DOE
EPA
EP 600/7
78-230
United States
Department
of Energy
Argonne National
Laboratory
Argonne, IL 60439
ANL/WR-78-1
United States
Environmental Protection
Agency
Office of Energy, Minerals, and
Industry
Washington, D.C. 20460
EPA-600/7-78-230
November 1978
Research and Development
Transport of Oily
Pollutants in the
Coastal Waters of
Lake Michigan
An Application of
Rare Earth Tracers
Interagency
Energy/Environment
R&D Program^ ..
Report fe
AGENCX
C317
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
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The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
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mental issues.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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DOE Distribution Category:
Environmental Control
Technology and
Earth Sciences (UC-11)
ANL/WR-78-1
EPA-600/7-78-230
WATER RESOURCES RESEARCH PROGRAM
TRANSPORT OF OILY POLLUTANTS IN THE
COASTAL WATERS OF LAKE MICHIGAN
An Application of Rare Earth Tracers
by
D. L. McCown, K. D. Saunders, J. H. Allender, J. D. Ditmars, and W. Harrison
Energy and Environmental Systems Division
Argonne National Laboratory Argonne, Illinois 60439
November 1978
Prepared under
EPA/DOE Interagency Agreement No. IAG-D6-E681
EPA Project Officer: Clint Hall
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development; Office of Energy, Minerals, and Industry
and
U.S. DEPARTMENT OF ENERGY
Assistant Secretary for the Environment, Office of Health and Environmental Research
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The facilities of Argonne National Laboratory are owned by the United States Govern-
ment. Under the terms of a contract (W-31-109-Eng-38) between the U. S. Department of En-
ergy, Argonne Universities Association and The University of Chicago, the University employs
the staff and operates the Laboratory in accordance with policies and programs formulated, ap-
proved and reviewed by the Association.
MEMBERS OF ARGONNE UNIVERSITIES ASSOCIATION
The University of Arizona
Carnegie-Mellon University
Case Western Reserve University
The University of Chicago
University of Cincinnati
Illinois Institute of Technology
University of Illinois
Indiana University
Iowa State University
The University of Iowa
Kansas State University
The University of Kansas
Loyola University
Marquette University
Michigan State University
The University of Michigan
University of Minnesota
University of Missouri
Northwestern University
University of Notre Dame
The Ohio State University
Ohio University
The Pennsylvania State University
Purdue University
Saint Louis University
Southern Illinois University
The University of Texas at Austin
Washington University
Wayne State University
The University of Wisconsin
NOTICE-
This report was prepared as an account of work sponsored
by the United States Government. Neither the United States
nor the United States Department of Energy, nor any of their
employees, nor any of their contractors, subcontractors, or
their employees, makes any warranty, express or implied,
or assumes any legal liability or responsibility for the ac-
curacy, completeness or usefulness of any information, ap-
paratus, product or process disclosed, or represents that its
use -would not infringe privately-owned rights. Mention of
commercial products, their manufacturers, or their suppli-
ers in this publication does not imply or connote approval or
disapproval of the product by Argonne National Laboratory
or the U. S. Department of Energy.
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TABLE OF CONTENTS
Page
FOREWORD x
ABSTRACT 1
EXECUTIVE SUMMARY 1
1 INTRODUCTION 5
1.1 Purpose and Scope of Study 5
1.2 Research Approach 7
1.2.1 Experimental Outline 7
1.2.2 Tagging and Tracing IHC Water and Associated
Oily Waste 7
1.2.3 Doucmentation of Lake Currents 8
1.3 Previous Work 9
2 EXPERIMENTAL PROCEDURES 13
2.1 Plume-Tracing Methodology . 13
2.1.1 Tagging Agents 13
2.1.2 Tagging Considerations 13
2.1.2.1 IHC Water Tag (Sm) 13
2.1.2.2 Oily Waste Tag (Dy) 14
2.1.3 Sampling Procedures 17
2.1.3.1 Boat Samples 17
2.1.3.2 Water-Intake Samples 20
2.1.4 Analytical Procedures 20
2.1.4.1 Sample Preparation, Irradiation, and
Counting 20
2.1.4.2 Error Analysis 26
2.2 Ancillary Environmental Data Acquisition 28
2.2.1 Meteorological Data 28
2.2.2 Lake Currents 28
3 RESULTS AND DISCUSSION — FLOATING PLUME 30
3.1 Summer Floating-Plume Results, September 24, 1976 30
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TABLE OF CONTENTS (contd.)
3.1.1 Tagging Operation, September 24, 1976 30
3.1.2 Shipboard Tracking, September 24, 1976 30
3.1.3 Data Analysis 33
3.1.4 Horizontal Migration of Cloud 35
3.1.5 Diffusion Coefficients 35
3.1.6 Average Concentrations 36
3.1.7 Percent of Dy and Sm above 1.25 m as
a Function of Time 36
3.2 Floating-Plume Discussion 36
3.2.1 Dy Tracer Loss from Oily Waste 36
3.2.2 Vertical Migration of the Cloud 39
3.2.3 Relationship Between the Movement of the
Oily Wastes and the Underlying Waters 41
4 RESULTS AND DISCUSSION — SINKING PLUME 43
4.1 Winter Sinking-Plume Results, March 2-4, 1977 43
4.1.1 Tagging Operation 43
4.1.2 Shipboard Tracking, March 2-4, 1977 43
4.1.3 Tracer Concentrations at the SWFP 54
4.1.4 Lake Currents and Meteorological
Conditions 54
4.1.4.1 Results of Lake Current Measurements .... 54
4.1.4.2 Meteorological Conditions 59
4.2 Sinking-Plume Discussion 61
4.2.1 General Considerations 61
4.2.2 Characteristics of IHC Effluent Plume
for January 4 - March 26, 1977 61
4.2.3 Transport and Dilution of Tagged
IHC Effluent 62
4.2.3.1 Interpretation of Experimental
Observations 62
4.2.3.2 Comparison of Simple Dilution
Estimates with Measurements 66
4.2.3.3 Dilution Estimates for the
Entire IHC Effluent 70
4.3 Comparison of the Potential for Pollutants from
Floating and Sinking Plumes of the IHC to Enter
the City of Chicago's Raw Water Intakes at the SWFP 73
5 SUMMARY 75
^v
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TABLE OF CONTENTS (contd.)
Page
ACKNOWLEDGMENTS 77
REFERENCES 79
APPENDIX A 83
APPENDIX B 91
y
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LIST OF FIGURES
No. Title Page
1.1 Location Map for Study Area and Current-Meter
Positions (I-IV) ±n Southwestern Lake Michigan 6
2.1 Percent of Dy in Oil Transferred into Water as
a Function of the Exchange of Underlying Water 16
2.2 Schematic of the Three-Dimensional Underway Water-
Sampling System as Set Up for a Sinking-Plume 18
2.3 Cross-Sectional View of the Sampling Chains
in Fig. 2.2 19
2.4 Schematic of Onboard Sampling Manifold and
Fluorometer 21
2.5 Schematic of CRT Display from Multichannel Analyzer
Indicating the Locations of the Sm and Dy Peaks and the
Regions Used to Determine Background. . . 25
3.1 REE Tagging Location and Contours of Lowest Detectable
Amount of Dy that was Contoured for Plume Mappings 1-4,
Floating-Plume 31
3.2 Positions of Sampling Transects Floating-Plume 32
3.3 Average Layer Concentration of Dy/Oil Over the
Measurable Cloud 38
3.4 Percent of the Total Dy/Oil and Sm Accounted For by
Measurement Found Above 1.25 m Vs. Time After Tracer
Release 40
4.1 REE Tagging Location, Temperature-Convergence
Zone, and Positions of Sampling Transects,
Sinking-Plume 45
4.2 Transect A: Dy Concentrations 47
4.3 Transect F: Dy Concentrations and Near-Bottom
Dye Concentrations 48
4.4 Transect I: Dy Concentrations and Near-Bottom
Dye Concentrations 49
4.5 Transect K: Dy Concentrations and Near-Bottom
Dye Concentrations 50
4.6 Transect L: Dy Concentrations and Near-Bottom
Dye Concentrations 51
v^
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LIST OF FIGURES (Contd.)
No. Title Page
4.7 Transect N: Dy Concentrations and Near-Bottom
Dye Concentrations 52
4.8 Relative Amount of Sm or Dy in the Samples
Collected at the SWFP as a Function of Time 58
4.9 Correlation Coefficients for the Principal and
Transverse Components of the Current as a Function
of the Distance Between Stations 60
4.10 Progressive-Vector Diagrams for March 1-4, 1977,
Midway Airport Winds 60
4.11 Schematic Reconstruction of the Velocity Field of
the Near-Bottom Water on March 3, 1977 65
4.12 Schematic Representation of the Expected Dilution
Ratios in the Nearshore Waters of Southwestern
Lake Michigan on March 3, 1977 71
Al Plan-View Contoured Plot of Dy Concentrations
at 0.0, 0.5, 1.0, 1.5, 2.5, 3.5-m Depths for
Floating-Plume #1 84
A2 Plan-View Contoured Plot of Dy Concentrations
at 0.0, 0.5, 1.0, 1.5, 2.5, 3.5-m Depths for
Floating-Plume #2 • 85
A3 Plan-View Contoured Plot of Dy Concentrations
at 0.0, 0.5, 1.0, 1.5, 2.5, 3.5-m Depths for
Floating-Plume #3 86
A4 Plan-View Contoured Plot of Dy Concentrations
at 0.0, 0.5, 1.0, 1.5, 2.5, 3.5-m Depths for
Floating-Plume #4 87
A5 Plan-View Contoured Plot of Sm Concentrations
at 0.0, 0.5, 1.0, 1.5, 2.5, 3.5-m Depths for
Floating-Plume //2 88
A6 Plan-View Contoured Plot of Sm Concentrations
at 0.0, 0.5, 1.0, 1.5, 2.5, 3.5-m Depths for
Floating-Plume #3 89
A7 Plan-View Contoured Plot of Sm Concentrations
at 0.0, 0.5, 1.0, 1.5, 2.5, 3.5-m Depths for
Floating-Plume #4 90
v^^
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LIST OF FIGURES (Contd.)
No. Title
Bl Transect A: Sm Concentrations 92
B2 Transect B: Sm Concentrations 93
B3 Transect C: Sm Concentrations 94
B4 Transect B: Dy Concentrations 95
B5 Transect C: Dy Concentrations 96
B6 Transects D and E: Dy Concentrations and Near-
Bottom Dye Concentrations 97
B7 Transects G and H: Dy Concentrations and Near-
Bottom Dye Concentrations 98
B8 Transect J: Dy Concentrations and Near-Bottom
Dye Concentrations 99
B9 Transect M: Dy Concentrations and Near-Bottom
Dye Concentrations 100
BIO Transect 0: Dy Concentrations and Near-Bottom
Dye Concentrations 101
Bll Transect P: Dy Concentrations and Near-Bottom
Dye Concentrations 102
?.>^^^
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LIST OF TABLES
No. Title
2.1 Neutron-Activation Characteristics of Dysprosium
and Samarium
2.2 Sampling Times at SWFP Crib and Shore Raw-Water
Intakes, 1977
3.1 Log for Shipboard Activities, Summer Floating-Plume,
September 26, 1976
3.2 Calculated Horizontal Diffusion Coefficients
35
3.3 Floating Plumes 1-4, Average-Concentration
Parameters
4.1 Log for Shipboard Activities, Winter Sinking-Plume
Study, 1977
4.2 Sm Concentrations of Samples Collected at the SWFP 55
4.3 Dy Concentration of Samples Collected at the SWFP 56
4.4 Dilution Ratios for Samples Collected at the SWFP 67
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FOREWORD
The U.S. Energy Research and Development Administration (ERDA) was
formed in January, 1975. Shortly thereafter, certain energy-related re-
search programs being conducted by the U.S. Environmental Protection Agency
(EPA) were transferred to the ERDA's jurisdiction. Funding for the programs
was also transferred ("passed through") from EPA to ERDA, giving rise to the
designation of such research programs as "pass-through" programs.
One of the EPA-to-ERDA pass-through programs was entitled "Offshore
Oil Extraction and Related Problems." A task within this program was en-
titled "Transport and Dispersion of Refinery Wastes in Freshwater Coastal
Regions." This research task was undertaken by Argonne's Energy and Environ-
mental Systems Division (EES) .
The original task description called for field experiments using rare
earth tracers to tag both a release of oily refinery wastes and the under-
lying waters in the Indiana Harbor Canal (IHC) that discharges into south-
western Lake Michigan. The IHC discharge forms a thermal plume in the lake
because the canal receives copious volumes of steel-mill process water. Also,
an oil refinery is situated on the canal, and its effluents, as well as those
from other industries and municipal wastewater treatment plants, provide
oily wastes to the canal waters. Subtask descriptions originally included
an experiment during winter sinking-plume conditions and three experiments
during several summer floating-plume conditions. Initial plans also called
for the development of a mathematical model, based on experimental data, for
prediction of the transport and dispersion of the refinery wastes. The orig-
inal task duration was to be five years.
Termination of the task after 2 1/2 years duration resulted, in a modi-
fied scope of work. One sinking-plume experiment and only one floating-plume
experiment were completed. The modeling effort proposed originally was not
undertaken. An earlier report, "Transport and Dispersion of Oil-Refinery
Wastes in the Coastal Water of Southwestern Lake Michigan (Experimental
Design—Sinking-Plume Condition)," ANL/WR-76-4, July, 1976, by McCown et al.
described initial experimental designs and procedures. The present report
is a final task report on the results of the application of the tracer
techniques in the sinking- and floating-plume experiments.
x
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TRANSPORT OF OILY POLLUTANTS IN THE COASTAL WATERS
OF LAKE MICHIGAN: AN APPLICATION
OF RARE EARTH TRACERS
by
D. L. McCown, K. D. Saunders, J. H. Allender,
J. D. Ditmars, and W. Harrison
ABSTRACT
An experimental method was developed to tag and to trace oily
pollutants in fresh water environments. The use of two rare earth
element tags (Dy and Sm) permitted simultaneous tracing of small
oil spills at the water surface and of the underlying water. Neu-
tron activation analysis was used to determine the tracer concentra-
tions in numerous, small water samples collected from a moving boat.
The method was applied in two field experiments with simu-
lated oily pollutants in the Indiana Harbor Canal (IHC). Industry
draws water from Lake Michigan for cooling, and the water is returned
to the Lake via the IHC. When the lake water temperature is > 4°C,
the IHC effluent floats out on the surface. When the lake water
temperature is < 4°C, the IHC effluent forms a sinking plume.
Tagged oily pollutants and IHC waters were traced under both
floating- and sinking-plume conditions.
Floating-plume results indicated that oily waste artificially
mixed downward by a ship did not resurface, no differences were
seen in the movement of the oily waste and the underlying water,
and mixing coefficients for tagged oil and water were similar to
those measured by others on the Great Lakes.
Sinking-plume results gave unequivocal evidence of the intake
of IHC effluent at Chicago's South Water Filtration Plant and
indicated partitioning of the oily wastes and water. Simple
dilution estimates for the sinking plume were supported by the
tracer data and similar estimates indicated plume center-line
dilution ratios for the entire IHC effluent at the water intakes
could be as low as 2.8.
EXECUTIVE SUMMARY
This report presents the results of research conducted by Argonne
National Laboratory for the U.S. EPA and U.S. ERDA. The objectives of the
research were to develop a method to tag simultaneously and trace oily wastes
and the underlying waters and to apply that method to specific contaminated
fresh coastal waters.
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The tagging technique utilized rare earth element (REE) tags. Dys-
prosium (Dy) was chosen to tag the oily waste and samarium (Sm) complexed
with a chelating agent (DTPA) was used to tag the underlying water. A three-
dimensional, underway sampling system employing electronic boat positioning
was developed for the over-water tracking phase of the project. Subsequent
tag detection and concentration determinations were by Neutron Activation
Analysis (NAA) performed at ANL's CP-5 reactor. The NAA technique developed
had the following significant features:
1. Minimum detectabilities of 6 x 10~10g for Dy and 2 x 10~8g for
Sm were achieved with small water samples (15 mL),
2. The samples were collected and subsequently irradiated in the
same polyethelene containers, Polyvials,
3. No pre-irradiation sample preparation except evaporation of
the liquid phase and cleaning of the outside of the Polyvial
was necessary,
4. The short half-lives of Dy and Sm permitted a rapid rate of
analysis (17 samples per hour), and
5. Dy and Sm could be easily detected and quantified at the same
time.
