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
       100 Europa Drive, Suite 590
       Chapel Hill, N.C. 27514-2355
            (919)968-4961

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                                  DISCLAIMER

The use  of trade  names or commercial products in this document does  not constitute
endorsement or recommendation for use.

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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
                                          14

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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

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    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

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    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

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 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

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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

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    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

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    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

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           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

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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

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             APPENDIX B
WORKSHOP PARTICIPANTS AND AFFILIATIONS
                 B-1

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                               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

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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

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                            APPENDIX C
GREAT LAKES STATES' ATMOSPHERIC MEASUREMENT OBJECTIVES AND DATA NEEDS
                           PRESENTATION
                          MS. JOANNE FOY
                               C-1

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      Great Lakes Toxics Monitoring
                    Total RGBs
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        11/9012/90 1/91 2/91 3/91 4/91 5/91 6/91 7/91 8/91 9/91
                 GTB
SAG
] SOO

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       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

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       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
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      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

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      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

-------
   of
/DCo
                     '
Pet?',
         8/0
    •. 8/0;
    +meT: 6*0^
     :
             D-2

-------

-------
 3)
(9
                    D-4

-------
D-5

-------
                     *srv$y *s
                     fteetftffS.
 ©
    Crvr^tvurft  6fl ee*R

              J**?L&*i*r9Sr
         P#OG~&AM.
y) \^w*r»fK.  ^ffTOcigiTMx O
-------
         IMPACT
            THfiT
;T
    D-7

-------
D-8

-------
6u$6fiT +
  O/O
       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







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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

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._














"„" _ 	 | •


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

-------
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         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

-------
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                .A.
A         A
      A
                    A
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                                          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

-------
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         Coarse Particle Size Distribution for
     Urban (Chicago) and Nonurban (South Haven)
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                        10
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                                          100
                       K-38

-------
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                                 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
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0.006

0.005

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0.003

0.002

0.001

0.000
                      100   1
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                                    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

-------
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              Coarse Particle  Size Distribution for  Crustal  Elements


                                         Nonurban vs.  Urban


                                     •  Urban      »  Nonurban
                   Si
          Na
          1.5



          1.2



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          0.6



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                                                        0.02
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1.0
0.8
0.6
0.2
                                                                   10
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                                           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

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 CD
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    1000
    500 -
        JLflt
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             Chesapeake Bay
             September,  1990
             PCBs  in  Precipitation
                              H
                   dissolved
                   participate
Jl
                        PCB Congeners
                             L-5

-------
J. BAKER
UNIVERSITY OF MARYLAND
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September, 1990

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                                  L-6

-------
J
•
                            UNIVERSITY OF MARYLAND
         8
                              PCB Congeners
                                L-7

-------
J. BAKER
UNIVERSITY OF MARYLAND
    m
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    D
    CO
              Percent  of "Dissolved"  PCB
              Supported by Vapor Phase Concentration
              hesapeake Bay, September,  1990
    c
    CD
    U
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    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
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                                                                              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 \ / /
\ / /



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-------
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
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                  PCB load (kg/day)
1 00
                   M-8

-------
     100
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                Lake Ontario  model  response

                      to PCB  loading  cutoff
                  10
20
              water (pg/1)

              sediment (rtg/g)
 i

30
 i

40
50
    600
3
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£   400-
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     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.

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         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
                  '

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CONTAMINANT MASS and LOADINGS WILL BE  MEASURED IN

  Lake Water              Tributaries
  Bottom Sediments        Suspended Sediments
  Atmosphere              Nonpoint  Sources
  Phytoplankton            Zooplankton
  Forage Fish               Target Fish

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  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
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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
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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
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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

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             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.
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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.
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             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

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     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
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      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.


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       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.
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