WATER QUALITY INVESTIGATIONS
LAKE MICHIGAN BASIN
PHYSICAL AND CHEMICAL QUALITY CONDITIONS
A technical report containing background data
for a water pollution control program.
January 1968
UNITED STATES DEPARTMENT OF THE INTERIOR
FEDERAL WATER POLLUTION CONTROL ADMINISTRATION
Great Lakes Region Chicago, Illinois
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TECTIOI
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CONTENTS
Page
INTRODUCTION 1
PARAMETERS, DEFINITIONS, AND SIGNIFICANCE 2
Parameters 2
Definitions and Significance 2
Nitrogen: Ammonia, Nitrate, and Nitrite 2
Total Soluble Phosphate 2
Silica 3
Dissolved Oxygen (DO) 3
Biochemical Oxygen Demand (BOD) h
Phenols h
Methylene Blue Active Substance (MBAS) £
Hydrogen Ion Concentration (pH) 5>
Dissolved Solids 5
Sodium 6
Potassium 6
Calcium 6
Magnesium 6
Specific Conductance 6
Alkalinity 7
Sulf ate 7
Chloride 7
Toxic Metals 8
LABORATORY PROCEDURES 10
Sample Preservation 10
Analytical Methods ,.. 10
NitrogenAmmonia and Organic 11
Nitrate and Nitrite Nitrogen 11
Method for Nitrate Nitrogen "by the Auto-Analyzer 11
Total Soluble Phosphate 12
Silica 13
Dissolved Oxygen 13
Phenols 13
Methylene Blue Active Substances (MBAS) 13
Biochemical Oxygen Demand ill
Hydrogen Ion Concentration (pH) llj.
Dissolved Solids lU
Sodium and Potassium ih
Calcium llj.
Conductance (Specific) llj.
Total Alkalinity llj.
Magnesium llj.
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CONTENTS (Continued)
Page
LABORATORY PROCEDURES (Continued)
Analytical Methods (Continued)
Sulfate
Chloride
Metals (Toxic)
RESULTS OF ANALYSIS ................................................ 16
Deepwater Studies .............................................. 16
Inshore Studies ................................................ 18
Major Lake Michigan Tributaries ................................ 20
Green Bay [[[ 21
Green Bay Tributaries .......................................... 22
Traverse Bay [[[ 23
Indiana Harbor ............................... . ................. 21;
Calumet Harbor ................................................. 2 5
Chicago Harbor ................................................. 26
Racine Harbor .................................................. 26
Mili/raukee Harbor ............................................... 2?
SUMMARY [[[ 29
Deepwater Studies .............................................. 29
Inshore Studies ................................................ 29
Major Tributaries .............................................. 29
Green Bay [[[ 30
Green Bay Tributaries .......................................... 30
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TABLES
Title
1 Lake Michigan Sampling Cruises ........................... 35
2 Minimum Detectable Concentrations of Physical and
Chemical Parameters Measured in the Lake Michigan
Basin, 1962-1961; ....................................... 38
3 Chemical Results of Parameters Measured in Lake
Michigan Basin in 1962-1963 Averages, Ranges,
and Number of Samples .................................. 39
Ij. Chemical Results of Toxic Metals Lake Michigan
Basin, 1962-1963 Averages, Ranges, and Number of
Samples ................................................ 1|0
5 Variations of Selected Chemical Constituents by
Seasons, Depth, and Averages Lake Michigan Basin,
1962-1963 .............................................. hi
6 Dissolved Oxygen and Percent Saturation in Deepwater
by Seasons Lake Michigan Basin, 1962-1963 ............. I;2
7a Chemical Results Lake Michigan Tributaries Averages,
Ranges, and Loadings ................................... l\3
?b Chemical Results Lake Michigan Tributaries Averages,
Ranges and Loadings
8 Chemical Results by Zones in Green Bay June 26-July ,
1963 Averages and Number of Samples ................... I|.8
9a Chemical Results Green Bay Tributaries 1963-1961;
Averages, Ranges, and Loadings .......... '. .............. 1|9
9b Chemical Results Green Bay Tributaries 1963-1961;
Averages, Ranges, and Loadings ......................... 5>1
10 Chemical Results Traverse Bay, Boardman River, and
Adjacent Region of Lake Michigan July 22-July 28,
196U [[[ 53
lla Chemical Results Indiana and Calumet Harbors Lake
Michigan Basin, 1962-1963 Averages, Ranges, and
Number of Samples ...................................... %k
lib Chemical Results of Toxic Metals Indiana and Calumet
Harbors Lake Michigan Basin, 1962-1963 Averages,
Ranges, and Number of Samples .......................... 55
12 Chemical Results Chicago and Racine Harbors
Lake Michigan Basin, 1962-1963 Averages, Ranges,
and Number of Samples .................................. 56
13 Chemical Results of Toxic Metals Chicago and
Milwaukee Harbors Lake Michigan Basin, 1962-1963
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TABLES (Continued)
Title Page
Chemical ResultsMilwaukee Harbor and Adjacent
Waters of Lake MichiganLake Michigan Basin,
October 1962-June 1963Averages, Ranges, and
Number of Sample ^ 5>8
15 Chemical ResultsAinmonia and Nitrate Nitrogen
Lake Michigan Harbors, 1962-1963Averages by
Seasons 59
16 Chemical ResultsDissolved Oxygen and Total Soluble
PhosphateLake Michigan Harbors, 1962-1963
Averages by Seasons 60
17 Chemical ResultsDissolved Oxygen and Percent
SaturationLake Michigan Harbors, 1962-1963
Averages by Seasons 6l
18 Chemical ResultsPhenolsLake Michigan Harbors,
1962-1963Averages by Seasons 62
IV
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FIGURES
No. Title Page
1 Ammonia - Nitrogen, Lake Michigan, 1962-1963 63
2 Total Soluble Phosphate, Lake Michigan 61;
3 Silica, Lake Michigan 6£
1; Green Bay, Sampling Stations-1963 66
5 Green Bay and Tributaries, Ammonia Nitrogen,
March, 1963-April, 1961; 6?
6 Green Bay and Tributaries, Total Soluble Phosphate,
March 1963-April 1961; 68
7 DO and BOD Profile - Lower Fox River, Wisconsin-
August 5, 1961; 69
8 Traverse Bay Area Sampling Stations 70
9 Ammonia Nitrogen, Indiana and Calumet Harbors,
1962-1963 71
10 Total Soluble Phosphate, Indiana and Calumet Harbors,
1962-1963 72
11 Phenols-Indiana and Calumet Harbors, 1962-1963 73
12 Ammonia Nitrogen, Chicago Harbor, 1962-1963 Ik
13 Total Soluble Phosphate, Chicago Harbor, 1962-1963 7%
Ik Ammonia Nitrogen, Racine Harbor, 1962-1963 76
15 Total Soluble Phosphate, Racine Harbor, 1962-1963 77
16 Phenols, Racine Harbor, 1962-1963 78
17 Milwaukee Harbor, Ammonia Nitrogen, 1962-1961; 79
18 Total Soluble Phosphate, Milwaukee Harbor, 1962-1961; 80
19 Milwaukee Harbor, Phenols, 1962-1961; 8l
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INTRODUCTION
This report presents the physical and chemical results of a
comprehensive study of Lake Michigan waters conducted by the Great
Lakes-Illinois River Basins Project from April 1962 to July 1961*.
The study was conducted through the collection of appropriate
samples during a series of 20 cruises made on the Lake by laboratory-
equipped vessels. Analyses which required immediate attention were
carried out aboard ship. Other analyses were performed at the GLIRB
Project laboratories. These procedures are described later.
The purpose of this study was to determine the present physical
and chemical water quality and to describe those areas of the Lake which
exhibited significant water quality degradation.
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PARAMETERS, DEFINITIONS, AND SIGNIFICANCE
Parameters
The parameters which were considered and reported in subsequent
sections of this report are: ammonia nitrogen; total soluble phosphate;
silica; dissolved oxygen (DO); phenols; methylene blue active substances
(MBAS); biochemical oxygen demand (BOD); hydrogen ion concentration (pH);
dissolved solids; nitrate; sodium; potassium; calcium; specific conduct-
ance; alkalinity; magnesium; sulfate; chloride; and toxic metals (copper,
cadmium, nickel, zinc, lead, and chromium). Certain of these parameters
were found to have practically no variation, either geographically or with
time, on all of the lake samples analyzed to date, whereas others exhibited
detectable changes in some areas and seasons. The parameters showing sig-
nificant changes were ammonia nitrogen, nitrate nitrogen, total soluble
phosphate, silica, DO, specific conductance, phenols, and BOD. Of these,
the first three cited exhibited appreciable variation in all areas of the
Lake. Deepwater samples showed fewer variable parameters than did the
inshore samples, and the greatest variability was shown in the harbor
areas.
Definitions and Significance
Nitrogen: A.mmonia, Nitrate, and Nitrite
Nitrogen in its chemically combined forms is a necessary constit-
uent to the life cycle of aquatic flora and fauna. If it is present in
the aquatic environment with phosphates in moderate concentrations, accel-
erated growths of algae can result. Ammonia in high concentrations, above
2 to 2.£ mg/1 and under alkaline pH conditions (pH 8-8.£) (l, 2)-):-, is a
substance toxic to many forms of aquatic life (3). At all levels, it is an
increased burden to municipal water treatment because of its high chlorine
demand. It is an indicator of sewage pollution because of its presence in
human and animal waste discharges, and may be a significant constituent in
some industrial wastes. Amines and cyanides have toxic properties peculiar
to specific compounds containing these chemical groupings. Nitrate nitrogen (3)
has been implicated as a cause of methemoglobinemia in infants; a limit of
1;5> mg/1 of nitrate (as nitrate) has been recommended in the U. S. Public
Health Service Drinking Water Standards (1|).
Total Soluble Phosphate
Phosphate, like the nitrogen compounds, is a necessary nutrient
for biological activity. Its presence in water is not considered harmful
^-Numbers in parentheses refer to references listed at end of report.
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to human health. However, excessive concentrations of phosphate, coupled
with other favorable conditions such as abundant nitrogen supply, optimum
temperature and sunlight, can result in dense algal blooms. These excessive
growths affect the quality of water, interfere with water treatment opera-
tions, increase taste and odor problems, cause unsightly scums and decaying
matter, and create problems due to fluctuations of dissolved oxygen. Con-
centrations of phosphates between 0.03 and 0.3 mg/1 are needed to stimulate
algal growth according to various authors (5). Sawyer (6) states that
"nuisance conditions can be expected when the concentration of inorganic
phosphorus equals or exceeds 0.01 mg/1" (0.03 mg/1 as phosphate).
Phosphate enters the water environment in treated sewage because it
is not normally removed by conventional treatment processes. It is normally
present in human and animal waste products. Synthetic detergents contain
high concentrations of phosphates and have further increased the quantities
discharged. Phosphate is also present in surface runoff, particularly from
fertilized fields, and may be a component of the effluent from certain indus-
trial processes.
Silica
Silica appears in water as a solution and as finely divided or col-
loidal suspended matter. Most silica probably occurs in water as a result
of contact with deposits of minerals high in silicate, such as feldspar,
kaolinite, etc. The concentrations of silica normally found in water have
no significant physiological effects. However, since diatoms require silica
for manufacture of their skeletons, it would follow that the availability of
the substance should be one of the factors limiting the production of large
crops of this important group of plankton. The presence of diatoms in large
numbers interferes with water treatment processes, especially the clogging
of filters.
Dissolved Oxygen (DO)
Dissolved oxygen is one of the most important constituents of a
natural water. The existence of desirable aquatic life is dependent on the
presence of adequate levels of oxygen at all times. The solubility of oxy-
gen in water is low and is affected by both physical and biochemical forces.
The maintenance of satisfactory levels depends upon the equilibrium established
between the forces utilizing oxygen and those contributing it.
Oxygen is utilized by aquatic organisms during the processes of res-
piration. It is replenished from the atmosphere by physical forces and can
also be added through photosynthesis by algae and higher aquatic plants.
When organic pollution enters an aquatic environment, the balance between
consumption and contribution is upset. The bacteria present in water or
introduced with the pollution begin active degradation of the organic matter,
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multiply rapidly in the process, and consume the oxygen dissolved in the
water. If they use oxygen at a great enough rate, the resultant oxygen
in the water may not be sufficient to support aquatic life. In polluted
waters, these conditions are particularly in evidence during warm weather
when the rate of oxygen consumption is increased and the ability of water
to hold oxygen in solution is decreased.
Biochemical Oxygen Demand (BOD)
The introduction of organic waste into water - whether the waste
originates from domestic sewage, industrial processes, land runoff, or
any other source - initiates a chain of events involving the organic mate-
rial, micro-organisms accompanying it, and the natural biota present in the
receiving water. Organic matter is rapidly utilized as food by those orga-
nisms capable of converting itj the net result of this action is consumption
of dissolved oxygen. Because control of dissolved oxygen is important in
water quality management programs, a means of measuring the oxygen-consuming
potential of wastes is necessary. The test commonly used for this purpose
is the BOD test.
The BOD test measures a biochemical reaction rather than a well
defined chemical reaction; it involves observation of oxygen usage by micro-
organisms which convert unstable organic matter into cellular material and
respiratory products. Toxic substances, if present, adversely influence
this test.
.Phenols
Phenolic material, which includes phenols, cresols, and xylenols,
when found in water is usually the result of pollution by industrial wastes
(7). Phenols are widely used in the synthesis of many organic compounds.
Waste products from oil refineries, coke ovens, and chemical plants may
contain high concentrations.
Lethal concentrations for fish are related to the species, duration
of contact, temperature, and other conditions. Experimental data, however,
show that 5>.0 mg/1 would be toxic to most fish (8), and some of the chlor-
inated phenols exhibit toxicity in concentrations as low as 0.2 mg/1 (9).
Very low concentrations of phenols will impart a disagreeable
taste to water when chlorinated. The chlorophenols produced by the addi-
tion of chlorine have a more disagreeable taste and odor than the parent
substance. Thresholds of taste and odor for chlorophenols range from
0.001 to 0.02 mg/1 (10). The drinking water standards of the U. S. Public
Health Service have set the upper limit for phenol at 0.001 mg/1 because
of its objectionable taste following chlorination.
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Methylene Blue Active Substance (MBAS)
Methylene blue active substances are anionic surface-active
agents. These surface-active agents have been a common ingredient of
many commercial synthetic detergents for a number of years. Their func-
tion in detergents is to impart foam and reduce surface tension to aid in
the removal of dirt particles during the cleaning process. Until just
recently, the most widely used surface-active agent was the group of
anionic alkyl benzene sulfonates, generally termed ABS. These compounds
are very resistant to biological degradation and persist in water many
miles from the point of entrance. MBAS is believed to be non-toxic to
man (11, 12) in the concentration found in contaminated water. Because
they produce unsightly, persistent foams and cause water to exhibit
undesirable taste, the concentration limit for drinking water used on
interstate carriers has been set at 0.5 mg/1 (li). These compounds have
now been replaced in commercial detergents by surface-active agents that
are biologically degradable so that their presence in the aquatic environ-
ment can be minimized, where adequate treatment is provided.
Hydrogen Ion Concentration (pH)
pH is defined as the logarithm of the reciprocal of the hydrogen
ion concentration or, more precisely, of the hydrogen ion activity - in
moles per liter (9). pH 7 is the neutral point, or dividing line between
an "acid" and an "alkali"; pH values below 7 indicate an acid condition;
values above 7 indicate an alkaline condition. Each unit change in pH
indicates a tenfold change in hydrogen ion concentration; e.g., pH 6 is
10 tines stronger than pH 7, and pH 5> is 100 times stronger than pH 7>
in terms of hydrogen ion concentration.
The pH value of water is significant for several reasons. Acidic
waters (low pH values) disrupt biological activity, cause corrosion of
steel and concrete, intensify the effect of toxic materials such as sulfides
and cyanides, interfere with water plant coagulation practices and tend to
add undesirable iron and manganese to the water. Alkaline waters (high pH
values) also disrupt biological activity, precipitate iron, calcium and
magnesium, and increase the toxicity of ammonia and amines.