The tracing technique was applied to experiments in the Indiana Harbor
Canal (IHC) which discharges into Southwestern Lake Michigan about ten miles
south of Chicago. The source of IHC water is Lake Michigan. Industry along
the canal draws water from the lake and uses it for cooling processes. The
water is heated 5-8 C° and dumped back into Lake Michigan via the IHC.
The flow regime in the IHC varies from winter to summer. In the
winter, when IHC effluent meets ambient Lake Michigan water (< 4°C), a plume
of 4°C (maximum density) water is formed and sinks near the IHC entrance.
However, in the summer (when ambient lake water is > 4°C) the canal effluent
flows out on the surface and lake water intrudes into the canal along the
bottom.
Waters of the IHC are heavily polluted by the industry along the
canal. When the plume is sinking and winds are southerly, the City of
Chicago's South Water Filtration Plant (SWFP) experiences periods when large
amounts of costly charcoal must be used to eliminate the high hydrocarbon
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odors from it's lake raw-water supplies (the SWFP's only source of fresh
water). These odors have long been theorized to come from IHC water migrating
up the coast along the bottom. Thus, a secondary objective of this study
was to attempt to provide proof of the transport of IHC water to the SWFP.
Tracing experiments were conducted on two occasions, once for the
floating-plume and once for the sinking-plume. On September 24, 1976 the
canal was tagged in situ with 4.5 kg (10 Ib) of Sm complexed with DTPA, and
with 3 Kg of rhodamine WT dye. At the same time and location 57 L of oily
waste tagged with 0.5 kg (1 Ib.) of Dy was poured on the canal surface.
Approximately thirty minutes after tagging an empty ore carrier passed
directly through the center of the dye patch. During the following ten hours,
the plume was mapped four times and about 1200 15-mL water samples were
collected. The results indicated that, after the oily waste was artificially
mixed into the water column by the passing ship, it did not resurface but
remained mixed, no distinguishable differences were seen in the movement of
the oily waste and underlying water, and calculated diffusion coefficients
for both Sm and Dy were similar to values measured by others on the Great
Lakes and were of the order 10 m2/s.
The sinking-plume experiment was conducted on March 2-4, 1977. The
canal was tagged in situ on March 2, 1977, with 13.6 kg (30 Ib.) of Sm com-
plexed with DTPA, and with 7.5 kg of rhodamine WT dye. At the same time and
location 170 L of oily waste tagged with 1.4 kg (3 Ib.) of Dy was poured on
the surface of the canal. The tagged patch was followed for about 50 hours
and about 1000 water samples were collected from a moving boat. During the
same time interval, 240 samples were collected from the raw-water streams at
the SWFP. The results of the sinking-plume experiment gave unequivocal evi-
dence of the transport of polluted IHC water to the SWFP, indicated a parti-
tioning of the surface oily wastes and the underlying water, and supported
simple plume dilution estimates at the SWFP. Furthermore, similar estimates
indicated plume center-line dilution ratios for the entire IHC effluent plume
could be as low as 2.8.
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1 INTRODUCTION
1.1 PURPOSE AND SCOPE OF STUDY
There is at present an inadequate understanding of the processes of
transport and dispersion of oily wastes in coastal waters. It was the pur-
pose of the present program:
1. To develop methods for simultaneously tagging both oily wastes
and the underlying waters, each with a unique tracer, and for
determining their individual motions in fresh coastal waters,
and
2. To apply these methods to specific, contaminated coastal
waters.
The studies by Argonne National Laboratory (ANL) were devoted to a
series of experiments conducted on oily wastes that move into the coastal
waters of southwestern Lake Michigan from the Indiana Harbor Canal (Fig. 1.1).
Several possible sources of oily pollutants in the canal exist. Effluents
from an oil refinery, steel mills, and municipal sewage treatment plants
contain such pollutants. Small spills from oil transfer facilities and run-
off from industrial sites also contribute to the oily-waste loading. For
this study no individual source was tagged, but rather a simulated oily-
waste was prepared (see Sec. 2.1.2.2) and spilled in the canal.
The source of water in the canal is Lake Michigan. Industry draws
water from the lake, uses the water for industrial cooling processes which
heat the water 5-8 C°, then returns the water to the canal. The canal water
moves into the lake as a thermal plume, sinking during much of the time in
winter, and forming a surface plume during the remainder of the year. Signi-
ficant differences in the oil-transport regime are expected during floating
and sinking-plume conditions. The most difficult transport/dispersion regime
to observe in the field is that of the sinking plume, because it is difficult
to follow and sample a tagged mass of canal water that forms only a thin
layer (commonly 1- to 5-m thick) as it spreads over the bottom. Nevertheless,
the importance of sinking-plume transport in carrying contaminants from the
Indiana Harbor Canal (IHC) to municipal water intakes in southwestern Lake
Michigan dictated devoting significant efforts and resources to the tagging
and tracing of IHC water during sinking plume conditions.
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CENTRAL tfATER
FILTRATION
PLANT
DEPTHS IN FEET
000 2000
METERS
o i
I
STATUTE MILES
AKE
MICHIGAN
ILLINOIS
INDIANA
SOUTH WAT
FILTRATION ~
V
Fig. 1.1. Location Map for Study Area and Current-Meter Positions (I-IV)
in Southwestern Lake Michigan
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Two major field studies were conducted during the project: a summer
floating-plume and a winter sinking-plume study. The results of both studies
are given in this report and the methods for tagging with rare earth elements
and analyzing water samples by neutron activation techniques are described.
1.2 RESEARCH APPROACH
1.2.1 Experimental Outline
In general, this study involved tagging a portion of IHC water and
simultaneously placing tagged simulated oily-wastes on the surface of that
portion of IHC water. The tagged oily-waste and water was then followed,
from a boat, and sampled numerous times at many depths. During the summer
study, the tagged cloud was tracked and sampled for about 10 hrs and for a
distance of about 3.5 km from the IHC entrance.
In the winter, the tagged cloud was tracked and sampled for about
54 hrs from a boat and, in addition, samples were collected at the raw-water
intakes of the City of Chicago's South Water Filtration Plant (SWFP) about
12 km north of the IHC entrance. (Fig. 1.1) Current meters were placed in
the study area (Fig. 1.1), for the winter study, so that appropriate features
of the water movement could be determined. The current meter data (current
speed and direction) were used to guide the interpretation of the results
of the tracer experiment and to develop a simple model for the transport of
IHC water northward to the SWFP.
1-2.2 Tagging and Tracing IHC Water and Associated Oily Waste
It is important to distinguish between the dynamics of waste-receiving
waters and the motions of the associated oily wastes within and upon these
waters. Adequate understanding of these separate but complementary motions
is essential for the development of predictive models. Accordingly, a method
was developed for the simultaneous tagging and tracing of oil and water. The
method allowed detection of tags with concentrations as low as = 40 ng/L.
Traditionally, two classes of substances have been used to tag water or
pollutants for tracing: fluorescent dyes and radionuclides. Fluorescent
dyes have several drawbacks. Some fluorescent dyes bleach in the sunlight.
Others that do not bleach may become absorbed onto suspended particles, which
then settle out of the water column. Radionuclides have several advantages
-------
8
for water and contaminant tracing, but have an unacceptably high radiation
hazard for all but very short-term studies.
The approach to tracing in the present study uses stable-element tags
and neutron activation analysis (NAA). Among the advantages of this method
are the following:
1) there is no radiation hazard to the environment,
2) with samples as small as 15 mL detection is possible to
- 40 ng/L of stable-element concentration in the tagged
water,
3) there appears to be negligible tracer loss to suspended matter
and sediments, and
4) the stable-element tags themselves can be chosen to be non-
toxic to the environment.
Certain rare-earth elements (REEs), such as dysprosium, samarium, lan-
thanum, europium, and ytterbium suggested themselves as likely candidates for
tags. Among the REEs available, dysprosium (Dy) and samarium (Sm) were
chosen as the most suitable for the present study principally because
1) they have high detectability (see Sec. 2.1.1) and short
half-lives, and
2) their natural occurrence in Lake Michigan is at concentra-
tions below the limits of detectability provided by the
methods used in the present study.
With regard to point 2 note that, prior to tagging, 24 samples of water were
taken from the shore and from the crib intakes of the SWFP and analyzed for
their natural Dy and Sm content. No Dy or Sm was detected in the 48 samples
that were used to determine background concentrations. Minimum detectabilities
in 15-ml samples are 6 x 1Q-10 g for Dy, and 2 x 1CT8 g for Sm, using the
Argonne method. The availability of a high-flux reactor and of superior radia-
tion-counting equipment at Argonne, and the existence of precision boat-posi-
tioning equipment within the Water Resources Research Program at ANL, made it
possible to design a relatively sophisticated experiment for studying the trans-
port of polluted IHC water and simulated oily waste to Chicago's water intakes.
1.2.3 Documentation of Lake Currents
No current data were specifically collected for the floating plume
study. Data from an ANL current meter deployed for a separate study about
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10 km north of the study area in Lake Michigan indicated lake currents of
about 0.03 m/s (the order of current meter threshold values) during the
period of the study. Moreover, plume motion was limited to a relatively
small region in the lake due to the small currents and short duration of
the floating plume experiment.
Three current meters were deployed in a close array directly off the
SWFP during the initial feasibility study (McCown et al., 1976). Data from
these meters revealed unexpected current patterns between the mouth of the
Indiana Harbor and the SWFP. Therefore, a more open deployment of four cur-
rent meters was made along the line of expected plume flow from the mouth of
the Indiana Harbor to the Dunne Crib (Fig. 1.1), during the winter 1977 study.
1.3 PREVIOUS WORK
Channell (1971) used a rare-earth element (La) and neutron activation
analysis for tagging and tracing estuarine water. To our knowledge, however,
the present study is the first to employ rare-earth elements as tracers in
fresh coastal waters. Channell's work will be discussed in detail below,
particularly in Sec. 2.1.2.1.
The impact of the IHC effluent on Lake Michigan water quality was in-
vestigated by Snow (1974) . Comprehensive water-quality data for the IHC and
adjacent lakes waters and pollution loadings were gathered from existing data
bases. A limited field survey (during floating-plume conditions) during this
study resulted in additional measurements of water quality parameters and of
currents and temperatures. In addition to suggesting relationships between
the loadings and water quality in the lake, Snow pointed out the physical
mechanisms thought to be important in the transport and mixing of IHC waters
into the lake, i.e. the jet-like efflux of the canal and the intrusion of
lake waters under the canal surface waters during the summer.
Lake currents just off the IHC in winter occasionally flow northward.
There is some evidence (P. A. Reed, 1975, personal communication) that, when
conditions are right for developing a sinking plume, plume-borne pollutants
may be transported as far north as the City of Chicago's Central Water Filtra-
tion Plant (CWFP),* which draws its water from either the Dever Crib, located
*Recently renamed the James W. Jardine Purification Plant.
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10
3.2 km NE of CWFP (Fig. 1.1) or the shore intake. According to Reed, when
currents are flowing northward plume water is commonly transported as far as
the intake crib for Chicago's South Water Filtration Plant (SWFP) during
winter months. During January 1975, for example, the (SWFP) experienced a
two-week period of hydrocarbon odors in its raw water. The severity of the
odors was greater in the SWFP's raw water from its shore supply than in the
raw water from its Dunne crib (Fig. 1.1). The hydrocarbon odors were accom-
panied by elevated concentrations of ammonia-nitrogen, and there can be
little doubt that a significant percentage of the hydrocarbon odors originated
from waters of the IHC. According to permit data (Snow, 1974, v. 1, p. 200),
for example, the ARCO refinery, Inland Steel, Youngstown Sheet and Tube, and
others are permitted to contribute up to 22,680 kg/day (50,000 Ib/day) of oil
and grease to the IHC. If the lake temperature is appropriate (less than
about 2°C), development of highly polluted sinking plume that is transported
northward occurs when
a) there is a significant rainfall in the area (0.64 cm [0.25 in]
of rain in a day will cause overflowing of some combined
sewers that enter the IHC), and
b) there are brisk winds from southerly quadrants.
Modern studies of currents off Chicago began with two surveys by the
U.S. Public Health Service (1963a, 1963b). The first of these used Geodyne
Savonius-rotor current meters at three stations off the coast of Chicago.
Two of these stations provided current information for the period December
18, 1962 - March 22, 1963. Of these two stations, only station 3 (42°01.7' N,
87°31' W) was near enough to shore (9 km) to be considered useful for coastal
current delineation. The prevailing direction of the currents for January
31 - March 22, 1963, was about 150°, with a minor peak at about 340°. The
third station (41°50.2' N, 87°29.7f W) was in operation for 6 days during
March 1963. These data are interesting and important as they represent the
first long-term time series of current measurements in Lake Michigan in the
winter. They are, however, not particularly useful in the context of this
study, as the current meters were located too far lakeward to resolve the
nearshore currents and too far north to be representative of the currents
near the Indiana Harbor-Calumet Harbor region.
The second study by the U.S. Public Health Service (1963b) used drogues
to measure lake currents in the nearshore zone. This study took place on
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11
April 11-12, 1963, and was of too short a duration to make any available
estimates of nearshore currents.
Saylor (1966) reported on the current patterns in Calumet Harbor under
various wind conditions. The current patterns were determined from a combi-
nation of current meter, drogue and dye measurements. He found that, under
southerly winds, the currents from the south did not penetrate into the har-
bor and were deflected around the end of the breakwater (Fig. 1.1). There
was little flow through the opening in the breakwater under these conditions.
During periods of northerly winds, a significant current is seen through the
breakwater opening with little flow around the end of the breakwater into
Calumet Harbor. He concluded that currents due to seiche modes were rela-
tively weak, but important for the flushing of stagnant water in the upper
reaches of the harbor.
The next study of currents in the southwestern region of Lake Michigan
was performed by D. Frye and L. S. Van Loon of Argonne National Laboratory
(Snow, 1974, pp. 117-126). Three Braincon 381 histogram-recording Savonius-
rotor current meters were deployed, one adjacent to the 68th St. Crib at a
depth of 5.2 m and the other two off the Inland Steel landfill at depths of
3 and 6 m. The currents were measured from November 8 to December 8, 1973.
The investigators found a cyclical variation of current speed with the speed
minima corresponding to shifts in the current direction. The current direc-
tions were generally shore-parallel, and the currents at the crib and off the
landfill were similar in direction. This study produced the first moderately
long time series of current velocities in the Indiana Harbor-Calumet Harbor
region under a period of low stratification, but it suffered from the twofold
drawbacks of limited time and the use of Savonius-rotor current meters in
shallow water, where waves may bias the recorded velocities.
Monahan and Pilgrim (1975) made current-meter measurements off Chicago
from July to October 1974. They found generally northward-flowing currents
during this period. This study was inadequate for assessing currents in the
Calumet Region, as the stations were located too far north and east (42°00' N,
87°30.0' W and 41°55.5' W), the current meters used were Savonius-rotor meters,
and the lengths of the time series were too short.
Saunders and Van Loon (1976) obtained current measurement for June-
December 1975, using ducted-impeller current meters. The current meters were
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12
located at mid-depth about 3 km SE of the Dunne Crib. Although the time
series was long and the current meters did not suffer from wave-enhanced
speeds, the data are still unsuitable for the present study, as most were
obtained under periods of strong stratification. Such data cannot be extra-
polated to winter conditions when the lake is well mixed.
Although the above measurements give some insight into lake currents
in the area of interest, they do not reflect conditions occurring at the time
of sinking-plume activity. For this reason, the special measurements de-
scribed in Sec. 2.3.2 were made.
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13
2 EXPERIMENTAL PROCEDURES
2.1 PLUME-TRACING METHODOLOGY
2.1.1 Tagging Agents
Dysprosium (Dy) was the agent chosen to tag the simulated oily waste,
and samarium (Sm) was selected to tag the IHC water. (The neutron-activation
characteristics of Dy and Sm are shown in Table 2.1.)
A third agent, the fluorescent dye rhodamine-WT, was used to tag the
canal water so that, by means of a pump and fluorometer, the tagged water
mass could be detected immediately and followed by the sampling boat.
2.1.2 Tagging Considerations
2.1.2.1 IHC Water Tag (Sm)
Waters of the IHC are turbid and highly polluted. Introduction of a
REE tag into the IHC water column in the ionic form would hazard removal of
the REE from solution by the formation of insoluble compounds by reaction
Table 2.1. Neutron-Activation Characteristics of Dysprosium
and Samarium (from Lederer, 1967)
Reaction
164Dy (n,Y) 165mDy 154Sm (n,Y) 155Sm
Half-life (T1/2) 75 s 22.5 min
Thermal neutron-
capture cross
section (a) 2000 barns 5 barns
Isotopic abundance 28% 23/4
Major gamma energy3 0.1082 MeV 0.1043 MeV
Minimum detectability per
15 mL sample as deter- in c -8 c
mined by experiment 6 x 10~ g 2 x 10 g
abarn = 10~21* cm2
From Bowman and Macurdo, 1974
°Irradiation time: 90 s; delay to count: 30 s; count: 90 s.
