentian
i—i—i—r~r
11 12
"i—i—i—m—i—i"!—r-r—i—i—i—i—i—i—i—i—i—i—i—i—i
23 24 25 26 27 567
en
c
40 -,
30 -
20 -
10 -
South Haven
llhLl.... i.liiill.ll l.ll.n.
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
July
Date
August
H-14
-------
Fe — Fine
400 -i
Konkakee
en
c
300 -
200 -
100 -
i.lMMillll
li.ll 1.1..
400 -i
300 -
200 -
100 -
T
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
558
I IT
-T-4-
T
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
•M-
cr>
C
400 -i
300 -
200 -
100 -
R/V Lourentian
401
i—i—i—i—i—i—i—i—i—i—i—i—i—i—r^r~i—n—r~i—i—i—i—i—i—r
11 12 23 24 25 26 27 567
400 -i
300 -
200 -
100 -
South Haven
ll.lll
i
Li..... iii...lni
l,...,,llll|,,
i r i i i i i i i i i i i i i i i~"~i n
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
July
Date
August
H-15
-------
R/V Laurentian
so.
CD
CO
CL
D-
10
9
8 -
7 -
6 -
5 -
4 -
3 -
2 -
1 -
0
ll
|
11 12
South Haven
10 -,
9 -
8 -
7 -
6 -
5 -
4 -
3 -
2 -
1 -
0 -
ln.l.
Jhi|.|i
1
1
1.
jl
1. ul
II ' 1 1 I 1 1 1 1 i I"
23 24 25 26 27
ll.ll.llnllllll.
(
If
I
i i T"
5 6
5 10
i r 'i
7 8
lull ll
I.J
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
July
August
Date
H-16
-------
As - Fine
O>
C
4 -I
3 -
2 -
1 -
Kankokee
I'. I iilllli . .1 mi linn
I" i I I I I 1 I I—F~|—|—T—I
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
4 -,
en
c
III
i!.!
• ' 1 I !• • • . I
en
c
3 -
2 -
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
R/V Lourentian
11 12
' ' ' i i i T"i I I i i i i i i i. i i IUT T-i i i
23 24 25 26 27 567
4 -i
3 -
2 -
South Haven
I I I
. ..
I .
H I ...
HI
III I I T T-| T I I l I I I | | | i
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
July
Date
August
H-17
-------
Fine Fraction of PM10
Kankakee
1.0 -i
0.8 -
0.6 -
0.4 -
0.2
o.o
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 26 29 30 31 1 23
I IT
4 5 6 7 8 9 10
1.0 -
0.8 -
0.6 -
0.4 -
0.2 -
0.0
...
Q n
1 /
-\ 1
1 1
T «
1 *
r 4
" *
—
.......
_.
II
1
" T
._
"„" _ | •
T T T
,
1
' T T
i
1.0
0.8
0.6
0.4 -
0.2 -
0.0
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 10
R/V Laurentian
11 12
i i i i I I I i i i i i i i i I I I i i i
23 24 25 26 27 567
1.0 -,
South Haven
0.2
0.0
I
ll
I
I
II
I
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9
July Date Au^ust
H-18
10
-------
Elemental Carbon
I
3.0
2.5
2.0
1.0
0.5
0.0
3.0
2.5
2.0
Kankakee
I....IIIIH.I..I Mill I.
I I I I I
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
4.6
0.5
0.0
— I — I — I — I — I — I — I — f—
I
III
ll.hl
I
I
I ill
I
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
3.0
2.5
2.0
1-5
1.0
0.5
0.0
R/V Laurentian
10 11 12
I I III I T I
23 24 25 26 27 28
i i i i i i ri'T'i i i
5678
3.0
2.5
\ 1.5 -
a>
D
1.0 -
0.5
0.0
South Haven
f I I I I f
TTlTTTTTTTlllllillTllilllli
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
I.I
-T-f
July
Date
August
H-19
-------
Organic Carbon
15 -,
12 -
3 6
3
0
15
12
IE *
^ 6
3 •
0 •
Kankakee
111
/i
~i—i—r
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
26 49
NT
u
15 -,
12 -
>
E 9 -
\
= 6-
3 -
~i—i—i—i—i—i—r
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9
R/V Laurentian
10
i — i — i — i — i — i — i — i
10 11 12
i — i — i — i — i — i — r— i — i — i — i — i — i — i — i — i — i — r— i — i — i
23 24 25 26 27 5678
a*
15
12
6 -
South Haven
ii..in.Mi.ill.I
~i i i i i i rn i i i i—i—i—i—i—i—i—i—i—i—i—p—i—i—r T T T T T T T i
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
July
Date
August
H-20
-------
Comparison of two samplers at South Haven
Elemental Carbon
2.0 -,
1.5 -
Sampler 333333
Sampler 444444
15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
Organic Carbon
12 -,
10 -
8 -
6 -
4 -
2 -
Sampler 333333
Sampler 444444
i i i i i i i iii
ill
15 16 17 18 19 20 21 22 23 2* 25 26 27 28 29 30 31 1 3456789
July
August
H-2iDate
-------
R/V Laurentian
SO
300 -
270 -
240 -
210 -
"V 180 -
\
"5 150 -
E
c 120 -
90 -
60 -
30 -
0 -
»||
..l...l.ll ,,|
' ' ' ! i i I I i I T T T T T I i — i — i — i — i — i — i T T T i — i — i
11 12 23 24 25 26 27 5678
South Haven
300 -,
270 -
240 -
210 -
"V 180 -
•x.
"5 150 -
E
c 120 -
90 -
60 -
30 -
0
«||
.
JllMi
-
I III
Li .illlllll
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
July
August
-------
R/V Laurentian
H
100 -
90 -
80 -
70 -
£ 60 -
IS 50 -
E
c 40 -
30 -
20 -
10 -
0
~i—i—rn I—i—i—r
11 12
n—i—i—i—i—i—i—i—i—i—i—r—i—i—i—i—i—i—i—i—r~r~r—i—i
23 24 25 26 27 5678
South Haven
100
90
80
70
•5 50
E
C 40
30
20
10
0
122 241 213
1.11
llllll.ll
I lull, l.lll.lilJL
i
...nllli
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 2 3 4 5 6 7 8 9 10
July
August
-------
APPENDIX I
INTERFACE OF ATMOSPHERIC AND AQUATIC MODELS
IN DESIGN OF MASS-BALANCE STUDIES
PRESENTATION
DR. WILUAM BENJEY
1-1
-------
TOXIC EMISSION INVENTORIES
FOR REGIONAL DISPERSION AND
DEPOSITION MODELING
1-2
-------
CLEAN AIR ACT AMENDMENTS
TITLE III
o SECTION 112(c)
o SECTION 112(k)
o SECTION 112(m)
1-3
-------
COMPOSITE TOXIC EMISSIONS
INVENTORY ASSEMBLY
COMPILATION OF EXISTING INVENTORIES,
DUPLICATE CHECKING AND QUALITY CONTROL
NAPAP > NESHAP > TRIS
SUPPLEMENTAL DATA
(LE. CORRECTED OR TYPICAL STACK DATA)
APPLICATION OF EMISSION FACTORS
o UNINVENTORIED SOURCES
o UNSPECIATED TOXICS
o NATURAL BACKGROUND
EXAMPLE
RFF PESTICIDE APPLICATIONS
DATA BASE
1-4
-------
INTERIM TOXIC EMISSION
INVENTORY
o PURPOSE
- INITIAL GENERAL ASSESSMENT
- DISPERSION MODELING
o CURRENT STATUS
- QUALITY CONTROL OF INPUT DATA
- MERGING OF EMISSIONS DATA
- REGIONAL
- STATE AND LOCAL
o MODELING APPLICATION PROCEDURES
- GRIDDING FOR GEOGRAPHIC
DISTRIBUTION
- ANALYSIS BY SOURCE TYPE (SCO
1-5
-------
INTERIM TOXIC EMISSION INVENTORY
CONTENTS AS OF MARCH 1992
*MERCURY
"LEAD
ETHYLENE DIBROMIDE
CARBON TETRACHLOR.