Dissolved Solids
The dissolved solids test measures the concentration of dissolved
material present. This includes both organic and inorganic matter. Exces-
sive dissolved solids in water can be unpalatable and increase the cost of
water treatment for many uses. The Drinking Water Standards of the U. S.
Public Health Service recommend the rejection of sources providing water
containing over 5>00 mg/1 of dissolved solids (if another water source is
available) because of a noticeable saline taste, and possible cathartic
effect on many individuals.
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Sodium
Sodium is an alkaline metal, the salts of -which are very soluble
in water and tend to remain in solution. The use of sodium salts is very
common in industry, and industrial wastes may contain large quantities of
the element.
Sodium salts are not particularly significant in drinking water,
except for those persons having abnormal sodium metabolism. It has been
disclosed (13) that sodium in excess of 200 mg/1 is significant to those
suffering from high blood pressure.
Potassium
Potassium, an alkaline metal, is abundant in the earth's crust,
yet its content in natural waters is usually small. In low concentrations
it is essential for plant and animal development (llO, but must be main-
tained in proper balance with phosphorus.
Potassium stimulates plankton growth (l£), but is otherwise insig-
nificant unless found in concentrations above ItOO mg/1, a level considered
toxic to fish (16).
Calcium
Calcium, an alkaline earth metal, is one of the constituents which
produces hardness in water. However, the amount of calcium usually found
in hard waters is less than the daily nutritional requirement. Hardness is
ordinarily considered undesirable because of scaling and reduced heat trans-
fer in heating and cooling systems and because of increased soap consumption.
Research (1?) has demonstrated that there may be a relationship between the
hardness of drinking water and a reduction in cardiovascular disease.
Magnesium
Magnesium, like calcium, is a hardness-producing mineral and con-
tributes to the hardness effects discussed under calcium. It is not known
to produce toxic effects, although in high concentrations magnesium salts
have a pronounced laxative effect.
Specific Conductance
Specific conductance yields a measure of a water's ability to
carry an electric current and is therefore an indication, within rather
wide limits, of the ionic concentration of the solution. The amount of
dissolved matter in a sample may often be estimated by multiplying the
specific conductance by an empirical factor. This factor may vary from
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0.£5> to 0.9 depending on dissolved substances and the temperature of
the water.
₯aters polluted by brines and chemical saline wastes will
produce a relatively high level of conductivity. This gives rise to an
increase in osmotic pressure which has a harmful effect on living orga-
nisms. Wide variations in total salinity or in the concentrations of
individual salts can have far-reaching effects upon water fauna, result-
ing even in the elimination of the species (18, 19).
Alkalinity
Alkalinity is defined as the capacity of a water to neutralize
hydrogen ions and is expressed in terms of an equivalent amount of calcium
carbonate. Alkalinity is caused by the presence of carbonates, bicarbon-
ates, hydroxides, and, to a lesser extent, by berates, silicates, phos-
phates, and organic substances.
In itself, high alkalinity is not considered detrimental to man,
but it is generally associated with high pH values, hardness, and excessive
dissolved solids, all of which may have an adverse effect on the quality of
the water.
Sulfate-
The sulfate anion is a component of the dissolved ionic solids
present in most surface waters. Large quantities of sulfates are often
added to the aquatic environment as industrial wastes, especially as
waste pickle liquor from steel mills. Sulfates in combination with sodium
or magnesium can produce a laxative effect. To control this effect, a
maximum of 2^0 mg/1 has been recommended for drinking water.
Chloride
Although chlorides are present to some extent in most surface
waters, they are also associated with man's activities, since the chloride
anion is a component of human waste and is widely used in many industrial
processes. Chlorides can impart a salty taste to drinking water and render
it unpalatable. Many waters are unsuitable for domestic use, irrigation and
industrial processes because of high chloride content. The Drinking Water
Standards of the U. S. Public Health Service recommend the rejection of
sources providing water containing over 2^0 mg/1 chloride if other water
of better quality is available. It is not removable by conventional water
and waste treatment methods. Increased chloride concentration would imply
deterioration in water quality for many beneficial uses.
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Toxic Metals
The U. S. Public Health Service Drinking Water Standards (I;)
limit the concentration of certain metals in drinking water because of
potential toxic properties to humans. These limits are as follows:
arsenic, 0.05 mg/1; barium, 1.0 mg/1; cadmium, 0.-01 mg/1; chromium,
0.05 mg/1; lead, 0.05 mg/1; selenium, 0.01 mg/1; and silver, 0.05 mg/1.
The presence of any of these elements in excess of the concentration
listed shall constitute grounds for the rejection of the water supply.
U. S. Public Health Service Drinking Water Standards (li) pro-
vide tolerance limits for metals that, if exceeded, can constitute
grounds for rejection of water supplies if other suitable supplies can
be made available. These are as follows: arsenic, 0.01 mg/1; copper,
1.0 mg/1; iron, 0.3 mg/1; manganese, 0.05 mg/1; and zinc, 5.0 mg/1.
The basis for rejection in this tolerance list is not toxicity in all
cases but is also related to consumer acceptance. In addition to
human toxicity, some of these metals are toxic to aquatic life and can
play an important part in the biological character of the aquatic environ-
ment.
In the studies of the Lake Michigan Basin, six metals, considered
as having toxic properties in relation to beneficial water uses, were
studied in detail. These were copper, cadmium, lead, chromium, nickel,
and zinc.
Copper occurs in natural waters only in trace amounts. Exces-
sive quantities are generally the result of pollution, attributable to
the corrosive action of water on brass or copper piping, to industrial
wastes, or to the use of copper for the control of undesirable plankton
organisms. Copper in water may be detrimental for some industrial uses
and has been found toxic to a wide variety of aquatic organisms, includ-
ing bacteria and fish (3).
Cadmium is one of the least abundant metals present in the
earth's crust and is rarely found in natural waters. It is invariably
present in zinc to some extent. Its uses are limited principally to
industrial applications, therefore quantities found in water are the
result of industrial pollution. It has been found to be toxic to man
when ingested, therefore its presence in water is a definite health
hazard. It is also toxic to aquatic life, including fish (3).
Lead occurs in natural waters only in trace amounts. Exces-
sive quantities are generally the result of pollution, attributable to
the action of water on lead pipe and industrial wastes. Lead is toxic
to man in low concentrations and is accumulative. It is also toxic to
aquatic life, including fish (3).
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Trace concentrations of chromium are found in some natural
waters, but excessive concentrations arise from its industrial uses.
It is extensively used in electroplating, tanning, paint manufacture,
and other industries, and is used to control corrosion in cooling water
systems of power plants. Its toxicity to humans when ingested in water
is subject to some question, but because of its pronounced toxicity and
carcinogenic properties when present in other paths of exposure, the
limits set for drinking water reflect these considerations as a factor
of safety. Its toxicity to aquatic life covers a broad range, being
toxic to some of the smaller organisms at levels as low as 0.05> mg/1 (3).
Nickel is not a common constituent of natural waters, its pres-
ence being related to industrial waste discharges. Its toxicity to humans
is low and is not considered to be a health hazard in concentrations usu-
ally present in natural waters. It is toxic to aquatic life, but less
than copper or zinc (3).
Zinc is present in most surface and ground waters only in trace
amounts, its presence being related to the corrosive action of water on
galvanized piping and to industrial wastes. Its toxicity to humans is
low when compared with the other metals. It is toxic to aquatic life,
but less than copper (3).
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LABORATORY PROCEDURES
Sample Preservation
After samples were collected, each sample was divided (on ship-
board) into half-gallon portions according to substances to be analyzed
and preservation requirements. Preservatives added to each half-gallon
polyethylene bottle of sample were as follows:
1. For phosphate analysis - 10 ml of chloroform.
2. For nitrogen analysis - 1.8 ml of sulfuric acid.
3. For phenol analysis - 20 ml of 10 percent copper
sulfate and 20 ml of phosphoric acid.
On Cruises 5> and 6, BOD analyses were performed on shipboard.
On the other cruises, BOD samples were packed in ice at the time of col-
lection and returned to Project headquarters for analysis. The average
time in transit for these samples was four hours, and the longest time
five hours.
Special preservation measures were not necessary for the sample
portions used for mineral analyses.
Analytical Methods
The physical and chemical data included in this report were
obtained, unless otherwise indicated, by following the procedures pub-
lished in "Standard Methods for the Examination of Water and Wastewater,"
llth Edition, I960, referred to throughout this report as Standard Methods.
While many methods may be used in water analysis, those described in the
Standard Methods have been selected for this study because the procedures
are supported by collaborative studies of capable analysts, throughout
the nation, who have demonstrated the methods to be accurate and reproduc-
ible within specified limits.
Minor modifications have been made on some of the methods used,
when they could better accomplish the purpose for which the procedure was
applied. Before adopting any change or modification, however, many repet-
itive analyses were made to determine the precision of the modified method
and also its agreement with the Standard Methods.
To assure continually reliable data, reference standards, of
known composition, and many blanks were analyzed simultaneously with all
tests.
A skeleton outline of tests performed is presented below. Where
the tests conform strictly to Standard Methods only the pages wherein the
10
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procedure may be found are cited, but "where modifications or changes are
made these have been described in detail. Tests marked by asterisks were
performed on shipboard.
NitrogenAmmonia and Organic
Free ammonia nitrogen was quantitatively determined by the
distillation method described on pages 298-299. Organic nitrogen was
measured by the Kjeldahl method using mercuric sulfate as a catalyst.
This procedure is described on pages 305-307.
Nitrate and Nitrite Nitrogen
Nitrogen in the form of nitrates was determined by the phenol-
disulfonic acid method described on pages 302-303. The nitrites, if
present, were oxidized to nitrates with hydrogen peroxide in acid medium.
This was the procedure used on the first five cruises of Lake Michigan.
This method was run in duplicate with the Greis method for the Technicon
Auto-Analyzer, described below, for analyses of 96 samples from the sixth
cruise. The results obtained by the Greis method proved superior and the
procedure was adopted for subsequent analyses.
Method for Nitrate Nitrogen by the Auto-Analyzer
Nitrogen in the form of nitrates was determined by the Greis
Method following its reduction to nitrite, utilizing the Technicon Auto-
Analyzer. The nitrates were reduced by means of a zinc column in an
medium. The following procedure was followed:
1. Apparatus used:
Technicon Auto-Analyzer. (20)
2. Reagents used:
a. Sodium Acetate Solution: 3h g. per liter.
b. Sodium Acetate Hydrochloric Acid Buffer Solution: 100
ml of hydrochloric acid (1 : 99) mixed with 1,000 ml of sodium acetate
solution (a).
c. Sulfanilic Acid Solution: 6.0 g. of sulfanilic acid
plus 200 ml of concentrated hydrochloric acid per liter.
d. Naphthylamine Hydrochloride Solution 6.0 g. of 1-
naphthylamine hydrochloride, 10 ml qf concentrated hydrochloric acid
and 500 ml of 95 percent ethyl alcohol per liter. (This reagent
11
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eventually becomes slightly discolored and may form a slight precipi-
tate. If discoloration occurred it was removed by mixing with nitrate
free activated carbon and filtering.)
e. Color Reagent: Equal volumes of sulfanilic acid
reagent (c) and naphthylamine hydrochloride reagent (d) were mixed and
stored in the dark for increased stability.
f. Zinc metal 30 mesh, granular, reagent grade. This
zinc was washed with chloroform just before use.
g. Stock Nitrate Solution: 7.2138 g. of anhydrous potas-
sium nitrate per liter. This solution contained 1 mg of nitrate nitrogen
per ml.
h. A series of working standards from 0.0£ to 3.0 mg per
liter of nitrate nitrogen was prepared from the stock solution (g).
3. Procedure:
a. The analytical system was set up in accordance with the
flow diagram provided by Technicon.
b. The instrument was standardized using standard solutions
listed in 2 h. A distilled water wash was interposed between each standard.
c. Samples were arranged on the analyzer with a distilled
water wash between each sample. A series of standards was introduced after
each 10 samples to detect possible drift in the instrumentation.
d. Standardization curves were prepared which show the
relationship of recorder response to concentration of nitrate as nitrogen.
Sample results were evaluated by reference to this curve.
The precision of this method was compared with the Standard
Method by analyzing 96 separate samples by both methods. The results
were found to be in good agreement. This method was therefore adopted
as a routine procedure because of its great superiority with respect
to speed of analysis as well as improved precision.
Total Soluble Phosphate
This test was performed in accordance with procedures described
in Standard Methods, Method C, Total Phosphate and Polyphosphate, pages
20lj.-206, on samples filtered to remove suspended matter.
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Silica
The procedure for silica was the Colorimetric Heteropoly
Blue Method described on pages 228-229.
Dissolved Oxygen*
This test was performed in accordance with the procedure
described as Method A, Alsterberg (Azide) Modification of the Vinkler
Method, pages 309-311.
Phenols
Phenols were determined as described on pages lj.0lt-i;08, using
the Aminoantipyrene Method.
Methylene Blue Active Substances (MBAS)
The methylene blue procedure for determining MBAS, as des-
cribed in Standard Methods, pages 21|5>-25>1, was modified by this
laboratory. The changes in no way affected the reproducibility of
the method, but did speed up the procedure and economize on the use
of time and reagents.
The modifications were as follows:
(a) The washing of extracts with wash solution was elim-
inated because comparative studies showed that values were equally
reproducible and accurate without this step.
(b) Twenty-five ml aliquots or aliquots diluted to 25 ml
were used for the analysis.
(c) Five ml of methylene blue solution was added to each
sample. An additional amount, if needed, would be indicated by the
water phase becoming clear after extraction with chloroform.
(d) The sample was extracted two times with 10 ml por-
tions of chloroform and filtered through a pledget of cotton in the
tip of the separatory funnel. This filtered and removed moisture
from the chloroform extract satisfactorily.
(e) The sample was collected, made up to volume and
read in the spectrophotometer at a wave-length of 6^0 millimicrons.
13
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Biochemical Oxygen Demand*
The procedure for biochemical oxygen demand was the same as
described on pages 318-323 in Standard Methods.
Hydrogen Ion Concentration (pH)#
This test was performed by the Glass Electrode Method as des-
cribed on page 191;.
Dissolved Solids
Dissolved solids were measured by the method described on
pages 326-330 of Standard Methods titled "Filtrable Residue."
Sodium and Potassium
Sodium and potassium content were measured by the Flame
Photometric Method as described on pages 231-232.
Calcium
The method used was the EDTA Titrimetric Method as recommended
in Standard Methods pages 67-68.
Conductance (Specific)-*
This test was performed using a specific conductance meter and
cell as described on pages llU-116.
Total Alkalinity
This test was performed using a mixed indicator, consisting of
two parts methyl orange and one part methyl purple, as described on pages
Magnesium
This test was performed by the Photometric Method as described
in Standard Methods on pages 11?3-15>U.
Sulfate
The Turbidimetric Method was used as described on pages
-------
Chloride
Chloride content -was measured by the Mercuric Nitrate Method
described on pages 326-330.
Metals (Toxic)
A polarographic technique "was used to analyze water for toxic
metals. Metals in concentrations as low as 0.01 mg/1 can be determined,
and with the addition of the range extender and/or greater concentration
of sample, lower levels may be detected.
The method has been demonstrated to be as accurate as, and
definitely more time-saving than, the usual colorimetric procedures for
these metals. The precision was in the range of ± 3 percent.
-------
RESULTS OF ANALYSIS
Samples of Lake Michigan -water were subjected to a large number
of physical and chemical analyses. The substances showing appreciable
variability and likely to provide the greatest threat to satisfactory
water quality for intended uses were found to be ammonia nitrogen, total
soluble phosphate, silica, dissolved oxygen, and phenol. Therefore, the
results of analysis of these constituents will be discussed in detail.
Average values and ranges of the various constituents found in
water are cited most frequently in this report. However, when large
variations or abnormalities are evident, individual results will be dis-
cussed in order to provide a more comprehensive account of the water
quality in the Lake Michigan Basin.
Deepwater Studies
The deepwater region of Lake Michigan is defined as that portion
of the Lake greater than 10 miles from shore. This region constitutes
the bulk of Lake Michigan waters, and because it is the least affected
-by various forms of pollution, it will be used as a base line of water
quality in the Basin.