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14
with some of the many species in solution in the 1HC or on the bottom of
the canal, and removal from solution by adsorption on suspended solids.
Chann.ell (1971) showed that the persistence of lanthanum in waters
that are in contact with bottom sediment is almost twice that for lanthanum
complexed with EDTA* than for lanthanum dissolved in acid. Channell suggest-
ed that chelation would be advantageous for an injection into an area where
suspended solids were flocculating or where the water depth would allow sig-
nificant contact of the tagged water mass with bottom sediments. IHC waters
contain an abundance of suspended solids, and, in a sinking plume, this water
remains in contact with bottom sediments. Chelation of REE tags, by complex-
ing with DTPA,** was therefore considered necessary.
2.1.2.2 Oily-Waste Tag (Dy)
Numerous bench tests were conducted to determine how well the simu-
lated oily waste retained the Dy tag. The simulated waste was made up from
equal parts of 30-W motor oil, #2 diesel fuel, and engine drain oil. The
results of the bench testing are discussed in detail, in the Argonne National
Laboratory Report ANL/WR-76-4 (McCown, Harrison, and Orvosh, 1976). In sum-
mary, the tests showed that - 0.5% of the Dy migrated from the oil into the
water over a five-day time span.
Recently, a new series of bench tests were conducted. In these tests,
the 1 L of water underlying the surface slick of 1 mL simulated waste was
sampled every two days for 12 days by inserting an automatic pipette to
mid-depth. Every second day, immediately after sampling, the underlying water
was pumped out of the beaker (leaving =10 mL) and fresh water was poured into
the beaker. After 12 days, the water samples were dryed then analyzed by
NAA to determine their Dy content. A very small amount (=1 uL) of the oil
was skimmed off the surface of the water after the last water sample was
drawn. These oil samples were irradiated to determine if they contained Dy.
All of the oil samples were far too radioactive from irridiated Dy to count
and quantify but they clearly indicate that a substantial amount of the Dy
remained in the oil.
*Ethylenediaminetretraacetic acid
**Diethylenetriamine-pentaacetic acid (DTPA was chosen because it is cheaper
and easier to complex with Sm than EDTA).
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15
The simulated waste of one of the three beakers was a 1-mL portion of
the actual tracer used for the floating plume experiment (Sec. 3.1) and was
about 1 year old. The percent of Dy that was detected in the water samples
from that beaker are shown by the lower curve in Fig. 2.1. The upper curves
show the results from beakers in which the simulated oily waste was mixed
just prior (~1 hr) to the beginning of the tests.
The bench tests discussed in ANL/WR-76-4 indicate that, for environ-
mentally reasonable conditions (very thin surface film),
=0.5% (5 x 10"^/mL oil/mL water) of the Dy in the 1 mL of oily waste on the
water in the beaker migrated into the underlying 1 L of water. In the new
tests the underlying 1 L of water was changed every two days and these tests
showed that, on the average, -0.4%* of the Dy in the simulated waste/1 mL
of simulated waste/1 L of underlying water migrated from the oil to the
water. Thus, a Dy "loss factor" (4 x 10-1% Dy lost/mL oil/mL water) de-
rived in these experiments was used, although different proportions of oil
and water may result in different values.
There are two issues that should be noted regarding the bench tests.
First, we share the reservations of most researchers concerning the ability
to represent natural phenomena in a beaker; however, no better means to
determine the retention of Dy by the simulated waste could be found.
Second, the Dy detected in the water could have been carried into
the water in small amounts of dissolved or suspended oil rather than actually
passing out of the oil solution. The resolution of this final issue is a
difficult problem which would require not only the detection of both the Dy
and oil in the drawn sample but also a determination whether or not the Dy
is dissolved in the oil. We know of no means to do this.
In summary, the bench testing indicates that Dy is a quite acceptable
tagging agent for oily type substances.
*0.4% Dy lost/mL oil/mL water is the average of the 10 points on the
upper two curves on Fig. 2.1. (Note, the samples corresponding to two
days for the upper curves could not be quantified because they were 10-mL
samples and were too radioactive to count. "This does not imply that the
Dy concentration was much greater; it means that the volumes were too
large. Subsequent samples were 5-mL each.)
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16
10"
T
Volumes: Water = 1L
Oil = ImL
Initial oil concentration: 8g Dy
L oil
New Mixture
10
-3
o
o
o
oo
10
-4
Actual Floating'
Plume Tracer
I yr. old
-5
I
10
Fig. 2.1.
I
6 8
Time, Days
10
12
Percent of Dy in Oil Transferred into Water as a Function
of the Exchange of Underlying Water (Water Changed Every
Two Days)
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17
2.1.3 Sampling Procedures
2.1.3.1 Boat Samples
Documentation of transport and dispersion in a plume requires many
data points. This requirement dictates the removal of water samples from
several depths and at many locations in the lake. In addition, it is of
great importance to know to a high degree of accuracy the position of the
boat when samples are being taken. Clearly, electronic boat-positioning
equipment and an underway sampling system are required if the area of inter-
est is to be sampled in a reasonable period of time.
Argonne National Laboratory (ANL) has developed a towed-depressor/
thermistor array (Frigo, Paddock, and McCown, 1975), and the knowledge gained
from ANL's research and development efforts was used to design a three-dimen-
sional water-sampling system. The sampling system includes:
1) a Motorola Mini-Ranger electronic positioning system inter-
faced with an x-y plotter for real-time positioning,
2) a fluorometer, pump, and hoses to follow the dye patch, and
3) a dynamically depressed faired cable with small tubes
attached which extend to the depths to be sampled.
During tracking of a sinking plume an additional large tube is placed
in the faired cable to draw bottom water samples. Schematics of the sampling
system, as set up for a sinking plume, are shown in Figs. 2.2 and 2.3.
The intermediate-depth water samples are pumped onboard, through
6.4 mm (0.25-in.)-O.D. [4.7-mm I.D.] nylon tubes, by a Masterflex multichannel
tubing pump. The flow rate, through =20 m of tube, is =100 mL/min. This
relatively low flow rate was sufficient because each sample was only 15 mL
in volume. The tubes are all the same length, so that sample-removal delay
times are all equal. The major retarding force in the tube is not hydrostatic
head, but friction with the tube sidewalls.
The bottom water sample, collected in the sinking-plume study, is
drawn through a 9.6-mm I.D. nylon tube (Fig. 2.3), which is connected to the
faired cable at a point 1 m above the depressor fin (Fig. 2.2). The end of
the bottom-sampler tube is connected to a 7.3 kg (16 Ib) shot that trails the
depressor fin by =12 m so that the shot is dragging on the bottom. The bottom
sampler has a relatively high flow rate, 7.5 L/min and it is driven by a
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18
MINI-RANGER RECEIVER/TRANSMITTER
FOR REAL TIME POSITIONING ON X'Y
PLOTTER
CABLE FAIRING
DEPTH VARIES
WITH BOTTOM
TOPOGRAPHY
DEPTH FIXED AT
CONSTANT SPEED
»8m
WATER INLET
V-FIN (0.6m WING SPAN)
UNDERWAY SAMPLING SYSTEM
Fig. 2.2.
Schematic of the Three-Dimensional Underway Water-Sampling System
as Set Up for a Sinking Plume
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19
SECTION B-B
A-6.4 mm (1/4") STEEL CABLE
B-6.4 mm (1/4") HOLLOW
NYLON TUBE
C-l3mm(l/2") HOLLOW
NYLON TUBE
D- 1.6 mm (1/16") STEEL CABLE
E - PLASTIC ELECTRIC
CABLE TIE
SECTION A-A
Fig. 2.3. Cross-Sectional View of the Sampling Chains in Fig. 2.2,
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20
positive-displacement 12-V DC "puppy" pump. Water from the bottom is fed
directly to the fluorometer; however, a valved-tee (Fig. 2.4) at the fluor-
ometer inlet diverts a small portion (~200 mL/min) of the water to the sampl-
ing manifold (Fig. 2.4) to be withdrawn for subsequent NAA at Argonne. All
the samples for NAA were drawn in new, 15-mL Polyvials.
The bottom sampler was not used for the floating plume study. For
the floating plume study, the flow to the fluorometer was independent of the
sampling chain and was drawn through a pipe attached to the boat with the
intake extending 0.5 m below the water surface. The fluorometer sampler
pipe was driven by a 12-V DC "puppy" pump and had a flow rate of =20 L/min.
After passing through the fluorometer, the flow was exhausted over the stern
of the boat.
In addition to the sampling equipment described above, a surface-skim-
ming water sampler was built; however, no acceptable means could be deter-
mined to calibrate the surface-skimmer. Samples drawn by the surface-skimmer
were collected in the field for both the floating and sinking plume, but the
results of the samples collected by the skimmer are presented in only one
instance, Fig. 3.6. The surface-skimmer results are not quantitative and
can only be an indication of tracer presence or absence.
2.1.3.2 Water-Intake Samples
During the sinking-plume study, water samples were drawn at the SWFP
from the raw-water streams for the shore and crib intakes. These 15-mL
samples were drawn every 10 min for almost all the period between 2200 hr on
March 3, to 1240 hr on March 4, 1977. From 1240 hr to 1600 hr CST March 4,
1977, samples were drawn every 20 minutes. (See Table 2.2 for precise
sampling schedule.) Water-intake samples were drawn in the same type of new,
15-mL Polyvials that were used for the shipboard samples. No water samples
were drawn at the SWFP for the floating-plume study.
2.1.4 Analytical Procedures
2.1.4.1 Sample Preparation, Irradiation, and Counting
Lake water in the Polyvial samples was evaporated by placing three
trays of -104 Polyvials each into an oven, set at 80°C, for about 48 hours.
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DRAIN
TURNER DESIGNS
MODEL 10
FLUOROMETER
t
VALVE
TEE
M
Li
FROM 1/2" TUBE - BOTTOM WATER SAMPLER
AIR RELEASE
r
D D D LT
mum;
SAMPLE POLYVIALS
TUBING PUMPS
DRAIN
SINKING PLUME
FLOATING PLUME
FROM SAMPLING CABLE
4 INLETS 1/4"
6 INLETS 1/4"
Fig. 2.4. Schematic of Onboard Sampling Manifold and Fluorometer (Bottom-Water Sampler Not Used For
Floating-Plume Study)
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22
Table 2.2. Sampling Times at SWFP Crib and
Shore Raw-Water Intakes, 1977
Date
Time, hr CST
Sampling Interval
3 Mar.
4 Mar.
2200-2350
0000-0220
0230-0330
0340-0420
0430-0520
0530-0620
0630-0730
0740-0750
0810-0900
0910
0930-1030
Every 10 min
Every 10 min
Every 10 min
Every 10 min
Every 10 min
Every 10 min
Every 10 min, except @0650
Every 10 min
Every 10 min, except @ Q830 &
0850
Every 10 min
Every 10 min, except @ 0940,
0950, & 1000
1040-1130 Every 10 min
1140-1230 Every 10 min, except @ 1230
1240-1600
Every 20 min
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23
Evaporation of the water eliminates 190 gamma-ray interference, the
necessity of sealing of the Polyvial before insertion into the reactor, and
sample expansion or hydrolysis during irradiation.
Immediately before irradiation, the outside of each Polyvial was wash-
ed several times with alcohol to remove NaCl or other surface contamination.
The polyvial was then filled with helium, packed into the "rabbit" capsule
for insertion into the reactor, and irradiated for 90 s* (timed by stopwatch)
in a flux of 2.5 x 1013 n/(cm2 s'1). During the 30 s that elapsed between
the end of irradiation and the start of counting, two steps were performed:
(1) the rabbit capsule was removed from the rabbit tube and taken to a hood
where the polyvial was extracted, and (2) the polyvial was placed in a sam-
ple holder for counting. All samples were counted for 90 s,* and counting
started 120 s after insertion of the sample into the reactor flux.
Making the time interval for irradiation, delay, and counting the same
for all samples permitted direct comparison of peak areas of particular
gammas with the peak areas of calibration samples. This simplified quanti-
fication of the amount of Sm and/or Dy in the lake-water samples. Because
the time intervals were of equal duration, the ratio of the number of counts
(Nc) in a calibration sample's peak to the amount of element (We) contained
was equal to the ratio of the number of counts in the unknown peak (Nu) to
the amount of unknown element (Wu) contained in the sample
Nc Nu T7 NuWc
= , or Wu = —r: .
We Wu ' Nc
(When time intervals are not equal, the radioactive delay must be accounted
for with an exponential decay term and the calculation becomes more difficult.)
The irradiated samples were counted with an Ortec, solid-state lithium-
drifted germamium [Ge(li)], low-energy, photon spectrometer (LEPS) with an
energy dispersion of 120 eV/channel and a resolution of approximately 250 eV.
This detector (Model #8013-25400) had an active surface area of 500 mm2. The
signal from the detector was fed into a Canberra (Model #1468) live-time cor-
rector and then to an Ortec (Model #452) spectroscopy amplifier for pulse
*A few samples taken in Transects C-F (Sec. 3.1.2) of the floating-plume study
were irradiated and counted for 120 or 180 s but these samples were quanti-
fied by comparing them to calibration samples that were irradiated and count-
ed for the same time as the water samples.
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24
shaping. Finally, the signal went to a Nuclear Data (Model #560), 4096-
channel, multichannel analyzer that had a CRT display and a teletype for
hard copy. The CRT display had two line markers that could be moved inde-
pendently through the spectrum for bracketing any particular area of interest,
A hard-copy output could be extracted in two modes. The first mode
was a totalizing function that averaged the number of counts in the two
channels designated by the markers, then subtracted that average from each
channel between the markers. The hard copy in this first mode gave a total
number of counts between the markers and a net number of counts. The second
mode of output was a channel-by-channel printout of the number of counts in
each channel between the markers.
The data were extracted by totaling three equal areas: one area on
each side of the peak for background, and the area containing the Sm or Dy
peak. The net number of counts due to the peak was calculated by
N = T - (2/3)BN - (1/3)BF,
where
N = net number of counts in the peak,
T = total number of counts in the peak region* (Fig. 2.5),
BN = total number of counts in the near background (Fig. 2.5),
and
Bp = total number of counts in the far background (Fig. 2.5).
The above-described method of using the total counts and not the net
counts to sum the counts under the Sm or Dy peak was superior to using the
machine's net calculation. For small peaks, the error, when using the ma-
chine calculation, could be quite large because only two channels are used
to determine background. When peaks are larger, there is no significant dif-
ference between the two methods of determining net counts so, for convenience,
the machine's net calculation was used for large peaks.
The NAA procedure allowed analysis of about 17 samples per hour be-
cause it was possible to irradiate one sample while the previous one was
still being counted.
of counts in the last channel.
-------
o
o
CHANNEL
NUMBER
B,
t
BN
Dy
Sm
I
I
706 738 770 802
BACKGROUND Sm PEAK REGION Dy PEAK REGION
= 0.1043 MeV =0.1080 MeV
834
BACKGROUND
Fig. 2.5. Schematic of CRT Display from Multichannel Analyzer Indicating the Locations of the Sm and
Dy Peaks and the Regions Used to Determine Background
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26
2.1.4.2 Error Analysis
Flux variation. The neutron flux in Argonne's CP-5 reactor was con-
trolled automatically to vary no more than 4-0.5%. Repeated irradiations of
a single calibration sample indicated that the actual variance was < +0.5%.
Sample-volume variation. Ten water samples taken in the field were
selected at random and weighed to determine volume variation. The volume
variation error (1 a) was found to be <3% by weight. The weight variation
of empty polyvials was <0.3%.
Counting statistics. The statistical counting error is generally
accepted as
with
e = error ,
N = number of counts,
and
a = one standard deviation.
This error reflects the Poisson distribution related to the random nature of
radioactive decay. For a detailed analysis, the reader is referred to Live-
sey's textbook (1966, p. 146-149). The summation of counts under a peak is
subject to two statistical errors. The first is the error in determination
of the total number of counts in the peak (T) . The second error is in the
determination of the number of counts in the background [B = (2/3)B + (1/3)B ]
that must be subtracted from T to obtain the net number of counts (N) in the
peak. That is,
N = T - (2/3)BN - (1/3)BF.