*1f3-BUTADIENE
"CHROMIUM
PERCHLOROETHYLENE
CHRYSENE
ACRYLONITRILE
BERYLLIUM
PHENANTHRENE
*BENZO(A)PYRENE
1,2 DICHLOROETHANE
ETHYLENE OXIDE
METHYLENE CHLORIDE
*CADMIUM
STYRENE
METHYL CHLORIDE
SELENIUM
"BENZENE
TRICHLROETHYLENE
EPICHLOROHYDRIN
DINBUTYLPHTHALATE
"CHLOROFORM
VINYL CHLORIDE
FLUORANTHRENE
"NICKEL
"ARSENIC
ETHYL ACRYLATE
"FORMALDEHYDE
I-6
-------
I/
MERCURY EMISSIONS IN TONS/YEAR
MAX IS 423.99 TONS/YEAR AND MEAN IS 4.30 TONS/YEAR
WITHOUT 305 SCC CODES. JANUARY 10,1992
5.0 TO 10.0
Aitu IIP, K.C.
-------
RELMAP MERCURY EMISSIONS IN TONS/YEAR
WITH THE 305 SCC CODES. JANUARY 23,1993
5000.0 TO 10000.0
10000.0 to 20000.0
20000.0 TO SOOOO.O
SOOOO.O TO 100000.0
00.0 TO 200000.0
200JQO.O TO 500000.0
ma IIP. ».c.
-------
VINYL CHLORIDE TOTALS FOR REGION V STATES
OHIO
INDIANA
MICHIGAN
ILLINOIS
WISCONSIN
MINNESOTA
POINT
513 .926
499 .355
143 .555
25589.973
87.224
100.976
AREA
956 .249
612.507
665.165
Il30 .704
328.185
398.575
TOTAL
1470 .175
1111.861
808 .720
26720.676
415.409
499.551
MERCURY TOTALS FOR REGION V STATES
(O
OHIO
INDIANA
MICHIGAN
ILLINOIS
WISCONSIN
MINNESOTA
POINT
17.598
301
512
149
406
16
12
31
13
14
811
AREA
496 .798
246 .854
413 .592
434 .602
243 .692
203 .966
TOTAL
514 .396
155
104
751
098
263
426
465
257
218
777
-------
EMISSIONS OF MERCURY IN REGION V BY PROCESS
NO 305 SCC CODES
SCC
EMISSIONS
21
23
902
5010
22
1010
5020
3020
3030
1020
5030
30
3040
27
28
3010
46
3900
99
3038
3060
3090
48
35
38
47
3070
3999
3080
36
1030
3140
3039
3099
4058
4020
4010
3079
4909
4050
4030
3089
3098
3600
1691.907
218.462
95.162
25.747
20.151
15.794
15.537
15.301
8.734
8.193
6.917
4.768
4.222
3.608
1.990
1.580
1.528
1.385
0.880
0.670
0.548
0.326
0.283
0.243
0.201
0.183
0.174
0.164
0.161
0.138
0.091
0.059
0.046
0.036
0.027
0.020
0.012
0.011
0.010
0.006
0.004
0.001
0.001
0.000
1-10
-------
I ? ,-l ? I VI '\ o ? n o i e e i m 3 I e u n n A
In i T 0 q a m I aJl n o b 9 b b i 1 0
''•, e n o T
.}.* .1TI JA3KA
-------
Annual Emission? of P.O.M.
G r i d d f- d n n L a P e ~ N I c h i g a n G r I d
F o n 5 -'yea r
0 T 0 0 • 1
n. I TO o.2
0.2 r 0 0.5
0.5 TO I.0
I . 0 T 0 2 . 0
2.0 TO 5.0
u m
= 223.8
AREAl KTP. K.C.
-------
A n n 1 1 ,:j I L m i s i> i o n •? ft \
P r i <: 1 1 I i "i i i.i r H i / I
Or i .-:! ,1 f: .1 n n I'; r i H :
o 1 1 ? •' f a r
A r i=> a S o u i L e
An n LI a I
5 TO 1C)
10 T 0 2 0
20 TO r>0
50 TO 1 00
I 00 TO 200
Max = 147.8' Sum - 3028.6
AIEAI IIP. i.e.
-------
TOXIC EMISSIONS INFORMATION
NEEDS FOR MODELING
roENTIFICATION OF UNKNOWN
TOXICS SOURCES
NEW (AND REVISED)
EMISSIONS FACTORS
NEW AND REVISED SPECIATION PROFILES
ACTIVITY INDICATORS TO
ESTIMATE EMISSIONS INVENTORIES
PROJECTION METHODOLOGIES
EPA/AREAL/wgb
1-14
-------
TOXIC EMISSION INVENTORY NEEDS
ATMOSPHERIC CHEMISTRY
SPATIAL AND TEMPORAL VARIABILITY OF
NATURAL TOXIC EMISSIONS
BACKGROUND CONCENTRATIONS OF
ANTHROPOGENIC TOXIC EMISSIONS
IMPLICATIONS OF ATMOSPHERIC
TRANSFORMATIONS ON TOXIC EMISSIONS
INVENTORIES
1-15
-------
APPENDIX J
INTERFACE OF ATMOSPHERIC AND AQUATIC MODELS
IN DESIGN OF MASS-BALANCE STUDIES
PRESENTATION (CONTINUED)
MR. TERRY CLARK
J-1
-------
Terry L. Clark
USEPA/ORD/AREAL
Lake Michigan Mass Balance Study
March 1992
UTILITY OF ATMOSPHERIC MODELS
FOR MASS BALANCE CALCULATIONS
(1) Estimates of dry/wet deposition to 40-km cells
(2) Attribution of source categories and geographic areas
(3) Seasonal variability of dry/wet deposition
(4) Optimization of surface monitoring network
J-2
-------
INPUT REQUIREMENTS FOR
ATMOSPHERIC DEPOSITION MODELS
MINIMUM
PREFERRED
Characterization of
Air Flow Patterns
Routine hourly land-
based and 12-h upper
air meteor, data
Gridded wind fields
produced by diag.
meteor, model
Concurrent Air/Water
Temperatures
Climatological water
temperatures and land-
based air temperatures
near shorelines
Daily measurements
at various distances
from shorelines
Air Emission Rates
Assume no daily
variability in
annual emissions
Daily estimates of
factors used to
calculate emissions
Precipitation Amounts
Routine hourly amounts
at land-based sites
interpolated to lake
Minimum plus
hourly radar images
to assist in the
interpolations
J-3
-------
ANNUAL MEAN AIR CONCENTRATIONS
OF LEAD RELATIVE TO MAXIMUM
-------
ANNUAL DEPOSITION TO LAKE MICHIGAN
— LEAD —
(kg/year)
Dry Deposition Wet Deposition Total
RELMAP (1992)
0.5 micron 62,500 (9.1%) 627,300 (91.3%) 689,800
5.0 micron 254,200 (37.7%) 420,800 (62.3%) 675,000
Strachan & Eisenreich (1988)
120,000 (22.2%) 420,000 (77.8%) 540,000
90,000 (16.7%) 450,000 (83.3%) 540,000
J-5
-------
APPENDIX K
ESTIMATION OF DRY DEPOSFTION FOR MASS-BALANCE STUDIES
PRESENTATION
DR. THOMAS HOLSEN
K-1
-------
ESTIMATION OF DRY DEPOSITION FOR MASS
BALANCE STUDIES
Thomas M. Holsen
Illinois Institute of Technology
Acknowledgments
Kenneth E. Noll
Guor-Cheng Fang, Jui-Min Lin, Wen-Jhy Lee, Shi-Ping Liu
K-2
-------
Talk Overview
Objectives
Instruments
Comparison of Measured and Modeled Dry
Deposition
Recent Metals and PCB Data
Implications for Mass Balance Studies
K-3
-------
Talk Summary
1. Realistic estimates of dry deposition can be
made with existing dry deposition models if
complete airborne size distributions are known.