The deepwater region was sampled during a series of seven
cruises which began in May 1962 and were discontinued in November 1963
(Table l). The average chemical results for this region are presented
in Tables 3 and 1;. Variations by season and depth of ammonia nitrogen,
total soluble phosphate, silica, dissolved oxygen, and percent saturation
are shown in Table £. Since more of the samples analyzed were in the
southern portion of the Lake, average values tend to be weighed in favor
of this region.
Ammonia nitrogen concentrations ranged from not detectable at
the limits of the test (N.D.) to 0.5 mg/1 throughout the deepwater region.
The maximum value was found at a depth of 75 meters about 12 miles from
Sturgeon Bay. The average ammonia nitrogen concentration was 0.06 mg/1.
The geographical distribution of ammonia nitrogen within the
Lake Michigan Basin is shown in Figure 1. The inshore and deep-water
regions are separated by a line located approximately 10 miles from
shore. It should be pointed out that this and similar figures present
only average values within a given area (a 15' quadrangle) and are used
only to represent variations in water quality and not exact concentrations
of any particular constituent at a specified point.
Figure 1 shows that, for the most part, there is little varia-
tion in ammonia concentrations throughout the deepwater region. The
16
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water leaving Lake Michigan at the Straits of Mackinac had an average
ammonia concentration of 0.0£ mg/1 which is only 0.01 mg/1 lower than
the average for the entire deepwater region. Several deepwater quad-
rangles had ammonia nitrogen concentrations above 0.08 mg/1. However,
these areas are scattered and do not appear to correspond to ammonia
sources.
Ammonia nitrogen concentrations are compared by season and
depth in Table 5. Little variation is apparent except that concentra-
tions found in the summer months were slightly higher than in the spring
and fall.
Total soluble phosphate concentration (Table 5>) averaged 0.02
mg/1 in deep water. A uniform distribution throughout this region is
evident from Figure 2. The highest phosphate concentration was O.llj
mg/1, found within 12 miles of Grand Haven. All other phosphate con-
centrations were below 0.09 wg/1.
Silica concentrations averaged 2.7 mg/1 throughout the deepwater
region. The concentration at individual stations ranged from 0.6 to 5>«5>
mg/1. The highest silica concentrations were found in the central and
northern regions of the Lake as shown in Figure 3. Lower concentrations
were evident near the shoreline and in the vicinity of harbors. In gen-
eral, these low silica concentrates were found in regions of high biologi-
cal activity (23).
Variations in silica concentrations by season and depth are
shown in Table £. Silica concentrations in the spring were fairly uniform
at all depths, which can be attributed to mixing during the spring turn-
over. During the summer and fall months silica concentrations increased
with depth. This effect may be attributed to thermal stratification of
the water and greater biological uptake of silica in the upper layers
of water than in the hypolimnion.
The average dissolved oxygen concentrations measured in the
deepwater region are listed in Table 3. The percent saturations these
dissolved oxygen concentrations represent are also included. As expected,
the percent oxygen saturation was found to average 6 to 7 percent less
below 30 meters than in the top few meters of water. Oxygen depletion
from other than natural causes was not evident in the deepwater region.
Table 6 indicates the minimum and maximum values encountered.
Toxic metal analyses were performed on a number of samples from
each region of the Lake. The frequency of occurrence of each metal is
given in Table 1;. All toxic metals but cadmium were detected at the limit
of sensitivity of the test (0.005 mg/l). This level is within the limits
set by the U. S. Public Health Service Drinking Water Standards
17
-------
Averages and ranges of the other chemical substances studied in
the deepwater region appear in Table 2. These parameters, namely nitrate
and organic nitrogen, sodium, potassium, dissolved solids, specific con-
ductance, pH, alkalinity, calcium, magnesium, chloride, and sulfate, showed
some variability, but were of little water quality significance at the
levels encountered.
Inshore Studies
Inshore areas of Lake Michigan were sampled during a series of
eight cruises (Table l) from August 1962 to October 1963. Samples were
collected at one, four, seven and ten miles from shore at several depths,
except in harbors. In addition to the parameters which were found sig-
nificant in the deepwater studies, phenols were found in significant
quantities in some of the inshore samples. The average chemical results
and ranges are tabulated in Table 3. A comparison with the deepwater
results shows higher average values and greater variations in all param-
eters analyzed in the inshore region.
Ammonia nitrogen concentrations in the inshore region ranged
from N.D. (none detected) to I.I; mg/1 with an average concentration of
0.13 mg/lj more than twice the average concentration found in the deep-
water region. Figure 1 shows that the highest concentrations were found
in the vicinity of Calumet, Milwaukee, Benton Harbor, Saugatuck, Grand
Haven, and Muskegon. Concentrations up to l.U mg/1 were found near
Calumet and 1.3 mg/1 near Milwaukee Harbor.
Since almost half of the samples analyzed in the inshore region
were taken in the vicinities of Calumet and Milwaukee, the average con-
centrations are heavily weighted by these two areas. However, excluding
these areas, the average concentration becomes 0.10 mg/1, which is still
substantially higher than found in deep water.
Total soluble phosphate concentrations in the inshore region
are shown in Figure 2. Very high concentrations of soluble phosphates
are found in the Milwaukee area. In quadrangles B-13, B-llj. and C-llj.,
the average concentrations were 0.10, 0.26, and 0.23 rag/1? respectively.
In the same order, maximum concentrations were 3-1, 3>k, and U.5 mg/1.
These values indicate phosphate-rich water moving southward from
Milwaukee Harbor.
Near the Calumet area, maximum phosphate concentrations of
O.i;5 mg/1 were found in quadrangles D-19 and E-19. The average concentra-
tions in these areas were 0.05 and O.Olj. mg/1, respectively.
Aside from these two areas, the rest of the inshore region averaged
less than 0.03 mg/1 total soluble phosphate, which is only 0.01 mg/1 higher
than the deepwater region.
18
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Silica concentrations found in the inshore region are shown in
Figure 3. The average silica concentration of 1.7 mg/1 is about half
that found in the deepwater region indicating possibly greater biologi-
cal uptake of the silica in the inshore region. The areas of low silica
concentrations have been found to correspond to regions of high phyto-
plankton populations (23).
Water samples from a number of inshore stations were analyzed
for phenolic materials. By far the highest concentrations were found
in the vicinities of Indiana and Calumet Harbors. The maximum value in
quadrangle D-19 was 72 micrograms per liter, while the average value
was 3 micrograms per liter. In quadrangle C-19, the maximum concentra-
tion was 32 micrograms per liter. In contrast, the next highest phenol
concentration in another quadrangle was 8 micrograms per liter found
near Michigan City. In the Milwaukee area, phenols ran as high as
7 micrograms per liter and averaged 2 micrograms per liter.
Some phenolic pollution is evident between Muskegon and
Kalamazoo where phenol concentrations up to 8 micrograms per liter were
found. However, phenols were not detected in many samples from this
area.
Chlorides were found in significant quantities near Ludington
and Manistee. In quadrangles H-10, 9, and 8, maximum values 69, 9ht and
77 mg/1, respectively, were found. The average values for these quad-
rangles were lU, 29, and 18 mg/1, respectively, while the overall average
inshore chloride concentration was 7.1 wg/1. The major contributors of
chlorides in the area are the Morton and Manistee Salt Companies which
discharge near the mouth of the Manistee River up to 260,000 and 1;1|,700
pounds of chloride per day, respectively.
The biochemical oxygen demand (BOD) was determined at a number
of inshore stations. Outside the Milwaukee Harbor, maximum BODs of
6.7 mg/1 were found in both quadrangles, B-13 and B-llj.. A BOD of 8.6
mg/1 was found near the mouth of the Grand River on the eastern shore.
In the inshore region adjacent to Gary, Indiana, BODs ranged up to
k.6 mg/1. These values indicate some degradation of the water quality
when compared to the inshore average of 1.1; mg/1.
Averages and ranges of the other chemical parameters studied in
the inshore region appear in Table 3. These parameters, namely nitrate
and organic nitrogen, sodium, potassium, dissolved solids, specific con-
ductance, pH, alkalinity, calcium, magnesium, and sulfate showed greater
variability and higher average values than found in the deepwater region.
Although the levels of these chemical substances encountered within the
inshore region were not high enough to be considered critical for most
water uses, they do indicate large amounts of pollutants being discharged
into Lake Michigan daily and annually.
19
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Major Lake Michigan Tributaries
A number of the major river systems entering into Lake Michigan
were sampled weekly from March 1963 to April 196U. The streams Manistique,
Manitowoc, Sheboygan, Milwaukee, Burns Ditch, St. Joseph, Kalamazoo, Grandj
Muskegon, and Pere Marquette will be discussed in this section of this
report. The tributaries to Green Bay will be discussed in subsequent sec-
tions, as will the Boardman River, Calumet River, and the Indiana Harbor
Canal.
Sampling stations at each tributary were located as close to the
river mouths as possible without becoming diluted with harbor or lake
water. The principal objective of this tributary mouth sampling was to
determine the loading of various substances carried by each river into
Lake Michigan. Average chemical results and loadings are shown in
Tables la and 7b.
Plows of each river were taken from U. S. Geological Survey
flow records for the study period (25). Average flows at the gaging sta-
tions were corrected for the portion of drainage basin between the gaging
station and the river's mouth.
Of all the chemical parameters measured for the tributaries, the
two nutrients, total soluble phosphate and ammonia nitrogen, showed the
most important variations. With respect to these two parameters, the
influence of the tributaries on the water quality can be seen in Figures
1 and 2.
Except for the Fox River, which is discussed later under Green
Bay, the greatest contributor of soluble phosphate to the Lake was found
to be the Grand River, contributing 5,330 pounds per day. The St. Joseph
River adds less than half this quantity, while Burns Ditch carries roughly
1,500 pounds of phosphate per day. Phosphate concentrations were found
to be higher in the immediate vicinities of these river mouths, but the
concentrations quickly dropped off moving out in the Lake. Although the
Milwaukee River carries comparatively minor loads of phosphates, the
Milwaukee area appears to have a major influence on the adjacent inshore
waters with respect to phosphate. This influence is primarily a result
of waste discharges from the Jones Island Sewage Treatment Plant, which
contributes an estimated 6,600 ppunds of total phosphates per day to the
harbor.
The largest discharge of ammonia nitrogen to the Lake, with the
exception of the Fox River, was found to originate from the Indiana Harbor
Canal. Using an average flow of 1,500 cfs, the calculated daily discharge
of ammonia nitrogen from the canal is 19,UOO pounds. This massive load
of ammonia nitrogen severely pollutes the adjacent inshore waters, where
an average concentration of 0.18 mg/1 was observed.
20
-------
Of the other tributaries considered, the Grand and St. Joseph
Rivers were found to be the largest contributors of ammonia nitrogen,
with 7,000 and 5>,900 pounds per day, respectively. The Kalamazoo
River carried roughly half this amount while the Milwaukee and Muskegon
Rivers contributed approximately a quarter as much at 1,600 per day.
Inshore waters adjacent to these tributaries averaged 0.16 mg/1 ammonia
nitrogen.
Toxic metals were found in appreciable concentrations in the
tributaries. Copper concentrations were usually highest, followed by
nickel and zinc. Copper concentrations ranged from 0.06 mg/1 to 0.15
mg/1. Although these values are well below the drinking water standard
of 1.0 mg/1, concentrations as low as 0.02 mg/1 have been reported harm-
ful to aquatic life (3). Zinc concentrations were also well within the
recommended limits for drinking water. Nickel concentrations were three
times higher in the Sheboygan River than those in the other rivers studied.
However, the levels of nickel encountered are not known to be a health
hazard. On the other hand, cadmium concentrations in the St. Joseph River
averaged 0.02 mg/1, which is twice the maximum limit recommended for drink-
ing water. Furthermore, chromium concentrations of O.Olj. mg/1, found in the
Grand River, were very close to the limit of 0.05 mg/1 (5). Such levels
of toxic metals indicate serious impairment of water quality in the trib-
utaries, especially in the Grand and St. Joseph Rivers.
For the most part, loadings of the other chemical constituents
in each river appeared to correlate well with concentrations found in the
inshore waters near the river mouths. These constituents may represent
dissolved materials leached from the soil, municipal or industrial waste
discharges, or urban and rural runoff. Dissolved solids and suspended
solids loadings ranged from £8 to 1,790 tons per day and 7 to 23 tons
per day, respectively. Aside from the nutrients and toxic metals, these
materials have relatively little influence on the water quality of Lake
Michigan.
Green Bay
The waters of Green Bay were sampled from June 26 to July 17,
1963. Figure k indicates the approximate locations of the stations
sampled and the selected zones into which the bay has been divided to
facilitate interpretation of the collected data. Each zone, except for
tributary mouths, harbors, and nearshore areas, represents a region of
similar water quality.
A summary of the physical and chemical findings is presented
by zones in Table 8. Examination of this Table shows the following
significant water quality effects:
21
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1. A severe depletion of dissolved oxygen is evident in zone 1.
Several samples with zero dissolved oxygen were found in this area. Some
oxygen depletion is also evident near the Peshtigo River, in zone 3.
2. The average concentration of soluble phosphate in zone 1 is
far above the level of 0.03 mg/1 considered critical for the stimulation
of algal blooms. In comparison, all the major harbors in Lake Michigan,
except Milwaukee, had average concentrations less than half the value
found in zone 1. Except for zone £, soluble phosphate concentrations
in the other zones in Green Bay were also at or above critical levels.
3. Ammonia nitrogen levels are by far the highest in zone 1.
Throughout the other zones, concentrations are comparable or higher
than those found in the inshore region of Lake Michigan.
1;. Nitrate nitrogen concentrations are significantly low
throughout the bay.
5. Phenol concentrations up to UO micrograms per liter were
found in zone 1. Higher concentrations within the Lake Michigan Basin
were found only in Indiana Harbor.
6. The other parameters measured in Green Bay, such as
chlorides, dissolved solids, and sulfates, also had much higher values
in zone 1 than in the other regions of the bay, indicating a high volume
of waste discharge and probably a lack of mixing in this area.
Green Bay joins Lake Michigan at zones 5 and 6. The water
quality of these two zones is comparable with the average inshore water
in Lake Michigan.
Green Bay Tributaries
The major tributaries into Green Bay were sampled weekly at
the river mouths from June 1963 to May 1961;. The physical and chemical
findings obtained during this study are summarized in Tables 9a and 9b.
In order to illustrate the seriousness of waste discharges into
Green Bay by the major tributaries, approximate average daily loadings
of the two significant nutrients, ammonia nitrogen and phosphates, are
compared in Figures 1? and 6, with the concentration of these constituents
found in the Bay. Examination of these figures reveals the Fox River
to be by far the most important contributor, discharging 6,6?0 pounds of
total soluble phosphate daily, or three times the amount discharged by
the Menominee, the next highest contributor of phosphate, and discharging
37,200 pounds of ammonia nitrogen, which is almost four times as much as
the Oconto, the next highest ammonia nitrogen contributor at 9,81j.O pounds.
22
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In fact, the Fox River adds more nutrients to Green Bay than all the
other tributaries combined, which results in the high concentration
found in zone 1.
The presence of toxic metals in detectable amounts can be
considered a potential threat to continuing water uses. The other
constituents measured in this study serve to differentiate the chemi-
cal water quality of the various streams. The composition of dissolved
matter found .may reflect the effects of minerals leached from the ground,
municipal or industrial waste discharges, or urban drainage such as result-
ing from street salting for ice control. Except for the nutrients previ-
ously cited, these chemical inputs have relatively little influence on
the chemical water quality of the Bay.
A special study consisting of intensive sampling of a stretch of
the Fox River was conducted to determine the effect of organic wastes on
stream oxygen resources. A typical profile of the dissolved oxygen and
biochemical oxygen demand concentration found during this study are shown
in Figure 7. The high BOD levels carried by the Lower Fox result in the
complete absence of dissolved oxygen for a stretch of eleven miles and
levels of less than 2 mg/1 for over twenty miles. Fish and desirable
aquatic life cannot survive under such degraded oxygen conditions. The
odors and anaerobic gases released by this pollution make the stream
esthetically undesirable and very objectionable for recreational uses.
The organic loadings causing this highly polluted condition are known
to originate primarily from the discharges of many pulp and paper mills
located along the Lower Fox River and from domestic wastes.
