&EPA
United States
Environmental Protection
Agency
Great Lakes
National Program Office
230 South Dearborn Street
Chicago, Illinois 60604
EPA-905/8-89/001
GLNPO Report 06-89
April 1989
Green Bay/Fox River
Mass Balance Study
DNR
S
*< *
b
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GREEN BAY MASS BALANCE STUDY PLAN
A STRATEGY FOR TRACKING TOXICS
IN THE BAY OF GREEN BAY, LAKE MICHIGAN
U.S. Environmental Protection Agency
Great Lakes National Program Office
230 South Dearborn Street
Chicago, Illinois 60604
Working Edition
February, 1989
Approved: March 1989
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Table of Contents
Procedure for Study Modifications i
Acknowledgments iii
List of Figures vi
List of Tables vii
Introduction 1
Study Plan Organization 8
Model Components and Work Element Descriptions .... 9
I. Inputs 9
A. 1. Tributaries 9
A. 2. Contaminant Loading from the Fox River. . 12
A. 3. Contaminant Loading - Fox River/
DePere Dam 12
A. 4. Contaminant Loading - Fox River/Mouth . . 15
B. Point Sources 17
C. Atmosphere 18
D. Evaluation of Potential Contributions of
Target Chemicals from Selected Landfills . . 19
E. Evaluation of Potential Contribution of
Target Chemicals from Urban Areas . . . .20
F. Evaluation of Potential Contribution of
Target Chemicals from Ground Water .... 21
II. Outputs 22
A. Water Volume Transport 23
B. Sediment Flux and Resuspension 26
C. Sediment Resuspension Quantification ... 29
D. Desorbtion Kenetics, Sedimentation Rates
and Volitilization 29
III. Active Pools and Interfaces 34
A. Lower Fox River Sediments 34
B. Water Column 34
B. 1. Method Evaluation 34
B. 2. Water Column - Bay 35
IV. Biota 37
A. Food Chain Model 37
V. Quality Assurance and Data Handling 44
VI. Administration 44
VII. Study Schedule 45
Appendix A 48
Appendix B 52
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PROCEDURE FOR STUDY MODIFICATIONS
The research project described in this document has not been conducted, as
far as we know, on a geographic scale now being attempted. In no small way it
encompasses the cutting edge of several facets of research regarding the fate
of toxic substances in large aquatic ecosystems. For these reasons, the plan,
as such, must be flexible. However, the successful outcome of the study requires
a closely coordinated, multimedia and multidisciplinary effort, it is therefore
essential that individual investigators or agencies do not unilaterlaly modify
schedules or procedures. The following procedure will be followed prior to
modification of any element of the Green Bay/Fox River Mass Balance Study.
1. Proposals for study modifications will be made in writing to the Chairman
of the Technical Coordinating Committee (TCC).
2. The TCC, after consultation with the appropriate operational committees,
will make the final determination on proposals of a technical nature which do
not impact study or agency resources.
3. When resources are impacted, or modifications involve other than
technical issues, the TCC will raise the issue to the Management Committee for
resolution.
When modifications have been approved they will be incorporated into the
Study Plan.
Member: Signature:
Carol Finch
Co-chair
Lyman Wible
Co-chair
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Members of the Management Committee (Continued)
Thomas Rohrer
Anders Andren
Al Beeton
Gilman Veith
Ken Fenner
Mary Gade
Bruce Robertson
ii
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ACKNOWLEDGMENTS
This study plan has been compiled from a variety of committee reports and
investigator proposals. The sources and authors are listed below.
A. W. Andren and D. N. Edgington
University of Wisconsin-Madison and
University of Wisconsin-Milwaukee
Application of the Mass Balance Approach to Green Bay: Sediment
Loading, Fluxes and Redistribution of PCBs, Dieldrin and Other
Chlorinated Hydrocarbons, Trace Inorganics and Radionuclides.
D. S. Cherkhuer and R. W. Taylor
Department of Geological Sciences
University of Wisconsin-Milwaukee
Milwaukee, WI 53201
Groundwater Flux in Western Green Bay
J. P. Connelly and R. V. Thomann
Department of Civil Engineering
Manhattan College
Bronx, New York 10471
Project Summary. Wastox, A Framework for Modeling the Fate of
Toxic Chemicals in Aquatic Environments; Part 2: Food Chain.
B. J. Edie
NOAA/GLERL
2205 Commonwealth Blvd.
Ann Arbor, MI 48105-1593
Resuspension and Particle Settling Velocities in Green Bay
J. C. Filkins
LLRS-USEPA
9311 Groh Road
Grosse He, MI 24138
Water Column Station Locations
W. A. Gebert
uses
6417 Normandy Lane
Madison, WI 53719-1133
Prestudy for Green Bay Mass Balance Study
D. F. Gatz and C. W. Sweet
Illinois State Water Survey
Atmospheric Chemistry Section
2204 Griffith Drive
Champaign, IL 61820-7495
Operation of a Master Atmospheric Deposition Measurement Site
at Green Bay
iii
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N. Hawley and B. Lesht
NOAA/GLERL
2205 Commonwealth Blvd.
Ann Arbor, MI 48105-1593
Measurement of Horizontal Sediment Flux and Sediment Resuspension
P. E. Hughes
USGS, Water Resources Division
6417 Normandy Lane
Madison, WI 53719-1133
USGS Field Operation Plan: Fox River at the Mouth and
Tributary Monitoring Green Bay/Fox River Mass Balance Study
J. G. Konrad
Wisconsin Department of Natural Resources
Madison, WI
WDNR Project Scope
R. G. Kreis
LLRS-USEPA
9311 Groh Road
Grosse He, MI 24138
Green Bay Biological Studies
B. M. Lesht
Atmospheric Physics Program,
Center for Environmental Research
Argonne National Laboratory
Argonne, IL 60439
Nonparametric Evaluation of the Size of the Limnological Sampling
Networks: Application to the Design of a Survey of Green Bay
W. J. Lick
University of California-Santa Barbra
Santa Barbra, CA
Sediment Resuspension Quantification
J. L. Martin
USEPA/LLRS
9311 Groh Road
Grosse He, MI 24138
Application of Food Chain Model (Wastox: Part II) to Green Bay Lake
Michigan: Screening and Sensitivity Analysis of PCBs in Lake Trout
T. J. Murphy
Chemistry Department, DePaul University
25 E. Jackson Blvd.
Chicago, Illinois 60604
Operation of Master Atmospheric Deposition Measurement
Site at Green Bay
IV
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W. L. Richardson (Chairman)
Green Bay Modeling Committee
LLRS/USEPA
9311 Groh Road
Grosse He, MI 24138
Modeling Toxic Substances in Green Bay
J. H. Saylor and G. S. Miller
NOAA/GLERL
2205 Commonwealth Blvd.
Ann Arbor, MI 48105-1593 - -
Water Volume Transport Measurements in Southern Green Bay
D. L. Swackhamer and S. J. Eisenreich
University of Minnesota, School of Public Health
Box 1970, Mayo
420 Delaware Street SE
Minneapolis, MN 55458
Intercomparison of Methodology for the Measurement of PCBs
in Particulate and Dissolved Phases in Green Bay
T. C. Young
Department of Civil and Environmental Engineering
Clarkson University
Potsdam, NY 13676
Analysis of Green Bay Tributary Sampling Scenarios: The Fox River
v
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List of Figures
Page
1. Graphic mass balance model showing pathways and
fates of toxic substances in an aquatic ecosystem. 2
2. Map of Green Bay showing relation to Lake Michigan
and other Great Lakes. 3
3. Water Sampling Stations in lower Fox River 14
4. Winter mooring locations for current meters. 24
5. Mooring locations for current meters during the
stratified season. 25
6. Transmisivity monitoring stations. 27
7.a & b. Sediment sampling stations to determine 32-33
sediment profiles and mass of PCBs in the whole bay.
8. Location of bay stations for water column sampling. 36
9. Morphometric zones in Green Bay to be used for
sampling biota. 38
10. Green Bay Mass Balance Study Plan Organization Chart 46
Frontpiece on title page by Nicole Yarborough
VI
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List of Tables
Page
1. Variables to be measured in a particular medium and
model compartment 11
2. Summary of Green Bay biota samples and variables to
be measured 40
3. Summary of Green Bay biota samples for food chain
modeling 43
4. Schedule of Activities for the Green Bay/Fox River
Mass Balance Study 47
vii
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INTRODUCTION
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 informal prioritization and allocation of research, remedial actions
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 balance budget has been established for each pollutant of
concern, the long-term effects on water quality of the lakes can be simulated by
mathematical modeling.
Mass balance modeling has been successfully applied to the regulation of
nutrient loads in the Great Lakes during the past decade. However, the sources,
pathways, and sinks for organic and inorganic toxic substances (toxics) are less
well understood. It is, therefore, necessary to pilot the mass balance approach
for toxics in a smaller ecosystem prior to expansion to whole lake situations.
Toxicants of interest include PCBs (at the congener level), dieldrin, lead, and
cadmium as representatives of classes of compounds. The physical/chemical models
will be coupled with a food chain model to allow estimation of body burdens (Figure
1). The integrated model will then be used to predict concentrations in the water,
sediment, and biota in response to differing regulatory and remedial action
scenarios. The predictions will include long-term extrapolation from the
short-term calibration.