2. Results obtained from dry deposition
measurements with smooth surrogate surfaces
with sharp leading edges are comparable to
modeled fluxes.
K-4
-------
Sampling Techniques for Complete Size
Distributions (WRAC)
Two sampler system
Cascade Impactor - particles < 1 0 jL/m
Noil Rotary Impactor (NRI) - coarse particles
• multi-stage rotary inertial impactor
• rectangular stages
• greased mylar strips weighed before and after sampling
• strips can be extracted and analyzed
• typical cut diameters of 6.5 /L/m, 1 1 .5 jum, 24.7 /^m and 36.
Deposition Plate -
• PVC plates with a sharp leading edge
. pointed into the wind by a wind vane
• greased mylar strips
• weighed before and after sampling
• strips can be extracted and analyzed
Smooth surrogate surfaces produce minimum deposition
velocities - deposition velocities measured with other collectors
changes with collector geometry
K-5
-------
100 F
10
0.1
0.01
0.001
0.0001
dC/dLog dp,
Mass
Chicago, sample 7
• AAPSS
v NRI
dF/dLog dp,
/ug/m sec
H 1—I I I I 1 l[ 1 1—I Mill] 1 1—I I I I I I
i midpoint cutoff diameters
Flux plate
Universal (PM10 & PM2.5)
AAPSS
NRI
-•—• •-
0.1
1 10
aerodynamic diameter, /xm
100
Range of particle sizes measured with various instruments are
compared to mass and flux distributions.
K-6
-------
120
o
_l
-D
100
80
60
40
20
0
A- Rubidoux, 1 20 f.ig/m (EPA)
B- E.St. Louis, 90 /J,g/m (EPA)
C- St. Paul suburb, 71 /zg/m
(Lundgren)
D- Chicago, sample 7, 87 /itg/m
E- Durham, 51 /xg/m (EPA)
F- St. Paul suburb, 26
(Lundgren)
G- Chicago, sample 2,
31
Density assumed to
2.0 g/cm
0.1
1 10
Particle diameter, /_/,m
100
Measured particle size distributions obtained from 3 different
studies at 5 different locations in the U.S.. The size distributions
labeled "EPA" are from a study by Rodes et al. (1985) and those
labeled "Lundgren" are from a study by Lundgren and Paulus
(1975). The size distributions labeled "Chicago" are 2 of the 9 five
day samples collected in 1991.
K-7
-------
Dry deposition models
Sehmel (1973), Slinn and Slinn (1980), Noll and Fang (1989) +
others
Predict deposition velocities as a function of particle diameter for a
variety of environmental and particle characteristics. In this
example a particle density of 1.5 g/cm, wind velocity of 6.7 m/sec
and U* of 34.1 were used.
o
0)
V)
E
u
^-
• ^
u
"CD
o
CL
0)
O
100
10
-2 0.1
0.01
0.001
0.0001
Noll and Fang/'
Sehmel
Slinn and Slinn
hydrophobia particle
0.001 0.01 0.1 1
Diameter, /.tm
10
100
K-8
-------
10
CM
O
0)
C/5
E
2» 0.1
CL
T)
0.01
0.001
0.0001
T 1 T
Rubidoux, 120
E.St. Louis, 90
51. Paul suburb, 71
3
1
3
• Chicago, S-SW wind, 87 ;u.g/m'
— Durham, 51 ^.g/m
. 3
— St. Paul suburb, 26
v Chicago, E-NE wind,
o
31
0.1
Slinn and Slinn model
i i—i—i—i i 11
i i—i—i 111
1 10
Particle diameter,
100
dF/dLog dp = dC/dLog dp • Vd where F is the flux in
Vd from Slinn and Slinn (1980).
K-9
-------
100
c
-------
1 ' ' "I
Chicago
T 1 1 1 1 I I I |
..O Q
~7 1 1 1 1 1 I I
calcium
'O
0.1
co
a>
o
_i
T3
O
TJ
lead
• o
0.01
wind 33% NE, 23% E
• cascade
o NRI
density assumed to be 2.0 g/cm
O
0.001
o
o
0.1
1 10
Particle diameter,
100
-------
Fo
1e-002
1e-003
1e-004
1e-005
1e-006
1e-007
1e-008
0.1
PCB
dC/dLog dp,
Assumed particle distribution
from Chicago, S-SW wind
/xg PCB/Vg
particle
(Holsen et al., 1991)
dF/dLog dp
/j-g/m sec
Slinn and Slinn model
i i i i i i i I i
1 10
Pariicle diameter,
100
-------
Table I. Chicago sample information.
Sample
No.
1 - mass
2 - mass
2 - lead
2-
calcium
3 - mass
4 - mass
5 - mass
6 - mass
7 - mass
8 - mass
9 - mass
Sampling
date,
1991
6/21-6/27
7/8 - 7/1 6
7/23-7/29
7/30-8/6
8/9-8/15
8/16-8/24
8/25-
8/29
8/31-9/8
9/1 7-9/29
% of % of
time time
exposed wind
was
from
land
75
85
88
81
94
72
100
87
69
41
25
53
46
38
46
92
59
69
Ave
wind
speed,
m/s
4.7
3.6
4.0
4.2
3.2
4.0
3.5
4.0
4.2
Fine Coarse
particle particle
cone., cone.,
A/g/m3 /,/g/m3
20.6
13.7
0.032
0.33
21.8
18.5
19.5
28.1
47.3
26.2
24.6
21.5
17.4
0.015
0.73
16.5
37.9
20.1
24.9
39.9
28.4
25.5
K-13
-------
100
1 I I I
c
-------
en
O
0
to
100
10
o
TJ
0.1
0.01
0.001
0.0001
• measured data Chicago (Watkin, 1986) •
Chicago, 1991 S-SW wind
Slinn and Slinn
Noll and Fang
U* assumed to be 40 cm/sec
l ...... '
1 - 1 - 1 1 1 1 - 1 - " - 1
0.1
1 10
Particle diameter,
100
-------
Comparison of Measured and Modeled Dry Deposition
Models
Product Model: Cj Vd(MMDj) where i is either the fine or coarse
particle phase.
Slinn and Slinn
modification of Noll and Fang.
1-step method (Slinn and Slinn, 1980): FI = C K(ag) Vd(MMD)
C is the mass concentration
is the geometric standard deviation
is the deposition velocity
MMD is the mass median diameter
K(ag) = exp{2(ln ag)2}
K(a)Vd(MMD) is the flux mean deposition velocity
fine and coarse particle mode - Slinn and Slinn
coarse particle mode with the modification of Noll and Fang
9-step method: F9 = | Cj Vd(Dj) where Dj = the is the midpoint
i=1
cut-off diameter of each impactor stage.