Traverse Bay
Traverse Bay and the adjacent region of Lake Michigan (Figure 8)
were sampled from July 22 to July 28, l°61j.. The average chemical results
and the ranges encountered in this area are tabulated in Table 10.
The Boardman River is the only major tributary into Traverse
Bay. This river was sampled weekly from April Ij., '1963 to April 23,
1961;. Samples were composited by flow prior to analysis. For compara-
tive purposes, these results are also tabulated in Table 10.
In general, the west arm of Traverse Bay was found to contain
higher concentrations of contaminants than the east arm. The Boardman
River, which enters the west arm, and Traverse City, contribute to
these higher values. The Boardman River influence is not large due to
its low flow (2££ cfs).
There appears to be no significant variation in general water
quality between Traverse Bay and the adjacent inshore waters of the Lake.
23
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Indiana Harbor
The Indiana Harbor receives drainage from the Grand Calumet
River in northern Indiana as well as from a large industrial complex
located along the harbor canal. Because of the large volume of waste
discharge from these sources, considerable variation in water quality
was observed between the Indiana Harbor and the adjacent inshore waters.
The average chemical results and ranges encountered in this area are
shown in Tables lla and lib.
The ammonia nitrogen concentrations in Indiana Harbor and
Canal are presented in Figure 9. The highest values were observed in
the Indiana Harbor Canal where concentrations up to lj..5> mg/1 were found;
the overall average in the Canal was 2.1; mg/1. In contrast, the highest
concentration found in the Harbor was 2.3 mg/1. The average concentration
in the Harbor was l.h mg/1, which is approximately eight times the average
ammonia concentration (0.18 mg/l) in the adjacent inshore waters and 23
times that of the deepwater zone. Such high concentrations of ammonia
indicate serious water quality degradation.
Seasonal variations of ammonia nitrogen concentrations appear
in Table 15>. Concentrations were found to increase substantially from
spring to fall.
Total soluble phosphate concentrations showed little variation
by station throughout the harbor, where average values ranged from 0.05
to 0.08 mg/1 (Figure 10). In contrast with ammonia nitrogen values,
phosphate concentrations were no higher in the Canal than in the Harbor.
Seasonal variations of phosphates were not significant.
Phenol concentrations in the Harbor and Canal are presented
graphically in Figure 11. Some of the highest phenol concentrations
in the Lake Michigan Basin were found in the Indiana Harbor Canal, where
concentrations as high as 35U micrograms per liter were found. Phenol
concentrations averaged respectively 1^6 micrograms per liter in the
Canal, 33 micrograms per liter in the Harbor, and 3 micrograms per liter
in the adjacent inshore waters. This phenolic pollution has been found
to be the major cause of frequent taste and odor problems in drinking
water from as far north as the City of Chicago's South District Filtra-
tion Plant. Seasonal variation of phenol concentrations are shown in
Table 18. Much lower concentrations were evident in the summer months
than in the spring and fall.
The results of toxic metal analyses of Indiana Harbor water
samples are shown in Table lib. Only lead and zinc were found in detect-
able concentrations.
21;
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905R68002
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WATER QUALITY INVESTIGATIONS
LAKE MICHIGAN BASIN
PHYSICAL AND CHEMICAL QUALITY CONDITIONS
A technical report containing background data
for a water pollution control program.
January 1968
UNITED STATES DEPARTMENT OF THE INTERIOR
FEDERAL WATER POLLUTION CONTROL ADMINISTRATION
Great Lakes Region Chicago, Illinois
Environmantal i'r'<'.: :'\\-~a
Region V, Libra.!;;
230 South Dearborn ~.\'
Ctaicago, Illinois - '"->;
-------
TECTIOI
-------
CONTENTS
Page
INTRODUCTION 1
PARAMETERS, DEFINITIONS, AND SIGNIFICANCE 2
Parameters 2
Definitions and Significance 2
Nitrogen: Ammonia, Nitrate, and Nitrite 2
Total Soluble Phosphate 2
Silica 3
Dissolved Oxygen (DO) 3
Biochemical Oxygen Demand (BOD) h
Phenols h
Methylene Blue Active Substance (MBAS) £
Hydrogen Ion Concentration (pH) 5>
Dissolved Solids 5
Sodium 6
Potassium 6
Calcium 6
Magnesium 6
Specific Conductance 6
Alkalinity 7
Sulf ate 7
Chloride 7
Toxic Metals 8
LABORATORY PROCEDURES 10
Sample Preservation 10
Analytical Methods ,.. 10
NitrogenAmmonia and Organic 11
Nitrate and Nitrite Nitrogen 11
Method for Nitrate Nitrogen "by the Auto-Analyzer 11
Total Soluble Phosphate 12
Silica 13
Dissolved Oxygen 13
Phenols 13
Methylene Blue Active Substances (MBAS) 13
Biochemical Oxygen Demand ill
Hydrogen Ion Concentration (pH) llj.
Dissolved Solids lU
Sodium and Potassium ih
Calcium llj.
Conductance (Specific) llj.
Total Alkalinity llj.
Magnesium llj.
-------
CONTENTS (Continued)
Page
LABORATORY PROCEDURES (Continued)
Analytical Methods (Continued)
Sulfate
Chloride
Metals (Toxic)
RESULTS OF ANALYSIS ................................................ 16
Deepwater Studies .............................................. 16
Inshore Studies ................................................ 18
Major Lake Michigan Tributaries ................................ 20
Green Bay [[[ 21
Green Bay Tributaries .......................................... 22
Traverse Bay [[[ 23
Indiana Harbor ............................... . ................. 21;
Calumet Harbor ................................................. 2 5
Chicago Harbor ................................................. 26
Racine Harbor .................................................. 26
Mili/raukee Harbor ............................................... 2?
SUMMARY [[[ 29
Deepwater Studies .............................................. 29
Inshore Studies ................................................ 29
Major Tributaries .............................................. 29
Green Bay [[[ 30
Green Bay Tributaries .......................................... 30
-------
TABLES
Title
1 Lake Michigan Sampling Cruises ........................... 35
2 Minimum Detectable Concentrations of Physical and
Chemical Parameters Measured in the Lake Michigan
Basin, 1962-1961; ....................................... 38
3 Chemical Results of Parameters Measured in Lake
Michigan Basin in 1962-1963 Averages, Ranges,
and Number of Samples .................................. 39
Ij. Chemical Results of Toxic Metals Lake Michigan
Basin, 1962-1963 Averages, Ranges, and Number of
Samples ................................................ 1|0
5 Variations of Selected Chemical Constituents by
Seasons, Depth, and Averages Lake Michigan Basin,
1962-1963 .............................................. hi
6 Dissolved Oxygen and Percent Saturation in Deepwater
by Seasons Lake Michigan Basin, 1962-1963 ............. I;2
7a Chemical Results Lake Michigan Tributaries Averages,
Ranges, and Loadings ................................... l\3
?b Chemical Results Lake Michigan Tributaries Averages,
Ranges and Loadings
8 Chemical Results by Zones in Green Bay June 26-July ,
1963 Averages and Number of Samples ................... I|.8
9a Chemical Results Green Bay Tributaries 1963-1961;
Averages, Ranges, and Loadings .......... '. .............. 1|9
9b Chemical Results Green Bay Tributaries 1963-1961;
Averages, Ranges, and Loadings ......................... 5>1
10 Chemical Results Traverse Bay, Boardman River, and
Adjacent Region of Lake Michigan July 22-July 28,
196U [[[ 53
lla Chemical Results Indiana and Calumet Harbors Lake
Michigan Basin, 1962-1963 Averages, Ranges, and
Number of Samples ...................................... %k
lib Chemical Results of Toxic Metals Indiana and Calumet
Harbors Lake Michigan Basin, 1962-1963 Averages,
Ranges, and Number of Samples .......................... 55
12 Chemical Results Chicago and Racine Harbors
Lake Michigan Basin, 1962-1963 Averages, Ranges,
and Number of Samples .................................. 56
13 Chemical Results of Toxic Metals Chicago and
Milwaukee Harbors Lake Michigan Basin, 1962-1963
-------
TABLES (Continued)
Title Page
Chemical ResultsMilwaukee Harbor and Adjacent
Waters of Lake MichiganLake Michigan Basin,
October 1962-June 1963Averages, Ranges, and
Number of Sample ^ 5>8
15 Chemical ResultsAinmonia and Nitrate Nitrogen
Lake Michigan Harbors, 1962-1963Averages by
Seasons 59
16 Chemical ResultsDissolved Oxygen and Total Soluble
PhosphateLake Michigan Harbors, 1962-1963
Averages by Seasons 60
17 Chemical ResultsDissolved Oxygen and Percent
SaturationLake Michigan Harbors, 1962-1963
Averages by Seasons 6l
18 Chemical ResultsPhenolsLake Michigan Harbors,
1962-1963Averages by Seasons 62
IV
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FIGURES
No. Title Page
1 Ammonia - Nitrogen, Lake Michigan, 1962-1963 63
2 Total Soluble Phosphate, Lake Michigan 61;
3 Silica, Lake Michigan 6£
1; Green Bay, Sampling Stations-1963 66
5 Green Bay and Tributaries, Ammonia Nitrogen,
March, 1963-April, 1961; 6?
6 Green Bay and Tributaries, Total Soluble Phosphate,
March 1963-April 1961; 68
7 DO and BOD Profile - Lower Fox River, Wisconsin-
August 5, 1961; 69
8 Traverse Bay Area Sampling Stations 70
9 Ammonia Nitrogen, Indiana and Calumet Harbors,
1962-1963 71
10 Total Soluble Phosphate, Indiana and Calumet Harbors,
1962-1963 72
11 Phenols-Indiana and Calumet Harbors, 1962-1963 73
12 Ammonia Nitrogen, Chicago Harbor, 1962-1963 Ik
13 Total Soluble Phosphate, Chicago Harbor, 1962-1963 7%
Ik Ammonia Nitrogen, Racine Harbor, 1962-1963 76
15 Total Soluble Phosphate, Racine Harbor, 1962-1963 77
16 Phenols, Racine Harbor, 1962-1963 78
17 Milwaukee Harbor, Ammonia Nitrogen, 1962-1961; 79
18 Total Soluble Phosphate, Milwaukee Harbor, 1962-1961; 80
19 Milwaukee Harbor, Phenols, 1962-1961; 8l
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INTRODUCTION
This report presents the physical and chemical results of a
comprehensive study of Lake Michigan waters conducted by the Great
Lakes-Illinois River Basins Project from April 1962 to July 1961*.
The study was conducted through the collection of appropriate
samples during a series of 20 cruises made on the Lake by laboratory-
equipped vessels. Analyses which required immediate attention were
carried out aboard ship. Other analyses were performed at the GLIRB
Project laboratories. These procedures are described later.
The purpose of this study was to determine the present physical
and chemical water quality and to describe those areas of the Lake which
exhibited significant water quality degradation.
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PARAMETERS, DEFINITIONS, AND SIGNIFICANCE
Parameters
The parameters which were considered and reported in subsequent
sections of this report are: ammonia nitrogen; total soluble phosphate;
silica; dissolved oxygen (DO); phenols; methylene blue active substances
(MBAS); biochemical oxygen demand (BOD); hydrogen ion concentration (pH);
dissolved solids; nitrate; sodium; potassium; calcium; specific conduct-
ance; alkalinity; magnesium; sulfate; chloride; and toxic metals (copper,
cadmium, nickel, zinc, lead, and chromium). Certain of these parameters
were found to have practically no variation, either geographically or with
time, on all of the lake samples analyzed to date, whereas others exhibited
detectable changes in some areas and seasons. The parameters showing sig-
nificant changes were ammonia nitrogen, nitrate nitrogen, total soluble
phosphate, silica, DO, specific conductance, phenols, and BOD. Of these,
the first three cited exhibited appreciable variation in all areas of the
Lake. Deepwater samples showed fewer variable parameters than did the
inshore samples, and the greatest variability was shown in the harbor
areas.
Definitions and Significance
Nitrogen: A.mmonia, Nitrate, and Nitrite
Nitrogen in its chemically combined forms is a necessary constit-
uent to the life cycle of aquatic flora and fauna. If it is present in
the aquatic environment with phosphates in moderate concentrations, accel-
erated growths of algae can result. Ammonia in high concentrations, above
2 to 2.£ mg/1 and under alkaline pH conditions (pH 8-8.£) (l, 2)-):-, is a
substance toxic to many forms of aquatic life (3). At all levels, it is an
increased burden to municipal water treatment because of its high chlorine
demand. It is an indicator of sewage pollution because of its presence in
human and animal waste discharges, and may be a significant constituent in
some industrial wastes. Amines and cyanides have toxic properties peculiar
to specific compounds containing these chemical groupings. Nitrate nitrogen (3)
has been implicated as a cause of methemoglobinemia in infants; a limit of
1;5> mg/1 of nitrate (as nitrate) has been recommended in the U. S. Public
Health Service Drinking Water Standards (1|).
Total Soluble Phosphate
Phosphate, like the nitrogen compounds, is a necessary nutrient
for biological activity. Its presence in water is not considered harmful
^-Numbers in parentheses refer to references listed at end of report.
-------
to human health. However, excessive concentrations of phosphate, coupled
with other favorable conditions such as abundant nitrogen supply, optimum
temperature and sunlight, can result in dense algal blooms. These excessive
growths affect the quality of water, interfere with water treatment opera-
tions, increase taste and odor problems, cause unsightly scums and decaying
matter, and create problems due to fluctuations of dissolved oxygen. Con-
centrations of phosphates between 0.03 and 0.3 mg/1 are needed to stimulate
algal growth according to various authors (5). Sawyer (6) states that
"nuisance conditions can be expected when the concentration of inorganic
phosphorus equals or exceeds 0.01 mg/1" (0.03 mg/1 as phosphate).
Phosphate enters the water environment in treated sewage because it
is not normally removed by conventional treatment processes. It is normally
present in human and animal waste products. Synthetic detergents contain
high concentrations of phosphates and have further increased the quantities
discharged. Phosphate is also present in surface runoff, particularly from
fertilized fields, and may be a component of the effluent from certain indus-
trial processes.
Silica
Silica appears in water as a solution and as finely divided or col-
loidal suspended matter. Most silica probably occurs in water as a result
of contact with deposits of minerals high in silicate, such as feldspar,
kaolinite, etc. The concentrations of silica normally found in water have
no significant physiological effects. However, since diatoms require silica
for manufacture of their skeletons, it would follow that the availability of
the substance should be one of the factors limiting the production of large
crops of this important group of plankton. The presence of diatoms in large
numbers interferes with water treatment processes, especially the clogging
of filters.
Dissolved Oxygen (DO)
Dissolved oxygen is one of the most important constituents of a
natural water. The existence of desirable aquatic life is dependent on the
presence of adequate levels of oxygen at all times. The solubility of oxy-
gen in water is low and is affected by both physical and biochemical forces.
The maintenance of satisfactory levels depends upon the equilibrium established
between the forces utilizing oxygen and those contributing it.
Oxygen is utilized by aquatic organisms during the processes of res-
piration. It is replenished from the atmosphere by physical forces and can
also be added through photosynthesis by algae and higher aquatic plants.
When organic pollution enters an aquatic environment, the balance between
consumption and contribution is upset. The bacteria present in water or
introduced with the pollution begin active degradation of the organic matter,
-------
multiply rapidly in the process, and consume the oxygen dissolved in the
water. If they use oxygen at a great enough rate, the resultant oxygen
in the water may not be sufficient to support aquatic life. In polluted
waters, these conditions are particularly in evidence during warm weather
when the rate of oxygen consumption is increased and the ability of water
to hold oxygen in solution is decreased.
Biochemical Oxygen Demand (BOD)
The introduction of organic waste into water - whether the waste
originates from domestic sewage, industrial processes, land runoff, or
any other source - initiates a chain of events involving the organic mate-
rial, micro-organisms accompanying it, and the natural biota present in the
receiving water. Organic matter is rapidly utilized as food by those orga-
nisms capable of converting itj the net result of this action is consumption
of dissolved oxygen. Because control of dissolved oxygen is important in
water quality management programs, a means of measuring the oxygen-consuming
potential of wastes is necessary. The test commonly used for this purpose
is the BOD test.