The bay of Green Bay, Lake Michigan, will serve as the study site. Green Bay
can be characterized as a long, relatively shallow extension of northwestern Lake
Michigan (Figure 2). The Green Bay watershed drains .land surfaces in both
Wisconsin and Michigan, and contains about one-third of the total Lake Michigan
drainage basin. The lower bay and Fox River have been recognized as a polluted
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Atmosphere
o
'l_
'»» '.--^:
• V.'r- >••-•-•
•Adsorption-
• Desorptior
•» •
Particulate
Toxicant
•Burial... •. .1.
1 . Graphic Mass Balance model showing
pathways and fates of toxic substances
in an aquatic ecosystem.
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88'
87°30'
87°
96°30
46-
GREEN BAY
SCALE
10 5 0
30'
45"—
30
Figure 2. Map of Green Bay showing
relation to Lake Michigan
and other Great Lakes
38°
37*30
37°
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water system. The Fox River Valley is heavily industrialized and contains the
largest concentration of pulp and paper industries in the world.
The hydrodynamics of the bay are generally controlled by rotational, wind,
and barometric forces. Currents tend to be counterclockwise with two main gyres
in the upper and lower bay. Currents are heavily influenced by seiche activity,
particularly in its southern portion. Central and northern portions of the bay
are known to stratify.
Presently the bay ranges from hypereutrophic in the southern portion to
mesotrophic-oligotrophic near the Lake Michigan interface. The extreme
productivity in the southern basin results in deposition of organic material and
associated hypolimnetic oxygen depletion in the central bay.
Toxic organic materials in the water, sediment, and biota of Green Bay has
adversely impacted both utilization and management of the Bay's fishery. The
commercial fisheries in the Bay, with the exception of yellow perch, are severely
restricted by PCB contamination, and consumption advisories have been issued to
anglers for most sport species. Due to exceedingly high PCB levels in all sizes,
the commercial carp fishery has been closed by WDNR for the past 5 years. Fish
eating birds have experienced reproductive failure and increased deformities
apparently related to PCB contamination. The Fox River is estimated to contribute
600-1200 Kg of PCBs annually to the bay. Sediment contributions of PCBs to the
water column within the bay are presently unknown.
The Green Bay Mass Balance Study (GBMBS) is intended to provide information
to aid and support regulatory activities. However, its major goal is to (1) carry
out a detailed mass balance of Great Lakes toxic substances, notably individual PCB
compounds or congeners in Green Bay, and (2) based on the mass balance data, apply
predictive tools that will aid resource managers evaluate the impact of management
decisions. The GBMBS will serve as a pilot for future modeling studies of Great
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Lakes ecosystems. The Green Bay Project will engage numerous investigators
involved in project design, field collection, analysis and processing of data,
quality assurance, data management and modeling activities. The project will be
coordinated by the USEPA Great Lakes National Program Office (GLNPO), Chicago,
Illinois. Modeling activities will be facilitated by the USEPA Large Lakes
Research Station.
The Green Bay Mass Balance Study Plan (GBMBSP) is intended primarily as a
communication device to link the activities of the standing technical committees
ie. Field and Technical Operations Committee (FTO), Modeling Committee (MOD), Field
and Analytical Methods Committee (FAM), and the Biological Committee (BC) to the
required actions of the Technical Coordination Committee and ultimately to the
Management Committee. It will serve to both guide the direction of the entire
research effort and also to monitor the progress of the various "study components"
and their attendent "work elements." The basis for the study plan eminates from
past research efforts, the original Green Bay Mass Balance Work Plan (October,
1986), activities and reports of the Technical Committees since that time, project
proposals from various agencies for particular work elements and several planning
workshops.
The study plan has been organized to help insure that the data and information
necessary to construct a mass balance for PCBs, dieledrin, cadmium, and lead
(hereafter referred to as target chemicals) in Green Bay become available for model
development in an orderly fashion. Essentially, the study plan is a design to
gather the data needed to construct and drive the mass balance model.
Risk Assessment and Mass Balance Models
Ultimately, toxic substances are evaluated in terms of the risk posed to
humans or other living organisms. The hazard posed to a natural water system by
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a toxic chemical is governed by the uptake of the chemical by the resident biota
and subsequent acute and chronic health effects. Evaluation of the risk involves
three basic steps:
1) estimation of the chemical concentrations in the water and sediment
2) estimation of the rate of uptake of chemical by segments of the
resident biota
3) estimation of the toxicity resulting from uptake of the chemical
The GBMBSP considers only the first two steps of this risk assessment process,
the third step goes beyond the bounds of the project. Execution of the first two
steps requires consideration of the transport, transfer, and reaction of the
chemical and the dependence of these processes on properties of the affected
natural water system and its biota (Figure 1) . Based on experimentation and
theoretical development each process has been, or can be, described mathematically,
specifying its functional dependence on specific properties. These expressions may
be combined using the principle of conservation of mass to form a mathematical
model that addresses one of the steps in the risk assessment.
Steps 1 and 2 of this risk assessment are addressed by the general modeling
framework entitled WASPIV, an acronym for Water Quality Analysis Simulation for
TOXics. This modeling framework is composed of two parts which may be termed the
exposure concentration (physical-chemical) and food chain components, respectively.
The exposure concentration component of WASPIV is the computational structure for
applying step 1 to a specific natural water system. The food chain component of
WASPIV is the computational structure for applying step 2 to a specific natural
water system.
The physical-chemical model simulates water column response to various loading
scenarios. The physical-chemical model is then coupled with a food chain model,
eutrophication model and solids model to simulate biotic response to different
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toxic loading scenarios. The biological end points chosen for Green Bay are tissue
residues in various size classes of three fish species: walley, brown trout, and
common carp. From simulations, the optimal strategy for remediation may be
determined. Expected biological end points will be predicted target chemical
concentrations found in the three species of fish.
Substantial "front end" planning has gone into the Green Bay Mass Balance.
Reconnaisance level modeling has been conducted to evaluate and rank the impact of
the various state variables and coefficients on model output. Surogate parameters
have been used to model and optimize tributary load monitoring as well as
collection frequency and station location in Green Bay proper. Additional studies
have been undertaken to identify those tributaries requiring load monitoring and
to delineate the forage base for the target species. The original goal of the
Green Bay Mass Balance was to predict concentrations of PCB, dieldrin, Pb and Cd
in walleye, brown trout and carp to within one half order of magnitude in order to
make the model useful in management decisions. It is estimated that this level of
accuracy (or better) will be achieved if major loading sources and compartments are
monitored within + 20-30% of the mean values. The tributary, atmospheric and open
bay portions of this plan are designed to meet this + 20-30% criteria.
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STUDY PLAN ORGANIZATION
The GBMBSP is partitioned into six major divisions, each reflecting particular
requirements to develop the mass balance model. These divisions are:
I. Inputs
II. Outputs
III. Active Pools and Interfaces
IV. Biota
V. Quality Assurance and Data Handling
VI. Administration
Divisions are further subdivided into particular "study components" eg.
Tributary loading, point source loading, atmospheric loading, etc. Each study
component is made up of particular "work elements" necessary to satisfy model
development and operation.
The format of the study plan consists of an abreviated narrative for each
study component addressing:
-- sampling design, experimental procedures or information gathering
activities
-- responsible agency or individual to conduct study
- - funding source
Details of individual work elements for particular study components will be
contained in separate appendices and will be used as the basis of quality control
and quality assurance review and will ultimately direct the field efforts. The
GBMBSP is of necessity a dynamic plan since particular work elements will be phased
in and out over a period of years, thus changing the action and progress status of
these work elements. In order to keep all parties informed about the current
status of particular work elements, a flow sheet containing all pertinent
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information will be updated and circulated to all interested parties every two
months. A narrative summary noting changes will accompany the flow sheet.
MODEL COMPONENTS AND WORK ELEMENT DESCRIPTIONS
I. INPUTS
Previous studies indicate that the Fox River contributes over 80 percent of
the total PCB tributary load to Green Bay. Other tributaries known to contribute
PCBs include the Oconto, Peshtigo, Menominee and Escanaba Rivers. Tributaries have
not recently been sampled for dieldrin or other target toxicants. Consequently,
a reconnaissance survey was conducted to identify those tributaries for which load
monitoring will be required. Sampling was conducted by the U.S. Geological Survey
starting in July, 1987, on the following tributaries to Green Bay: Duck Creek,
Suamico River, Ford River, Days River, Rapid River, Whitefish River, Wilson River,
and Fishdam River. The Oconto, Peshtigo, Menominee and Escanaba Rivers were not
sampled because they have already been determined to be sources of PCBs and will
require monitoring. Separate sampling was done for dieldrin on Egg Harbor
tributary, Keger Creek, and the Red Riverbecause a likely source of dieldrin may
be from orchard areas surrounding these streams.
Based on the findings of the reconnaissance survey, the Menominee, Escanaba,
Oconto, Peshtigo, and Fox River, (Figure 2) will be monitored to determine loading
of target chemicals into Green Bay.
A. 1. Tributaries
Sampling frequencies for different rivers varies according to volume flows
and the delivery of suspended solids. The Peshtigo, Oconto and Escanaba Rivers
will be sampled once monthly. Duplicate samples will be collected on six trips.
The Menominee River will be sampled thirty-four (34) times during the open water
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period and four (4) times during the winter. A total of 16 duplicate sampales will
be taken.