Slinn and Slinn
modification of Noll and Fang.
K-16
-------
X
D
(D
L-
CO
O
0)
E
TJ
0)
O
o
1000
100
10
0.1
0.01
0.001
perfect prediction
X
0.0001
1 1
1 2 3
\B/ :
I I I li I i
45 6 789 2-Ca2-
a.
Sample No.
- 1 step MMD(, S&S d. v - 9 step, S&S f.
e. D - 9 step, N&F g.
b. v - 1 step MMD S&S
C i
c. A - 1 step MMDc, N&F
• — product,, S&S
A - productc, S&S
h. O - productc, N&F
-------
oo
Particle Size Distribution for Anthropogenic Elements
Lake vs. Land
• Lake * Land
n
6
tio
0.000
V
Cd
0.020
0.016
0012
0.1
10
10
0005
0.004
0003
0.002
0.001
0.000
100 0.1
10
100
Particle Size
100
-------
Particle Size Distribution for Crustal Elements
Lake vs. Land
• Lake * Land
(0
^e
bO
O
o.o
0.05
0.04
0.03
0.02
0.01
0.00
IOO 0.1
Ti
100
Particle Size
-------
•
Comparison of Flux between Land and Lake
(0
CM
1000
900
800
700
600
g
0 500
400
300
200
100
0
c
X
I—I
fc
Land
Lake
Element
-------
For Each Metal:
Total Flux = Vdf - Cf + V
-------
100
u
0)
w
u
^>
o>
n
o
Q.
0)
O
T I I 1 1 1 1 1 T
• Coarse Particle Phase
• Fine Particle Phase
0.1
Si Ca Ti Fe Al Mg V Cu Zn Cd Pb Cr Mn
Sampling Time (1991)
-------
i
feS
o>
o
Q_
100
90
80
70
60
50
4O
3O
20
1O
0
Ooarse Particle Flux
Fine Particle Flux
O
rxl
o
cd
-------
'if
B
B
FILTER
8" PIPE
I
Deposition Plate
(1) A, B, C : Flow Straightor, see Figure 2
(2) Deposition Plate : detail see Figure 3
DUAL CHAMBER
BALL VALVE
BLOWER c
FLOW
METER
0
Exhaust Gas
-------
Deposition of Semi-Volatile Compounds (compounds with both a
gas and particle phase)
Experiments in which deposition plates were exposed to filtered,
PAH and PCB containing air for periods up to 30 days continuously
collected these compounds. Calculated deposition velocities for
these compounds remained constant and in the range of expected
values (0.01-0.02 cm/sec).
K-25
-------
O
•a
•
N
E
\
E
(A
M
O
350
300 -
250 -
200 -
150 -
100 -
50 -
Deposition
Plate
- 1 and 2 arc duplicate
.
*
-
.
™
-
\\X\\\\\\\\\X1
IT]
III
1
May June July Aug
1
1 2
•amplei
I
I
Sept
I
I
Oct
I
i
i
I
9
I
^
's
/
/
/
/
/
/
/
/
/
kxxxxxxxxxxxx
y
/
/
/
/
y
y
y
/
/
/
y
/
'*
/
/
/
•
—
1 2 _
7-
\
\
-
Nov June July
989
1990
Chicago
10
-^
0>
m
o
a.
Deposition plate
1 and 2 ar» dupllcat* iompl*i
1 2
1 2
17
X
X
v
X
\
1 2 .
May June July Aug Sept Oct Nov June July
1989
1990
Chicago
-------
Deposition Velocities
By phase: Flux = VgCg + VfCf + VCCC
where: V - deposition velocity
C - concentration
g - gas phase
i f - fine particle phase
c - coarse particle phase
Fluxes and concentrations measured - deposition velocities solved for using
multiple regression (24 equations and 3 unknowns)
Problems - poor definition of fine particle phase -> new instrument
- filter artifact formation (gas and fine particle phase) -» denuder
-------
o
w 10.0
E
o
o
-2 1.00
o
c
o
w
o
0.10
0.01
O Gas Phase A Coarse Particle
' Fine Particle
.A.
A A
A
A
A
o
9
J L
May June July August September Oct.
Sampling Time (1990)
K-28
-------
Particle vs. gas phase deposition
Total PCB Flux = Vdg . Cg + Vdf. Cf + Vdc - Cc
where the measured values are:
Total PCB flux = 6.04jL/g/m2-day
Cg = gas phase PCB concentration = 10.4 ng/m3
Cf = fine particle PCB concentration = 3.2 ng/m3
Cc = coarse particle PCB concentration = 0.9 ng/m3
and the literature values are:
Vdg = PCB gas phase deposition velocity to a smooth surface
= 0.01-0.1 cm/sec
Vdf = PCB fine particle deposition velocity to a smooth surface
= 0.1-0.5 cm/sec
Comparison of gas phase, fine particle phase and coarse particle phase PCB flux to a
smooth surrogate surface with a sharp leading edge.
Vdg,
cm/s
0.01
0.01
0.10
0.10
Vdf,
cm/s
0.1
0.5
0.1
0.5
Vdc,
cm/s
7.3
5.9
6.3
4.8
Gas phase
flux,
ng/cm2-s
1.04E-7
(1.5%)
1.04E-7
(1.5%)
1.0E-6
(15%)
1 .OE-6
(15%)
Fine
particle
flux,
ng/cm2-s
3.2E-7
(4.6%)
1.6E-6
(23%)
3.2E-7
(4.6%)
1 .6E-6
(23%)
Coarse
particle
flux,
ng/cm2-s
6.6E-6
(94%)
5.3E-6
(76%)
5.7E-6
(81%)
4.3E-6
(62%)
Total flux,
ng/cm2-s
7.0E-6
7.0E-6
7.0E-6
7.0E-6
-------
Large Particles Control Flux
. Davidson and Friedlander (1978) - Pb in LA
. Murphy (1984)-PCBs near Lake Huron
. Davidson et al. (1985) - sulfate
• Dulac et al. (1989) - metals and mass in Mediterranean
. Injuk et al. (1990) - metals in North Sea
K-30
-------
Conclusions
1. Realistic estimates of dry deposition can be
made with existing dry deposition models if
complete airborne size distributions are known.
2. Results obtained from dry deposition
measurements with smooth surrogate surfaces
with sharp leading edges are comparable to
modeled fluxes.
3. Coarse particles are responsible for the
majority of dry deposition flux.
K-31
-------
Future Work
Determine the effect of variations in particle size distribution and
turbulence on indirect and direct fluxes using short-term urban
data
Compare indirect and direct fluxes in low concentration/flux
environments (non-urban data)
Compare indirect and direct fluxes on a size distribution basis by
counting particles on the deposition plate
Compare data collected simultaneously with the NRI and PM10
sampler to see if a relationship can be developed that would
allow PM10 data to be utilized in indirect flux modeling studies
Compare urban and non-urban data so that global transport and
fates of atmospheric particles and pollutants associated with
them can be determined.
K-32
-------
Implications for Mass Balance Studies
To quantify dry deposition either measure the flux directly with a
smooth surrogate surface or measure the total size distribution of
ambient particles and the gas phase and apply deposition velocity
models (or both).
Using partial size distributions (PM2.5 or PM10) and effective or
average deposition velocities has little physical meaning.