The BOD test measures a biochemical reaction rather than a well
defined chemical reaction; it involves observation of oxygen usage by micro-
organisms which convert unstable organic matter into cellular material and
respiratory products. Toxic substances, if present, adversely influence
this test.
.Phenols
Phenolic material, which includes phenols, cresols, and xylenols,
when found in water is usually the result of pollution by industrial wastes
(7). Phenols are widely used in the synthesis of many organic compounds.
Waste products from oil refineries, coke ovens, and chemical plants may
contain high concentrations.
Lethal concentrations for fish are related to the species, duration
of contact, temperature, and other conditions. Experimental data, however,
show that 5>.0 mg/1 would be toxic to most fish (8), and some of the chlor-
inated phenols exhibit toxicity in concentrations as low as 0.2 mg/1 (9).
Very low concentrations of phenols will impart a disagreeable
taste to water when chlorinated. The chlorophenols produced by the addi-
tion of chlorine have a more disagreeable taste and odor than the parent
substance. Thresholds of taste and odor for chlorophenols range from
0.001 to 0.02 mg/1 (10). The drinking water standards of the U. S. Public
Health Service have set the upper limit for phenol at 0.001 mg/1 because
of its objectionable taste following chlorination.
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Methylene Blue Active Substance (MBAS)
Methylene blue active substances are anionic surface-active
agents. These surface-active agents have been a common ingredient of
many commercial synthetic detergents for a number of years. Their func-
tion in detergents is to impart foam and reduce surface tension to aid in
the removal of dirt particles during the cleaning process. Until just
recently, the most widely used surface-active agent was the group of
anionic alkyl benzene sulfonates, generally termed ABS. These compounds
are very resistant to biological degradation and persist in water many
miles from the point of entrance. MBAS is believed to be non-toxic to
man (11, 12) in the concentration found in contaminated water. Because
they produce unsightly, persistent foams and cause water to exhibit
undesirable taste, the concentration limit for drinking water used on
interstate carriers has been set at 0.5 mg/1 (li). These compounds have
now been replaced in commercial detergents by surface-active agents that
are biologically degradable so that their presence in the aquatic environ-
ment can be minimized, where adequate treatment is provided.
Hydrogen Ion Concentration (pH)
pH is defined as the logarithm of the reciprocal of the hydrogen
ion concentration or, more precisely, of the hydrogen ion activity - in
moles per liter (9). pH 7 is the neutral point, or dividing line between
an "acid" and an "alkali"; pH values below 7 indicate an acid condition;
values above 7 indicate an alkaline condition. Each unit change in pH
indicates a tenfold change in hydrogen ion concentration; e.g., pH 6 is
10 tines stronger than pH 7, and pH 5> is 100 times stronger than pH 7>
in terms of hydrogen ion concentration.
The pH value of water is significant for several reasons. Acidic
waters (low pH values) disrupt biological activity, cause corrosion of
steel and concrete, intensify the effect of toxic materials such as sulfides
and cyanides, interfere with water plant coagulation practices and tend to
add undesirable iron and manganese to the water. Alkaline waters (high pH
values) also disrupt biological activity, precipitate iron, calcium and
magnesium, and increase the toxicity of ammonia and amines.
Dissolved Solids
The dissolved solids test measures the concentration of dissolved
material present. This includes both organic and inorganic matter. Exces-
sive dissolved solids in water can be unpalatable and increase the cost of
water treatment for many uses. The Drinking Water Standards of the U. S.
Public Health Service recommend the rejection of sources providing water
containing over 5>00 mg/1 of dissolved solids (if another water source is
available) because of a noticeable saline taste, and possible cathartic
effect on many individuals.
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Sodium
Sodium is an alkaline metal, the salts of -which are very soluble
in water and tend to remain in solution. The use of sodium salts is very
common in industry, and industrial wastes may contain large quantities of
the element.
Sodium salts are not particularly significant in drinking water,
except for those persons having abnormal sodium metabolism. It has been
disclosed (13) that sodium in excess of 200 mg/1 is significant to those
suffering from high blood pressure.
Potassium
Potassium, an alkaline metal, is abundant in the earth's crust,
yet its content in natural waters is usually small. In low concentrations
it is essential for plant and animal development (llO, but must be main-
tained in proper balance with phosphorus.
Potassium stimulates plankton growth (l£), but is otherwise insig-
nificant unless found in concentrations above ItOO mg/1, a level considered
toxic to fish (16).
Calcium
Calcium, an alkaline earth metal, is one of the constituents which
produces hardness in water. However, the amount of calcium usually found
in hard waters is less than the daily nutritional requirement. Hardness is
ordinarily considered undesirable because of scaling and reduced heat trans-
fer in heating and cooling systems and because of increased soap consumption.
Research (1?) has demonstrated that there may be a relationship between the
hardness of drinking water and a reduction in cardiovascular disease.
Magnesium
Magnesium, like calcium, is a hardness-producing mineral and con-
tributes to the hardness effects discussed under calcium. It is not known
to produce toxic effects, although in high concentrations magnesium salts
have a pronounced laxative effect.
Specific Conductance
Specific conductance yields a measure of a water's ability to
carry an electric current and is therefore an indication, within rather
wide limits, of the ionic concentration of the solution. The amount of
dissolved matter in a sample may often be estimated by multiplying the
specific conductance by an empirical factor. This factor may vary from
-------
0.£5> to 0.9 depending on dissolved substances and the temperature of
the water.
₯aters polluted by brines and chemical saline wastes will
produce a relatively high level of conductivity. This gives rise to an
increase in osmotic pressure which has a harmful effect on living orga-
nisms. Wide variations in total salinity or in the concentrations of
individual salts can have far-reaching effects upon water fauna, result-
ing even in the elimination of the species (18, 19).
Alkalinity
Alkalinity is defined as the capacity of a water to neutralize
hydrogen ions and is expressed in terms of an equivalent amount of calcium
carbonate. Alkalinity is caused by the presence of carbonates, bicarbon-
ates, hydroxides, and, to a lesser extent, by berates, silicates, phos-
phates, and organic substances.
In itself, high alkalinity is not considered detrimental to man,
but it is generally associated with high pH values, hardness, and excessive
dissolved solids, all of which may have an adverse effect on the quality of
the water.
Sulfate-
The sulfate anion is a component of the dissolved ionic solids
present in most surface waters. Large quantities of sulfates are often
added to the aquatic environment as industrial wastes, especially as
waste pickle liquor from steel mills. Sulfates in combination with sodium
or magnesium can produce a laxative effect. To control this effect, a
maximum of 2^0 mg/1 has been recommended for drinking water.
Chloride
Although chlorides are present to some extent in most surface
waters, they are also associated with man's activities, since the chloride
anion is a component of human waste and is widely used in many industrial
processes. Chlorides can impart a salty taste to drinking water and render
it unpalatable. Many waters are unsuitable for domestic use, irrigation and
industrial processes because of high chloride content. The Drinking Water
Standards of the U. S. Public Health Service recommend the rejection of
sources providing water containing over 2^0 mg/1 chloride if other water
of better quality is available. It is not removable by conventional water
and waste treatment methods. Increased chloride concentration would imply
deterioration in water quality for many beneficial uses.
-------
Toxic Metals
The U. S. Public Health Service Drinking Water Standards (I;)
limit the concentration of certain metals in drinking water because of
potential toxic properties to humans. These limits are as follows:
arsenic, 0.05 mg/1; barium, 1.0 mg/1; cadmium, 0.-01 mg/1; chromium,
0.05 mg/1; lead, 0.05 mg/1; selenium, 0.01 mg/1; and silver, 0.05 mg/1.
The presence of any of these elements in excess of the concentration
listed shall constitute grounds for the rejection of the water supply.
U. S. Public Health Service Drinking Water Standards (li) pro-
vide tolerance limits for metals that, if exceeded, can constitute
grounds for rejection of water supplies if other suitable supplies can
be made available. These are as follows: arsenic, 0.01 mg/1; copper,
1.0 mg/1; iron, 0.3 mg/1; manganese, 0.05 mg/1; and zinc, 5.0 mg/1.
The basis for rejection in this tolerance list is not toxicity in all
cases but is also related to consumer acceptance. In addition to
human toxicity, some of these metals are toxic to aquatic life and can
play an important part in the biological character of the aquatic environ-
ment.
In the studies of the Lake Michigan Basin, six metals, considered
as having toxic properties in relation to beneficial water uses, were
studied in detail. These were copper, cadmium, lead, chromium, nickel,
and zinc.
Copper occurs in natural waters only in trace amounts. Exces-
sive quantities are generally the result of pollution, attributable to
the corrosive action of water on brass or copper piping, to industrial
wastes, or to the use of copper for the control of undesirable plankton
organisms. Copper in water may be detrimental for some industrial uses
and has been found toxic to a wide variety of aquatic organisms, includ-
ing bacteria and fish (3).
Cadmium is one of the least abundant metals present in the
earth's crust and is rarely found in natural waters. It is invariably
present in zinc to some extent. Its uses are limited principally to
industrial applications, therefore quantities found in water are the
result of industrial pollution. It has been found to be toxic to man
when ingested, therefore its presence in water is a definite health
hazard. It is also toxic to aquatic life, including fish (3).
Lead occurs in natural waters only in trace amounts. Exces-
sive quantities are generally the result of pollution, attributable to
the action of water on lead pipe and industrial wastes. Lead is toxic
to man in low concentrations and is accumulative. It is also toxic to
aquatic life, including fish (3).
-------
Trace concentrations of chromium are found in some natural
waters, but excessive concentrations arise from its industrial uses.
It is extensively used in electroplating, tanning, paint manufacture,
and other industries, and is used to control corrosion in cooling water
systems of power plants. Its toxicity to humans when ingested in water
is subject to some question, but because of its pronounced toxicity and
carcinogenic properties when present in other paths of exposure, the
limits set for drinking water reflect these considerations as a factor
of safety. Its toxicity to aquatic life covers a broad range, being
toxic to some of the smaller organisms at levels as low as 0.05> mg/1 (3).
Nickel is not a common constituent of natural waters, its pres-
ence being related to industrial waste discharges. Its toxicity to humans
is low and is not considered to be a health hazard in concentrations usu-
ally present in natural waters. It is toxic to aquatic life, but less
than copper or zinc (3).
Zinc is present in most surface and ground waters only in trace
amounts, its presence being related to the corrosive action of water on
galvanized piping and to industrial wastes. Its toxicity to humans is
low when compared with the other metals. It is toxic to aquatic life,
but less than copper (3).
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LABORATORY PROCEDURES
Sample Preservation
After samples were collected, each sample was divided (on ship-
board) into half-gallon portions according to substances to be analyzed
and preservation requirements. Preservatives added to each half-gallon
polyethylene bottle of sample were as follows:
1. For phosphate analysis - 10 ml of chloroform.
2. For nitrogen analysis - 1.8 ml of sulfuric acid.
3. For phenol analysis - 20 ml of 10 percent copper
sulfate and 20 ml of phosphoric acid.
On Cruises 5> and 6, BOD analyses were performed on shipboard.
On the other cruises, BOD samples were packed in ice at the time of col-
lection and returned to Project headquarters for analysis. The average
time in transit for these samples was four hours, and the longest time
five hours.
Special preservation measures were not necessary for the sample
portions used for mineral analyses.
Analytical Methods
The physical and chemical data included in this report were
obtained, unless otherwise indicated, by following the procedures pub-
lished in "Standard Methods for the Examination of Water and Wastewater,"
llth Edition, I960, referred to throughout this report as Standard Methods.
While many methods may be used in water analysis, those described in the
Standard Methods have been selected for this study because the procedures
are supported by collaborative studies of capable analysts, throughout
the nation, who have demonstrated the methods to be accurate and reproduc-
ible within specified limits.
Minor modifications have been made on some of the methods used,
when they could better accomplish the purpose for which the procedure was
applied. Before adopting any change or modification, however, many repet-
itive analyses were made to determine the precision of the modified method
and also its agreement with the Standard Methods.
To assure continually reliable data, reference standards, of
known composition, and many blanks were analyzed simultaneously with all
tests.
A skeleton outline of tests performed is presented below. Where
the tests conform strictly to Standard Methods only the pages wherein the
10
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procedure may be found are cited, but "where modifications or changes are
made these have been described in detail. Tests marked by asterisks were
performed on shipboard.
NitrogenAmmonia and Organic
Free ammonia nitrogen was quantitatively determined by the
distillation method described on pages 298-299. Organic nitrogen was
measured by the Kjeldahl method using mercuric sulfate as a catalyst.
This procedure is described on pages 305-307.
Nitrate and Nitrite Nitrogen
Nitrogen in the form of nitrates was determined by the phenol-
disulfonic acid method described on pages 302-303. The nitrites, if
present, were oxidized to nitrates with hydrogen peroxide in acid medium.
This was the procedure used on the first five cruises of Lake Michigan.
This method was run in duplicate with the Greis method for the Technicon
Auto-Analyzer, described below, for analyses of 96 samples from the sixth
cruise. The results obtained by the Greis method proved superior and the
procedure was adopted for subsequent analyses.
Method for Nitrate Nitrogen by the Auto-Analyzer
Nitrogen in the form of nitrates was determined by the Greis
Method following its reduction to nitrite, utilizing the Technicon Auto-
Analyzer. The nitrates were reduced by means of a zinc column in an
medium. The following procedure was followed:
1. Apparatus used:
Technicon Auto-Analyzer. (20)
2. Reagents used:
a. Sodium Acetate Solution: 3h g. per liter.
b. Sodium Acetate Hydrochloric Acid Buffer Solution: 100
ml of hydrochloric acid (1 : 99) mixed with 1,000 ml of sodium acetate
solution (a).
c. Sulfanilic Acid Solution: 6.0 g. of sulfanilic acid
plus 200 ml of concentrated hydrochloric acid per liter.
d. Naphthylamine Hydrochloride Solution 6.0 g. of 1-
naphthylamine hydrochloride, 10 ml qf concentrated hydrochloric acid
and 500 ml of 95 percent ethyl alcohol per liter. (This reagent
11
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eventually becomes slightly discolored and may form a slight precipi-
tate. If discoloration occurred it was removed by mixing with nitrate
free activated carbon and filtering.)
e. Color Reagent: Equal volumes of sulfanilic acid
reagent (c) and naphthylamine hydrochloride reagent (d) were mixed and
stored in the dark for increased stability.
f. Zinc metal 30 mesh, granular, reagent grade. This
zinc was washed with chloroform just before use.
g. Stock Nitrate Solution: 7.2138 g. of anhydrous potas-
sium nitrate per liter. This solution contained 1 mg of nitrate nitrogen
per ml.
h. A series of working standards from 0.0£ to 3.0 mg per
liter of nitrate nitrogen was prepared from the stock solution (g).
3. Procedure:
a. The analytical system was set up in accordance with the
flow diagram provided by Technicon.
b. The instrument was standardized using standard solutions
listed in 2 h. A distilled water wash was interposed between each standard.
c. Samples were arranged on the analyzer with a distilled
water wash between each sample. A series of standards was introduced after
each 10 samples to detect possible drift in the instrumentation.
d. Standardization curves were prepared which show the
relationship of recorder response to concentration of nitrate as nitrogen.
Sample results were evaluated by reference to this curve.
The precision of this method was compared with the Standard
Method by analyzing 96 separate samples by both methods. The results
were found to be in good agreement. This method was therefore adopted
as a routine procedure because of its great superiority with respect
to speed of analysis as well as improved precision.
Total Soluble Phosphate
This test was performed in accordance with procedures described
in Standard Methods, Method C, Total Phosphate and Polyphosphate, pages
20lj.-206, on samples filtered to remove suspended matter.
12
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Silica
The procedure for silica was the Colorimetric Heteropoly
Blue Method described on pages 228-229.
Dissolved Oxygen*
This test was performed in accordance with the procedure
described as Method A, Alsterberg (Azide) Modification of the Vinkler
Method, pages 309-311.
Phenols
Phenols were determined as described on pages lj.0lt-i;08, using
the Aminoantipyrene Method.
Methylene Blue Active Substances (MBAS)
The methylene blue procedure for determining MBAS, as des-
cribed in Standard Methods, pages 21|5>-25>1, was modified by this
laboratory. The changes in no way affected the reproducibility of
the method, but did speed up the procedure and economize on the use
of time and reagents.