Water and suspended sediments will be sampled with a high-capacity submersible
pump. The samples will be integrated over depth and cross-section. For PCB
analysis, samples will be filtered (glass fiber filter) and extracted at the sample
site. Extracts from prefliters and filters will be combined to produce one com-
posite particulate extract per sample. Dissolved phase organics will be extracted
using XAD-2 resin columns. PCB analyses will identify specific congeners as well
as quantify particulate and dissolved fractions. In addition to the other target
chemicals, water samples will be analyzed for several variables (see Table 1).
Daily suspended sediment loads will be determined for each tributary using
continuous discharge data and daily or weekly suspended sediment samples. Daily
samples will be collected by automated sampler on the Peshtigo, Menominee and
Escanaba Rivers, while weekly or daily high-flow samples will be collected by a
local observer at the Oconto River.
Investigating Agency - USGS
Funding Source - GLNPO/USGS
Contact person: Peter Hughs 608-276-3833
10
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TABLE 1. VARIABLES TO BE MEASURED IN A PARTICULAR MEDIUM AND MODEL COMPARTMENT
Variable /Medium
Diss. PCB Conge
Part. PCB Conge
Total PCB Conge
Diss. Dieldrin
Part. Dieldrin
Total Dieldrin
Diss. Lead
Part. Lead
Total Lead
Diss. Cadmium
Part. Cadmium
Total Cadmium
Total Phosphorus
Sol. React. Pho
Nitrate
Ammonia
TKN
Diss. Avail. Si
Chloride
Conductivity
Temperature
Suspended Solid
Size Fractions
DOC
TOC
POC
Chlorophyll- a
Mn
Fe
Hardness
PH
Alkalinity
DO
Total Incid. Ra
Light Extinction
Porosity
Grain size
% solids
X water
Redox Pot.
Eh
River Flow
Wind Vel. Direc
Continuous Flow
Bay and
Lower Fox
X
X
s
X
X
s
X
X
s
X
X
s
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Tributary
Loads Mater
X
X
s
X
X
s
X
X
s
X
X
s
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Atmosphere
Loads Water
X
X
s
X
X
s
X
X
s
X
X
s
X
X
X
X
X
X
X
X
X
X
X
Bay and Bay and Bay and Point
Lower Fox Lower Fox Lower Fox Sources
Sediments Pore Water Biota
X XXX
X XXX
X XXX
X XXX
X
X
X
X
X
X
X X
X X
X
X
X
XX X
X
X
X
X
X
X
X X
X
Growth Rate/Age
Lipid
Stomach Contents
x
X
Carp
Legend: S = Sum of particulate and dissolved required
11
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A.2. Contaminant Loading from the Fox River
An accurate determination of the particulate and dissolved load of PCBs
transported into Green Bay by the Fox River is an essential component of the Green
Bay/Fox River Mass Balance Project. It is feasible to estimate the PCB load from
the Fox River by computing the load at the DePere Dam and adding the point source
inputs downstream in addition to nonpoint source and sediment flux estimates.
These data are then used in conjunction with the application of hydrodynamic and
water quality models to the Fox River. However, the lower reach of the Fox River
is affected by seiche and wind which results in bi-directional flow. This
hydrodynamic complexity and the wide range of possible loadings from the point
sources, nonpoint sources, and in-place sediments can result in significantly
different estimates of the contaminant load to Green Bay. Consequently, two methods
of estimating the Fox River load are proposed. Both methods involve measurement
and modeling. The first method (A.3) involves measurement of loads at the DePere
Dam and modeling of the gradients of concentrations in the Fox River and Green Bay
to determine loading. The second method (A.4) involves measurement of flows and
concentrations at the Fox River mouth and modeling of the chloride concentrations
(or other tracers) to determine which river mouth measurements represent upstream
and downstream fluxes. Comparison of the two methods of load estimation will be
used to determine which method would be more useful and practical to undertake on
a larger scale.
A.3. Contaminant Loading -- Fox Rlver/DePere Dam
This method requires an estimate of contaminant loading at the DePere Dam as
a boundary condition to drive a model for the Lower Fox River. The U.S. Geological
Survey will sample water 8.04 miles upstream of the mouth on the upstream side of
the dam 39 times during the open water season and 3 times during the winter period.
12
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The modeling effort will also use six stations in the river (Figure 3) between the
DePere Dam and the mouth to collect depth integrated water samples which will
coincide with the open bay sampling surveys.
Three stations (numbered 50 - 55) will be sampled three times (every 8 hours)
during a 24 hour period as part of the Green Bay Mass Balance October Survey.
Samoline Location:
STA.
50
51
52
53
54
55
Sampling
west
44A27
88A04
44
88
44
88
44
88
A28
A02
"30
A01
A31
Aoo
44A32
88A00
Points:
.26'
.19'
.78'
.74'
.18'
.49'
.39'
.73'
.16'
.46'
center
44A27
88A04
44
88
44
88
44
88
44
88
A28
A02
A30
A01
A31
Aoo
A31
Aoo
44A32
88A00
.23'
.08'
.76'
.62'
.17'
.45'
.10'
.45'
.38'
.72'
.13'
.44'
east
44A27
88A04
44A28
88A02
44A
88A
44A
88A
44A
88A
30
01
31
00
32
00
.20
.06
.72
.50
.18
.40
.36
.65
.13
.40
t
t
9
t
1
t
t
t
t
t
Station 53 located on the East River will be sampled at a single point,
mid-channel, mid-depth. The remaining five stations will be sampled from
mid-depth at three points along a transect perpendicular to the river,
mid-channel and 1/3 the channel width on each side.
Compositing:
Equal volumes of water will be collected from each of the 3 sampling
sites along the transect to provide a composite volume sufficient for the
measurement of the parameters described in Table 1 of the variables to be
measured.
13
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14
Figure 3. Water Sampling Stations
in lower Fox River.
Lower Fox River
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Filtered Water Collection:
Station 53 will be sampled 3 times during the 24 hour period. At each
of the 3 samplings 18 Liters of river water will be pumped through 2 Whatman
GF/F filters (293 mm) and the filtered water collected in a glass carboy.
Upon return to the R/V Simons the 18 Liters of filtered water will be pumped
through an XAD resin column extracting the organic compounds from the water.
The same XAD column will be used to extract each of the 3 collections from
station 53. The XAD column will represent a composite organic extraction
sample for the 24 hour period. The 6 filters used during the 24 hour
collection period at station 53 will be wrapped in foil, labeled and placed
in a plastic zip-lock bag and frozen.
At each of the remaining 5 stations 6 Liters of river water will be filtered
at each of the 3 sampling points along the station transect and the filtered water
composited in a glass carboy providing 18 Liters of filtered water. The 18 Liters
of filtered water and 2 filters shall be treated as described for station 53.
Net tows as described in the biological work plan shall be collected once
during the 24 hour period at stations 50, 51, 52, 54 and 55.
It will also be necessary to estimate the flux of contaminants from the
sediments. Surficial contaminant concentrations will be measured at 25-30 stations
in the lower river and fluxes estimated at three stations 3 times during the field
season. Fluxes will be estimated at those stations having the highest contaminant
concentrations. Estimates of point sources and urban non-point sources will be
required (see I.E., D., E., and F.).
A.4. Contaminant loading -- Fox River/Mouth
Transport of contaminants (target chemicals) from the Fox River to Green Bay
will be determined for the period March 1989 to February 1990. The field
15
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water-quality sampling site for this element is at the mouth of the Fox River and
is downstream of all but one point source discharger (GBMSD). Continuous
streamflow data will be available from the USGS Acoustic Velocity Meter (AVM)
gaging station located 0.75 miles upstream from the mouth.
For the purpose of contaminant load estimates, routine water samples will be
collected on 36 days (33 open water and 3 winter) at the mouth of the Fox River.
A total of 86 replicate samples will be taken. Intensive sampling events will also
occur at the mouth with the following frequency:
Spring High Flow - 14 days, 2 samples/day
Summer Low Flow - 14 days, 2 samples/day
Fall Medium Flow - 14 days, 2 samples/day
In addition, automated pump samplers will be installed at the mouth to collect
a minimum of three samples per day at two depths (0.2 and 0.8 times the normal
total depth). Samples will be analyzed for total and volatile suspended solids and
chloride. The solids data will be used to compute the suspended sediment load
transported by the Fox River into Green Bay. The solids concentrations will also
be statistically evaluated to determine their relationship to PCB concentrations.
Chloride data will be used to track migration of water from Green Bay into the Fox
River estuary during periods of flow reversal. Continuous monitoring for dissolved
oxygen, temperature, conductivity and pH will be done at 0.2 and 0.8 times the
total depth.
The field sampling and organic extraction procedure will be the same as those
used for tributary sampling. The channel section at the mouth will be divided into
a minimum of three approximately equal flow cells with the cell centroids
identified on a field map or by Loran-C coordinates. At each of the cell
centroids, water samples, dissolved oxygen, pH, conductivity, temperature, velocity
and flow directions will be obtained at 0.2 and 0.8 times the total depth.
16
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Investigating Agency - USGS/GLNPO/WDNR
Funding Source - USGS/GLNPO
Contact Person - Peter Hughes (608-276-3833)
B. Point Sources
The potential exists for all paper mills and some municipalities to discharge
PCBs. The discharge of PCBs from point sources to the Fox River has primarily been
attributed to paper mills recycling wastepaper. There are seven major point
sources between the DePere Dam and the mouth of the Fox River. An additional 2
dischargers are located above the monitoring station on other tributaries. These
nine point source dischargers will be monitored to determine the PCB loads. Seven
dischargers will be monitored quarterly and two will be monitored monthly. Both
influent and effluent samples will be obtained so that net loading can be
determined.