The error in N is due to the error in T, denoted by e , and the error in
determining B, denoted by eR = /[(2/3)eM]2 + [(1/3) e,.,]2. The percent total
error in N, e , is
N N
(1/9) (4£2 + E2 )
~ - - X 100'
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27
The statistical error increases with decreasing elemental concentra-
tion (lower peaks) and, generally, only becomes a significant factor, con-
sidering other errors, when elemental concentrations are approaching the
minimum detectable amounts .
Counting geometry. The geometric counting error can be the largest
error in activation analysis and one of the most difficult to quantify.
This error occurs because the REE, upon drying, becomes distributed in places
other than the center of the bottom of the Polyvial. The geometric error was
measured by making a number of 1-mL calibration samples with precisely the
same amount of Sm. Then some of the calibration samples were filled with
distilled water, capped, and shaken by hand. The 1-mL and the full samples
(== 15 mL) were dried in the oven, irradiated, and counted to determine if a
significant difference in the number of counts could be detected. The results
for 24 low- concentration full samples were:
mean = y,, = 397 counts
r
lo = 32.2 counts
- x 100 = 8.1%
and the results for ten 1-mL (same concentration) samples were:
mean = y^ = 426 counts
la = 21.5 counts
- x 100 = 5.0%.
But the statistical error for a typical 1-mL sample that had 429 counts (~Vl)
was 6.0%, and the statistical error for a full sample with 395 counts (=yp)
was 6.5%. Consequently, for these samples, with amounts of Sm approaching
the minimum detectable number of counts (100 cts), the geometric variability
is of the same order as the statistical error. To be conservative, we will
add 7.3% (% difference of y"F and y^) to the counts of each sample.
Sampling procedures. Undoubtedly, errors are associated with the
sampling procedure; however, no way is known of putting a numerical value on
these errors. The method of tagging in no way ensures a homogeneous mixture,
although with time the mixture should become more homogeneous, so that sam-
ples taken in close proximity can differ markedly from each other and not be
indicative of the average concentration in the general area. This type of
error is inherent in any type of tracing experiment and is usually neglected,
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28
not because It does not exist, but because it generally cannot be quantified.
Error summary. Of the six types of errors discussed above, three are
relatively minor, one is basically undetermined, one increases with decreas-
ing tracer concentration, and one (the geometric error) is treated as con-
stant. For the purpose of reporting results, the errors due to calibration
solution, sample volume, and flux variation will be considered insignificant
compared to the other errors, and results will be reported as follows:
sample^weight (g) + 7.3% (from geometry) ± statistical counting
Normally, there would also be some error due to the preparation and counting
statistics of the calibration sample; however, we have mixed, irradiated, and
counted hundreds of calibration samples, and constructed a calibration curve
so that these errors are insignificant.
2.2 ANCILLARY ENVIRONMENTAL DATA ACQUISITION
2.2.1 Meteorological Data
Wind data were of primary interest to this study for comparisons with
measured currents and pollution events at the SWFP. The closest National
Weather Service reporting meteorological station to the study area was at
Midway Airport, Chicago. Wind data were generally obtained from the Midway
Axrport records because the quality of the wind data was slightly better than
that which could be obtained at the SWFP and the Midway wind data were avail-
able in magnetic-tape format.*
2.2.2 Lake Currents
Because of the short duration (* 10 hr) of the floating-plume study,
detailed current meter data were not deemed necessary. However, ANL current
meters were deployed offshore of the Calumet area for a different study and
these data were available to determine the general offshore currents during
the floating-plume study. For the sinking-plume study, lake-current data
*V
lnterc°mParison of Midway and SWFP wind data as this
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29
were gathered at the four stations (I-IV) shown on Fig. 1.1. A Bendix Q-15R
current-meter sensor was positioned 1.5 m above the bottom at each station;
at Station I, a second meter was positioned 5 m above the bottom in order to
obtain information on the vertical structure of the currents.
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30
3 RESULTS AND DISCUSSION—FLOATING PLUME
3.1 SUMMER, FLOATING-PLUME RESULTS, SEPTEMBER 24, 1976
3.1.1 Tagging Operation, September 24, 1976
IHC water was tagged in situ with 4.5 kg (10 Ib) of samarium that had
been complexed with DTPA, and with 3 kg of rhodamine WT dye. Volumes released
were 38 L (10 gal) of samarium/DPTA solution and 15 L (4 gal) of rhodamine
WT solution, respectively. The Sm/DPTA/Rh-WT tag was dispersed in IHC water
by pumping the tag through a pipe with small holes drilled along one side.
The pipe was lowered over the rail of the boat, and the solution was pumped
into the pipe and dispersed at various depths between the surface and -1.0 m
through the holes in the pipe. The dispersion process required 20 min and
occurred at the location in the canal indicated by the "X" on Fig. 3.1.
The Dy-tagged, simulated oily waste was poured on the surface of the
IHC effluent at the same time and in the same location that the in situ, water
tag (Sm) was injected. The oily-waste and tracer consisted of 57 L of the
waste mixed with 0.5 kg (1 Ib) of Dy. The Dy had been dissolved in a 50%
acetic acid solution. Approximately thirty minutes_after the end of the
tagging operation and before sampling had started, an empty ore carrier passed
directly through the center of the dye patch.
The flow in the IHC during the floating-plume study was two-layer.
Cool Lake Michigan water flows into the canal along the bottom while warmer
IHC water flows out the canal on the surface. Near the canal mouth, where
the tagging occurred, each layer is =5 m thick. The physical situation in
the canal is somewhat analogous to a salt wedge in an estuary and is discuss-
ed in detail in Ippen, A. T., 1966.
On the day of the study, September 24, 1976, winds were very light,
there were no waves, and lake currents in the study area were <0.1 kts flow-
ing shore parallel to the NW.
3.1.2 Shipboard Tracking September 24, 1976
The cloud that resulted from the tracers release and subsequent mixing
by the passing ore carrier was mapped four times in the next 10 hr and over
1300 15-mL water samples were collected. Figure 3.2 is a plot showing the
-------
\ \2(G-J)\ \ '
'
Fig. 3.1. REE Tagging Location and Contours of Lowest Detectable Amount of Dy that was Contoured for
Plume Mappings 1-4, Floating-Plume
-------
32
150 300 450
Fig. 3.2. Positions of Sampling Transects - Floating Plume
(Direction of Boat Travel Indicated by Arrows)
-------
33
sampling transects for the floating plume. The ends of each transect corres-
pond to the first and last sampling locations in the transect. The arrow on
each transect indicates direction of boat travel. Table 3.1 lists the sam-
pling times, depths, and number of samples drawn for the transects shown on
Fig. 3.2. Plan view contour plots of Dy and Sm concentrations at each sam-
pling depth are shown in Appendix A. The fluorescent dye was used only as
an indication of where to sample for the Dy and/or Sm, and thus no dye con-
centration records were recorded.
3.1.3 Data Analysis
About 800 of the collected water samples were analyzed by neutron
activation. Generally, the sample that was collected at the surface in the
middle of each transect was analyzed first. The order in which the remainder
of the samples were analyzed was from the center of the transect outward
until relatively little Dy or Sm was detected in the samples. The same pro-
cess was followed at the other five depths. The only exception to the above
selection process was Transect 0 (60 stations) where every fourth sample was
analyzed.
The raw data, the net number of counts in the Dy or Sm peak, were
extracted from the multi-channel analyzer by one of the two modes discussed
in Sec. 2.1.4.1. Computer cards were punched from the raw data and computer
graphics was used to post all the Dy or Sm counts from a given depth at cor-
rect relative locations for each of the four separate plume mappings (Table
3.1). This process was repeated for each depth. The resulting plan-views
of tracer counts were contoured by hand in convenient intervals as dictated
by the raw data.
A transparent, rectangular grid was then placed over the contoured
raw data. The plan-view maps of the plumes thus were divided into about 40
rectangles of equal area. A visual estimate was made of the average number
of net counts in a square and that estimate was punched onto computer cards.
A short Fortran program was written and used to calculate:
1. Total amount of tracer in each plume (1-4) inferred from the
analyzed samples,
-------
Table 3.1. Log for Shipboard Activities, Summer Floating Plume, September 26, 1976
Activity
Tracer Dumped
Plume 1 [C-F]
Plume 2 [G-j]
Plume 3 [K-N]
Plume 4 [O-R]
a
Time
(hr COST)
0815-0835
0933-0939
0954-0958
0959-1002
1004-1006
1052-1106
1112-1116
1119-1124
1130-1137
1320-1342
1346-1353
1359-1411
1420-1427
1608-1646
1700-1706
1711-1721
1729-1740
Transect
ca
D
E
F
G
H
I
J
K
L
M
N
0
P
Q
R
Sampling Depths # Stations
(meters below surface) in Transect
0, 0.5, 1.0, 15, 2.5, 3.5 5
" 5
" ii it ..
5
5
ii n
9
" II n
9
II II _
I
" II II
10
11 II II
12
IT It
14
12
11 n M
59
ii n it
13
ii n n
20
II II n
18
Total Stations = 213
@ 6 samples/station
Total Samples = 1278
-------
35
2. The position of the center of mass of each layer,*
3. The variance about this center of mass in each layer, and
4. The amount of tracer in each layer.
3.1.4 Horizontal Migration of the Cloud
Figure 3.1 is a plot showing the contour of the lowest Dy concentration
that was contoured for the four plume mappings. Note that clouds 1 and 2 are
in a relatively protected zone behind the Inland Steel Company's landfill but
clouds 3 and 4 are in the unprotected lake.
3.1.5 Diffusion Coefficients
Diffusion coefficients were calculated using elapsed time and observed
variance for the last two cloud mappings [3(K-N) and 4(0-R)] at the 0.5 m
level. These two mappings were in Lake Michigan proper and thus would be
subject to lake-type diffusion. The calculated horizontal diffusion coeffi-
cients are shown in Table 3.2 with appropriate values reported by Murthy
(1976) for Lake Ontario. With one exception (K -Sm), the values are very sim-
ilar. The reason that the K for Sm is different by about an order of magni-
tude is probably because the Sm in cloud 0-R is approaching minimum detectable
amounts and the corresponding statistical error is high. The calculation of
diffusion coefficients was done only to show that our data are reasonable
when compared to data resulting from other tracing methods.
Table 3.2. Calculated Horizontal Diffusion Coefficients (m2/s)
2.5
Dy/Oil Sm/Water
Time K b K c K K
y x y x
x 101* sec 2.2 8.4 0.2 6.9
Murthy '
K
y
1.5
o
s Values
K
x
10.5
aLake Ontario
Longitudinal
Lateral
*The layers were 0-0.75, 0.75-1.25, 1.25-2.0, 2.0-3.0, and 3.0-4.0 m (results
from the surface sampler were not used due to sampler calibration problems
discussed in Sec. 2.1.3.1).
-------
36
3.1.6 Average Concentration
Figure 3.3 is a plot of the Dy/oil concentration (Kg/m3) averaged
over the horizontal extent of the measurable cloud for each depth sampled.
Table 3.3 lists the elapsed time after tagging, the percent of original Dy
that was accounted for in each plume, the average concentration integrated
over the depth, and the dilution ratios as compared to Plume 1.
3.1.7 Percent of Dy and Sm above 1.25 m as a Function of Time
The percent of the total Dy/oil and Sm accounted for that is above
1.25 m plotted vs. time after tracer release is shown in Fig. 3.4. The
separate cloud mappings are indicated by the times on the bottom horizontal
axis and the transition from the area protected by the Inland Steel Landfill
to the nearshore zone of Lake Michigan is indicated by the vertical dashed
line.
3.2 FLOATING-PLUME DISCUSSION
3.2.1 Dy Tracer Loss from Oily Waste
The Dy loss factor (4 x 10-1% Dy lost/mL oil/mL water) that was deter-
mined from the bench testing and discussed in Sec. 2.1.2.2 may be used to
estimate if Dy losses were significant during the floating-plume study. The
Dy is detected in plume 3 over a volume of 1.6 x 109 L (400m x 1000m x 4m).
That volume would indicate only a 4% loss of Dy from the oily waste. There-
fore, the loss of Dy from the oily waste into the water through cloud 3 is
not thought to be significant.
In cloud 4, Dy can be detected over a volume of 6.2 x 109 L
(600m x 2400m x 4m) for a maximum Dy loss of 15%. It is doubtful if even
a 15% loss would significantly affect the trends exhibited by the results.
Note that the Dy tracer loss from the oily waste discussed above is
not necessarily related to the percent Dy accounted for in Table 3.3. If
some of the Dy were lost from the oily waste it could remain in nearby
waters and thus be sampled and detected.
-------
Table 3.3. Floating Plumes 1-4 Average Concentration Parameters
Plume
1
2
3
4
Elapsed Time
After Tagging (Sec)
4.8 x 103
1.1 x 104
2 x 104
3 x 104
% Dy
Accounted For
131
83
77
67
Average
Over the
4.8
4.6
2.2
4.9
Concentration
Depth (Kg/m3)
x 10~7
x 10-7*
x 10~7
x 1(T8
Dilution
Compared to 1
= 1:1
2:1
10:1
*Plumes 1 and 2 were too close in time to significantly distinguish between them.
-------
CO
cr
Q_
LU
O
10
-8
1 I
J I I I I I I
10
-7
T I I 1—I I f I
10
-6
U)
oo
Fig. 3.3. Average Layer Concentration (Kg/m3) of Dy/Oil Over the Measurable Cloud
-------
39
The "percent Dy accounted for" was determined by integrating the con-
centrations at sampling points over the three-dimensional structure of the
measurable plume and comparing that weight with the original amount of Dy
in the oil spilled. Deviations from 100% are probably due to the sampling
grid spacing and the diffusion of Dy to undetectable concentrations at the
plume edges. Plume 1, which shows 131% of the original Dy accounted for
appears strange but the seeming disparity is due to the non-synopticity of
measurement of that plume. Plume 1 was sampled in a region where the flow
of the canal was relatively fast and the direction of movement was changing
from directly out the canal to a more lakeward heading. Consequently, plume
1 was the least synoptic of the four measured plumes.
3.2.2 Vertical Migration of the Cloud
Figure 3.4 shows that the amount of Dy and Sm above 1.25m changes with
time and horizontal position. Both Sm and Dy migrate toward the surface un-
til the cloud passes into the nearshore zone of Lake Michigan. After passing
into the nearshore zone, the cloud tends to mix downward.
The warm canal water flows out and rises over the inflowing, colder
Lake Michigan water. When the IHC plume enters Lake Michigan proper, it is
then subjected to large-scale, lake-type diffusion and it is more dense
due to cooling. These two factors, large-scale diffusion and the decrease
of the density difference between the two layers due to cooling of the
upper layer, cause some downward migration of the cloud when it enters the
lake proper.
Initially, it was thought that the oily waste would resurface even
after the extreme downward mixing that occurred due to the passing ore car-
rier; however, (in light of the data) it was hypothesized that the oily
waste must have been reduced in size to oil droplets that were so small that
positive buoyancy was less important than lake diffusion acting to mix the
oil droplets. Recent literature was reviewed to see if others have found
evidence of oils remaining suspended in the water column.
McAuliffe (1977) interpretated findings by others and reported that,
"under agitation by wind and waves, many oils break up, and small droplets
disperse into the underlying waters" and "as surface slicks break into oil
droplets or particles and disperse in near-surface waters, most remain
-------
40
PROTECTED ZONE
I.lx 10
TIME (SECONDS)
.2-xlO
3x10
Fig. 3.4. Percent of the Total Dy/Oil and Stn Accounted for by Measurement
Found Above 1.25 in vs. Time After Trar«. P«IMM asurement,
Time After Tracer Release
-------
41
suspended and move with the water." Certainly, the agitation caused by the
passing ore carrier was equivalent to severe agitation by wind and waves and
thus explains why the oil was found at depth and why the oil did not immedi-
ately resurface but moved with the water.
The explanation of why the oil did not resurface is related to the oil
particle size after agitation. Shaw (1977), in a discussion on colloidal
hydrocarbons says, "Larger oil particles rapidly float to the surface, as
described by Stoke's law, when mixed into water. Colloids, however, remain
in suspension for extended periods." Colloidal particles are roughly 10 9
to 10~6 m (1 ran to 1 ym) in size. Shaw goes on to say, "Evidence is indirect
but substantial that colloidal size hydrocarbon particles are formed in sea-
water under conditions of turbulent mixing, " The results of Peake and
Hodgson (1966, 1967) and Gordon et al. (1973) were discussed by Shaw. Both
groups mixed hydrocarbons with water and, "...found that the quantities of
hydrocarbons less than 1 ym, as determined by filtration, were greatly in
excess of the values for a saturated solution."