The modifications were as follows:
(a) The washing of extracts with wash solution was elim-
inated because comparative studies showed that values were equally
reproducible and accurate without this step.
(b) Twenty-five ml aliquots or aliquots diluted to 25 ml
were used for the analysis.
(c) Five ml of methylene blue solution was added to each
sample. An additional amount, if needed, would be indicated by the
water phase becoming clear after extraction with chloroform.
(d) The sample was extracted two times with 10 ml por-
tions of chloroform and filtered through a pledget of cotton in the
tip of the separatory funnel. This filtered and removed moisture
from the chloroform extract satisfactorily.
(e) The sample was collected, made up to volume and
read in the spectrophotometer at a wave-length of 6^0 millimicrons.
13
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Biochemical Oxygen Demand*
The procedure for biochemical oxygen demand was the same as
described on pages 318-323 in Standard Methods.
Hydrogen Ion Concentration (pH)#
This test was performed by the Glass Electrode Method as des-
cribed on page 191;.
Dissolved Solids
Dissolved solids were measured by the method described on
pages 326-330 of Standard Methods titled "Filtrable Residue."
Sodium and Potassium
Sodium and potassium content were measured by the Flame
Photometric Method as described on pages 231-232.
Calcium
The method used was the EDTA Titrimetric Method as recommended
in Standard Methods pages 67-68.
Conductance (Specific)-*
This test was performed using a specific conductance meter and
cell as described on pages llU-116.
Total Alkalinity
This test was performed using a mixed indicator, consisting of
two parts methyl orange and one part methyl purple, as described on pages
Magnesium
This test was performed by the Photometric Method as described
in Standard Methods on pages 11?3-15>U.
Sulfate
The Turbidimetric Method was used as described on pages
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Chloride
Chloride content -was measured by the Mercuric Nitrate Method
described on pages 326-330.
Metals (Toxic)
A polarographic technique "was used to analyze water for toxic
metals. Metals in concentrations as low as 0.01 mg/1 can be determined,
and with the addition of the range extender and/or greater concentration
of sample, lower levels may be detected.
The method has been demonstrated to be as accurate as, and
definitely more time-saving than, the usual colorimetric procedures for
these metals. The precision was in the range of ± 3 percent.
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RESULTS OF ANALYSIS
Samples of Lake Michigan -water were subjected to a large number
of physical and chemical analyses. The substances showing appreciable
variability and likely to provide the greatest threat to satisfactory
water quality for intended uses were found to be ammonia nitrogen, total
soluble phosphate, silica, dissolved oxygen, and phenol. Therefore, the
results of analysis of these constituents will be discussed in detail.
Average values and ranges of the various constituents found in
water are cited most frequently in this report. However, when large
variations or abnormalities are evident, individual results will be dis-
cussed in order to provide a more comprehensive account of the water
quality in the Lake Michigan Basin.
Deepwater Studies
The deepwater region of Lake Michigan is defined as that portion
of the Lake greater than 10 miles from shore. This region constitutes
the bulk of Lake Michigan waters, and because it is the least affected
-by various forms of pollution, it will be used as a base line of water
quality in the Basin.
The deepwater region was sampled during a series of seven
cruises which began in May 1962 and were discontinued in November 1963
(Table l). The average chemical results for this region are presented
in Tables 3 and 1;. Variations by season and depth of ammonia nitrogen,
total soluble phosphate, silica, dissolved oxygen, and percent saturation
are shown in Table £. Since more of the samples analyzed were in the
southern portion of the Lake, average values tend to be weighed in favor
of this region.
Ammonia nitrogen concentrations ranged from not detectable at
the limits of the test (N.D.) to 0.5 mg/1 throughout the deepwater region.
The maximum value was found at a depth of 75 meters about 12 miles from
Sturgeon Bay. The average ammonia nitrogen concentration was 0.06 mg/1.
The geographical distribution of ammonia nitrogen within the
Lake Michigan Basin is shown in Figure 1. The inshore and deep-water
regions are separated by a line located approximately 10 miles from
shore. It should be pointed out that this and similar figures present
only average values within a given area (a 15' quadrangle) and are used
only to represent variations in water quality and not exact concentrations
of any particular constituent at a specified point.
Figure 1 shows that, for the most part, there is little varia-
tion in ammonia concentrations throughout the deepwater region. The
16
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water leaving Lake Michigan at the Straits of Mackinac had an average
ammonia concentration of 0.0£ mg/1 which is only 0.01 mg/1 lower than
the average for the entire deepwater region. Several deepwater quad-
rangles had ammonia nitrogen concentrations above 0.08 mg/1. However,
these areas are scattered and do not appear to correspond to ammonia
sources.
Ammonia nitrogen concentrations are compared by season and
depth in Table 5. Little variation is apparent except that concentra-
tions found in the summer months were slightly higher than in the spring
and fall.
Total soluble phosphate concentration (Table 5>) averaged 0.02
mg/1 in deep water. A uniform distribution throughout this region is
evident from Figure 2. The highest phosphate concentration was O.llj
mg/1, found within 12 miles of Grand Haven. All other phosphate con-
centrations were below 0.09 wg/1.
Silica concentrations averaged 2.7 mg/1 throughout the deepwater
region. The concentration at individual stations ranged from 0.6 to 5>«5>
mg/1. The highest silica concentrations were found in the central and
northern regions of the Lake as shown in Figure 3. Lower concentrations
were evident near the shoreline and in the vicinity of harbors. In gen-
eral, these low silica concentrates were found in regions of high biologi-
cal activity (23).
Variations in silica concentrations by season and depth are
shown in Table £. Silica concentrations in the spring were fairly uniform
at all depths, which can be attributed to mixing during the spring turn-
over. During the summer and fall months silica concentrations increased
with depth. This effect may be attributed to thermal stratification of
the water and greater biological uptake of silica in the upper layers
of water than in the hypolimnion.
The average dissolved oxygen concentrations measured in the
deepwater region are listed in Table 3. The percent saturations these
dissolved oxygen concentrations represent are also included. As expected,
the percent oxygen saturation was found to average 6 to 7 percent less
below 30 meters than in the top few meters of water. Oxygen depletion
from other than natural causes was not evident in the deepwater region.
Table 6 indicates the minimum and maximum values encountered.
Toxic metal analyses were performed on a number of samples from
each region of the Lake. The frequency of occurrence of each metal is
given in Table 1;. All toxic metals but cadmium were detected at the limit
of sensitivity of the test (0.005 mg/l). This level is within the limits
set by the U. S. Public Health Service Drinking Water Standards
17
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Averages and ranges of the other chemical substances studied in
the deepwater region appear in Table 2. These parameters, namely nitrate
and organic nitrogen, sodium, potassium, dissolved solids, specific con-
ductance, pH, alkalinity, calcium, magnesium, chloride, and sulfate, showed
some variability, but were of little water quality significance at the
levels encountered.
Inshore Studies
Inshore areas of Lake Michigan were sampled during a series of
eight cruises (Table l) from August 1962 to October 1963. Samples were
collected at one, four, seven and ten miles from shore at several depths,
except in harbors. In addition to the parameters which were found sig-
nificant in the deepwater studies, phenols were found in significant
quantities in some of the inshore samples. The average chemical results
and ranges are tabulated in Table 3. A comparison with the deepwater
results shows higher average values and greater variations in all param-
eters analyzed in the inshore region.
Ammonia nitrogen concentrations in the inshore region ranged
from N.D. (none detected) to I.I; mg/1 with an average concentration of
0.13 mg/lj more than twice the average concentration found in the deep-
water region. Figure 1 shows that the highest concentrations were found
in the vicinity of Calumet, Milwaukee, Benton Harbor, Saugatuck, Grand
Haven, and Muskegon. Concentrations up to l.U mg/1 were found near
Calumet and 1.3 mg/1 near Milwaukee Harbor.
Since almost half of the samples analyzed in the inshore region
were taken in the vicinities of Calumet and Milwaukee, the average con-
centrations are heavily weighted by these two areas. However, excluding
these areas, the average concentration becomes 0.10 mg/1, which is still
substantially higher than found in deep water.
Total soluble phosphate concentrations in the inshore region
are shown in Figure 2. Very high concentrations of soluble phosphates
are found in the Milwaukee area. In quadrangles B-13, B-llj. and C-llj.,
the average concentrations were 0.10, 0.26, and 0.23 rag/1? respectively.
In the same order, maximum concentrations were 3-1, 3>k, and U.5 mg/1.
These values indicate phosphate-rich water moving southward from
Milwaukee Harbor.
Near the Calumet area, maximum phosphate concentrations of
O.i;5 mg/1 were found in quadrangles D-19 and E-19. The average concentra-
tions in these areas were 0.05 and O.Olj. mg/1, respectively.
Aside from these two areas, the rest of the inshore region averaged
less than 0.03 mg/1 total soluble phosphate, which is only 0.01 mg/1 higher
than the deepwater region.
18
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Silica concentrations found in the inshore region are shown in
Figure 3. The average silica concentration of 1.7 mg/1 is about half
that found in the deepwater region indicating possibly greater biologi-
cal uptake of the silica in the inshore region. The areas of low silica
concentrations have been found to correspond to regions of high phyto-
plankton populations (23).
Water samples from a number of inshore stations were analyzed
for phenolic materials. By far the highest concentrations were found
in the vicinities of Indiana and Calumet Harbors. The maximum value in
quadrangle D-19 was 72 micrograms per liter, while the average value
was 3 micrograms per liter. In quadrangle C-19, the maximum concentra-
tion was 32 micrograms per liter. In contrast, the next highest phenol
concentration in another quadrangle was 8 micrograms per liter found
near Michigan City. In the Milwaukee area, phenols ran as high as
7 micrograms per liter and averaged 2 micrograms per liter.
Some phenolic pollution is evident between Muskegon and
Kalamazoo where phenol concentrations up to 8 micrograms per liter were
found. However, phenols were not detected in many samples from this
area.
Chlorides were found in significant quantities near Ludington
and Manistee. In quadrangles H-10, 9, and 8, maximum values 69, 9ht and
77 mg/1, respectively, were found. The average values for these quad-
rangles were lU, 29, and 18 mg/1, respectively, while the overall average
inshore chloride concentration was 7.1 wg/1. The major contributors of
chlorides in the area are the Morton and Manistee Salt Companies which
discharge near the mouth of the Manistee River up to 260,000 and 1;1|,700
pounds of chloride per day, respectively.
The biochemical oxygen demand (BOD) was determined at a number
of inshore stations. Outside the Milwaukee Harbor, maximum BODs of
6.7 mg/1 were found in both quadrangles, B-13 and B-llj.. A BOD of 8.6
mg/1 was found near the mouth of the Grand River on the eastern shore.
In the inshore region adjacent to Gary, Indiana, BODs ranged up to
k.6 mg/1. These values indicate some degradation of the water quality
when compared to the inshore average of 1.1; mg/1.
Averages and ranges of the other chemical parameters studied in
the inshore region appear in Table 3. These parameters, namely nitrate
and organic nitrogen, sodium, potassium, dissolved solids, specific con-
ductance, pH, alkalinity, calcium, magnesium, and sulfate showed greater
variability and higher average values than found in the deepwater region.
Although the levels of these chemical substances encountered within the
inshore region were not high enough to be considered critical for most
water uses, they do indicate large amounts of pollutants being discharged
into Lake Michigan daily and annually.
19
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Major Lake Michigan Tributaries
A number of the major river systems entering into Lake Michigan
were sampled weekly from March 1963 to April 196U. The streams Manistique,
Manitowoc, Sheboygan, Milwaukee, Burns Ditch, St. Joseph, Kalamazoo, Grandj
Muskegon, and Pere Marquette will be discussed in this section of this
report. The tributaries to Green Bay will be discussed in subsequent sec-
tions, as will the Boardman River, Calumet River, and the Indiana Harbor
Canal.
Sampling stations at each tributary were located as close to the
river mouths as possible without becoming diluted with harbor or lake
water. The principal objective of this tributary mouth sampling was to
determine the loading of various substances carried by each river into
Lake Michigan. Average chemical results and loadings are shown in
Tables la and 7b.
Plows of each river were taken from U. S. Geological Survey
flow records for the study period (25). Average flows at the gaging sta-
tions were corrected for the portion of drainage basin between the gaging
station and the river's mouth.
Of all the chemical parameters measured for the tributaries, the
two nutrients, total soluble phosphate and ammonia nitrogen, showed the
most important variations. With respect to these two parameters, the
influence of the tributaries on the water quality can be seen in Figures
1 and 2.
Except for the Fox River, which is discussed later under Green
Bay, the greatest contributor of soluble phosphate to the Lake was found
to be the Grand River, contributing 5,330 pounds per day. The St. Joseph
River adds less than half this quantity, while Burns Ditch carries roughly
1,500 pounds of phosphate per day. Phosphate concentrations were found
to be higher in the immediate vicinities of these river mouths, but the
concentrations quickly dropped off moving out in the Lake. Although the
Milwaukee River carries comparatively minor loads of phosphates, the
Milwaukee area appears to have a major influence on the adjacent inshore
waters with respect to phosphate. This influence is primarily a result
of waste discharges from the Jones Island Sewage Treatment Plant, which
contributes an estimated 6,600 ppunds of total phosphates per day to the
harbor.
The largest discharge of ammonia nitrogen to the Lake, with the
exception of the Fox River, was found to originate from the Indiana Harbor
Canal. Using an average flow of 1,500 cfs, the calculated daily discharge
of ammonia nitrogen from the canal is 19,UOO pounds. This massive load
of ammonia nitrogen severely pollutes the adjacent inshore waters, where
an average concentration of 0.18 mg/1 was observed.
20
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Of the other tributaries considered, the Grand and St. Joseph
Rivers were found to be the largest contributors of ammonia nitrogen,
with 7,000 and 5>,900 pounds per day, respectively. The Kalamazoo
River carried roughly half this amount while the Milwaukee and Muskegon
Rivers contributed approximately a quarter as much at 1,600 per day.
Inshore waters adjacent to these tributaries averaged 0.16 mg/1 ammonia
nitrogen.
Toxic metals were found in appreciable concentrations in the
tributaries. Copper concentrations were usually highest, followed by
nickel and zinc. Copper concentrations ranged from 0.06 mg/1 to 0.15
mg/1. Although these values are well below the drinking water standard
of 1.0 mg/1, concentrations as low as 0.02 mg/1 have been reported harm-
ful to aquatic life (3). Zinc concentrations were also well within the
recommended limits for drinking water. Nickel concentrations were three
times higher in the Sheboygan River than those in the other rivers studied.
However, the levels of nickel encountered are not known to be a health
hazard. On the other hand, cadmium concentrations in the St. Joseph River
averaged 0.02 mg/1, which is twice the maximum limit recommended for drink-
ing water. Furthermore, chromium concentrations of O.Olj. mg/1, found in the
Grand River, were very close to the limit of 0.05 mg/1 (5). Such levels
of toxic metals indicate serious impairment of water quality in the trib-
utaries, especially in the Grand and St. Joseph Rivers.
For the most part, loadings of the other chemical constituents
in each river appeared to correlate well with concentrations found in the
inshore waters near the river mouths. These constituents may represent
dissolved materials leached from the soil, municipal or industrial waste
discharges, or urban and rural runoff. Dissolved solids and suspended
solids loadings ranged from £8 to 1,790 tons per day and 7 to 23 tons
per day, respectively. Aside from the nutrients and toxic metals, these
materials have relatively little influence on the water quality of Lake
Michigan.
Green Bay
The waters of Green Bay were sampled from June 26 to July 17,
1963. Figure k indicates the approximate locations of the stations
sampled and the selected zones into which the bay has been divided to
facilitate interpretation of the collected data. Each zone, except for
tributary mouths, harbors, and nearshore areas, represents a region of
similar water quality.
A summary of the physical and chemical findings is presented
by zones in Table 8. Examination of this Table shows the following
significant water quality effects:
21
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1. A severe depletion of dissolved oxygen is evident in zone 1.
Several samples with zero dissolved oxygen were found in this area. Some
oxygen depletion is also evident near the Peshtigo River, in zone 3.