Samples will be taken by the individual dischargers and will be 24-hour
composites. Dischargers will be directed to collect the samples to coincide with
river surveys when possible and also to provide continuous discharge flow
measurements. Samples will be iced and shipped to the Wisconsin State Laboratory
of Hygiene for analyses. Total sample size will be 1-4 liters. It is anticipated
that this sample size will provide levels of detection of about 2-12 ng/L for
individual PCB congeners. PCB analysis will be done on the particulate and
dissolved fraction. Analysis will also be conducted for the other target
contaminants.
Investigating Agency - WDNR
Funding Source - WDNR/GLNPO
Contact Person - John Konrad (608-267-7480)
17
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C. Atomosphere
Three atmospheric sampling stations will be used to quantitate target
chemical loads to Green Bay. These will include a Master Station comprised of
three wet precipitation collectors with XAD-2 columns, two directionally operated
high volume dry air samplers with absorbent columns to quantify vapor and
particulate phase PCBs as well as other target chemicals. Additional "Master
Station" equipment will also include a high volume collector dedicated to total
suspended particulate and organic carbon, two cascade impactors and a meterological
tower providing hourly data on wind speed, direction, humidity, temperature,
precipitation, and solar radiation. Organic samples will be taken every 6 days for
dry deposition and every 2 weeks plus events for precipitation (see Table 1 for
other variables to be measured) . The Master Station will be located on the
University of Wisconsin-Green Bay campus approximately one-half mile inland on the
east bay shore.
Routine monitoring stations will also be located at Fayette State Park in
Upper Michigan and Peninsula State Park in Door County, Wisconsin. Each will
provide trace organics from precipitation on a two week basis. In addition,
routine sites include two wind directionally operated high volume samplers with
XAD-2 resin cartridges for collection of trace organics in ambiant air every sixth
day for a twenty-four (24) hour period.
Investigating Agency-Illinois State Water Survey,
DePaul University and USEPA
Funding Source - GLNPO
Contact Person - Edward Klappenbach (312-353-1378)
18
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D. Evaluation of Potential Contribution of PCBs from Selected Landfills
Numerous waste disposal sites are located in the Lower Fox River and Green
Bay watersheds. Present day regulations require the selection of environmentally
compatible sites and use of engineering controls such as impermeable clay liners
and leachate collection systems. Earlier landfills did not benefit from such
planning. Most of these early sites were inappropriate for waste disposal. The
Wisconsin Department of Natural Resources (WDNR) has inventoried the landfill and
waste disposal sites within the Green Bay/Fox River mass balance study area. There
are 16 abandoned landfills within this area. Several of the sites have monitoring
wells installed, although in most cases the number of wells is insufficient to
adquately evaluate the site.
There are three sites along the Fox River below the DePere Dam and along lower
Green Bay which have monitoring wells. Samples will be collected from these wells
and analyzed for PCBs, dieldrin, lead and cadmium. Approximately 6 monitoring
wells exist at each site. During 1988-89, a total of 30 samples will be obtained.
Some wells will be sampled once. Others will be sampled more often, since wells
which are definitely not appropriate will not be sampled.
A separate research project has been developed to design a monitoring and
evaluation protocol for waste disposal areas which do not currently have monitoring
wells. This proposal is being considered for inclusion in WDNR's 1989-91 budget
request. If funded, this project would develop methodology which would be applied
to further monitoring and evaluation of landfill sites in the Lower Fox River and
Green Bay area.
Investigating Agency - WDNR
Funding Source - WDNR
Contact Person - John Konrad (608-267-7480)
19
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E. Evaluation of Potential Contribution of PCBs from Urban Areas
Estimates of PCB, dieldrin, cadmium and lead loading from the Green Bay
Metropolitan Area will be done in two phases. The first phase will be a unit area
load calculation based on existing data applied to the land use types found in
Green Bay. A large data base exists for cadmium and lead in urban nonpoint source
runoff. Unit area load calculations should provide accurate loading estimates for
these parameters. Less information is available for PCB and dieldrin.
With respect to dieldrin, a unit area load calculation will not be performed.
In urban nonpoint source studies, dieldrin is seldom detected and when detected its
source is residential areas. Since dieldrin is banned as a pesticide and has not
been detected to date in pre-surveys, it will be assumed that urban areas are not
significant sources of dieldrin to the lower Fox River and to Green Bay.
PCB concentrations in urban stormwater runoff have been determined in several
studies. The results obtained from the Nationwide Urban Runoff Program have been
applied to the Green Bay area. PCB concentration in all but one out of 120 samples
collected in commercial and residential areas in Milwaukee and other cities were
below detection limits (0.021 to 0.50 ug/1). Because of these very low levels of
PCB associated with commercial and residential areas, unit area loads for these
land uses were not calculated. In industrial areas in Milwaukee, eight out of nine
samples collected exceeded PCB detection levels (0.021 to 0.05 ug/1). The highest
concentration was 7.9 ug/1 with an average of 2 ug/1. These results indicate that
industrial areas can be a significant source of PCBs.
The estimated annual nonpoint source PCB loading from industrial areas in
Green Bay is 12 kilograms assuming the average concentration of 2 ug/1 and 47
kilograms assuming the highest concentration (7.9 ug/1). The annual load of PCBs
from the Fox River has been estimated at 600 to 1200 kilograms. The PCB loading
from industrial areas in the City of Green Bay could account for 1 to 9 percent of
20
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the annual load. These relatively low PCB loadings suggest that intensive
monitoring is not warranted.
The second phase of the Nonpoint Source Element will be to inventory the
existing industrial areas to determine similarities and differences from the areas
monitored in Milwaukee. This inventory will document possible wet and dry weather
sources of PCBs. For example, electrical transformers stored in an industrial yard
are a potential wet weather source of PCBs and the heavy use of hydraulic fluid
inside a plant is a potential source of dry weather PCBs. The survey will also
delineate the subbasins the industries are in. The survey results will be used to
determine the potential for PCBs from industrial sources. Residues from selected
stormsewers will be analyzed for PCBs. These samples will be of sludge and/or
scrapings from the wall of the stormsewers. The results of the industrial survey
and the stormsewer residues will be used to determine if additional monitoring of
urban stormwaters is necessary. All analyses will be for specific PCB congeners.
Investigating Agency - WDNR
Funding Agency - WDNR
Contact Person - John Konrad (608-267-7489)
F. Evaluation of Potential Ground Water Contributions
Existing information is currently being evaluated to summarize what is known
about the groundwater flow system between the surrounding aquifers and the Bay.
Special emphasis is placed on describing the shallow flow systems, since these will
likely carry most of the pollutant load. This existing information has been
supplemented with additional monitoring data and is being used to calibrate a
groundwater flow model developed under the auspices of UW Sea Grant Institute.
Once calibrated, this model will be applied to Door County and used to predict
21
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contaminant loading to the Bay and the importance of these loadings as an input to
the mass balance.
Groundwater and soil monitoring for PCBs, dieldrin, cadmium and lead was
initiated during the spring of 1988. This monitoring will be continued during
1988-89. The additional samples will fill in where current efforts have identified
data needs. These are areas of known contamination from lead and based on use
patterns, areas of possible dieldrin contamination. New sample sites will be
selected to. define the area of Door County that could be contributing lead or
dieldrin to the Bay. Additional sample sites for PCBs and cadmium will be targeted
at suspected locations since documented contamination sites are not available.
Suspected locations could include spill sites, old material handling locations, or
waste disposal sites thought to contain cadmium or PCBs.
Investigating Agency - WDNR
Funding Source - WDNR
Contact Person - John Konrad (608-267-7489)
II. OUTPUTS
Contaminants in Green Bay can leave via a water route dissolved in the water
or as suspended particles through the passages north of the tip of Door County.
Biotic transport, although possible, has been evaluated as insignificant. Some may
also leave by way of volitilization into the atmosphere or conversely by permanent
burial in the sediments of Green Bay. To understand the true fate of contaminants
in Green Bay, all routes must be monitored to establish the flux rates across the
compartments of interest. Projects will be conducted to establish:
1) Water volume transport from the bay
2) Horizontal sediment flux and sediment resuspension
3) Particle settling velocities, and
22
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4) Desorption kinetics, sedimentation rates, and
volitilization
Three separate projects have been developed to address these modeling
requirements. Two of these projects will be conducted by investigators from the
Great Lakes Environmentnal Research Laboratory/National Oceanic and Atmospheric
Administration (NOAA).
A. Water Volume Transport
The water exchange processes with Lake Michigan are very complex with, on the
average, intense outflows of bay waters in the surface layers and inflows of Lake
Michigan water penetrating deep into Green Bay in the near-bottom layers. The
inflowing Lake Michigan waters can be identified flowing southward west of Chambers
Island, causing accelerated flushing of the lower bay. Measuring water volume
exchanges between the lower and upper bays with enough accuracy for use in the mass
balance approach will require current velocity recordings in the channels on both
sides of Chambers Island. Winter moorings (17 current meters total) will be
installed at eight locations in September 1988 and retrieved in April 1989 (Figure
4) . It is expected that after an energetic fall season of circulation in an
unstratified water mass, currents under the ice will be driven mainly by the lunar
tide and seiches interacting with northern Lake Michigan.