The final bit of evidence comes from McAuliffe (1977) who discussed
the work of Brown et al. (1973), Brown and Huffman (1976), and Brown and
Searl (1976). They measured non-volatile hydrocarbons along tanker routes
in the Atlantic, Pacific, Indian, and Caribbean and determined that, "con-
centrations at 10 and 30 m were about 40% of those in surface samples. This
indicates the hydrocarbons are particles (droplets?) and not in solution."
3.2.3 Relationship Between the Movement of the Oily Wastes and the Underlying
Waters
After the oily wastes were mixed into the water column their movement
did not differ significantly from the underlying Sm-tagged waters. As in-
dicated in Sec. 3.1.5, mixing coefficients for the Dy/oil and Sm/water are
similar. Moreover, Fig. 3.4 indicates no significant differences in the gross
vertical movement of the Sm/water and Dy/oil. There is clearly a difference
between the small, limited spill (57 L) artificially mixed into the water
column discussed in this study and a major spill involving millions of liters.
Extrapolations from the results above to the case of a major spill may not be
valid. Therefore, different relative motions between the oil and underlying
water might be expected for a major spill. This would be particularly true
-------
42
during the initial phases of spreading of a major spill where gravity
viscosity, and surface tension are dominant. However, when such a slick
beco.es thin and oil mixes into the water column behavior similar to that
reported in this study might be found.
-------
4 RESULTS AND DISCUSSION—SINKING PLUME
4.1 WINTER SINKING-PLUME RESULTS, MARCH 2-4, 1977
4.1.1 Tagging Operation, March 2, 1977
IHC water was tagged in situ with 13.6 kg (30 Ib) of samarium that had
been complexed with DTPA, and with 7.5 kg of rhodamine WT dye. Volumes re-
leased were 114 L (30 gal) of samarium/DTPA solution and 38 L (10 gal) of
rhodamine WT solution, respectively. The samarium/DTPA/Rh-WT tag was dis-
persed in IHC water by pumping the tag through a pipe with small holes drill-
ed along one side. The pipe was lowered over the rail of the boat and the
samarium solution was pumped into the pipe and dispersed at various depths be-
tween the surface and -1.0 m through the holes in the pipe. The dispersion
process required 10 min and occurred at the "REE tagging location" (Fig. 3.5).
On March 2, 1977, the tagging location was approximately 900 m upflow from
the point where the canal water was sinking. The zone of convergence of canal
and lake water was easily determined with a temperature probe and is indicated
in Fig. 3.5 by "surface temperature convergence." As the survey vessel
NEPTUNE proceeded lakeward in the canal, the surface water temperature dropped
from 7.5 to 1.8°C within a few meters. Canalward of the sinking zone, the
water temperature was vertically isothermal. Just lakeward of the sinking
zone, however, the temperature profile showed warm (K4.0°C) water near the
bottom, overlain by colder (~1.8°C) water.
The Dy-tagged, simulated oily waste was poured on the surface of the
IHC effluent at the same time and in the same location that the in situ water
tag (Sm) was injected. The oily waste and tracer consisted of 170 L of the
waste mixed with 1.4 kg (3 Ib) of Dy. The Dy had been dissolved in a 50%
acetic acid solution.
4.1.2 Shipboard Tracking. March 2-4, 1977
About 1000 water samples were collected in Polyvials aboard the
NEPTUNE while tracking the dye that was used to tag the IHC effluent. Perti-
nent water-sampling parameters such as time, date, and depth are shown in
Table 4.1 and sampling transects are plotted on Fig. 4.1. Approximately 200
of the samples were collected in Transects A, B, and C (Fig. 4.1) in the
-------
Table 4.1. Log for Shipboard Activities, Winter Sinking-Plume Study, 1977
Day
Wed.
"
"
"
Thurs .
n
"
"
"
"
"
"
Fri.
»
"
n
n
Time
Date (hr CST)
2 Mar. 1300-1310
1806-1823
2015-2025
" 2226-2040
3 Mar. 0408-0424
0424-0426
0430-0447
0449-0455
" 0505-0508
0509-0528
1246-1316
" 1345-1401
4 Mar. 1057-1127
11 1214-1228
1504-1516
1516-1556
1652-1706
Sampling Depths
(meters below
Activity surface)
Tracer dumped
a b
IHC Transect A 0,1,4,7,B
" B 0,1,4,7,8
" C 0,1,4,7,B
Cal. Hbr. " D 0,0.5,3.5,6.5,8
n M M IP ii n M n ii
It II II -p M II II II II
II II II Q II II It It II
II It It TI It II II M II
II II II j II It " M II
II II II j It It II II It
II It II J7 II II » " "
" " L 0,1,4,7,B
" M 0, 0.5, 3. 5, 6. 5, B
" " " N 0,1,4,7,8
" 0 0,1,4,7,8
" P 0,1,4,7,8
No. Stations
in Transect
18
11
13
7
7
17
6
3
17
15
17
28
17
6
17
7
See Fig. 4.1 for location of transects
B-Bottom
-------
45
LAKE MICHIGAN
BOTTOM CONTOUR
DEPTHS IN FEET
Fig. 4.1. REE Tagging Location, Temperature-Convergence Zone, and Positions
of Sampling Transects, Sinking-Plume
-------
46
canal-entrance and near-entrance areas. All 200 were analyzed by NAA for
their Dy and Sm concentrations. Of the remaining 800 samples collected in
the Calumet Harbor area, 350 were analyzed* and only ten of those indicated
the presence of Sm (canal water); however, many of the samples from Calumet
Harbor indicated the presence of Dy (simulated oily waste).
In Figs. 4.2-4.7, the sampling stations are numbered in ascending
order corresponding to the direction of boat travel. The transect locations
are plotted on Fig. 4.1. Each transect (on Fig. 4.1) has an arrow indicating
the direction of boat travel and the ends of each transect correspond to the
first or last sampling station. The distance between sampling stations varies
slightly but is =100 m.
Contours of constant concentration values in Figs. 4.2-4.7 are in
nanograms per liter (ng/L); that is 10~9 g/L. The Dy-concentration contour
interval is based upon a two-standard-deviation spread (statistically, the
96% confidence level) in the net number of counts in the peak. This spread
is close to 100 counts. Thus, each ng/L contour interval on Figs. 4.2-4.7
reflects a 100-count interval in the raw data. Owing to rounding, and
significant-digit considerations, the conversions from counts to ng/L may give
nonuniform differences in contour values. Note that 100 counts corresponds
to the minimum detectable amount of Dy or Sm.
Figures 4.3-4.7 show, in addition to the Dy concentration, the near-
bottom dye concentration. The dye was used merely to indicate the presence
of IHC effluent and exact correspondence between the concentrations of the
Dy and dye should not be expected. The Dy values on Figs. 4.3-4.7 represent
"instantaneous" values, inasmuch as they were determined from 15-mL grab
samples. The dye values represent integrated averages over a much larger
flow of water (=125 mL/s) and a much longer time period. The purpose of
monitoring the dye was to indicate water masses to be sampled for Dy and Sm.
Figure 4.2 is a plot of the Dy concentrations (oily-waste tag) with
depth in Transect A (Fig. 4.1). Transect A passed directly through the strong
surface-temperature gradient at the mouth of the IHC, and Fig. 4.2 clearly
shows a zone of sinking Dy (between Stations 1 and 6) and a region of high
*That is, every other or every third sample along a transect was analyzed
(unless a high value was observed, in which case samples on either side were
analyzed).
-------
TO LAKE MICHIGAN
LIGHT TOWER AT INDIANA
'HARBOR CANAL ENTRANCE
en
Q.
LU
O
O
Q-
•<
eo
10
(BOTTOM)
ENTRANCE TO
INDIANA HARBOR
TURNING BASIN
SAMPLING STATIONS
500 meters
Fig. 4.2. Transect A: Dy Concentrations. (Concentrations in ng/L All 90 samples collected were
analyzed. The dashed contours indicate how the figure would look if concentration values
for the surface samples could have been considered.)
-------
(W
UJ
H- /-N H
3 CU i-i
O P
3 rt 3
OQ CO
•^ H- fD
f 3 O
O
(U
CO
(b O
P O
T) 3
H* n
n> ft
B> rt
3 H
fu to
N O
(D 3
(X CO
3-
»j
n>
p:
i-i
•d I
O W
H- O
3 rt
rt rt
O fD
O
3 n
o o
n> 3
3 n
rt (D
i-l 3
cu rt
rt i-l
H- 03
O rt
co
o
3
co
NEAR BOTTOM
DYE CONCENTRATION (ppb)
SAMPLING DEPTHS (m)
CD
O
O
O
O
cn
CJ1
— O
CO
-o
o
CO
CJl
X ' A
\J>» £-
c»
V
4*
O
.o A
-------
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15 17
E
CO
CL.
UJ
O
a.
CO
7,5
(BOTTOM)
80
• •/•—8,5m
/ (BOTTOM)
o -
o
I
5 10
SAMPLING STATIONS
15 17
Fig. 4.4,
Transect I: Dy Concentrations and Near-Bottom Dye Concentrations
(dot indicates sample analyzed at that point, Dy concentrations
in ng/L)
-------
50
—*
CO
Q.
UJ
O
Zj
n
0
0.5
3,5
1 5
1 HO40
_
-------
OQ
NEAR BOTTOM
DYE CONCENTRATION (ppb)
SAMPLING DEPTHS (m)
3
TO
o P
rt 3
CD
H- (D
3 O
&• rt
tD
CO O
*
rt pi
H
13 I
O W
H- O
3 rt
rt rt
- O
o n>
o
3 n
o o
n> 3
3 n
rt o>
i-i 3
»> rt
rt
H-
O rt
3 H-
cn O
3
H- CD
3
B>
— o
A
4*
O
CO
o
ro
O
ro
en
ro
oo
-------
52
0
JE
CO
h-
Q.
\jj
O
40
o
-------
53
Dy concentration near the bottom. Thus, Fig. 4.2 shows the sinking of the
simulated oily waste; however, the dashed contours, which indicate how the
raw data would have been contoured if the results of the uncalibrated surface
sampler (Sec. 2.1.3.1) were considered, suggest that some of the oily waste
does cross the subduction zone and does not sink.
Dy transects B and C and Sm transect A, B, and C are shown in Appen-
dix B. The Sm transects show little similarity to Dy transect A. Diffusion
calculations for the Sm tracer in the canal (Sec. 4.2.3.2) indicate that the
Sm plume had diffused considerable less than expected from its initial size
at tagging (24m x 2m x 1m) while traveling to the subduction zone. Conse-
quently, the main body of Sm was missed during the sampling of transect A
but the main body of the Dy-tagged oil which had spread over the canal surface
to a much greater extent, was sampled. Transects B and C occurred after
most of the tracer had left the canal. In fact, the plume, as indicated by
the dye, was lost for about 8 hrs and transects B and C were made during
this period in the hope of relocating the main body of the plume. A portion
of the plume was relocated in the region of transects D-I (Fig. 4.1); however,
a partitioning of the Dy/oily-waste and Sm/water had occurred prior to re-
location. This partitioning is discussed in detail in Sec. 4.2.3.1.
Figure 4.3, for Transect F (Fig. 4.1), shows both the Dy concentrations
through the water column and the dye concentration near the bottom. Along
this transect, the simulated oily waste and its Dy tag seem to be relatively
well mixed with depth. There is one sample point with a very high Dy con-
centration; the high value may be due to an unusually large drop of oil drawn
through the sampling tubes. These singular spots of high concentration occur
in many transects.
Figure 4.4 for Transect I, shows a relatively high concentration of
Dy at the lakeward end of the transect. Again, the Dy/oily-waste appears to
be relatively well-mixed, as in Transect F. A peculiar occurrence in Tran-
sect I is that the dye does not reflect the increasing Dy/oily-waste concen-
tration at the lakeward end of the transect.
Transect K data (Fig. 4.5) reveal the close proximity of the oily
waste to the shore. Figure 4.1 shows that the NEPTUNE steamed obliquely into
and then away from shore. The region of highest concentration was only about
500 m from shore. Concentrations may have been higher further inshore, but,
because of the shallow depth, the NEPTUNE could not sample there.
-------
54
Transect L (Fig. 4.1) was made by steaming southeastward along the
centerline of the dredged ship channel, which runs parallel with the Calumet
Park Breakwater. Concentrations (Fig. 4.6) along this transect show that
the Dy/oily waste, and the dye, made a clockwise circuit of the Calumet Har-
bor, because no dye had been detected in the channel on the previous day.
Transect N (Fig. 4.1) was made by steaming out of the Calumet River,
starting about 900 m upstream of the river entrance. The Dy data (Fig. 4.7)
indicate that some of the oily waste from the IHC entered the Calumet River.
Stations 1-4 (Station 4 is at the river entrance) were in the river, and
there were detectable amounts of Dy at those stations.
Plots of the remaining transects D, E, G, H, J, M, 0, and P are shown
in Appendix B because they provide little additional information.
4.1-3 Tracer Concentrations at the SWFP
Some 240 Polyvial water samples were drawn at the SWFP from the raw
water streams of the shore and crib intakes. All 240 samples were analyzed
by NAA, and concentration data for the samples that contained Sm and/or Dy
are shown in Tables 4.2 and 4.3. For all the samples that contained detectable
Sm end/or Dy, Fig. 4.8 gives relative amounts as a function of time for each
raw-water intake. Relative amount is computed as the amount of a given REE
found in a Polyvial sample divided by the quantity of that REE was released
in the IHC effluent times 100.
4.1-4 Lake Currents and Meteorological Conditions
4.1.4.1 Results of Lake Current Measurements
The current meters were deployed for this study for the period January
4 to March 26, 1977. All meters returned useful data, except the meter at
Station II which had sporadic malfunctions. Data from that meter, when oper-
ating properly, were consistent with those at Station I but were not used in
time-series analyses. The major features of the observed currents during the
study period were:
1) the mean flow was toward the southeast, though there were
four major direction reversals of the generally southeast-
ward flow during the recording period;
-------
55
Table 4.2. Sm Concentrations of Samples
Collected at the SWFP
Date
3 Mar.
it
4 Mar.
If
II
M
It
II
„
"
M
3 Mar.
M
ii
4 Mar.
M
M
II
II
Time,
GST
2220
2310
0030
0300
0430
0450
0720
1040
1200
1220
1520
2200
2250
2340
0300
0450
0710
1100
1200
Concentration,
Pg/L
Crib Samples
61. Ob
7.7b
2.8b
6.7b
102. lb
6,lb
2.4b
5.0b
2.1b
5.1b
1.6
Shore Samples
2.9b
1.6
4.0b
1.6
1.6
2.7b
1.8
1.9
% error
2.0
8.3
23
9.6
1.4
10
24
13
27
12
34
22
42
18
46
41
25
34
32
Minimum detectable amount, Sm - 100 counts -
1.4 yg/L
Indicates average of two irradiations.
-------
56
Table 4.3.
Dy Concentration of Samples
Collected at the SWFP
Time
Date CST
3 Mar. 2210
" 2230
2310
2320
2340
2350
" 2400
4 Mar. 0020
0030
0050
0100
0110
0140
0400
0710
3 Mar. 2200
2230
2250
2300
2350
4 Mar. 0020
0050
0100
" 0120
0130
0220
0230
0250
0300
, Concentration,3
ng/L
Crib Samples
54
82
54b
61b
55b
70b
47
57
60b
43
43
43
48
51b
45
Shore Samples
74b
158b
45
48
62
45
74b
46b
64
58
48
71
67
74
% error
29
20
29
27
30
24
33
26
26
36
39
37
34
32
33
21
14
44
39
31
43
29
45
32
31
40
26
29
28
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57
Table 4.3. (Contd.)
Time,
Date CST
4 Mar. 0330
0410
" 0420
0430
0550
0630
11 0720
0730
0840
1010
1050
1100
" 1110
1240
1320
1500
1520
a
Concentration,
ng/L
Shore Samples
43
52
47
69
55
49
68
55
45
64
50
62
56
49
47b
45
62
% error
45
36
40
27
32
36
26
31
40
28
35
28
35
36
35
37
27
Minimum detectable amount, Dy - 100 counts
43 ng/L
Indicates average of two irradiations.
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58
io-'H
io-9-
10°-
...
Iff*
Sm CRIB INTAKE
I I
Sm SHORE INTAKE
i i r
Dy CRIB INTAKE
Dy SHORE INTAKE
,0*
ir"
??
i
00
Ul
y
»ci
?