2. The average concentration of soluble phosphate in zone 1 is
far above the level of 0.03 mg/1 considered critical for the stimulation
of algal blooms. In comparison, all the major harbors in Lake Michigan,
except Milwaukee, had average concentrations less than half the value
found in zone 1. Except for zone £, soluble phosphate concentrations
in the other zones in Green Bay were also at or above critical levels.
3. Ammonia nitrogen levels are by far the highest in zone 1.
Throughout the other zones, concentrations are comparable or higher
than those found in the inshore region of Lake Michigan.
1;. Nitrate nitrogen concentrations are significantly low
throughout the bay.
5. Phenol concentrations up to UO micrograms per liter were
found in zone 1. Higher concentrations within the Lake Michigan Basin
were found only in Indiana Harbor.
6. The other parameters measured in Green Bay, such as
chlorides, dissolved solids, and sulfates, also had much higher values
in zone 1 than in the other regions of the bay, indicating a high volume
of waste discharge and probably a lack of mixing in this area.
Green Bay joins Lake Michigan at zones 5 and 6. The water
quality of these two zones is comparable with the average inshore water
in Lake Michigan.
Green Bay Tributaries
The major tributaries into Green Bay were sampled weekly at
the river mouths from June 1963 to May 1961;. The physical and chemical
findings obtained during this study are summarized in Tables 9a and 9b.
In order to illustrate the seriousness of waste discharges into
Green Bay by the major tributaries, approximate average daily loadings
of the two significant nutrients, ammonia nitrogen and phosphates, are
compared in Figures 1? and 6, with the concentration of these constituents
found in the Bay. Examination of these figures reveals the Fox River
to be by far the most important contributor, discharging 6,6?0 pounds of
total soluble phosphate daily, or three times the amount discharged by
the Menominee, the next highest contributor of phosphate, and discharging
37,200 pounds of ammonia nitrogen, which is almost four times as much as
the Oconto, the next highest ammonia nitrogen contributor at 9,81j.O pounds.
22
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In fact, the Fox River adds more nutrients to Green Bay than all the
other tributaries combined, which results in the high concentration
found in zone 1.
The presence of toxic metals in detectable amounts can be
considered a potential threat to continuing water uses. The other
constituents measured in this study serve to differentiate the chemi-
cal water quality of the various streams. The composition of dissolved
matter found .may reflect the effects of minerals leached from the ground,
municipal or industrial waste discharges, or urban drainage such as result-
ing from street salting for ice control. Except for the nutrients previ-
ously cited, these chemical inputs have relatively little influence on
the chemical water quality of the Bay.
A special study consisting of intensive sampling of a stretch of
the Fox River was conducted to determine the effect of organic wastes on
stream oxygen resources. A typical profile of the dissolved oxygen and
biochemical oxygen demand concentration found during this study are shown
in Figure 7. The high BOD levels carried by the Lower Fox result in the
complete absence of dissolved oxygen for a stretch of eleven miles and
levels of less than 2 mg/1 for over twenty miles. Fish and desirable
aquatic life cannot survive under such degraded oxygen conditions. The
odors and anaerobic gases released by this pollution make the stream
esthetically undesirable and very objectionable for recreational uses.
The organic loadings causing this highly polluted condition are known
to originate primarily from the discharges of many pulp and paper mills
located along the Lower Fox River and from domestic wastes.
Traverse Bay
Traverse Bay and the adjacent region of Lake Michigan (Figure 8)
were sampled from July 22 to July 28, l°61j.. The average chemical results
and the ranges encountered in this area are tabulated in Table 10.
The Boardman River is the only major tributary into Traverse
Bay. This river was sampled weekly from April Ij., '1963 to April 23,
1961;. Samples were composited by flow prior to analysis. For compara-
tive purposes, these results are also tabulated in Table 10.
In general, the west arm of Traverse Bay was found to contain
higher concentrations of contaminants than the east arm. The Boardman
River, which enters the west arm, and Traverse City, contribute to
these higher values. The Boardman River influence is not large due to
its low flow (2££ cfs).
There appears to be no significant variation in general water
quality between Traverse Bay and the adjacent inshore waters of the Lake.
23
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Indiana Harbor
The Indiana Harbor receives drainage from the Grand Calumet
River in northern Indiana as well as from a large industrial complex
located along the harbor canal. Because of the large volume of waste
discharge from these sources, considerable variation in water quality
was observed between the Indiana Harbor and the adjacent inshore waters.
The average chemical results and ranges encountered in this area are
shown in Tables lla and lib.
The ammonia nitrogen concentrations in Indiana Harbor and
Canal are presented in Figure 9. The highest values were observed in
the Indiana Harbor Canal where concentrations up to lj..5> mg/1 were found;
the overall average in the Canal was 2.1; mg/1. In contrast, the highest
concentration found in the Harbor was 2.3 mg/1. The average concentration
in the Harbor was l.h mg/1, which is approximately eight times the average
ammonia concentration (0.18 mg/l) in the adjacent inshore waters and 23
times that of the deepwater zone. Such high concentrations of ammonia
indicate serious water quality degradation.
Seasonal variations of ammonia nitrogen concentrations appear
in Table 15>. Concentrations were found to increase substantially from
spring to fall.
Total soluble phosphate concentrations showed little variation
by station throughout the harbor, where average values ranged from 0.05
to 0.08 mg/1 (Figure 10). In contrast with ammonia nitrogen values,
phosphate concentrations were no higher in the Canal than in the Harbor.
Seasonal variations of phosphates were not significant.
Phenol concentrations in the Harbor and Canal are presented
graphically in Figure 11. Some of the highest phenol concentrations
in the Lake Michigan Basin were found in the Indiana Harbor Canal, where
concentrations as high as 35U micrograms per liter were found. Phenol
concentrations averaged respectively 1^6 micrograms per liter in the
Canal, 33 micrograms per liter in the Harbor, and 3 micrograms per liter
in the adjacent inshore waters. This phenolic pollution has been found
to be the major cause of frequent taste and odor problems in drinking
water from as far north as the City of Chicago's South District Filtra-
tion Plant. Seasonal variation of phenol concentrations are shown in
Table 18. Much lower concentrations were evident in the summer months
than in the spring and fall.
The results of toxic metal analyses of Indiana Harbor water
samples are shown in Table lib. Only lead and zinc were found in detect-
able concentrations.
21;
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dissolved oxygen concentrations in the Harbor averaged 2.7
mg/1. Concentrations varied from O.It to 10 mg/1, with corresponding
saturation values ranging between Ij.2 and 99 percent. Seasonal varia-
tions in dissolved oxygen were very pronounced. During the summer
months the maximum saturation was only 39 percent, while in the spring
saturations ranged up to 99 percent. Such values indicate massive loads
of organic wastes within the Harbor.
Oil and grease averaged U.It mg/1 in the Harbor, where concentra-
tions ran as high as 29 mg/1. These values are quite high when compared
to the Lake waters, where the concentration is practically nil, and
emphasize the magnitude of industrial wastes discharged through the
Harbor.
Calumet Harbor
Under normal conditions, the waters of Calumet Harbor move from
the Lake toward the Calumet River due to diversion of water from the Lake.
However, contamination of the Harbor from industrial and municipal wastes
discharged into the Calumet River occurs during periods of heavy storms,
when the usual direction of flow is reversed. The average chemical results
and the ranges encountered during the study of Calumet Harbor are shown in
Tables lla and lib.
Average ammonia nitrogen concentrations at the stations sampled
are shown in Figure 9. Noting the scale differences in Figure 9, inspec-
tion shows that ammonia concentrations in the Calumet Harbor average less
than one-quarter the concentration found in Indiana Harbor. However, the
average concentration in the Calumet Harbor of 0.23 mg/1 is still relatively
high when compared to adjacent inshore average of 0.18 mg/1 and the deep-
water average of 0.06 mg/1. The seasonal variations in ammonia nitrogen
concentrations are shown in Table 15. Maximum ammonia concentrations were
found in the summer months.
Total soluble phosphate concentrations in Calumet Harbor are com-
parable with the levels found in Indiana Harbor (Figure 10). There were
no significant seasonal variations in phosphate concentrations (Table 16).
Average phenol concentrations at the individual sampling stations
are shown in Figure 11. Inspection of this figure reveals that all values
were relatively low and did not vary significantly.
Dissolved oxygen concentrations averaged 8.5 mg/1, with a cor-
responding saturation of 90 percent. The minimum and maximum percent
saturations in Table 17 indicate a slight seasonal variation, with the
summer months showing the lower percent saturation.
-------
As in Indiana Harbor, lead and zinc were the only toxic metals
detected. Copper, cadmium, chromium, and nickel concentrations were all
less than 0.005 mg/1 - the sensitivity of the test. The average concen-
trations and ranges for toxic metals appear in Table lib.
No significant variation was noted in the other parameters
measured.
Chicago Harbor
The average chemical results for Chicago Harbor are shown in
Tables 12 and 13. The geographical distribution of phosphate and
ammonia nitrogen concentrations appear in Figures 12 and 13. Phenols
were not detected in the Harbor. All parameters studied showed higher
values in the southern end of the Harbor. However, in general, average
results within the Harbor did not vary significantly from results of
the adjacent inshore waters. Such results are expected since inshore
waters normally flow through the Harbor toward the Chicago River, except
during periods of heavy storms, when the flow may be reversed in a simi-
lar manner as the Calumet River, though less frequently.
Racine Harbor
The water quality of Racine Harbor is comparable to the Chicago
Harbor, except for higher soluble phosphate and phenol concentrations.
Average ammonia nitrogen and phosphate concentrations at indi-
vidual stations within the Harbor arer-shown in Figures lit and 15>,
respectively. The range of phosphate concentrations for all stations
is 0.07 to 0.10 mg/1, except for one station near the breakwall and one
at the breakwall opening, where the concentrations were 0.03 and 0.01
mg/1, respectively. The adjacent inshore water had an average phosphate
concentration of 0.03 mg/1.
Phenol concentrations are shown in Figure 16. A band of higher
phenol concentrations was observed running north and south through the
center of the Harbor. Concentrations at these stations ranged from
2 to 3 micrograms per liter, whereas all other stations showed levels
of about 1.0. This may indicate a plume of phenolic pollution moving
out from the mouth of the Root River, which drains into this Harbor,
during the sampling period.
None of the other parameters measured showed significant dif-
ferences between Racine Harbor and the adjacent inshore waters.
26
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Milwaukee Harbor
Two studies of Milwaukee Harbor were made - one in the fall of
1962 and the second in the summer of 1963. Table ~Lh presents the number
of samples, averages, and ranges for Milwaukee Harbor and waters adjacent
to the Harbor.
Figures 17, 18, and 19 present sample station locations and con-
centration variations observed in each area for ammonia nitrogen, soluble
phosphate, and phenol, three of the more critical water quality parameters.
In Figure 17, the highest ammonia nitrogen levels, 1.00-2.20 mg/1,
are shown to be in the central area of the Harbor and in the Milwaukee
River. These concentrations extended about one mile north of the mouth of
the Milwaukee River and approximately three miles south along the shoreline,
Levels of 0.50-0.99 mg/1 were found in the southeastern portion
of the Harbor and in the northwestern side of the Harbor. The very
northern section had concentrations of 0.15-0.h9 mg/1. Waters adjacent
to the breakwater from the center opening to the southern end, and with
bands extending out into the Lake, had levels ranging from O.l5 to 0.1|9
mg/1. North of the breakwall along the shoreline, an area outside the
Harbor and near the center of the breakwater, and an area south of the
Harbor were 0.05-0. ll; mg/1. All of the remaining waters adjacent to the
Harbor had concentrations of N.D.-0.05 mg/1, which is typical of the
background levels found in the lake proper.
As shown in Figure 18, the soluble phosphate values form a simi-
lar pattern to that of ammonia nitrogen. Concentrations of O.lj.9-1.3 mg/1
extended generally from about one mile north of the river mouth to the
southern end of the Harbor. A section in the southeast portion had
levels of 0.15-0.k9 mg/1. In the northwestern area of the Harbor, the
concentrations were 0.15-0. lj.9, and in the northeastern section 0.03-
O.lli mg/1.
As stated previously, the major sources of phosphate within the
area are the Milwaukee River, its tributaries, and the Jones Island Sew-
age Treatment Plant. The combined discharge from these sources has been
estimated at 9,300 pounds of total phosphate per day (21;).
In waters adjacent to the Harbor at the southern end of the
breakwater, levels were observed ranging from O.it9-1.3 mg/1. A band
extending along the entire length of the Harbor with tongues extending
out into the Lake had concentrations of O.03-O.ll| mg/1. In all of the
remaining waters adjacent to the Harbor the levels ranged from N.D.-0.03
mg/1, which is the level found throughout the Lake where no local inputs
exist.
27
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Figure 19 presents the phenol concentrations observed in Mil-
waukee Harbor and the adjacent waters of Lake Michigan. The phenol
levels ranged from 5> "to 8 micrograms per liter at the mouth of the
Milwaukee River and for one mile north along the western side of the
Harbor, in the very northern end, and on the southeastern side of the
Harbor. Levels of 3-h micrograms per liter were observed in a large
area extending from the eastern side of the Harbor one mile north of
the river to three miles south along the western side. A band in the
adjacent waters extending from the north to the south along the shore-
lines and the breakwater had phenol concentrations of 1-2 micrograms
per liter. Opposite the center opening in the breakwater, a band
extended out into the Lake with concentrations of 3.0 micrograms per
liter. Phenols were not detected in the remainder of the adjacent
waters of Lake Michigan.
The other parameters listed in Table lU, except for dissolved
oxygen, are higher in concentration than in the adjacent Lake waters.
These high levels of chemical pollutants appeared to move into the
Lake primarily from the southern end of the Harbor, as did ammonia
nitrogen, phosphates, and phenols.
Evidence for substantial building-up of organic wastes within
the Harbor is further provided by the depressed levels of dissolved
oxygen encountered.
These gross Indicators of chemical pollution are the result
of effluent discharges from the Milwaukee Metropolitan Sewage District's
Jones Island Treatment Plant, which services a domestic and industrial
waste discharge of over two million population equivalents, plus the
overflow during storms from combined sewers also serving this large
population.
28
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SUMMARY
Studies of chemical water quality were undertaken throughout
Lake Michigan and environs. Of the chemical parameters considered,
ammonia nitrogen, nitrate nitrogen, total soluble phosphate, dissolved
oxygen, silica, toxic metals, and phenols were found to be significant
in assessing variations in water quality. Although analyses were also
conducted for organic nitrogen, sodium, potassium, dissolved solids,
specific conductance, pH, alkalinity, calcium, magnesium, chloride,
and sulfate, these substances were not considered to be of critical
importance in the levels encountered.
Deepwater Studies
The deepwater studies provided a base line of water quality
within the Lake Michigan watershed. Considerable uniformity was dis-
played throughout the deepwater region for most of the parameters meas-
ured. Lower silica concentrations found in surface samples during the
summer months are believed to be due to uptake by plankton. There was
little evidence of water quality deterioration within the deepwater
region.
Inshore Studies
In contrast to the deepwater area, the inshore region of Lake
Michigan was characterized by higher concentrations of dissolved sub-
stances and much greater variability in the parameters measured. In
general, the largest variations were evident in the vicinity of local-
ized inputs such as harbors and tributary mouths. The highest ammonia
nitrogen concentrations were found just outside Indiana Harbor. The
highest soluble phosphate concentrations, by far, were localized to the
southeast of Milwaukee Harbor. Phenols, resulting from industrial pol-
lution, were found in significant quantities in the vicinity of many
tributaries and harbors. Major phenolic pollution was evident near
Indiana Harbor. Within the inshore region, areas showing the greatest
degradation in water quality were found in the vicinities of Indiana
Harbor, Milwaukee Harbor, Benton Harbor, Grand Haven, and Saugatuck.
Major Tributaries
The major tributaries discharging directly to Lake Michigan
were sampled at the river mouths over a period of one year. Loadings
of numerous chemical substances carried by these rivers were calculated
and appeared to correlate well with findings in the adjacent inshore
waters.
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Green Bay
Areas of degraded water quality were found in Green Bay.
Serious pollution problems were especially evident in the southern
end of the bay, near the mouth of the Fox River. These problems were
due primarily to high concentrations of ammonia nitrogen, soluble phos-
phate, and phenol, and low dissolved oxygen concentrations resulting
from organic wastes. Lack of mixing with other portions of the bay
and large volumes of waste discharged intensify degradation of the
waters in the southern end of the bay.