Moorings at sixteen locations and employing 37 meters total for the
stratified season will be installed during May 1989 and retrieved during October
1989 (Figure 5). To extend the velocity profiles through the entire water column
acoustic doppler current meters will be placed on the bay floor in the channels on
both sides of Chambers Island. Measurements of flow in the surface layers of the
water column are critical to the goal of computing water volume transports. Four
thermistor chains placed at strategic locations will be used to measure water
23
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87*
86'30
GREEN BAY
SCALE
10 5 Q
C
Figure 4. Winter mooring locations for
current meters.
-------
GREEN BAY
Martin Is Passage
St Martin Is
T
•Porte des Morts
,83 Passage
Figure 5. Mooring locations for
current meters during
stratified season.
-------
temperature variations and thermocline depth.
Flow trajectories in the lower bay during varying surface wind stresses will
be studied during a two-week long interval in June 1989 using combinations of
satellite-tracked surface drifters and drogues, as well as a satellite
transmitting meteorological station GLERL will install for the duration of these
measurements. These measurements will establish a time history of the water volume
exchange quantities between the upper and lower parts of Green Bay at Chambers
Island. The volume fluxes will establish boundary conditions for improved
hydrodynamics modeling and are necessary for the contaminant mass balance.
Investigating Agency - Great Lakes Environmental
Research Lab (GLERL-NOAA)
Funding Agency - GLERL/GLENPO
Contact Person - J. H. Saylor (312-668-2118)
B. Sediment Flux and Restispension
To measure horizontal sediment flux in and out of Green Bay and the amount of
sediment resuspension, instrument packages will be deployed at several locations
in the bay. Instruments that measure current velocity approximately one meter above
the bottom, and water temperature, transparency, and conductivity one and five
meters above the bottom and five meters below the surface will be deployed at five
sites in Green Bay: Stations 40, 41, 43, 44, and 46 (Figure 6). Stations 40, 41,
and 42 will be deployed beginning in May 1989, and will be maintained until May
1991 with the exception of station 40, which will be reviewed during the winter;
the other stations will be deployed as soon as the necessary instruments are
available (this is dependent on receipt of funding by GLERL and cannot be further
specified at this time). The stations will be maintained at these locations until
October, 1990 with the exception of station 40, which will be removed during the
winter. All stations will be serviced monthly, except during the winter. Monthly
26
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88'
87 30'
87'
86*30'
GREEN BAY
BAY DE NOG
SCALE
10 5 Q
Gladstone
I
LITTLE BAY DE NOC
Summer Is
Martin Is Passage
Martin Is
5
30
Figure 6. Transmisivity monitoring
stations.
I
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servicing will include retrieval of data, cleaning the transparency meters, and
changing the power supplies.
A bottom-resting flume will also be deployed at selected sites to
experimentally determine the bottom current necessary for sediment resuspension
for various types of sediment (characterized by grain size distribution).
The time series data will be analyzed to determine an empirical criterion for
sediment resuspension, and be combined with the water volume fluxes (GLERL Project
II.A.) to calculate a time series of the horizontal mass flux of suspended
material. All analyses will be in terms of measured velocities. The conductivity
measurements will be used to identify the path of water coming from the Fox River.
The transparency meters will be calibrated by comparing the measurements to
direct measurements of total suspended material (TSM) made by filtering known
volumes of water through pre-weighed glass fiber filters. The decreased response
of the meters due to material growing on the lenses during the summer will be
monitored by making weekly profiles of water transparency using a clean meter at
each of the deployment sites between May and October. These profiles, which will
also measure temperature and conductivity, will also provide data on the vertical
structure of these properties. These measurements will be used to develop a set
of empirical equations relating sediment resuspension to current velocity for
various bottom types (as defined by grain size) and an equation for the horizontal
flux in and out of the bay.
Investigating Agency - NOAA
Funding Agency - GLNPO/NOAA-GLERL
Contact Person - Nathan Hawley (GLERL) (313-668-2273)
28
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C. Sediment Resuspension Quantification
The above field measurements will be conducted by a battery of experiments
designed to understand and characterize the physical and chemical processes
affecting particle resuspension and the subsequent dynamics of particle size
distribution and floe morphology of the resuspended material. The objective is a
quantitative understanding of sediment resuspension as a function of sediment
characteristics and bottom shear stress. This will involve vicometer experiments,
settling studies, annular flume experiments and field resuspension experiments.
The intent is to provide a synthesis of experimental results and field measurements
into a mathematical framework that can predict the spatial and temporal
distribution of solids and contaminants (solid and dissolved phases) that result
from a resuspension event.
Investigating Agencies - GLERL.
University of California Santa Barbra
Funding Agency - GLNPO
Contact Persons - Wilbert Lick (805-961-4295)
D. Desorbtion Kinetics. Sedimentation Rates and Volitilization.
The total mass of contaminants in the sediments and water column influence
the rates of contaminant exchange between the sediment, water and air. Most of
the mass of pollutants such as PCBs, dieldrin, Pb and Cd reside in the sediments
of the Green Bay ecosystem. The concentration of pollutants in the sediments will
exert a dominant effect on the concentrations in other compartments. Consequently,
it is necessary to:
1) Quantify the spatial distributions of PCBs, dieldrin, Pb and Cd, both
horizontally and vertically. This also includes:
a) Development of a strategy to determine the total mass of
29
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these pollutants in the Bay, and for PCBs, the mass of each
individual congener. If possible, other hydrophobic
pollutants will be included.
b) Determination of sedimentary organic carbon and particle
size distribution (sand and clay/silt fractions) to
examine the relationship between these parameters and
pollutant concentrations.
2) Determine sedimentation rates and surface mixed-layer thicknesses
throughout Green Bay using 137Cs and 210Pb geochronology.
3) Using data generated from the tasks of objective 2, calculate:
a) the mass of active sediments (i.e. sediment effectively
remaining in contact with the overlying water) in the bay
and the rate of leakage to the permanently buried sediments;
b) the mass of PCBs, both as total Aroclors and on an individual
congener basis, in the active and inactive sediment layers.
4) Evaluate diffusive fluxes of PCBs across the sediment/water interface
and the effects of changes in the partitioning of PCBs between
interstitial water and sediment on these fluxes as a result of
variations in the concentration of dissolved organic carbon.
5) Evaluate the importance of volatilization of these compounds from
the water when a mass balance is considered.
In order to meet the requirements of objectives enumerated above, a two-tiered
sediment sampling and analysis program is proposed covering two field seasons.
In the first year of the study (1988) sediment cores will be retrieved from
approximately 50 stations, chosen to provide an initial best estimate of the
spatial distribution of the mass of PCBs in the whole Bay and a first estimate of
the sediment mass balance (Objectives 1, 2, and 3). These stations will include
30
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10 from south of Long Tail Point and 5 from the extreme northern end of the Bay
where samples have not previously been taken (Figure 7a & b) . A variety of coring
devices will be used and cores obtained typically are sectioned in 1 cm intervals
down to 10 cm, in 2 cm intervals down to 30 cm and in 5 cm intervals down to the
end of the core.
While all cores will be sectioned in their entirety, and the gamma-ray spectra
of radionuclides will be measured on as many sections as are required to reach
sediments that are older than 200 years before present, it is planned that to meet
objective 1 for the mass balance 8 sections will be analyzed from each core for
base/neutral organic compounds. The numbers of individual sections to be composited
into each single sample to be analyzed for PCBs, other organics, as well as Cd and
Pb, will be determined on the basis of the observed depth of the 1952 horizon of
4137cs in each core.
In addition to providing the first estimate of the total mass of PCBs present
in the sediments and their areal and vertical homogeneity, these results will
provide the basis for the Green Bay Modeling Committee to recommend refinements to
the sediment sampling program for the second field season (summer 1990) .
Investigating Agency - UW Sea Grant Institute,
Madison/Milwaukee
Funding Agency - UW/GLNPO
Contact Person - Anders Andren (608-262-0905)
David Edgington (414-649-3008)
31
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f
88'
87*30
86*30
GREEN BAY
BIG BAY DE MOC
SCALE
10
Martin U. Passage
St. Manin !•
Figure 7a Sediment sampling stations to
determine sediment profiles
and mass of PCBs in the whole
bay.
88'
37*30
86*30
-------
33
Figure ?b- Sediment sampling stations to determine
sediment profiles and mass of PCBs in the
whole bay.
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III. ACTIVE POOLS AND INTERFACES
A. Lower Fox River Sediments
The sediments below the DePere Dam are known to be contaminated with PCBs.
Suspension and subsequent transport of these contaminated sediments could result
in significant PCB loading to Green Bay. The soft sediments in this portion of
the river will be characterized based on core samples. Approximately 36 cores will
be obtained using a private contractor. Each core will be divided into four
sections. Particle size, % solids, total organic carbon and total PCBs will be
determined on all samples ; lead, Cd and Dieldrin concentrations will be
determined. Specific congener PCB analyses will be conducted on 10% of the core
samples. The results of this activity will provide needed information to link the
Fox River PCB transport model with the model developed for Green Bay.