H 3
.
KM
-
}
It
'
0?OC
,
'k
340
9 0
T
.
600
ME
(*
•
0800
r)
IOC
•
10
1
1200
M*f
"H
(
1400
4
1600
Fig. 4.8. Relative Amount of Sm or Dy in the Samples Collected
at the SWFP as a Function of Time. (Dashed line
indicates the minimum detectable amount; two dots at
a sample indicate the sample was irradiated twice
and shows the value of each irradition.)
-------
59
2) the average speed was about 0.015 m/s and the rms speed was
about 0.074 m/s;
3) most of the energy of the currents was in the low frequency
region of the spectrum, between 1.0 x 10~6 Hz and 1.4 x 10~5
Hz;
4) the vertial variation of the current was small at Station I
with a cross-correlation coefficient between the major veloc-
ity components at the two meters of 0.80; and
5) the currents at Stations I, III, and IV, when parallel to
the depth contours, were relatively uniform with high coher-
ence between currents at the different stations at frequen-
cies below 1.4 x 10"5 Hz. Low coherence existed above that
frequency, except at the frequency bands near 3.3 x 10~5 Hz
and 1.3 x I0~k Hz.
Although sampled only sparsely, the flow field seems to have been
rather uniform over the region between the IHC and SWFP intakes. Near-bottom
currents at Stations I, III, and IV were resolved into components parallel
and perpendicular to the major axis of current fluctuations (the major axis
was defined as that on which the cross-correlation coefficient of the two
components at the single station was zero). Cross correlations were then
calculated between the major velocity components of the three stations for
about 22 days of the record. Similar calculations were made for the minor
velocity components. The results of these calculations are shown in Fig. 4.9
where cross-correlation coefficients for the major and minor near-bottom
velocity components between stations are given as a function of the spatial
separation between the meters correlated. The circled points represent
values from this study. The triangles represent values from data from another
Argonne study in which current meters deployed at mid-depth were located
along a northeasterly line (perpendicular to shore) between Stations I and
III. These data, while not synoptic with those of the present study, in-
dicate similar relationships but for separation distances along a line in the
offshore direction. Major velocity components are well-correlated within
the study area for the period of measurement and suggest the existence of a
rather uniform flow field.
4.1.4.2 Meteorological Conditions
Figure 4.10 is a progressive-vector diagram of Midway Airport Winds dur-
ing the sinking-plume study. The figure shows that the wind was from the SE
from about 0800 hr on March 2 until about 0800 hr on March 4. Total wind
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60
movement
averaged
during the period of SE winds was about 103 km and maximum speed
over an 8-hr period (length of longest vector/8 hr) was about 6.5 m/s.
T
T
T
T
T
WINTER SUMMER
4 6 8 10
SEPARATION L(km)
12
14
Fig. 4.9.
Correlation Coefficients for the Principal and Transverse Com-
ponents of the Current as a Function of the Distance Between
Stations
1.0 -•
MIDWAY WINDS
(8-HR VECTORS)
MAR I
Fig. 4.10. Progressive-Vector
Diagrams for March 1-4,
1977, Midway Airport
Winds
MxlO
1.0
-------
61
4.2 SINKING-PLUME DISCUSSION
4.2.1 General Considerations
In this part of the report we examine and extend certain aspects of
the above work involving the sinking plume. The results of the field exper-
iment are summarized and employed to provide descriptions of the sinking
plume behavior of the IHC effluent. Results of the tracer experiment, in
which a portion of the IHC effluent was tagged, are compared with estimates
of dilution using a similar turbulent-diffusion model to gain some under-
standing of the applicability of such models in the study region. Then,
based on the characteristics of lake currents during the study period, a
simple model is proposed to estimate the mixing by turbulent diffusion of
the entire IHC effluent as it moves northwestward.
4 2.2 Characteristics of IHC Effluent Plume for January 4 - March 26, 1977
The South Water Filtration Plant's intakes are located at the shore
near the plant, and at the Dunne Crib (Fig. 1.1). These intakes lie on a
northwesterly bearing from the IHC. In order that the effluent from the IHC
reach the SWFP's intakes, it must be advected by the nearshore currents in
the lake. This section discusses the advection of the effluent and the dilu-
tion of the effluent as based on the random motions of the observed currents.
This discussion is limited to the period January 4 - March 26, 1977. It
should be remembered that the ice-cover observed during this period may not
apply to other years, as this winter was the severest on record. The advec-
tion and dispersion physics, on the other hand, are generally applicable and
may be used to deduce the expected transport and mixing of IHC effluent under
similar wind and ice-cover conditions.
If the IHC effluent is to reach the intakes, a northward current along
the shore is a necessary but not completely sufficient condition. The current
must be of sufficient magnitude and persistence for the water to move the dis-
tance between the IHC and one or the other of the intakes. During the winter
of 1977 such events were not common — only four occurred. Each of these was
marked by elevated levels of hydrocarbon odors in the raw water drawn in
from the SWFP's intakes.
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62
There were also several northward current episodes of lesser magnitude,
Weak hydrocarbon odors were detected during these periods, but they were not
significant. (The maximum level observed during one of these episodes was
4 Ch.*)
During March 8-10 an episode of generally westward flow occurred. The
hydrocarbon-odor levels, generally low during the preceding days, were most
likely the remnants of the March 2-4 episode. On March 9, a maximum hydro-
carbon odor level of 7 Ch was reached at the shore intakes and on March 10
an odor level of 10 Ch was reached at the Dunne Crib.
Generally, hydrocarbon odors are not observed at the SWFP until north-
ward-flowing currents have continued for about a day. Hydrocarbon odors then
persist even after the current has reversed direction. The structure of the
currents both before and after the northward-current episodes indicates that
any tracer in the IHC effluent will tend to be confined to the shore region
by the current field. Also, mixing will likely occur only slowly and will
be due to advection of the surface waters offshore by wind along with the
slow replacement by deeper water from the lake.
4.2.3 Transport and Dilution of Tagged IHC Effluent
4-2.3.1 Interpretation of Experimental Observations
Results of the plume-tracking field study (Sec. 4.1) show that the
effluent from the IHC enters the City of Chicago's water-purification system
at the SWFP's Dunne Crib and shore intakes. Unfortunately, a detailed pic-
ture of the effluent's path to the crib or shore intake cannot be established
from the tracer data. However, two paths may exist for transport of IHC
effluent to the SWFP's water intakes. Each path is governed by the nature of
entry of IHC effluent into the lake, incompletely mixed near-surface water
taking one path and well-mixed, 4°C bottom water taking the other.
During the development of a sinking plume, when the IHC waters mix
with Lake Michigan waters at the subduction zone, not all the IHC water sinks
to the bottom. If all the IHC water sank to the bottom, then the near-surface
*Ch - "hydrocarbon" odor (Standard Methods for the Examination of Water and
Wastewater, 1965, Table 18).~ ~~
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63
temperatures immediately lakeward of the convergence zone would be the same
as ambient Lake Michigan water. But temperature profiles immediately lake-
ward of the convergence zone show the near-surface water to be 1-1.5°C, not
near 0°C as is typical for ambient Lake Michigan water. Also, the data from
the surface sampler in Fig. 3.6 indicates that some portion of the oily wastes
do not sink but remain on the surface. Therefore, some portion of IHC water
stays near the surface and moves toward the shore due to the action of winds
blowing from the southerly quadrants. This is the portion of the IHC efflu-
ent that was tracked by the NEPTUNE, and it typically follows a path along
the shoreline.
The other path, followed by the portion of IHC water that sinks to the
bottom, roughly parallels the 9.1-m (30-ft) depth contour (Fig. 4.1). This
isobath coincides with the lakeward end of the IHC entrance channel. Such
bottom water from the IHC would move directly into the lake and then north-
eastward along the coast, missing the area enclosed behind the Calumet Har-
bor Breakwater. This sinking-plume portion of the IHC effluent would follow
the second path to travel directly to the SWFP. Topographically, the depths
of the crib intake and of the IHC entrance channel are about the same, 9.1 m
(30 ft). Effluent flowing out of the IHC along the bottom would tend to
remain near the 9.1-m (30-ft) contour as it moved northwestward parallel to
shore, and this path would carry it directly to the crib intake. Further
evidence of the existence of a direct lakeward path is found in the high con-
centrations of Sm detected in the crib samples and the fact that these sam-
ples were drawn at the time that the NEPTUNE was drawing water samples in
Calumet Harbor, water samples that contained Dy (oily waste) but virtually
no Sm (canal water).
The results from Transect I (Figs. 4.1 and 4.4), which ends near the
9.1-m (30-ft) isobath, indicate an increasing concentration of Dy in a lake-
ward direction, but no corresponding increase in dye. In approaching the
9.1-m (30-ft) isobath, the NEPTUNE may have entered a segment of the plume
moving northwestward along the bottom. However, the fact that the dye con-
centrations do not reflect the increasing Dy concentrations is puzzling.
Because the Dy-tagged oil spread over the surface of the canal much faster
than the Sm- and dye-tagged water spread beneath the surface, the Dy-tagged
oily waste reached the subduction zone first. Transect I may have reached
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64
the leading edge of the tagged oily waste that had been mixed into the sink-
ing plume before the Sm and dye became mixed.
Table 4.2 shows the Sm concentrations in the raw-water samples collect-
ed at the SWFP. Seven of the eleven crib samples contained higher concentra-
tions of Sm than any of the eight shore samples. Two of the crib samples
(March 3 at 2220 hr and March 4 at 0430 hr) contained very high concentrations
of Sm. In contrast, fourteen of the crib samples contained Dy and all but
two of these were in a three-hour-and-ten-minute span (2210-0120) . Thirty-
one of the shore samples contained Dy, however, and these were fairly equally
spaced throughout the entire 17-hour sampling interval at the SWFP.
These results indicate that significantly more Sm (the water tracer)
went to the crib intake than to the shore intake. Also, significantly more
Dy (the oil tracer) went to the shore intake than to the crib intake. This
appears reasonable, because a large portion of the oily waste (Dy) would tend
to remain on the surface and thus would be blown toward the shore by the SE
winds that occurred during the experiment. Therefore, the oily waste would
have had a higher probability of being drawn into the shore intake. The
water (Sm tracer), however, would be more likely to sink at the subduction
zone and be carried along the 9.1-tn (30-ft) isobath with the prevailing north-
westerly directed current to pass over the crib's bottom water intake. As
mentioned above, further evidence of this partitioning of the oily waste and
IHC water is found in the fact that so little Sm (the water tag) was seen in
the Calumet Harbor area.
A representation of the average current field for the near-bottom
waters in the vicinity of the IHC and SWFP has been constructed from the
current-meter records for March 3, 1977, as an aid in determining the path
of the IHC and tagged effluents. This day was chosen because it coincides
with the period of maximum current during the tracer experiment. The flow
field is shown in Fig. 4.11. Streamline directions were drawn at the loca-
tions of the current meters and aligned with the average direction of current
during the period. The spacing between streamlines was made inversely propor-
tional to the observed average speeds. The current field was modified in
the vicinity of the mouth of the IHC to reflect the outflow from the canal.
This representation is clearly limited by the small number of data points;
however, it does not appear to be inconsistent with other observations of the
tracer transport.
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65
DEPTHS IN FEET
CENTRAL WATER
FILTRATION PLANT
LAKE
MICHIGAN
SOUTH WATER
FILTRATION PLANT
Fig. 4.11. Schematic Reconstruction of the Velocity Field of the Near-Bottom
Water on March 3, 1977
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66
Several features of the velocity field are shown in this representa-
tion. First, the turning of the current after passing the Inland Steel
Breakwater will advect the IHC effluent into the nearshore region between
the IHC and Calumet Harbor. This is a relatively shallow region that can
experience considerable wave action under southeasterly or easterly winds.
Strong mixing under such conditions would act to weaken or destroy the ver-
tical stratification of the sinking plume. Second, the IHC effluent advected
into the region between Calumet and Indiana Harbors must return to the lake.
The only return paths are through the opening in the Calumet Harbor Break-
water or around the end of the breakwater. Third, the IHC effluent would,
if there were no mixing across the streamlines, be confined to a narrow region
near the shore as it passed the South Water Filtration Plant.
4.2.3.2 Comparison of Simple Dilution Estimates with Measurements
The lack of detailed sampling of the plume between the IHC and the
SWFP and the partitioning of the tagged portion of the plume, described
above, make definitive statements concerning the transport and mixing im-
possible. However, a simple estimate of the dilution of the tracer along an
assumed pathway can be compared with tracer measurements at the SWFP.
Table 4.4 presents dilution ratios for the Sm samples collected during
the experiment at the SWFP's crib and shore intakes. The dilution ratio is
defined as the ratio of the initial concentration in the water at the tagging
location to the concentration in the collected samples. Initially, 13.62 kg
of Sm were mixed in the IHC waters over a region about 24 x 2 m in area and
1 m in depth, yielding an initial concentration of 0.284 g/L.
The estimate of the dilution of the tagged portion of IHC effluent be-
tween tagging and the intakes neglects several of the complexities of the
process. Horizontal spreading of the tagged patch in the IHC is computed for
the transport between the initial tagging location and the lake. Partition-
ing at the sinking location and additional mixing there are neglected.
After sinking, the patch is assumed to be advected at an average speed toward
the SWFP along the streamlines indicated in Fig. 4.11, and horizontal spread-
ing of the patch during travel to the vicinity of the intakes is calculated.
Vertical mixing is neglected.
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67
Table 4.4. Dilution Ratios for Samarium Samples
Collected at the SWFP
Time
Date GST
3 Mar. 2220
" 2310
4 Mar. 0030
" 0300
0430
" 0450
" 0720
" 1040
" 1200
" 1220
" 1520
3 Mar. 2200
2250
" 2340
4 Mar. 0300
" 0450
0710
11 1100
" 1200
c , ci
V' Dilution Ratio, —
UgM CF
Crib Samples
61.0
7.7
2.8
6.7
102.1
6.1
2.4
5.0
2.1
5.1
1.6
Shore Samples
2.9
1.6
4.0
1.6
1.6
2.7
1.8
1.9
4.7 x 103
3.7 x 104
1.0 x 105
4.2 x 10"
2.8 x 103
4.7 x 10"
1.2 x 105
5.7 x 10"
1.4 x 105
5.6 x 10"
1.8 x 105
9.8 x 10"
1.8 x 105
7.1 x 10"
1.8 x 105
1.8 x 105
1.1 x 105
1.6 x 10s
1.5 x 105
Note: Initial concentration (Cj) = 0.284
C = final concentration.
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68
The advection-diffusion equation for these estimates becomes
|i+D|*..L_ /„ aA + a_
3t 9x 3x I H 9x J 3y
where = concentration
U = current speed parallel to the streamlines, assumed uniform
in time and space,
t = time
x,y = longitudinal and lateral coordinates, respectively (curvature
of the streamlines is neglected), and,
°H = horizontal or lateral mixing coefficient.
For mixing in the canal, solution to Eq. (1) for an instantaneous
source of finite size was found for the case of a constant lateral mixing
coefficient (Csanady, 1972). On March 2, 1977, the average transport velocity
from the tagging point, in the canal, to a point 2 km into the lake was about
0.085 m/s. The lateral mixing coefficient was estimated to be about 0.01 m2/s
(Fischer., 1973). Computations indicate that in the lake offshore of the
canal, about 2 km from the tagging location, the tagged patch has nominal
dimensions (four standard deviations of the concentration profile) of about
80 m on a side. The dilution ratio, based on the initial concentration of
Sm and the maximum concentration at the center of the patch, was about 127.
Mixing of the tagged effluent as it is transported along the bottom
in the lake, from the location offshore of the IHC to the vicinity of the
SWFP's intakes, was estimated for the case of a variable horizontal mixing
coefficient. Experimental observations of mixing in the Great Lakes (Csanady,
1972, Huang, 1971) and the oceans (Okubo, 1971) have indicated that D may
* H
not be constant, but rather that it increases as the scale or width of the
plume increases. The relationship for these observations takes the form,
°H - k SS (2)
where SH = the standard deviation of the concentration distribution, and
k,n = experimental constants.
Values for n vary from 0-1.5 and, for the estimates of mixing made here,
n = 1 and 4/3 were used for linear and "4/3's law" mixing, respectively.