Using complete size distributions (WRAC)
Advantages
• linked with meteorological models
. used with models which account for deposition on natural water
surfaces (waves, spray, particle growth)
• simulate changes in size distribution and flux with changes in
env. factors
Disadvantages
• short term samplers (12-24 h for NRI)
. difficult to measure and expensive to obtain
. not a direct measurement of flux
K-33
-------
Eagle (II) Automated Flux Measurement
Advantages
• Simple and easy to use
. directly measures flux of mass, metals, or organics
• compares to modeled data
• can operate unattended long or short term
Disadvantages
• Is not a natural surface
• collected particles need to be counted to obtain mass-size
distributions
• can not do chemistry by size
K-34
-------
Days needed to obtain measurable samples with various
instruments in urban and non-urban areas.
Flux
plate
UAS
AAPSS
NRI
mass
0.5
0.5
1-3
0.5
Urban
metals
0.5
0.5
3-5
0.5
semi-
volatile
organics
15
1-2
5-10*
5-10
mass
1-2
1-2
3-5
1-2
Non-
urban
metals
3-5
2-4
5-10
2-4
semi-
volatile
organics
15-30
2-4
1 0-30*
10-20
particle phase only UAS - Universal Air Sampler
AAPSS - Anderson 1 ACFM non-viable ambient particle sizing
sampler
NRI - Noll Rotary Impactor
K-35
-------
Flux
Chicago _ South Haven _ Lake
98.2 36.2
102.9 44.1 27.2
195.4 37.9 24.9
K-36
-------
7/30/91-8/6/91
(0
TJ
c
o
^
X
700
600
500
400
300
200
100
0
^ South Haven, MI
DID Chicago, IL
S Lake Michigan
p
X
K
X
__ X
n H
fl El!
i a. jn JiL JTI Jil j. Kid 3
1
DOOOOOOOOod
;
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Illlllllll
N
M
II II 1 1 1 1 1 1
boooooooooi
X
K
K
OCJ
MCLO
-------
_o
TJ
Coarse Particle Size Distribution for
Urban (Chicago) and Nonurban (South Haven)
35
30
E 25
\
CO
^ 20
-^.
Q.
D
co 15
O 10
0
7/30/91 - 8/6/91
• Urban (Chicago)
A Nonurban (South Haven)
10
Particle Size, um
100
K-38
-------
6
00
O
c—I
T3
\
O
T3
7/30/91 - 0/06/91
Coarse Particle Size Distribution for Anthropogenic Elements
Nonurban vs. Urban
• Urban » Nonurban
0.10
0.09
0.08
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0.00
0.009
0.008
0.007
0.006
0.005
0.004
0.003
0.002
0.001
0.000
1
Zn
10
Cr
0.030
0.025
0.020
0.015
0.010
0.005
0.000
100 I
10
0.006
0.005
0.004
0.003
0.002
0.001
0.000
100 1
Cu
i—r~rr mi
V
10
0.000
100 1
0.002
0.001
0.001
0.001
0.000
0.000
100 1
10
Cd
10
Particle Size (/J.m)
100
-------
* a,
h 3,
00
o
o
TJ
I / <-s\J / {is i. — Of wO/ £7 J.
Coarse Particle Size Distribution for Crustal Elements
Nonurban vs. Urban
• Urban » Nonurban
Si
Na
1.5
1.2
0.9
0.6
0.3
0.0
1.2
1.0
0.8
0.6
0.4
0.2
0.0
T—I I I I I II
100 I
10
0.9
O.B
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
100 1
0.04
0.03 -
0.02
0.01
0.00
100 1
Ca
1.0
0.8
0.6
0.2
10
0.0
100 t
100
Mg
1-T-TTl
10
100
Particle Size
-------
We have not succeeded in answering all your
questions. The answers we have found only serve
to raise a whole new set of questions. In some
ways, we feel as confused as ever, but we believe
we are confused on a higher level about more
important things.
K-41
-------
APPENDIX L
ESTIMATION OF WET DEPOSITION FOR MASS-BALANCE STUDIES
PRESENTATION
DR. JOEL BAKER
L-1
-------
a
n
3
AIR
WATER
Wet and Dry
Deposition
N -
-------
J. BAKER UNIVERSITY OF MARYLAND
2
-------
J. BAKER
UNIVERSITY OF MARYLAND
• •
:/)
L-4
-------
J. BAKER
UNIVERSITY OF MARYLAND
3500
3000
2500
2000
D
"c 1500
CD
O
C
O
o
1000
500 -
JLflt
Ml
111
Chesapeake Bay
September, 1990
PCBs in Precipitation
H
dissolved
participate
Jl
PCB Congeners
L-5
-------
J. BAKER
UNIVERSITY OF MARYLAND
•+uu
_J
cn 300
CL
C
£ 200
D
•i— '
C
(D
0
c 100
O
J>
0
12
"O
\ 10
cn
Q- 8
-
1 6
D
i_
-4— '
C 4
CD
O
C
0 2
0
n
—
—
-
i
IL
~
\ L
n
.1
-
-
_
ill
Hi,
1
l
i,,.
J
nl,
ii
Chesapeake Bay
Dissolved PCBs
September, 1990
~
_
L
-
y,
, . Id 1
-
Chesaapeake Bay -
Vapor PCBs
September, 1990
_
1 ,
llJlltJ, 1,1 ,
PCB Congeners
L-6
-------
J
•
UNIVERSITY OF MARYLAND
8
PCB Congeners
L-7
-------
J. BAKER
UNIVERSITY OF MARYLAND
m
o
Q_
CD
-4— '
D
CO
Percent of "Dissolved" PCB
Supported by Vapor Phase Concentration
hesapeake Bay, September, 1990
c
CD
U
i_
CD
Q_
Log K
ow
L-8
-------
J. BAKER UNIVERSITY OF MARYLAND
WET
3. *R/»/»i IS
>
5
L-9
-------
J. BAKER
UNIVERSITY OF MARYLAND
Z.
L-10
-------
J. BAKER
UNIVERSITY OF MARYLAND
10
f 3
L-11
-------
J. BAKER
UNIVERSITY OF MARYLAND
11
L
MM.
L-12
-------
J. BAKER
UNIVERSITY OF MARYLAND
12
EviJ
L-13
-------
J. BAKER
UNIVERSITY OF MARYLAND
13
UAP/lfc EXCMKfeg
&ISS
M-r.c
(?T
L-14
-------
J. BAKER
UNIVERSITY OF MARYLAND
14
Fluxes of PCBs Across the Air-Water Interface of
the Great Lakes.
ng/m2 «d Reference
Volatilization
Deposition
Wet
Dry
19
15
23
63
18
.0
8
(1)
(2)
(3)
(4)
(4)
(4)
1.
2.
3.
4.
Lake Superior, Baker and Eisenreich, 1989
Lake Michigan, Swackhamer and Armstrong, 1986
Siskiwit Lake, Swackhamer et al., 1988
Lake Superior, Strachan and Eisenreich, 1988
CCW
C ftcVmAU,
- /o;
L-15
-------
J. BAKER UNIVERSITY OF MARYLAND 15
LIQUID-FILM MASS TRANSFER COEFFICIENT
(Liss and Merlivat, 1986)
k p 0.17u u < 3.6 m/s smooth surface
k |= 2.85u - 9.65 3.6 m/s < u <13 capillary waves
k |= 5.9u - 49.3 u > 13 bubble breaking
If
-------
J. BAKER UNIVERSITY OF MARYLAND 16
TEMPERATURE INFLUENCES
Henry's Law Constants
. u ™H 3414
log H = 7.91 - —-—
Tateya, eta/(1988)
Vapor-Aerosol Distribution
log . = - +b
m- 2755-5870 Bidleman and Foreman (1987)
b: 14.3-22.8
Mass Transfer Coefficient
DcxT
i7
-------
J. BAKER
UNIVERSITY OF MARYLAND
Wet and Dry
Deposition
N"(DR*DD)fA
17
AIR
WATER
Dissolved
CoHoids (f c)
Particles (f s)
UP ^MB I>0u)*J
-PU fa.