Investigating Agency - WDNR
Funding Source - WDNR
Contact Person - John Konrad
B. Water Column
B. 1. Method Evaluation
Measuring minute quantities of PCBs in natural water bodies presents some
formidable problems. The best method to separate particulate and dissolved phases
of PCBs has heretofore not been well defined. Consequently, research to evaluate
two methods of particulate PCB isolation, including continuous flow centrifugation
and high volume flow filtration was undertaken. Investigators evaluated three
methods of isolating dissolved phase PCBs (high volume liquid-liquid extraction,
batch extraction, and XAD column extraction), both in combination with
centrifugation or filtration so that the best combination of dissolved /
particulate separation methods could be determined.
34
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This work was conducted in November 1987 in preparation for the 1988 field
testing. It was determined that while high volume liquid to liquid extraction
holds substantial promise, it currently is not develped to the extent necessary
for this study. Dissolved phase organics will therefore be determined by
extraction on XAD-2 resin.
B. 2. Water Column - Bay
In general, water and suspended sediments will be collected on each of five
surveys per year during the 1989 navigable season. If possible, a winter (under
ice cover) survey will also be conducted in the winter of 1989-1990. The frequency
of frontal passage (3-4 days), the large number of sampling stations twenty-seven
(27), and requirements for synoptic surveys (6 days or less) will require the use
of a vessel capable of operating 24 hours a day for periods of up to one week.
Twenty-seven (27) stations (Figure 8) were selected for monitoring
contaminants and conventional variables in the water columns.
Approximate survey schedule for 1989 will be (to be modified based on
phytoplankton and thermal events):
1. February 15 (under ice) 4. June 26
2. April 15 5. August 14
3. May 15* 6. October 16
* May be modified depending on "ice out" date.
Parameters to be measured at each station are found in Table 1.
At each of the 27 stations lake water is pumped on board through polyethylene
pipe or tubing of approximately one inch diameter by use of a submersible
centrifugal pump. A portion of this water is filtered through a 293 mm diameter
glass fiber filter to collect a suspended solids sample of about 50 mg. The
filtrate from this filtration is collected in a suitable storage container (glass,
35
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GREEN BAY
Martin Is Passage
Si Martin Is
• Rock Is Passage
j^Rock Is
GREEN
BAY
Figure 8. Location of bay stations for
water column sampling.
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stainless steel, or Teflon) for extraction with XAD resin columns. A mid-depth
sample is taken from non-stratified water columns, and mid-hypolimnion and
mid-epilimnion samples are collected from stratified water columns. The samples
are filtered while at the sampling location. The filtrate is subjected to the
extraction while enroute to the next sampling location. The collected sediment on
the filter is retained in a glass jar with Teflon lined closure.
IV. BIOTA
A. Food Chain Model
General biological study components to meet modeling requirements will
include: contaminant body burden determinations of primary fish species and their
respective supporting food chains, phytoplankton species composition and abundance
estimates, chlorophyll a measurements, and bioenergetic characters for biotic
components.
Six major morphometric zones (Figure 9) have been identified for the study
which exhibit and correspond to physical/chemical/biological gradients in the Bay;
these include eutrophication, chemical contaminant, forage, and habitat gradients.
Besides the gradient factors, zonation has been based on distribution of fish
populations, availability of fish, and the number of samples which could be
reasonably collected and analyzed during this study.
Biota will be sampled three times during the navigational period and represent
three general seasons: April--June 20th, June 21--September 20, and September 21-
-November. Walleye, brown trout, and carp have been chosen as the target species
for the Green Bay study. These species meet most or all of the criteria for target
species selection. The study of these species and their respective, supporting
food chains will be the primary biological effort in the Green Bay study.
37
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38
45-3*
I
•7-30-
Seal* In km
I I I I I I I
0 10 20 30
Contours in meters *.:,
Green Bay
~ljt
•raw;
Figure 9. Morphometric zones in Green Bay to be
used for sampling biota.
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The major biological field effort for the Green Bay study will be to collect
specimens for contaminant analyses for all biological components in food chain
models. Beyond specimen collections for body burden analyses, the weight, length,
and age (target species only, forage species to be separated by size groups) of
fish will be determined in order to calculate bioenergetic parameters for modeling
(See Table 2 for biota parameters).
Gut content analyses were conducted in 1987 to determine the species-specific
forage bases of walleye and brown trout in several areas of the Bay; these data
have been used to determine the sampling strategy for forage species. Results of
gut content analyses indicated that rainbow smelt and alewife were the primary
forage bases of walleye and brown trout and gizzard shad were a forage component
of walleye in zones I, IIA, and IIB (Figure 9). Carp gut contents will be excised
from specimens collected to represent their forage base because of the difficulty
in obtaining meaningful information on the feeding of carp. Target and forage
species will be collected from each zone during the 3 time windows outlined
previously. Multiple size classes of each species of fish will be required for
modeling and sought; however, it is recognized that not all size classes for each
species, in each zone, for each seasonal sampling period will be available and this
has been factored into the sampling scheme and number of samples to be collected.
For walleye and carp three size classes will be sampled, for brown trout two size
classes in addition to fall and spring stock specimens, for alewife and smelt two
size classes, and for gizzard shad one size class.
For target species, five replicate samples per zone per season will be
obtained for each size class. Each replicate will consist of 5 fish (5-fish
composite) and weigh a minimum of one-half pound. For the forage species, five
replicate samples per zone per season will be obtained for each size class. One
half pound of each size class will be collected and represent one sample/replicate.
39
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Table 2. SUMMARY 0? GREEN BAY BIOTA SAMPLES AND VARIABLES TO BE MEASURED
WALLEYE
WEIGHT x
LENGTH x
AGE x
LIPID X
PCS X
DIELDRIN x
Cd x
Pb x
Al
Fe
Chlorophyll
Phaeophytin
BROWN CARP SMELT ALEWIFE SHAD PHYTOPLANKTON \
XXX X X
XXX X X
X X
X X X X X X
X X X X X X
X X X X X X
X X X X X X
X X X X X X
X
X
X
X
SOOPLAN!
X
X
X
X
X
X
X
40
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For target species, each fish collected will be weighed and measured. A scale
sample or fin spine will be taken in order to age each fish. Each fish will remain
whole and will not be eviscerated. Stomach contents of carp will be excised from
partially thawed carcasses. Five stomachs from each carp composite will be
ground, homogenized, and subsampled in the same manner and quantities as the fish
tissue.
Phytoplankton and zooplankton samples for food chain modeling will be
collected from the R/V Roger R. Simons or associated support vessels. Size
fractionation and manual separation will be the two techniques used to allow
analyses of these biotic compartments. Three seasonal sampling periods will be
used for collections representing the spring, summer, and fall and will coincide
with the Green Bay Mass Balance cruises scheduled for these seasons. Seasonal
collection windows will be May-June, July-September and September-October;
phytoplankton-zooplankton sampling will not occur during all Mass Balance cruises,
only 3 designated cruises. Similarly, stations to be sampled will be the same as
for the Green Bay Mass Balance, with some exclusions.
Stations to be sampled include 23 of the 27 Green Bay Mass Balance stations
in the Bay proper plus 5 stations in the lower Fox River for a total of 28
stations; these will be collected during three cruises. Five replicate samples
(each representing 5 phytoplankton and 5 zooplankton samples) will be required from
each of the biological zones for the size fractionation technique. Phytoplankton-
zooplankton samples will be collected concurrently using a double net apparatus.
A coarse mesh net (100-130 urn), with an approximate lengthrwidth ratio of 3:1,
mounted inside a fine mesh net (10 urn), with an approximate length:width ratio of
5:1, will allow simultaneous collection of both biotic compartments from the water
column. The nets must be detachable for appropriate processing. Collection jars
will be attached to the bottom of each respective net. A flowmeter will be mounted
41
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at the mouth of the double net apparatus to measure water volume filtered.
Manual separation of phytoplankton and zooplankton in the laboratory will be
accomplished through a combination of sieving and picking when appropriate; this
necessitates preservation with formalin. Whether seiving is applicable or not, the
zooplankton will be separated from the phytoplankton using binocular scopes at a
magnification of 100-400X. After all large zooplankton are removed from a
particular aliquot (this may include Ponteporeia or other invertebrates suspended
in the water column), the remainder of the sample is added to the phytoplankton
fraction originally collected in the fine mesh net. When sufficient mass is
obtained, these phytoplankton and zooplankton fractions will be analyzed. During
the separation process, the dominant genera of phytoplankton and zooplankton will
be recorded.
A summary of all samples/analyses are presented in Table 3. Although the
sampling scheme has been developed with the consideration that all samples will
not be obtained for each zone, season, size class, or sample type, additional
samples may not be obtained. This possibility is evident for all fish species as
well as phytoplankton and zooplankton collections. Considering this factor, it is
anticipated that approximately 75% of the projected samples will be collected.
Investigating Agencies- EPA-GLNPO,
Duluth Lab, WDNR
Funding Agency - EPA
Contact Person - Dave Rockwell (312-353-1373)
Russell G. Kreis (313-675-7706)
42
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Table 3. Summary of Green Bay Biota Samples for Food Chain Modeling: 6 zones, 3 seasons, 5 replicates
per zone, each replicate a 5-fish composite, and number of age classes.