-------
69
For the tagged patch measuring approximately 80 m x 80 m outside the
IHC, a mean lake current of 0.13 m/s,* and patch transport of 12 km northwest-
ward to the intakes, the calculation with n = 1 and k = 0.00142 m/s (Okubo,
1971) yields a patch with a nominal diameter of 530 m in the vicinity of the
intakes. The dilution ratio for mixing in the lake, based on the maximum
concentration at the center of the patch, is about 24. Together with the
dilution due to mixing in the canal, this yields a dilution ratio, based on
the initial tagged-water Sm concentration of (24)(127) = 3.0 x 103.
A similar calculation, employing n = 4/3 and k = 0.000463 m2/3/s,
indicates a patch with a nominal diameter of 770 m in the vicinity of the
intakes with a dilution ratio for mixing in the lake of about 48. Thus, the
dilution ratio based on the initial tagged water Sm concentration is (48)(127)
= 6.1 x 103.
The dilution ratios calculated are for the center of the patch and are
thus minimum values for the tagged effluent. The exact location of the patch
relative to the intakes is not known as no measurements of the tagged water
mass were made in the intake area. However, the dilution ratios calculated
for the center of the patch are of about the order of magnitude of and smaller
than those determined from sampling at the crib and shore intakes (Table 4.4).
The travel time from the tagging location to the intakes, based on the mean
currents used in the mixing estimates, was about 32 hr. (Sm was detected
in the intake waters about 33 hr after tagging.)
The results of these comparisons should be viewed with some caution.
Models with alternate mixing laws and assumptions about the trajectory of
the patch might give reasonable results as well. The small amount of tagged
IHC water may not have moved as a single discrete patch toward the intakes
but rather in several patches due to interruption by the Calumet Harbor
*In an earlier report on these estimates (Harrison, McCown, Raphaelian, and
Saunders, 1977) a mean speed of 0.08 m/s (based on time-averaged current-
meter records) was used. Subsequent analysis of the current-meter records
for the specific period of the experiment indicated that lake currents as
large as 0.13 m/s were measured. Speeds of this magnitude are consistent
with those estimated from time-of-travel data for the tracer, and are used
in this report. Minor, and insignificant, differences in dilution estimates
result from this change that was made to provide consistent tracer time-of-
travel values.
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70
Breakwater. What can be stated is that the application to the tracer experi-
ment of a turbulent diffusion model yielded dilution results which were not
vastly different from dilutions inferred from measurements.
4-2.3.3 Dilution Estimates for the Entire IHC Effluent
The estimates, given above, of dilution of the tagged portion of the
IHC effluent, while not verified, do not contradict the values inferred from
experimental data. They suggest that the application of a turbulent mixing
model together with the inferred advection field may be an appropriate re-
presentation of the behavior of an IHC sinking plume. It is instructive to
apply a similar model to estimate the dilution of the entire IHC effluent
sinking plume as it was transported toward the SWFP's intakes under the con-
ditions that prevailed during the tracer experiment.
For the case of a sinking plume formed by the entire IHC effluent,
the plume is considered to be a steady, continuous source of some conserva-
tive tracer emanating from the mouth of the IHC and to be transported north-
westward by the flow field given in Fig. 4.12. In this case, vertical mixing
is again neglected and, now, horizontal mixing is considered important only
in the lateral (normal to streamline) direction. Eq. 1 reduces to the form
Tjlt. 3_
8x 3y
where D = lateral (y) mixing coefficient
and is given by
Dy = k Sy ' (4)
The centerline of the plume (x coordinate) was assumed to follow the
streamline in Fig. 4.11 that is nearest to shore and was assumed to begin
(x = 0) on that streamline in the lake opposite the IHC entrance with an
initial width of 300 m, approximately the width of the IHC entrance. Solu-
tions to Eqs. (3) and (4) were found (Brooks,, 1960) as a function of distance
along the plume for mean current of 0.13 m/s, n = 4/3, and k = 0.000463 m2/3/s.
The effects of the shoreline, as a reflective boundary, have been included
but are minor.
At 12 km, in the vicinity of the shore and crib intakes, the center-
line (minimum) dilution-ratio is about 2.8. If it is assumed that the plume
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71
CENTRAL WATER
FILTRATION PLANT
STATUTE MILES
LAKE
MICHIGAN
SOUTH WATER
FILTRATION PLANT
Fig. 4.12. Schematic Representation of the Expected Dilution Ratios in the
Nearshore Waters of Southwestern Lake Michigan on March 3, 1977.
(The cross hatching represents dilution ratios in the range 10-100;
solid black represents dilution ratios in the range 1-10)
-------
72
centerline coincides with the streamline nearest shore in Fig. 4.11, the
dilution ratio at the shore intake is about 1.3 x 102 and at the crib is
greater than 105. Figure 4.12 depicts the contours of dilution ratios of
10 and 100 determined in the calculations for the conditions stated above.
These results provide only an approximate description of the mixing of the
IHC plume under a specific set of inferred currents and plume trajectory.
Although this type of estimate may have some validity for the case studied,
the effects of vertical mixing, of the unsteady nature of the currents, of
interactions with harbor structures, and of transport along other stream-
lines could act either to increase or decrease dilution ratios at the crib
or shore intake.
Finally, the information gathered on the current structure can be
used to estimate a bound on the average dilution ratio that may be expected
should the entire IHC effluent mix uniformly with the nearshore lake waters.
The volume flux out of the IHC during the study was about 120 m3/s. The
average speed of the lake water in the vicinity of the canal was about 0.08 m/s,
If we assume that all of the water within 4 km of shore mixes with the IHC
effluent, for an average depth of 10 m, a volume flux of about 3200 m3/s of
lake water mixes with the IHC effluent. This results in an average dilution
ratio of about 27.
In summary, for the set of environmental conditions studied, it ap-
pears that uniform mixing of the entire IHC effluent with nearshore lake
waters produces an average dilution of 27 at the intakes. In the more likely
event that the IHC effluent moves northwestward as a plume, the minimum dilu-
tion ratio estimate on the plume centerline is about 2.8. Larger dilution
ratios are found at the shore and crib intakes, if the plume centerline does
not cross them. The values of those dilution ratios depend on the particular
trajectory of the plume relative to the intakes. For the conditions assumed
above, dilution ratios of about 1.3 x 102, and >105, were estimated for the
shore and crib intakes, respectively.
Clearly, verification of even the simple estimates of mixing proposed
for the tagged portion of the IHC effluent and the entire IHC effluent re-
quires more detailed flow field data and tracer measurements in the tagged
patch. However, the transport of the Sm tracer from the IHC to the SWFP's
intakes provides unequivocal evidence that the sinking plume from the IHC
-------
73
reaches the intakes, and dilution estimates suggest the possibility of rather
limited dilution of the IHC effluent by the time it reaches the intakes for
some transport paths.
4 3 COMPARISON OF THE POTENTIAL FOR POLLUTANTS FROM FLOATING AND SINKING
PLUMES OF THE IHC TO ENTER THE CITY OF CHICAGO'S RAW WATER INTAKES AT
THE SWFP
Historically, water quality data from Chicago's SWFP have shown that
major pollution episodes occur almost exclusively in the winter when the IHC
plume is sinking. That these episodes do not occur in summer would be ex-
plained if lake stratification prevented pollutants from crossing the thermo-
cline to reach the depth of the crib intake. However, the fact that the lake
is stratified during the summer (floating plume) is not sufficient to explain
why pollution episodes do not occur in the summer because the thermocline is
rarely above the 9.1-m (30-ft) depth of the Dunne Crib's intake on the lake
bottom. The average intake water temperature at the Dunne Crib during June-
October is =16-21°C (60-70°F) (M. Kniahynycky, per. comm., 1978) but water
below the thermocline is =4°C (40°F). In addition, water temperature data
collected off the Chicago coast in the summer of 1976 (Harrison, W., et al,
1977) indicate that the thermocline was below 22 m (72 ft) much of the period
from July through mid-October, 1976.
The most significant difference between winter sinking-plume conditions
and summer floating-plume conditions, in terms of severe pollution events,
is that the sinking-plume carries IHC water along the bottom directly to the
Dunne Crib intake which is also near the bottom. Although vertical diffusion
acts to mix IHC water upward in the winter and downward, from the surface,
in the summer, that mixing is apparently not significant enough to mitigate
the intake of sinking-plume waters in the winter nor to result in the intake
of large amounts of floating-plume waters in the summer.
Another contributing factor is that the core of :=40C water that forms
after sinking at the IHC mouth during a period of northwestward flowing lake
currents, may be horizontally constrained. As discussed in Sec. 4.2.3.1,
the IHC entrance and the Dunne Crib's intake are both at 9.1m (30 ft) depth.
IHC water which has sunk to the bottom may be constrained in horizontal mix-
ing by the "uphill" bottom slope on the shoreward side. In contrast, the
floating plume at the surface is horizontally constrained only by the shoreline.
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74
The final factor investigated was the existence, in winter, of currents
of longer and/or stronger duration than in the summer. Unfortunately, there
are little current data available, thus, no conclusive evidence exists. In
reviewing the current data that are available, one instance (mid-July, 1976)
was found when the currents would have been sufficient to move IHC water
from the IHC to the SWFP intakes. There was no odor problem at the SWFP during
this period (Phil Reed, personal communication, 1978). One instance, however,
is certainly not conclusive.
Of the mechanisms discussed above, the two significant factors, intense
downward forces at the subduction zone and horizontal mixing constraints,
combine to allow the transport of considerably less diluted IHC water north-
ward to the SWFP's raw water intakes during the winter when the IHC plume
is sinking than during the summer when the plume is floating.
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75
5 SUMMARY
The purpose of the program discussed in this report was:
1. To develop methods for simultaneously tagging both oily wastes
and the underlying waters, each with a unique tracer, and for
determining their individual motions in fresh coastal waters, and
2. To apply these methods to specific, contaminated coastal waters.
The method developed to trace the oily wastes involved using the rare
earth element (REE) dysprosium (Dy) to tag the oily waste. Dy was chosen
because it could be detected in very low concentrations by neutron activation
analysis (NAA). Numerous bench tests were performed to test the retention
of Dy by the oily-waste as discussed in Sec. 2.1.2.2. Dy seems to be a good
tag for oily-wastes with only a maximum of 0.4% Dy migration into the under-
lying waters during the bench tests and probably even smaller percentages
during field experiments.
A second REE samarium (Sm) was chosen to tag the water under the
oily waste. Sm was chosen because it's NAA characteristics are similar to
Dy, although it cannot be detected in concentrations as low as Dy. The Sm
was chelated with DTPA (Sec. 2.1.2.1) to increase its persistence in the
water.
A rapid NAA method was developed in this program for the detection of
Dy and Sm. The method required no sample preparation other than evaporation
of the liquid and cleaning of the Polyvial. The.sample size required was only
15 mL for detection in the ng/L range; approximately 17 samples an hour could
be analyzed; and each sample was analyzed simultaneously for both Dy and Sm.
Finally, the unique tracer technique was applied to the Indiana Har-
bor Canal (IHC) to trace both the oily-waste poured on the canal surface
and the underlying canal effluent. Two experiments in the IHC and adjacent
waters of Lake Michigan were carried out. They occurred in the summer when
the canal water floats on the surface of Lake Michigan (Sec. 3) and in the
winter when the canal water sinks to the lake bottom (Sec. 4).
The summer floating-plume experiment indicated that:
1. When the tagged oil was subjected to severe downward mixing
by a passing ore carrier, it did not resurface but remained
mixed in the water column (Sec. 3.1.7),
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76
2. Lake diffusion coefficients calculated from the Dy and Sm
data were similar to diffusion coefficients determined by
others in the Great Lakes (Sec. 3.1.5) using other tracer
techniques, and
3. After the oil was mixed into the water column by the ore
carrier there were no distinguishable differences between
the movement and diffusion of the oil/Dy and the movement
of the water/Sm (Sec. 3.2.3).
The winter sinking-plume experiment indicated that:
1. Unequivocal evidence of the transport of IHC effluent to
the raw water intakes of the City of Chicago's South Water
Filtration Plant (SWFP) was provided by means of the tracer
(Sec. 4.1.3),
2. A partitioning of the oily wastes and underlying water was
made apparent by the employment of the unique dual tracer
system (Sec. 4.2.4.1), and
3. Simple model estimates of IHC plume dilution at the SWFP
were supported by the experimental measurements and these
estimates showed centerline dilution ratios may be as low
as 2.8 (Sec. 4.3.3.2).
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77
ACKNOWLEDGMENTS
This study could not have been accomplished without the support of the
Department of Water and Sewers, City of Chicago, R. A. Pavia, Commissioner.
N. J. Davoust, former Deputy Commissioner of Water Operations, was most help-
ful in arranging for the use of the Department of Public Works' tug, the
VERSLUIS. Thanks are due to the captain and crew of the VERSLUIS for their
assistance in laying the winter current-meter moorings. The assistance pro-
vided to Argonne personnel, for collecting raw-water samples, by staff of
the water-quality laboratory at Chicago's South Water Filtration Plant is
also acknowledged, as is the assistance in locating historical water-quality
and environmental data provided by P. A. Reed, H. M. Pawlowski, and M.
Kniahynycky of the Bureau of Water Operations.
The following members of the Water Resources Section of Argonne's
Energy and Environmental Systems Division are thanked for their efforts:
J. H. Walters, for his work on tracer preparation, shipboard sampling, sample
irradiation, and data reduction; L. S. VanLoon and C. Tome for their assist-
ance with the lake-current monitoring and field water-sampling program; and
A. A. Frigo, and R. A. Paddock for their assistance in the collection of water
samples at the SWFP. P. S. Raschke is thanked for her patient typing of the
many drafts of this report and S. L. Vargo is thanked for typing the final
draft.
Special thanks are extended to Dr. A. Keith Furr of the Office of
Occupational Health and Safety, Virginia Polytechnic Institute and State Uni-
versity. Dr. Furr provided many helpful suggestions to develop and improve
the neutron activation analysis technique.
Our appreciation is extended to E. T. Cobb, J. J. Hartig, A. W.
Schulke, and J. H. Talboy of the Argonne Research Reactor Operations Division
for their help with the irradiation of samples. Special thanks are extended
to C. J. Luebes, who spent many hours working on the CP-5 reactor's rabbit
system and who eventually fixed the system to the extent that our irradiations
were no longer interrupted by system malfunctions. R. Brandenburg, J. J.
Vronich, J. F. Staroba, and L. D. Edwards of the Argonne Special Materials
Division were most helpful in providing and operating the nuclear counting
equipment for the sample analysis. Thanks are also due to G. Ketchmark of
the Occupational Health and Safety Division.
-------
78
The sinking-plume portion of this study was supported in part by the
Illinois Institute for Environmental Quality under IIEQ Project No. 20.076.
Some of the material reported herein related to that work has also been re-
ported separately (Harrison j* sil., 1978).
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79
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Standard Methods for the Examination of Water and Waste Water, American Public
Health Assoc., Amer. Water Works Assoc., 12th ed., 769 pp., 1965.
Bowman, W.W., and K.W. Macurdo, Radioaotive-Deoay Gammas Ordered by Energy
Nuclide, Atomic Data and Nuclear Data Tables, 13(2-3), Academic Press,
New York, 1974.
Brooks, N.H., Diffusion of Sewage Effluent in an Ocean-Current, Proc. First
Intern. Conf. on Waste Disposal in the Marine Environment, Pergamon
Press, p. 246-267, 1960.
Brown, R.A., T.D. Searl, J.J. Elliott, B.C. Phillips, D.E. Brandon, and P.H.
Monaghan, Distribution of Heavy Hydrocarbons in Some Atlantic Ocean Waters.
Proc. Joint Conf. on Prevention and Control of Oil Spills, American
Petroleum Institute, Washington, p. 505-519, 1973.
Brown, R.A. and H.L. Huffman, Jr., Hydrocarbons in Open Ocean Waters, Science
191, p. 847-849, 1976.
Brown, R.A. and T.D. Searl, Nonvolative Hydrocarbons Along Tanker Routes of the
Pacific Ocean, Offshore Technology Conf. 1, p. 259-274, 1976.
Channell, J.K., Activable Rare Earth Elements as Estuarine Water Tracers,
Ph.D. dissertation, Stanford University, 1971.
Csanady, G.T., Turbulent Diffusion in the Environment, D. Reidel Publishing
Co., Boston, 1972.
Fischer, H.B., Longitudinal Dispersion and Turbulent Mixing in Open-Channel
Flow, Annual Review of Fluid Mechanics, 5, p. 59-76, 1973.
Frigo, A.A., R.A. Paddock, and D.L. McCown, Field Studies of the Thermal Plume
from the D. C. Cook Submerged Discharge with Comparisons to Hydraulic-
Model Results, Argonne National Laboratory Report ANL/WR-75-4, June 1975.