•L
L-18
-------
J. BAKER
UNIVERSITY OF MARYLAND
18
r1
20%
L-19
-------
J. BAKER
/
UNIVERSITY OF MARYLAND
I A
-«L
19
a.
L-20
-------
UNIVERSITY OF MARYLAND
20
2-3
VA \
Of
rwr
L-21
-------
APPENDIX M
OVERVIEW OF PRESENT TRANSPORT/FATE,
FOOD CHAIN MODELS FOR THE GREAT LAKES
PRESENTATION
MR. WILLIAM RICHARDSON
M-1
-------
STRAITS OF
MACKINAC
seasonally-stratified
water column
completely-mixed
water column
surficial sediment
qrey scale intensity
indicates lake depth
FIGURE 2
SPATIAL SEGMENTATION FOR
17-SEGMENT MICHTOX MODEL
M-2
-------
Toxic Chemical Model Schematic
Deposition Volatilization/
Loading
Water
Column
iranbpuri
and
cxcndiiyu ^
Surficlal
Sediment
Deep
Sediment
Z Absorption
'*
Outflow
' Photolysis ' /
Degradation v / Bioconcentratlon
V \ / /
\ / /
r~
boi
cher
NS
diffusion
s"1 tf '
s%v
dif
"* " / f
/* ff f'f J
^^ -'-^
f'.ffi > '-
^; .,
?i*t' ff
,?' " "''.
"\
jnd
nical
DM
N
\ / /
( \
dissolved L^ ^
chemical!^
i J
j
diffusion
- DC
r \
bound
chemical
NSOM
<. , ^~y--;--' ".
-;;.''* :%","*' '*
>>?'•', , "&',
,„'<„'^'
"5 ••
',
',
' ' ''''**
"W&-
f ^
sorbed
chemical
POC
V -^
'/^:^,
J.r&&''
f f <
! :>;',?''",
, ' ' /
•
-^- Transport
and
^ Exchange
-------
Lake Ontario (level 1) Toxics Model Parameters
water column volume
surficial sediment volume
air-water cross-section area
water-sediment cross-section area
outflow
suspended solids concentration
surficial sediment porosity
sediment particle density
settling 'flux
resuspension flux
deposition flux
sediment-water diffusive exchange coefficient
water column NSOM (non-settling organic matter)
sediment pore water NSOM
suspended solids foe
sedimented solids foe
octanol-water partition coefficient
organic carbon partition coefficient
water column NSOM binding coefficient
sediment NSOM binding coefficient
liquid film transfer coefficient
gas film transfer coefficient
henry's constant
transformation (photolysis) rate
load
dissolved oxygen concentration
phytoplankton BCF
lipid fraction (mysis, ale wife and lake trout)
dry weight fraction (" ")
chemical assimilation efficiency (" ")
chemical transfer efficiency (" ")
food assimilation efficiency (" ")
growth rate (" ")
respiration rate (" ")
Total number of parameters = 48 (16 chemical-specificl
IVU
-------
Bioaccumulation Model Processes
food chain transfer
uptake from water
elimination
(loss by gill diffusion,
excretion, metabolism)
chemical mass balance in fish:
bioaccumulation = uptake +
from water
food chain
transfer
elimination
-------
Lake Trout
1
- 2
3
- 12
0>
Diporcia spp
1
- 2
3
4
f"
-------
PCB loading time function used in MICHTOX
and reported PCB load estimates
10000 7
~ 1000-
•o
n
o
CO
o
CL
100:
1040 1950
2000
total load
atmospheric load
tributary load
Thomann and Di Toro (tributary)
Swackhamer and Armstrong (tributary)
Marti and Armstrong (tributary)
Thomann and DI Toro (air)
Swackhamer and Armstrong (air)
Rodgers and Swain (total)
Strockon and Elsenrelch (total)
-------
Load-Concentration Relationships for PCBs
in Lake Ontario lake trout
Sensitivity to PCB Air Concentration (Ca)
~ 100 i
C5
!-io*
re
o
u
c
o
u
CO
o
Q.
o
.X
C3
1 •:
.01
Ca=1ng/m3
.01
.1 1 10
PCB load (kg/day)
1 00
M-8
-------
100
80-
c
JO
g 60-
e
c
c
o
« 40 H
m
o
o.
20-
Lake Ontario model response
to PCB loading cutoff
10
20
water (pg/1)
sediment (rtg/g)
i
30
i
40
50
600
3
o
o
^c
a
CD
O
0.
500-
£ 400-
o
S 300-
200 H
"c
o
u
1CO -
with pcntoporeia
no pontcporeia
10
20
30
40
50
time (y)
M-9
-------
Figure 24. Sources of Uncertainty in
Lake Trout Concentration Predictions
0.6
HI alawlfo llpld
D plankton log BCF error
0 trout al) error
rj vd
B trout G
• alewlfeR
D alewlfe O
H trout R
B kv
H log Koe ragrasslon error
• logKow
0.0
PCB3 dleldrln HCB PCB-chterdan. DDT OCS PCB5 PCB8 TCDD PCB7 mlrex PCB8
-------
Figure 20. Results of Monte Carlo Analysis for Lake Ontario Toxics
1ECO
g 1000
I
•c
e
"o
5CO-
C5
I
o
• tower 95% confidence limit
E2 togmean
E3 upper 95% confidence Emit
dieldrin HCB chlordane DDT PCBs OCS TCOD mirex
150
1CO-
50 -
dieldrin HCB chlordane DDT PCBs OCS TCDD mirex
12CCX)
1CCOO-
8000 -
3 6CCO -
o
4CCO -
2000 -
0
I
dieldrin HCB chlordane DDT PCBs OCS TCDD mirex
M-11
-------
Figure 23. Sources of Uncertainty in
Water Concentration Predictions
1.50
ro
D Kow
0 kp
E3 sodlmonlatlon flux
H kv
•' Koc error
0.00
PCB3 dleldrln HCB PCB^chterd.n. DDT OCS PCB5 PCB6 TCDD PCB7 mlr.x PCBB
-------
Sensitivity of Computed Volatilization
Rate to Wind and Temperature
2.5'
2.0-
« 1.5
1.0-
0.5-
0.0
February kv (H=9.67E^4)
August icv (H=4.85E-3)
9 12 15 18
wind speed (mis)
M-13
-------
APPENDIX N
PRELIMINARY OBJECTIVES FOR LAKE MICHIGAN MASS-BALANCE MODEL
PRESENTATION
MR. DAVID DEVAULT
N-1
-------
LAKE MICHIGAN
Mass Balance
-------
WHAT IS IT?
INPUT - ACCUMULATION - CONSUMPTION • OUTPUT
Loads
Concentrations
-------
PARAMETERS and TARGETS
Target Parameters:
PCBs
Trans Nonachlor
Dieldrin
Lead
Target Fish:
Lake Trout
Coho Salmon
Bloater Chubs
-------
Ul
WHAT DO WE GET?
. Mass Budget Quantifying Sources and Sinks of Contaminants.
. Fully Calibrated Model Predicting Concentrations in Fish
From Loadings. This will allow:
1. Prediction of Environmental Response to Regulatory/
Remedial Activities.
2. Reduction in Future Monitoring Efforts.
. Coordination and Focusing of research and Monitoring
Activities of Several Govermental and Academic
Institutions.