Age Class Wt (Ibs)
WALLEYE 1+
3+
4+
Length (in)
8-12
15 - 18
> 29
# of samples/
analyses
Whole:
90
90
90
# of individual fish - 1350
270
BROWN TROUT
stocked yearling (spring)
stocked fingerling (fall)
2+
3+
# of individual fish = 500
3-8
10 - 13
8-11
5-8
17 - 23
10 - 13
5
5
45
45
100
CARP
1+
7+
10+
# of individual fish = 1350
< 2
5-6
< 12
21
> 24
90
90
90
270
ALEWIFE
YOY
Adult
< 100 mm
> 100 mm
90
90
180
RAINBOW SMELT
YOY
Adult
< 100 mm
> 100 mm
75
75
150
GIZZARD SHAD
YOY
< 130 MM
45
CARP GUT CONTENTS
90
ANALYSES
PHYTOPLANKTON
ZOOPLANKTON
Size Fractionation (<100-130 mm)
Manual Separation
Size Fractionation (>100-130 mm)
Manual Separation
SUBTOTAL 1,105
TOTAL FISH 1,375
90
24
90
24
Total Plankton Analyses
228
Expected 75? Success Rate:
TOTAL ANALYSES 1,603
0.75 X 1603 = 1,202 Analyses
43
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V. QUALITY ASSURANCE AND DATA HANDLING
The GBMB will generate hundreds of samples in different media which will be
analyzed by different laboratories. This, coupled with the fact that parameters
such as PCB congeners have not previously been monitored on a large scale, requires
an aggressive quality assurance component to the study. High quality, comparable
data will be assured by:
1. Requiring all participating laboratories to follow the procedures and
meet the criteria defined in "Quality Assurance Plan, Green Bay Mass
Balance Study: I. PCBs and Dieldrin and II: Lead and Cadmium." This
includes the analysis of a series of blindly coded QA samples.
2. Requiring that all Green Bay projects be reviewed and approved by the
Green Bay Quality Assurance Coordinator (GBQAC) prior to implementation.
This is in addition to any QA review procedures required by funding
agencies.
Following completion of conditions 1 and 2, sample collection and analysis
may proceed. As data sets are completed, the data and supporting QA information
will be forwarded (on a quarterly basis) to the GBQAC for acceptance or rejection.
Rejection will result in the implemenntation of appropriate corrective actions
including, if necessary, reanalysis. Data sets which are accepted will be
transferred to U.S. EPA, LLRS for electronic storage.
VI. ADMINISTRATION
Planning and ultimately the conduct of the Green Bay Mass Balance Study has
and will continue to require close cooperation between government and university
scientists and managers. Members of the Management Committee, Technical
Coordinating Committee and four Operational Committees are listed in Figure 10.
For "network purposes" a list of contacts is included in Appendix A.
44
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VII. SCHEDULE FOR GREEN BAY/FOX RIVER MASS BALANCE STUDY
Generally, study activities are being conducted during a four year study
period beginning in 1987 and continuing until the end of 1991. A summary of the
anticipated schedule is shown in Table 4.
45
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Figure 10. GREEN BAY MASS BALANCE ORGANIZATION CHART
MANAGEMENT COMMITTEE
Carol Finch - USEPA GLNPO Co-chair
Lyman Wible - WDNR Co-chair
Thomas Rohrer - WDNR
Anders Andren - Wisconsin Sea Grant
Al Beeton - NOAA GLERL
Gilman Veith - USEPA GLERL, DuLuth
Ken Fenner - USEPA Water Division
Mary Gade - USEPA Waste Management Division
Bruce Robertson- Green Bay Citizens Advisory Council
Warren Gebert - USGS
TECHHICAL COORDINATING
Wayne Willford
John Konrad
William Richardson
William Sonzogni
Russ Kreis
George Boronow
Anders Andren
Hallett Harris
Deborah Swackhamer
David Devault
Peter Hughes
COMMITTEE
USEPA GLNPO Co-chair
WDNR Co-chair
USEPA LLRS
WI State Lab of Hygiene
USEPA LLRS
WDNR
Wisconsin Sea Grant
University of Wisconsin
University of Minnesota
USEPA GLNPO
USGS
RESPOHSIBILITY
Overall management
Coordination of interagency planning
Funding commitments
RESPOHSIBILITY
Coordination of technical activities of
operational committees
Recommend study design to management
committee
Recommend resolutions of technical dispute
to management committee
J
MODELING
William Richardson,
Thomas Fontaine
John Paul
Dale Patterson
David Dolan
Steve McCutchen
Victor Bierman, Jr.
John P. Connolly
Joseph DePinto
Dominic DiToro
Douglas Endicott
Russell Kreis, Jr.
James L. Martin
Paul W. Rodgers
William Roth
Chair
FIELD AND TECHNICAL OPERATIONS
Anders Andren, Chair
John Sullivan
John Filkens
Nathan Hawley
Hallett Harris
David Devault
BIOTA
Russ Kreis
George Boronow
Michael Mac
David Devault
Brian Belonger
Lee Liebenstein
Terrence Lychwick
Co-chair
Co-chair
FIELD AND ANALYTICAL METHODS
William Sonzogni Chair
Larry Burkhart
Steven Eisenreich
Mike Mullin
Ron Rossman
Anders Andren
Deborah Swackhamer
DUTIES
Define modeling requirements
Direct the modeling effort
Review and evaluate proposals for compliance with modeling
goals and objectives
DUTIES
Review monitoring plan and procedures for water and sediments
Assist in planning and corxdinate field operations
Review and evaluate proposals for technical procedures and
investigator competency
DUTIES
Prepare biota monitoring plan
Review and evaluate proposals for technical procedures and
investigator competency
Evaluate and recommend field and analytic methodology
Development and oversight of QC program
Provide AQ evaluation of proposals and monitoring plan
46
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Table 4. SCHEDULE OF ACTIVITIES FOR THE GREEN BAY/FOX RIVER MASS BALANCE STUDY
FY'87 FY'88 FY'89 FY'90 FY'91
Study Plan x x
Quality Assurance x x x x
Field Reconnaissance x x
Modeling x x x x x
Monitoring x x x*
Sample Analysis x x x
Interim Reports x x x
Data Evaluation x x x x
Final Reports x
* Additional monitoring as required
47
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APPENDIX A. LIST OF PRINCIPAL INVESTIGATORS AND CONTACT PERSONS
Mohamad Abdelrham
Computer Sciences Corporation
Environmental Research Laboratory
South Ferry Road
Narragansett, Rhode Island 02382
Telephone: (401) 782-3041
FTS: 383-6239
Anders W. Andren
Water Chemistry Program
University of Wisconsin
660 N. Park Street
Madison, Wisconsin 53706
Telephone: (608) 262-2470
Alfred M. Beeton
Great Lakes Environmental Research
Laboratory
NOAA
2205 Commonwealth Boulevard
Ann Arbor, Michigan 48105
Telephone: (313) 668-2235
FTS: 378-2235
Brian J. Belonger
Wisconsin Dept. of Natural Resources
P.O. Box 16, Industrial Parkway
Marinette, Wisconsin 54143
Telephone: (715) 732-0101
Paul E. Bertram
U.S. Environmental Protection Agency
Great Lakes National Program Office
230 South Dearborn Street - 5GL-PUB-10
Chicago, Illinois 60604
Telephone: (312) 353-0153
Victor J. Bierman, Jr.