Gordon, D.C., P.D. Keizer, and M.J. Prouse, Laboratory Studies of the Accommo-
dation of Some Crude and Residual Fuel Oils in Seawater, J. Fish. Res.
Bd. Can., 30, p. 1611-1618, 1973.
Harrison, W., A.A. Frigo, G.T. Kartsounes, D.J. Santini, S.J. LaBelle, and
F.H. Davis, District Heating and Cooling Utilizing Temperature Differences
of Local Waters-Preliminary Feasibility Study for the Chicago 21} South
Loop New Town Project, Argonne National Laboratory Report ANL/WR-77-1,
May 1977.
Harrison, W., D.L. McCown, L.A. Raphaelian, and K.D. Saunders, Pollution of
Coastal Waters Off Chicago by Sinking Plumes From the Indiana Harbor
Canal, Argonne National Laboratory Report ANL/WR-77-2, December 1977.
Huang, J.C.K., Eddy Diffusivity in Lake Michigan, J. Geophys. Res. 76(33),
p. 8147-8152, 1971.
-------
80
REFERENCES (Contd.)
Ippen, A.T., ed., Estuary and Coastline Hydrodynamics, McGraw Hill Book Co.
Inc., New York, p. 598-627, 1966.
Lederer, C.M., J.M. Hollander, and I. Perlman, Table of Isotopes, 6th Ed., John
Wiley and Sons, New York, 1967.
Livesey, D.L., Atomic and Nuclear Physics, Blaisdell Publishing Co., Waltham,
Mass., 1966.
McAuliffe, C.D., Dispersal and Alteration of Oil Discharged on a Water Surface,
Proc. Symposium, Fate and Effects of Petroleum Hydrocarbons in Marine
Ecosystems and Organisms, Seattle, November 10-12, 1976, D.A. Wolfe,
Ed., Pergamon Press, NY, p. 19-35, 1977.
McCown, D.L., W. Harrison, and William Orvosh, Transport and Dispersion of Oil-
Refinery Wastes in the Coastal Waters of Southwestern Lake Michian
(Experimental Design — Sinking Plume Condition), Argonne National
Laboratory Report ANL/WR-76-4, 51 pp., 1976.
Means, J.C., et al., Identification of Organic Pollutants in the Illinois
River Basin and Associated Waterways: Special Rpt. 6, Water Resources
Center, Univ. Illinois (Urbana-Champaign), p. 199-212, 1977.
Monahan, E.G., and P.E. Pilgrim, Coastwise Currents in the Vicinity of Chicago,
and Currents Elsewhere in Southern Lake Michigan, Univ. of Michigan,
Ann Arbor, Office of Sea Grant Rept. No. 04-5-158-16, 1975.
Murthy, C.R., Horizontal Diffusion Characteristics in Lake Ontario, Jour.
Phys. Oceanogr., 6(1), p. 76-84, 1976.
Okubo, A., Oceanic Diffusion Diagrams, Deep Sea Res. 13(8), p. 789-802, 1971.
Peake, E., and G.W. Hodgson, Alkanes in Aqueous Systems, I, Exploratory
Investigations on the Accommodation of C -C n-Alkanes in Distilled
Water and Occurrence in Natural Water Systems, J. Am. Oil Chemists'
Soc., 43, p. 215-222, 1966.
Peake, E., and G.W. Hodgson, Alkanes in Aqueous Systems, II, The Accommodation
of C7 -C n-Alkanes in Distilled Water, J. Am. Oil Chemists' Soc., 44,
p. 695-702, 1967.
Risley, C., Jr., and F.D. Fuller, Chemical Finding from Pollution Studies in
the Calumet Area of Indiana and Illinois and the Adjacent Waters of Lake
Michigan, Proc. 9th Conf. Great Lakes Res., Great Lakes Res. Div. Publ.
No. 15, Univ. Michigan, p. 423-429, 1966.
Saunders, K.D., and L.S. Van Loon, Nearshore Currents and Water Temperatures
in Southwestern Lake Michigan (June-December 1975), Argonne National
Laboratory Report ANL/WR-76-2, May 1976.
Saylor, J.H., Modification of Nearshore Currents by Coastal Structures, U.S.
Army Corps of Eng., U.S. Lake Survey, Misc. Pap. 66-1, 14 pp., 1966.
-------
81
REFERENCES (Contd.)
Schwab G M P.L. Katz, and K.D. Saunders, Modeling Nearshore Cur-rents in
the Calumet Harbor Shore Region, Proc. Vol. Benjamin Goldberg Symposium
of Engineering in the Health Sciences, Univ. Illinois Chicago Circle
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Shaw D.G., Hydrocarbons in the Water Column, Proc. Symposium, Fate and Effects
of Petroleum Hydrocarbons in Marine Ecosystems and Organisms, Seattle
November 10-12, 1976, D.A. Wolfe, Ed., Pergamon Press, NY, p. 8-18, 197/.
Snow R H. Water Pollution Investigation: Calumet Area of Lake Michigan,
'vols. 1 and 2 of U.S. EPA, Great Lakes Initiative Contract Prog. Rept.
No. EPA-905/9-74-011-A, 306 pp., 1974.
U.S. Public Health Service, Currents at Fixed Stations Near Chicago, Spec.
Rept. LM 11, 1963a.
U.S. Public Health Service, Drogue Surveys of Lake Currents Near Chicago,
Spec. Rept. LM 10, 1963b.
Vaughn, J.C., and P.A. Reed, Progress Report on Water Quality of Lake Michi-
gan Near Chicago, Water Sewage Works, 120(5):73-80, 1973.
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82
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83
APPENDIX A
Plan-View Contoured Plots of Dy and Sm Concentrations,
Floating Plume (Refer to Fig. 3.1 for position of cloud)
-------
84
0.0
m
0.68
0.34
0.5 m
85M
1.0 m
0.067
85 M
1.5
m
85 M
2.5 m
.0.067
85M
Fig. Al. Plan-View Contoured Plot of Dy Concentrations (yg/1) at 0.0, 0.5,
1.0, 1.5, 2.5, 3.5-m Depths for Floating-Plume #1
-------
85
0.0 m
75M
0.5 m
75M
34
75M
2.5 m
75M
3.5 m
Fig. A2. Plan-View Contoured Plot of Dy Concentrations (yg/1) at 0.0, 0.5,
1.0, 1.5, 2.5, 3.5-m Depths for Floating-Plume #2
-------
86
1.0 m
1.5 m
Fig. A3. Plan-View Contoured Plot of Dy Concentrations (yg/L) at 0.0, 0.5,
1.0, 1.5, 2.5, 3.5-m Depths for Floating-Plume #3
-------
87
-007,
0.0 m
2IOM
028
.014
0.5 m
007
2IOM
028
2IOM
1.0 m
307
007
1.5 m
2.5 m
2IOM
3.5 m
Fig. AA. Plan-View Contoured Plot of Dy Concentrations (yg/L) at 0.0, 0.5,
1.0, 1.5, 2.5, 3.5-m Depths for Floating-Plume #4
-------
88
1.5 m
2.5 m
75M
3.5 m
Fig
. A5. Plan-View Contoured Plot of Sro Concentrations (yg/L) at 0.0, 0.5,
1.0, 1.5, 2.5, 3.5-m Depths for Floating-Plume #2
-------
.1.4'
IOOM
2.5 m
1 IOOM
3.5 m
00
Fig. A6.
Plan-View Contoured Plot of Sm Concentrations (ug/L) at 0.0, 0.5, 1.0, 1.5, 2.5, 3.5-m Depths
for Floating-Plume #3
-------
90
'2IOM
U.U m
2IOM
0.5 m
'2.
1.4'
2IOM
1.0 m
Q
2K)M
1.5 m
2IOHI1
2.5 m
2IOM
3.5 m
Fig. A7. Plan-View Contoured Plot of Sm Concentrations (yg/L) at 0.0, 0.5,
1.0, 1.5, 2.5, 3.5-m Depths for Floatine-Plume #4
-------
91
APPENDIX B
Vertical Section Plots of Dy and Sm Concentrations
and Near Bottom Dye Concentrations, Sinking Plume
(Refer to Fig. 3.5 for Position of Transects)
-------
TO LAKE MICHIGAN
CO
I—
Q_
UJ
O
CO
Z]
Q-
S
CO
10
(BOTTOM)
SAMPLING STATIONS
Fig. Bl. Transect A: Sm Concentrations,
Analyzed.)
(Concentrations in yg/L. All 90 Samples Collected Were
-------
o
0.5 |—
3.5
co
in
Q_
UJ
O
Q_
S
CO
6.5
10
(BOTTOM)
271
1.4
10
i r
I L
bO
111
10
SAMPLING STATIONS
Fig. B2 .
Transect B: Sm Concentrations. (Concentrations in yg/L.
Samples Collected Were Analyzed.)
All 55
-------
0
0.5
_ 3.5
CO
CL
LU
Q
CD
-------
LAKE MICHIGAN
CO
Q_
LU
Q
Q.
CO
10
(BOTTOM)
LIGHT TOWER AT
IHC ENTRANCE
6.5 -
Fig. B4.
SAMPLING STATIONS
Transect B: Dy Concentrations. (Concentrations in ng/L.
Samples Collected Were Analyzed.)
All 55
Ui
-------
CO
Q_
LLJ
O
Q_
CO
10
(BOTTOM)
SAMPLING STATIONS
Fig. B5. Transect C: Dy Concentrations. (Concentrations in ng/L
Samples Collected Were Anlyzed.)
All 65
-------
0
CO
01
t—
Q_
UJ
O
CD
(BOTTOM)
i—i—r
1 T
>40
VO
o.
Q.
1.0
or
O
CJ
0.5
00
NO DYE RECORD
I
I I I L
I
SAMPLING STATIONS SAMPLING STATIONS
Fig. B6. Transects D and E: Dy Concentrations and Near Bottom Dye Concentrations (Dot
Indicates Sample Analyzed at that Point, Dy Concentrations in ng/L)
-------
CO
:r
i—
o.
UJ
O
40
<40
00
-Q
Q.
Q.
0.50
O
LU
Q
0.25
0.00
• •
T?.
Fig.
-r SAMPLING STATIONS SAMPLING STATIONS
Transects G and H: Dy Concentrations and Near Bottom Dye Concentrations (Dot
Indicate Sample Analyzed at that Point, Dy Concentrations in ng/L)
-------
CO
Q-
UJ
a
0-
S
co
(BOTTOM)
40
5 —
-Q
Q.
a.
0.50 —
O
QQ
8
Q
0.00
Fig. B8.
SAMPLING STATIONS
Transect J: Dy Concentrations and Near Bottom Dye Concentrations (Dot Indicate
Sample Analyzed at that Point, Dy Concentrations in ng/L)
-------
NEAR BOTTOM
DYE CONCENTRATION (ppb)
SAMPLING DEPTHS (m!
o
o
°
CD
O
01
W
CO H
-
ro ro
n
> rt
3
N
ro o
fo n
n § 01
rt 0
a4 ro
CD a
TJ Co
0 rt
H- H*
D 0
rt 3
- W J>
— |
~~™ (
-
— —
OPO ^
^ 3 r2
f^j r™^^
g> z
3 ro °
n co
ro n ^3
3 fc!
rt td _i
t-j 0 —
Co rt 0
rt rt ^
H- O ^^ O
^
1
1
•
-------
0
CO
Q_
LLJ
O
Q-
S
CO
8.!
(BOTTOM)
1 T
<40
-Q
ex
Q.
o o
UJ
UJ
8
Fig. BIO.
5 10 l5
SAMPLING STATIONS
Transect 0: Dy Concentrations and Near Bottom Dye Concentrations (Dot Indicate
Sample Analyzed at that Point, Dy Concentrations in ng/L)
-------
102
co
^
I—
Q_
LU
Q
Q_
CO
-O
Q.
o (BOTTOM)
8.5 —
5
>40
CD
o=
-------
103
Distribution for DOE/EPA Interagency Energy-Environment Report,
EPA-600/7-78-230. ANL/WR-78-1
Internal:
J. H. Allender (5)
R. P. Carter
C. Chow
E. J. Croke
J. D. Ditmars (5)
R. D. Flotard
P. F. Gustafson
L. Habegger
W. Harrison (5)
L. J. Hoover
D. 0. Johnson
A. B. Krisciunas
K. S. Macal
D. L. McCown (24)
D. McGregor
R. A. Paddock
E. G. Pewitt
L. A. Raphaelian
J. J. Roberts
D. M. Rote
K. D. Saunders(S)
W. K. Sinclair
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President, Argonne Universities Association
Energy and Environmental Systems Division Review Committee:
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R. E. Gordon, U. Notre Dame
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-------
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R. Robbins, Lake Michigan Federation
G. Saunders, Div. of Biomedical and Environmental Research, USDOE
R. M. Shane, Tennessee Valley Authority, Knoxville
Vernon Snoeyink, Dept. Civil Engineering, U. of Illinois, Urbana
W. C. Sonzogni, Great Lakes Basin Commission, Ann Arbor
G. E. Stout, Director, U. Illinois, Urbana
Judy Thatcher, American Petroleum Institute, Washington D.C. (10)
Virginia Institute of Marine Science, Library
W. Waldrop, Tennessee Valley Authority, Norris, Tenn.
Dr. Henry Walter, Div. of Environmental Control Technology, USDOE (5)
P. M. Wege, Center for Environmental Studies, Grand Rapids
W. L. Wood, Great Lakes Coastal Res. Lab., Purdue U.
H. Zar, U. S. Environmental Protection Agency, Region V, Chicago
Canada Centre for Inland Waters, Library, Burlington, Canada
D. Mackay, University of Toronto, Toronto, Canada
M. Palmer, Ministry of Environment, Toronto, Canada
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105
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/7-78-230
3. RECIPIENT'S ACCESS I ON-NO.
4. TITLE AND SUBTITLE
Transport of Oily Pollutants in the Coastal Waters of
Lake Michigan: An Application of Rare Earth Tracers
5. REPORT DATE
November 1978 issuing date
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
D. L. McCown, K. D. Saunders, J. H. Allender,
J. D. Ditmars, and W. Harrison
8. PERFORMING ORGANIZATION REPORT NO.
ANL/WR-78-1
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Energy and Environmental Systems Division
Argonne National Laboratory
Argonne, Illinois 60439
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
EPA-IAG-D6-E681
12. SPONSORING AGENCY NAME AND ADDRESS
Off. of Energy, Minerals & (0ff. Environ. Programs
Industry Div. Biomed. & Environ-
Off, of Research & Development mental Research
U.S. EPA Dept. of Energy
Washington, D.C. 20460 Washington, D.C. 20545
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA/600/17
15. SUPPLEMENTARY NOTES
This joint project with the Department of Energy is part of the federal Interagency
Energy/Environment R&D Program coordinated by EPA.
16. ABSTRACT
A method was developed for tagging oily waste with dysprosium and the associated
fresh water with samarium. Neutron activation analysis permitted determination of rare
earth concentrations as low as 40 ng/L in 15-mL water samples. Shipboard sampling
procedures were developed that allowed measurement of the three-dimensional distribu-
tion of the spreading wastes and associated water. The method was applied in two
field experiments that involved tracing oily wastes and polluted water from the Indian;
Harbor Canal (IHC) into Lake Michigan.
For a summer, floating-plume experiment, about 1400 shipboard samples were
collected. Employment of the dual-tracer technique led to the following results:
(1) after artificial mixing into the water column by a passing ship, the tagged oil
did not immediately resurface, and (2) there were no distinguishable differences
between the movement of, the oil and water over 4 km of travel.
During a winter, sinking-plume experiment, 1200 lake-water samples were collected
from a boat and from the raw-water intakes of Chicago's South Water Filtration Plant
(SWFP). These data provided positive evidence of the intake of IHC effluent and oily
waste at the SWFP. The different tracers for the oily waste and underlying water
gave evidence of separate pathways to the SWFP, reflecting differing transport modes
for surface and near-bottom waters.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDEDTERMS
c. COSATI Field/Group
Rare Earth Elements
Neutron Activation Analysis
Dysprosium
Samarium
Oily Waste
Oil Tracing
Water Tracing
Limnology
Processes & Effects
Charac., Meas., & Monit
Energy Cycle
Processing
Conversion
Transport Processes
7C
48G
8. DISTRIBUTION STATEMEN1
19. SECURITY CLASS (This Report)
21. NO. OF PAGES
103
20. SECURITY CLASS (This page)
22. PRICE
EPA Form 2220-1 (9-73)
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