-------
POSSIBLE APPROACH
USE CALIBRATED MODEL DEVELOPED FOR GREEN BAY
FOCUS 1992 DATA COLLECTION ON:
-Loadings
-Process Rates
I -Relativly Small Verification Data Set for Open Lake
'
-------
CONTAMINANT MASS and LOADINGS WILL BE MEASURED IN
Lake Water Tributaries
Bottom Sediments Suspended Sediments
Atmosphere Nonpoint Sources
Phytoplankton Zooplankton
Forage Fish Target Fish
-------
LAKE MICHIGAN MASS BALANCE
WORK PLAN
D. De Vault and J. Giattina, Co-chairs
Lake Michigan Mass Balance Technical Coordinating Committee
DRAFT - APRIL 24, 1991
N-8
-------
Study Purpose
Significant progress has been made on control and reduction of pollution in the Great Lakes.
However accumulation of toxic substances remains a serious problem in each of the lakes, as
well as, in many of the 28 areas of concern. In 1983, the Water Quality Board reported to the
LIC that 900 chemicals and heavy metals, potentially dangerous to human health and the biota,
have been identified in the Great Lakes.
Concern about the potential effects of these chemicals has increased with growing evidence of
links between the presence of contaminants and carcinogenicity in fish, genetic defects in fish
eating birds, and reproductive disorders in biota. Further, possible links have been reported
between developmental disorders in human infants and prenatal exposure to contaminants
through consumption of certain Great Lakes fish by their mothers.
Traditionally, the management of water quality has focused on control of direct releases of
pollutants. Such sources were the easiest to identify, characterize and control. The regulatory
laws to control sources of pollutants are media specific with air, water and land as separate,
compartmentalized media. For these reasons, restoration and maintenance of water quality were
largely tied to control of point sources from which contaminants were discharged directly into
the nations waterways.
With recognition that pollutants are also introduced indirectly from contaminated air, soil and
sediments, the entire approach to management of Great Lakes water quality had to be reassessed.
The reassessment led to the conclusion that adequate management of contaminants requires that
the total contribution of pollutants from all media be quantified and a mass balance approach be
employed. This approach was successfully applied to the regulation of nutrient loadings during
the past decade.
In a mass balance approach, the law of conservation of mass is applied in the evaluation of the
sources, transport and fate of contaminants. This, in turn, allows prioritization, allocation of
resources and regulatory efforts for water quality management. The approach requires that the
quantities of contaminants entering the system, less quantities stored, transformed or degraded
within the system, must equal the quantities leaving the system. Once a mass budget has been
established for each pollutant of concern, the long term effects on water quality can be simulated
by mathematical modeling. The model will provide water quality managers the ability to evaluate
the impact (at various levels of the ecosystem) of potential regulatory or remedial actions, and
to determine the reductions in amount and types of loadings that will result in criteria being met.
Study Goal
In Green Bay, a modeling and monitoring framework was established and tested to provide
greater understanding of the sources, transport and fate of toxic substances and to ultimately
guide and support regulatory activity. In Lake Michigan the lessons learned on Green Bay will
be employed on a whole lake basis to develop mathematical models and monitoring tools to
predict the response of Lake Michigan and Lake Michigan fish to proposed regulatory actions.
To accomplish this goal, the transfer of contaminants from sources to important fish species will
N-9
-------
be modeled. To allow predictive capacity able to cope with the complex interactions occurring
in the environment the toxicant model will be coupled with existing nutrient and solids models.
Due to the high analytical costs associated with development of a calibration data base for
contaminants, compounds which are themselves problematic and are representative of larger
groups of compounds have been selected for modeling.
Parameters to be modeled are:
o PCB congeners (all for nonplanar, subset for planer)
o Dieldrin
o Trans Nonachlor
o Lead
Additional parameters required for model calibration include:
o Organic Carbon (dissolved and paniculate)
o Nutrients (P.N.Si)
o Chlorophyll
o Alkalinity
o Water Temperature
o Suspended Solids
o PH
o Conductivity
o Dissolved Oxygen
o Chloride
o Incident Light
o Wind Speed and Direction
o Length, Weight, Age of Target Fish
The model will predict concentrations of target chemicals in whole Lake Michigan fish. The
species chosen are important to the Lake Michigan sport or commercial fisheries and represent
differing exposure routes and histories. They include:
o Lake Trout
o Coho Salmon
o Bloater Chubs
(Additional biota and forge species will be analyzed to support the food chain model)
It is anticipated that a fully calibrated toxicant model will be produced. To accomplish this, the
mass of target contaminants will be monitored in each significant environmental compartment
and, to the extent possible the rates of contaminant exchange between compartments. Monitoring
N-10
-------
and research efforts will be directed at measuring target contaminant mass in and exchange
between:
o Lake Water (dissolved and paniculate phases)
o Tributary Loadings (dissolved and paniculate phases)
o Bottom Sediments (multiple layers, mass, loadings, and sedimentation rates)
o Suspended Sediments
o Atmospheric Loadings (wet and dry participation, gas phase fluxes both into and
out of the lake)
o Significant Nonpoint Loadings
o Phytoplankton
o Zooplankton
o Forage Fish
o Target Fish Species
The modeling effort will focus on Lake Michigan with the Green Bay interface treated as a
source function. As a result the majority of the calibration data base will be collected from Lake
Michigan and tributaries to Lake Michigan. To the extent possible, tributaries will be considered
as point sources to the Lake. Limited sampling in Green Bay may be required to characterize
the Bay-Lake exchange for compounds not included in the Green Bay Mass Balance Study.
Data Quality Objective and Quality Assurance
The final data quality objectives (DQO) can not be developed until detailed the study planning
is underway. However, the study will be designed to produce a final modeling output that
produces predictions accurate to within a factor of five. This will allow the use of modeling
output to make risk assessment based management decisions. As modem risk assessment is
accurate to no better than a fector of ten, we believe that modeling output accurate to a factor
of five is sufficient.
Because of the extremely low concentrations of organic and metal contaminants in the waters
of Lake Michigan, tributaries, and the atmosphere, and of the necessity for an internally
consistent data base across several media and laboratories, very stringent quality assurance
procedures will be required. The following approach will be used to achieve this.
An independent Lake Michigan Mass Balance Quality Assurance Coordinator will be
appointed. This individual will be a highly respected , recognized expert in trace level
analysis, and interpretation, of organic contaminants in environmental media. The
individual will not be an employee of an agency or laboratory participating in routine
data collection. The responsibilities of this individual will include:
o Preparation of a generic "Mass Balance Quality Assurance Management Plan' in
conjunction with the Sampling and Analysis Committee (see section VH). This
N-11
-------
document will describe the minimum QA requirements such as blanks,
duplicates, spikes and detection limits (both analytical and environmental) for the
study, as well as, procedures for identification, quantitation, surrogate correction
etc for organic and metal contaminants. Each participating laboratory and
principal investigator will formally agree to follow the procedures outlined in this
document.
o Conducting a laboratory round robin and certifying laboratory performance on
round robin samples prior to actual sample analysis.
o Trouble shooting analytical problems at participating laboratories and, if problems
can not be solved, recommending appropriate actions (including that a laboratory
be dropped from the study) to the Technical Coordinating Committee.
o Review and approve organics, metals, solids, and carbon data bases prior to their
inclusion in the study data base and release to modelers or others.
In addition to the above, each participating organization will be required to prepare and
follow a Quality Assurance Project Plan (QAPP) specific to their activities. This QAPP
will be approved by the Project Officer, Region V Quality Assurance Office and Lake
Michigan Mass Balance Quality Assurance Coordinator prior to collection or analysis of
samples.