Department of Civil Engineering
University of Notre Dame
Notre Dame, Indiana 46556
Telephone: (219) 239-7380
Sandra L. Bird
AScI, Inc.,
Center for Exposure Assessment Modeling
College Station Road
Athens, Georgia 30613
Telephone: (404) 546-3255
FTS: 250-3255
George Boronow
Wisconsin Dept. of Natural Resources
200 N. Jefferson St., Suite 511
Green Bay, Wisconsin 54301
Telephone: (414) 497-4022
Lawrence P. Burkhard
U.S. Environmental Protection Agency
Environmental Research Laboratory
6201 Congdon Boulevard
Duluth, Minnesota 55804
Telephone: (218) 720-5558
FTS: 780-5558
John P. Connolly
Department of Civil Engineering
Manhattan College
Bronx, New York 10471
Telephone: (212) 920-0276
John G. Konrad
Wisconsin Dept. of Natgural Resources
Bureau of Research
P.O. Box 7921
Madison, Wisconsin 53707
Telephone: (608) 267-7480
Philip M. Cook
U.S. Environmental Protection Agency
Environmental Research Laboratory
6201 Congdon Boulevard
Duluth, Minnesota 55804
Telephone: (218) 720-5553
FTS: 780-5553
Joseph V. DePinto
Department of Civil & Environmental
Engineering
Clarkson University
Potsdam, New York 13676
Telephone: (315) 268-6532
David F. Devault
U.S. Environmental Protection Agency
Great Lakes National Program Office
5GL-PUB-10
230 South Dearborn Street
Chicago, Illinois 60604
Telephone: <312) 353-1375
FTS: 353-1375
Dominic M. DiToro
28 Hillside
Englewood, New Jersey 07731
Telephone: (212) 920-0276
David M. Dolan
International Joint Commission
Great Lakes Regional Office
P.O. Box 32869
Detroit, Michigan 48232
Telephone: (313) 226-2170
48
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APPENDIX A - CONTINUED
Brian J. Eadie
Great Lakes Environmental Research
Laboratory
NOAA
2205 Commonwealth Boulevard
Ann Arbor, Michigan 48105
Telephone: (313) 668-2280
FTS: 378-2280
Steven Eisenrich
Environmental Engineering Program
Department of Civil & Mineral
Engineering
103 Experimental Engineering Bldg
University of Minnesota
Minneapolis, Minnesota 55455
Telephone: (612) 373-2507
(612) 376-8026
Douglas D. Endicott
U.S. Environmental Protection Agency
Large Lakes Research Station
9311 Groh Road
Grosse lie, Michigan 48138
Telephone: (313) 675-7708
Kenneth A. Fenner, Chief
Water Quality Branch, Region V
U.S. Environmental Protection Agency
230 South Dearborn Street
Chicago, Illinois 60604
Telephone: (312) 886-6777
FTS - 886-6777
John C. Filkins
U.S. Environmental Protection Agency
Large Lakes Research Station
9311 Groh Road
Grosse lie, Michigan 48138
Telephone: (313) 675-7705
Carol Finch
U.S. Environmental Protection Agency
Great Lakes National Program Office
5GL-PUB-10
230 South Dearborn Street
Chicago, Illinois 60604
Telephone: (312) 353-2117
FTS - 353-2117
Thomas D. Fontaine
Great Lakes Environmental Research
Laboratory
NOAA
2205 Commonwealth Boulevard
Ann Arbor, Michigan 48105
Telephone: (312) 668-2354
FTS - 378-2354
Mary A. Gade
Associate Division Director
Waste Management Division
Office of Superfund
U.S. Environmental Protection Agency
230 South Dearborn Street
Chicago, Illinois 60604
Telephone:(312)353-9773
FTS - 353-9773
Donald F. Gatz
Illinois State Water Survey
Atmospheric Chemistry Section
2204 Griffith Drive
Champaign, Illinois 61820-7495
Telephone: (217) 333-2512
Warren A. Gebert
U.S. Geological Survey
6417 Normandy Lane
Madison, Wisconsin 53719
Telephone: (608) 274-3535
David A. Griesmer
Computer Sciences Corporation
Large Lake Research Station
9311 Groh Road
Grosse He, Michigan 48138
Telephone: (313) 675-8251
Hallett J. (Bud) Harris
Professor and Director
Institute for Land and Water Studies
University of Wisconsin
2420 Nicolet Drive
Green Bay, Wisconsin 54301-7001
Telephone: (414) 465-2796
Nathan Hawley
Great Lakes Environmental Research
Laboratory
NOAA
2205 Commonwealth Boulevard
Ann Arbor, Michigan 48105
Telephone: (313)668-2273
FTS - 378-2273
Peter E. Hughes
U.S. Geological Survey
Water Resources Division
6417 Normandy Lane
Madison, Wisconsin 53719-1133
Telephone: (608) 276-3833
Russell G. Kreis, Jr.
U.S. Environmental Protection Agency
Large Lakes Research Station
9311 Groh Road
Grosse lie, Michigan 48138
Telephone: (313) 675-7706
49
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APPENDIX A - CONTINUED
Wilbert J. Lick
Department of Mechanical Engineering
University of California
Santa Barbara, California 93106
Telephone: (805) 961-4295
Lee L. Liebenstein
Wisconsin Dept. of Natural Resources
Bureau of Water Resources Management
P.O. Box 7921
Madison, Wisconsin 53707
Telephone: (608) 266-0164
Terrence J. Lychwick
Wisconsin Dept. of Natural Resources
200 North Jefferson, Suite 511
Green Bay, Wisconsin 54301
Telephone: (414) 497-4340
Michael J. Mac
U.S. Fish and Wildlife Service
NFCGL
1451 Green Road
Ann Arbor, Michigan 48105
Telephone: (313) 994-3331
James L. Martin
AScI, Inc.
Center for Exposure Assessment Modeling
College Station Road
Athens, Georgia 30613
Telephone: (404) 546-3160
FTS - 250-3160
Steven C. McCutcheon
Center for Exposure Assessment Modeling
U.S. Environmental Protection Agency
College Station Road
Athens, Georgia 30613
Telephone: (404) 546-3301
FTS - 250-3301
Michael D. Mullin
U.S. Environmental Protection Agency
Large Lakes Research Station
9311 Groh Road
Grosse lie, Michigan 48138
Telephone: (313) 675-7707
Thomas J. Murphy
Chemistry Department
DePaul University
1036 Belden Avenue
Chicago, Illinois 60614
Telephone: (312) 321-8191
Dale J. Patterson
Wisconsin Dept. of Natural Resources
P.O. Box 7921
Madison, Wisconsin 53707
Telephone: (608) 266-0155
John F. Paul
Environmental Research Laboratory
U.S. Environmental Protection Agency
South Ferry Road
Narragansett, Rhode Island 02882
Telephone: (401) 782-3037
Bruce B. Robertson
James River Corporation
P.O. Box 790
Green Bay, Wisconsin 54305-0790
Telephone: (414) 433-6239
David C. Rockwell
U.S. Environmental Protection Agency
Great Lakes National Program Office
5GL-PUB-10
230 South Dearborn Street
Chicago, Illinois 60604
Telephone: (312) 353-1373
FTS - 353-1373
Paul W. Rodgers
Limno-Tech, Inc.
2395 Huron Parkway
Ann Arbor, Michigan 48103
Telephone: (313) 973-8300
Thomas K. Rohrer
Surface Water Quality
Michigan Dept. of Natural Resources
Stevens T. Mason Building
P.O. Box 30028
Lansing, Michigan 48909
Telephone: (517) 335-3300
Ronald Rossman
Center for Great Lakes
Aquatic Sciences, 1st Building
University of Michigan
2200 Bonisteel Boulevard
Ann Arbor, Michigan 48109
Telephone: (313) 764-7527
James H. Saylor
Great Lakes Environmental Research
Laboratory
NOAA
2205 Commonwealth Boulevard
Ann Arbor, Michigan 48105
Telephone: (312) 668-2118
FTS - 378-2218
William C. Sonzogrti
State Laboratory of Hygiene
465 Henry Mall
University of Wisconsin
Madison, Wisconsin 53706
Telephone: (608) 262-8062
(608) 262-3458
50
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APPENDIX A - CONTINUED
John R. Sullivan
Wisconsin Dept. of Natural Resources
Bureau of Water Resources Management
P.O. Box 7921
Madison, Wisconsin 53707
Telephone: (608) 267-9753
Deborah L. Swackhamer
School of Public Health
Environmental and Occupational Health
University of Minnesota
P.O. Box 197-UMHC
420 Delaware Street, S.E.
Minneapolis, Minnesota 55455
•Telephone: (612) 626-0435
Gilman D. Veith, Director
Environmental Research Laboratory
U.S. Environmental Protection Agency
6201 Congdon Boulevard
Duluth, Minnesota 55804
Telephone: (218) 720-5550
FTS - 780-5550
Lyman F. Wible
Division for Environmental Quality
Wisconsin Dept. of Natural Resources
P.O. Box 7921
Madison, Wisconsin 53707
Telephone: (608) 266-1099
Wayne A. Willford
U.S. Environmental Protection Agency
Great Lakes National Program Office
5GL-PUB-10
230 South Dearborn Street
Chicago, Illinois 60604
Telephone: (312) 353-1369
FTS - 353-1369
51
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APPENDIX B.
GREEN BAY STATIONS
STATION
NUMBER
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
LATITUDE
44
44
44
44
44
44
44
44
44
44
44
44
44
44
44
45
44
45
45
45
45
45
45
45
45
45
45
"32'45"
"35'01"
"34-57"
"36-22"
"39-31"
-37-50"
-36'24"
-40'20"
-43'40"
"42'37"
"40'40"
"39'29"
"52' 11"
"51-02"
"49-44"
"01'02"
"53-49"
"05'27"
"11-01"
"07-07"
-19-30"
"17-36"
"31'41"
"29-37"
"IS'OO"
"26 '54"
"34-24"
LONGITUDE
087-56'
087-59'
087-57-
087"57'
087"57'
087"55'
087"57'
087"53'
087"54-
087"51'
087"48'
087-46'
087-47'
087*43'
087"39'
087-34'
087"30'
087"24'
087"28'
087"18'
087"18-
087-09'
087"10'
087-01'
086-58'
086*48'
086*48'
48"
45"
29"
16"
45"
35"
32"
43"
01"
19"
29"
27"
30"
40"
27"
18"
08"
41"
36"
30"
55"
54"
34"
58"
07"
03"
08"
LORAN
32486
32486
32474
32470
32456
32456
32455
32435
32420
32414
32413
32410
32350.
32340.
32329.
32252,
32270,
32190.
32180.
32156.
32100.
32069.
32010.
31981.
32015.
31930.
31898.
.8
.8
.0
.9
.5
.9
.6
.4
.3
.5
.0
.4
.7
.8
.6
.7
.0
,6
.5
.0
.1
4
4
2
2
5
7
48274
48240
48251
48235
48201
48225
48248
48206
48171
48191
48221
48241.
48106.
48131,
48159,
48062.
48149.
48050.
47981.
48055.
47930.
47980.
47841.
47889.
48014.
47960.
47889.
.0
.0
.6
.9
.4
.3
.8
.3
.4
.9
.9
.1
.3
.2
.6
,5
.6
.8
.3
.1
9
1
1
5
6
3
4
WATER
DEPTH COPTER
(M) SITE
3 P
3
1 P
6
5 S
6 S
5 P
7
6 S
9 S
8 S
7 S
5 S
15 P
14 S
15
21
30 P
23
21
27
27
19
19 P
37
35
18
NUMBER OF
SAMPLES
STRAT UNSTRAT
1
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
TOTAL 41
27
52
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