Organization and Study Management
A Three level management structure will be employed.
Management Committee:
Decision makers in organizations with responsibilities for water quality monitoring and
management in the Lake Michigan watershed. To assure consistency with the Lake
Michigan Lake Wide Management Plan (LaMP), which the model will support, the Mass
Balance Management Committee will be synonymous with the Lake Michigan LaMP
Management Committee.
Responsibilities: Approval of final study plan (including compounds to be modeled
and level of model accuracy), commitment of resources to conduct
necessary planning, monitoring and modeling activities.
Technical Coordinating Committee:
Chairs of the Technical Committees, Study Quality Assurance Coordinator and selected
technical experts.
N-12
-------
Responsibilities: Preparation of the Study Plan, recommendation of funding
commitments to the Management Committee, study coordination
and resolution of technical conflicts.
Technical Committees:
Several technical committees, as outlined below, will be required for study planning and
design. It is anticipated that the majority of the technical committee activity will occur
during the planning stages. Once the Study Plan and the Mass Balance Quality Assurance
Plans are completed, and the individual components of the study are funded and
underway, the study will be managed by the Technical Coordinating Committee with
Technical Committees being consulted as necessary.
o Modeling Committee (MC) - Government and funded academic modelers.
Responsibilities: Development of Modeling Plan, identification of modeling
data needs.
o Sampling and Analysis Committee (SAC) - Mass Balance Quality Assurance
Coordinator (Chair), EPA Region V Quality Assurance Office, and leads from
participating analytical laboratories.
Responsibilities: Preparation of Mass Balance Quality Assurance
Management Plan. Decisions and recommendations on
analytical methods, practicality of parameter list, sample
collection, extraction and analytical methods.
o Biota Committee (BC) - lead fisheries and biological staff from participating
organizations.
Responsibilities: In cooperation with SAC and MC prepare biological
sampling Plan.
o Tributary Loadings Committee(TLC) - Lead state, federal, and university staff
with tributary monitoring expertise.
Responsibilities: In cooperation with MC and SAC develop tributary
monitoring plan.
o Atmospheric Loadings Committee - Lead State, Federal and University staff with
expertise in atmospheric loading estimation.
N-13
-------
Responsibilities: In cooperation with MC and SAC Prepare atmospheric
monitoring/modeling plan to provide atmospheric fluxes as
defined by the modeling committee.
Critical (Fast Track) Planning Activities
Successful completion of the Lake Michigan Mass Balance Study will require the cooperation
and coordination of several Federal Agencies and offices, multiple agencies and offices from the
Lake Michigan States, as well as, universities and contractors. This coupled with the high cost
involved with collection and analysis of trace level organics samples argues for substantial up
front planning. The above described committee structure is designed to conduct the majority of
this planning and to produce the final study plan. However, the compressed time schedule in
effect for the Lake Michigan study requires the some planning activities begin prior to full
implementation of the committee process. These include:
o Formation of Modeling Committee and begin planning.
o Evaluation of existing data on fish and sediments to develop a preliminary list of
tributaries for load monitoring.
o Evaluation of existing open lake data for contaminants or surrogate compounds
to determine numbers and locations of stations, and number and timing of surveys
required to describe open lake conditions at differing levels of accuracy.
o Fund the Mass Balance Quality Assurance Coordinator and begin preparations for
the analytical laboratory round robin.
o Determine number of atmospheric monitoring stations required and select sites
and sampling methods.
o Fund study for determination of short range urban atmospheric loadings.
Major Work Activities
March 1991: 1. Prepare draft Work Plan
2. Decisions on FY91 planning activities
3. Evaluate existing tributary mouth data.
April-May 1991: 1. Establish Management and Technical
Committees.
2. Management Committee agrees on
N-14
-------
June-July 1991
parameter list and level of
modeling.
3. Fund FY91 projects.
4. Technical Committees meet/planning
begins.
1. Planning continues.
Aug.-Sept. 1991
Oct.-Dec. 1991
Jan.-Feb. 1992
Mar.-April 1992
May-Dec. 1992
Jan.-Mar. 1993
April-May 1993
Major Products
1. Modeling Com. identifies data
requirements.
1. Draft Study Plan Complete.
2. Draft Quality Assurance Management Plan
complete.
3. Train tributary monitoring teams/
field shake down.
4. Atmospheric sites constructed.
5. Lab QA evaluation underway.
6. Sampling shakedown for open water.
1. Final Study Plan Complete.
2. Supply procurement continues.
3. Funding complete for
grants/contracts.
4. Atmospheric sites fully operational.
5. Final Quality Assurance Management Plan
complete.
1. Begin Field season.
1. Continue field work.
2. Sample analysis underway.
1. Sample analysis continues
2. Winter survey(if required)
3. Atmospheric and tributary monitoring
continues
1. Final spring survey (if required)
2. Sample analysis continues
N-15
-------
1. Work Plan draft March 91
final April 91
2. Quality Assurance draft Oct 91
Management Plan final Jan 92
3. Study Plan draft Oct 91
final Jan 92
4. Sampling SOPs draft Dec 91
final Feb92
5. Initial mass budget Dec 93
6. Final Report Dec 94
Relationship to Other Lake Michigan and Great Lakes Activities
There are several monitoring and planning activities underway on Lake Michigan and the other
Great Lakes. In order to avoid competition between these activities, we are taking this
opportunity to present our vision of how the Lake Michigan Mass Balance Study, the Lake
Michigan LaMP, and the Great Lakes Monitoring Review complement each other.
Monitoring Review
The Great Lakes Monitoring Review is a review and revision of Great Lakes monitoring
activities to address specific management questions identified by Great Lakes water
quality managers. Among the questions identified are several relating to loadings and
ambient conditions. Thus it is likely that the programs developed will provide loadings
from at least generalized (tributaries, atmosphere) sources, as well as, possibly, processes
for determining specific sources.
Lake Michigan LaMP
The Lake Michigan LaMP is an action oriented effort that will, among other activities,
describe a program to monitor loads, ambient conditions, locate sources, and devise and
implement load reduction programs. Because of the action orientation of the LaMP, it
is likely that the monitoring program will include a process to locate and quantify specific
sources once a generalized source (tributary, atmospheric etc.) has been identified.
N-16
-------
Mass Balance
The Lake Michigan Mass Balance will result in a one year intense effort to monitor loads
and ambient concentrations with a very high level of accuracy. This data base will then
be used to calibrate toxic chemical models for Lake Michigan. This effort will, to the
extent possible, consider tributaries as point sources. Thus, limited effort will be
expended on location or quantification of specific sources to tributaries or the
atmosphere. However, the estimates of ambient concentrations, tributary and atmospheric
loads will probably be much more precise than those required for either of the above
Conger term) monitoring efforts.
The Management Questions that the Great Lakes Monitoring Review will address are those
identified by Great Lakes water quality managers, including those involved in the LaMP process.
The programs developed through the review should, therefore, meet most, if not all, of the
LaMP monitoring requirements. The Mass Balance Study will, through intensive monitoring,
provide actual data that may be used to design longer term monitoring efforts so that the desired
level of precision is achieved without costly over-sampling. The development of calibrated
models for Lake Michigan will further reduce the amount of sampling required for known
contaminants, allowing more resources to be directed at locating specific sources and identifying
and preventing future problems. Through the involvement of State and other Federal agencies,
the Mass Balance will also provide an arena for transferring monitoring technology and assuring
comparable collection and analytical methods in four of the Great Lakes states.
N-17
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