Green Bay Tributaries
Of the major tributaries discharging directly into Green Bay,
the Fox River exhibited the most degraded water quality. This river was
found to carry more nutrients into Green Bay than all the other tribu-
taries combined. Massive amounts of organic contaminants discharged by
municipalities and the many pulp and paper industries into the river helped
produce, at times, little or no dissolved oxygen for distances exceeding
20 miles. The gross pollution evident in this river has been found to
have a pronounced influence on the southern reaches of Green Bay.
The other tributaries to Green Bay were not as seriously degraded
as the Fox River, but some evidence of industrial and municipal pollution
was still apparent, especially in the Oconto and Menominee Rivers, which
carried the next highest loads of ammonia nitrogen and soluble phosphates,
respectively.
Traverse Bay
High concentrations of ammonia nitrogen and soluble phosphate
were observed at the mouth of the Boardman River, resulting from the
discharge of municipal and industrial wastes. The Boardman River enters
the west arm of Traverse Bay causing slightly elevated levels of ammonia
nitrogen and soluble phosphate in the western arm. Otherwise, there
appears to be no significant variation in general water quality between
Traverse Bay and the adjacent inshore waters of the Lake.
Harbors
Discharges of municipal and industrial wastes through the major
harbors on Lake Michigan have a noticeable detrimental influence on the
neighboring inshore waters. Indiana Harbor was found to be the most
seriously polluted and showed the greatest degrading influence on the
adjacent inshore waters of Lake Michigan. Some of the highest phenol and
ammonia nitrogen concentrations in the Lake Michigan Basin were found in
30
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the harbor and the adjoining canal. The high concentrations of dissolved
substances, such as chlorides and sulfates, detected in this area indicate
massive industrial pollution. Low concentrations of dissolved oxygen,
evident during the summer months, underline the seriousness of organic
contamination.
Studies of tfre water of Calumet Harbor indicated some water qual-
ity degradation, but at a lower level than found in Indiana Harbor. Under
normal conditions, lake water passes through the harbor and down the
Little Calumet River so that little contaminated water enters the harbor.
However, during periods of heavy rainfall the flow can reverse and over-
flow from combined sewers and industrial waste discharges pass through the
harbor into the Lake. Such a reversal can 'result in serious contamination
of the adjoining Lake water.
The Chicago Harbor studies showed no significant differences
between the harbor and adjacent inshore waters indicating no major pollu-
tion sources within the immediate area. However, since these values are
higher than those found in the deepwater region (the base line within
the watershed), contamination of this inshore region is evident, espe-
cially from the Calumet-Indiana Harbor area.
Studies of the Racine Harbor waters showed no significant dif-
ferences between the harbor and adjacent inshore waters, indicating no
major pollution source within the immediate area. However, phenols were
observed in the harbor, indicating a source of industrial pollution. The
inshore and harbor values are higher than those found in the deepwater
region. Contamination of this inshore region can be attributed to the
discharges of municipal and industrial wastes.
Milwaukee Harbor was found to be seriously polluted, second to
Indiana Harbor, and showed a serious influence on the adjacent waters in
this region. Some of the highest ammonia nitrogen and soluble phosphate
concentrations in the Lake Michigan Basin were found in this harbor. The
high concentrations of dissolved substances, such as chlorides and sulfates,
detected in this area indicate massive municipal and industrial pollution.
Low concentrations of dissolved oxygen and high biochemical oxygen demand
underline the seriousness of organic contamination.
31
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REFERENCES
1. Ellis, M. M. Detection and Measurement of Stream Pollution.
Bulletin No. 22, U. S. Department of Commerce, Bureau of
Fisheries
2. Brockway, D. R. Metabolic Proauu&s and Their Effects. Fish
Culturist, 12:126 (1950).
3. Water Quality Criteria. State ₯ater Pollution Control Board,
Sacramento, California.
li. Public Health Service Drinking Water Standards. U. S. Department
of Health, Education, and Welfare, Public Health Service, Washington,
D. C. (1962).
5. Hutchinson, G. Evelyn. A Treatise on Limnology. John ₯iley and
Sons, Inc., New York (1957T p. 732-735.
6. Sawyer, Clair N. Fertilization of Lakes by Agricultural and
Urban Drainage. Journal New England Water Works Association,
61-2:109-127
7. Balicek, J. Phenolic Waste Waters. Public Health Engineering
Abstracts, No. 31 (Sept. 195"!).
8. Belding, D. L. Toxicity Experiments with Reference to Trade
Waste Pollution. Transactions of the American Fish Society,
57:100 (1927).
9. Standard Methods for the Examination of Water and Wastewater.
12th Edition. American Public Health Association, Inc. New York
(1965).
10. Warric, L. F. Relative Importance of Industrial Waste in Stream
Pollution. Sewage Works Journal, 6:l58 (1931;).
11. The Relation of Surface Activity to the Safety of Surfactants in
Food. Food Protection Committee - National Academy of Sciences,
National Research Council Publication No. h£>3, Washington, D. C.
(1956).
12. Freeman, S. et al. The Enzyme Inhibitory Action of an Alkyl Aryl
Sulfonate and Studies on Its Toxicity When Ingested by Rats, Dogs
and Humans. Ga stroentherology , 1;: 332-3U3 (I9l;5).
32
-------
REFERENCES (Continued)
13. Bills, C. E. et al. Sodium and Potassium in Food and Water.
Journal American Dietetic Association. 25: 301; (I9l;9).
ll;. Wilcox, L. V. Agricultural Uses of Reclaimed Sewage Effluent.
Sewage Works Journal. 20:£92 (I9i;8).
15. Lackey, J. B. and Sawyer, C. N. Plankton Productivity of Certain
Southeastern Wisconsin Lakes. Sewage Works Journal, 17:563 (19l;5).
16. Brandt, H. J. Intensified Injurious Effects on Fish, Especially
the Increased Toxic Effect Produced by a Combination of Sewage
Poisons. Chemical Abstracts, No. 1;2 (I9l;8).
17. Muss, D. L. Relationship Between Water Quality and Deaths from
Cardiovascular Disease. Journal American Water Works Associa-
tion, 51;: 1371-1378 (1962).
18. Ellis, M. M., Westfall, B. H. and Ellis, Marion D. Determination
of Water Quality. Department of Interior Research Report 9 (I9l;6).
19. Ellis, M. M. Detection and Measurement of Stream Pollution.
Bulletin No. 22, Bureau of Fisheries, U. S. Department of Commerce,
Washington, D. C. (1937).
20. Technicon Auto-Analyzer. Instruction Manual AA1. Technicon
Instruments Corporation, Chauncey, New York.
21. Report on the Illinois River System, Water Quality Conditions.
Part 1 Text, U. S. Department of Health, Education and Welfare,
Public Health Service, Division of Water Supply and Pollution
Control, Great Lakes-Illinois River Basins Project (January 1963).
22. Water Quality Monitoring Program, Water Quality Records, State of
Michigan Water Resources Commission (1963).
23'. Report on Pollution of the Waters of the Grand Calumet River, Little
Calumet River, Calumet River, Lake Michigan, Wolf Lake and Their
Tributaries. Illinois - Indiana. U. S. Department of Health, Educa-
tion and Welfare, Public Health Service, Division of Water Supply
and Pollution Control, Region V, Chicago, Illinois (February, 1965).
21;. A Comprehensive Water Pollution Control Program, Lake Michigan
Basin, Milwaukee Area, II. S. Department of the Interior, Federal
Water Pollution Control Administration, Great Lakes Region, Chicago,
Illinois, June 1966.
33
-------
REFERENCES (Continued)
Surface Water Records, United States Department of the Interior,
Geological Survey, Indiana, Michigan, and Wisconsin, 1961;.
-------
TABLE 1
LAKE MICHIGAN SAMPLING CRUISES
EXTENDED RANGE
Cruise
No.
1
2
3
8
11
16
19
h
$
Vessel
M/V Cisco
M/V Cisco
M/V Cisco
M/V Kaho
M/V Cisco
T-509
T-509
M/V Cisco
M/V Cisco
Inclusive
Dates
ll/2ii/62-5/7/62
6/5/62-6/18/62
7/17/62-7/30/62
11/28/62-12/6/62
5/23/63-6/3/63
7/15/63-7/26/63
10/15/63-11/7/63
INSHORE AND HARBOR
8/29/62-9/9/62
10/10/62-10/22/62
No. of
Stations
36
29
31
22
22
51;
70
65
Area Sampled
Entire lake below
Frankfort, Michigan.
Northern section and
Green Bay.
Entire portion of
lake below Ludington,
Michigan.
Central portion of
southern basin.
East shore from
Saugatuck to Mackinaw
City, Michigan.
West shore from Upper
Peninsula to Sturgeon
Bay, Wisconsin.
Northern section of
lake.
Southern half to
Milwaukee -Muskegon li;
Southwest shore - Gar;
Ind. to Milwaukee, Wi
Southeast shore -
R/V Fitzgerald 10/18/62-11/30/62 195
Michigan City, Ind. to
Muskegon, Mich.
Chicago, Racine &
Milwaukee Harbors and
35
-------
TABLE 1 (Continued)
LAKE MICHIGAN SAMPLING CRUISES
INSHORE AND HARBOR (Continued)
Cruise
No.
Vessel
Inclusive
Dates
No. of
Stations
Area Sampled
6 (Cont'd)
12
13
15
17
18
M/V Kaho
10 T-509
11 M/V Cisco
T-509
T-509
T-509
T-509
T-509
T-509
10/2V62 -11/7/62
5/8/62-5/23/63
5/23/63-6/3/63
5M/63-6/9/63
6/9/63-6/13/63 l»l
6/13/63-6/25/63 no
6/26/63-7/17/63
8/8/63-8/12/63 &
9/23/63-10/8/63
8/20/63-9/12/63
southwest shore from
Gary, Ind. to Milwaukee,
Wise.
26 Southwest shore -
Chicago, 111. to
Milwaukee, Wise.
70 Calumet & Indiana
Harbors.
k9 East shore from
Saugatuck to Mackinaw
City, Michigan.
West shore from Upper
Penninsula to Sturgeon
Bay, Wise.
110 Southwest shore -
Michigan City, Ind.
to Milwaukee, Wise.
Milwaukee Harbor.
Northwest shore -
Milwaukee, Wise, to
Sturgeon Bay, Wise.
115 Green Bay, Escanaba
and Menominee Harbors
and all of Green Bay.
Eastern shore from
Frankfort, Mich, to
Michigan City, Ind.
50 Calumet, Ind., Gary,
Burns Ditch Harbors.
36
-------
TABLE 1 (Continued)
LAKE MICHIGAN SAMPLING CRUISES
INSHORE AND HARBOR (Continued)
Cruise
No. Vessel
Inclusive
Dates
'No. of
Stations Area Sampled
20*
22
T-509
10/20/63-12/8/63 U2
7/22/6U-7/28/6U Ii2
Calumet, Indiana,
Gary, and Burns
Ditch Harbors.
Traverse Bay
*This cruise was designed primarily for tracing phenols.
Only ammonia nitrogen, oil, and phenol samples were taken.
37
-------
TABLE 2
MINIMUM DETECTABLE CONCENTRATIONS*
OF PHYSICAL AMD CHEMICAL PARAMETERS MEASURED
IN THE LAKE MICHIGAN BASIN, 1962-196U
Parameter
Acidity-
Alkalinity
Aluminum
Calcium
Chloride
Chlorine Demand
COD (0.025N K2Cr20 )
Cyanide
DO
Iron
Manganese
Magnesium
MBAS
Nitrogen
Ammonia :
Sodium Phenate
Nesslerized
Titrated
Cone. & Ness.
Total Kjeldahl
Ne s sleri za tion
Titrated
Cone. & Ness.
Min. Det. Cone.
2.0
2.0
0.02
1.0
0.5
O.OU
2.0
0.02
0.1
0.02
0.01
1.0
0.0^
0.01
0.02
0.10
0.002
0.02
0.10
0.02
Parameter Min. Det. Cone.
Nitrogen
Nitrate
Nitrite
Oil and Grease
pH (pH units)
Phenols (micrograms
per liter)
Potassium
Silica
Sodium
Solids
Spec. Cond. (micromhos
per centimeter)
Sulfate
Sulfide
Total Soluble Phosphate
Toxic Metals
Rivers and Wastes
Lakes
0.01
0.01
0.2
0.05
1
0.10
0.02
0.10
1.0
0.5
1.0
0.01
0.01
0.01
0.005
^Concentration expressed as mg/1 unless otherwise stated.
38
-------
TABLE 3
CHEMICAL RESULTS OF PARAMETERS MEASURED IN
LAKE MICHIGAN BASIN IN 1962-1963
AVERAGES, RANGES, AND NUMBER OF SAMPLES
Deepwater
Parameter
DO
Percent Saturation
BOD
NHo-N
N03-N
Organic -N
Total Sol. P0^
Si02
Na
K
Dissolved Solids
Spec. Cond. (micro-
mhos per centimeter)
pH (pH units)
Alkalinity
Ca
Mg
Cl
SOh
Phenols (micrograms
No. of
Samples
1,080
U97
US*
lj.29
595
313
388
299
321
325
la?
918
l,0l|0
858
395
318
607
561
NS
Average
(mg/1)
12
102
_
0.06
0.13
0.19
0.02
2.5
3.9
1.1
155
260
110
33
12
6.5
20
-
Range
(mg/1)
8.U-17
73-152
_
ND-0.50?Hf
ND-0.65
ND-0.52
ND-O.ll;
0.6-5.5
2.7-6.5
O.k-2.0
100-2UO
l85-3l;5
7.5-8.9
75-130
25-l;0
8-16
3.3-11
12-30
-
No. of
Samples
2,51a
1,701
730
1,751
1,651;
529
1,382
61;5
liOO
1;53
976
2,1;52
2,113
2,169
616
898
1,611
1,51;7
1,033
Inshore
Average
(mg/1)
10
102
1.1;
0.13
O.lli
0.21
o.oU
1.7
U.o
1.2
175
285
105
35
12
7.1
20
2
Range
3.7-16
l;3-li;8
ND-8.6
ND-1.1;
ND-0.90
0.01-0.70
ND-5-0
0.1;-!;. U
1.8-7.5
0.5-3.8
86-810
33-1130
6.U-9.3
70-210
17-1*0
7-11;
1.5-91;
10-76
ND-32
per liter)
#-NS = Not sampled.
3H;-ND = Not detectable at sensitivity of test.
See Table 2.
39
-------
TABLE h
CHEMICAL RESULTS OF TOXIC METALS
LAKE MICHIGAN BASIN, 1962-1963
AVERAGES, RANGES, AND NUMBER OF SAMPLES
Metal
Copper
Cadmium
Chromium
Nickel
Zinc
No. of
Samples
58
3
61
57
3
33
28
U8
13
Deep-water
Average
(mg/1)
-------
TABLE 5
VARIATIONS OF SELECTED CHEMICAL CONSTITUENTS
BY SEASONS, DEPTH, AND AVERAGES
LAKE MICHIGAN BASIN, 1962-1963
Depth (Meters)
Parameters
DO
Percent
Saturation
NH3-N
Total Sol. PO^
Si°2
Season
Spring
Stunner
Fall
Spring
Summer
Fall
Spring
Summer
Fall
Spring
Summer
Fall
Spring
Summer
Fall
0-5
13*
11
11
115
10?
98
0.05"
0.08
0.06
0.02
0.02
0.03
2.9
1.6
1.8
6-10
13
11
11
105
109
98
o.oU
0.08
NS5Hf
0.01
0.01
0.03
2.7
1.6
NS
11-30
13
13
10
ioU
112
96
0.07
0.09
0.06
0.02
0.02
0.02
2.1*
2.3
1.9
31+
13
13
12
103
103
93
0.05
0.09
0.06
0.02
0.02
0.03
2.8
ii.5
2.2
^-Concentration expressed in mg/1.
#*NS - not sampled.
-------
TABLE 6
DISSOLVED OXYGEN AND PERCENT SATURATION
IN DEEPWATER BY SEASONS
LAKE MICHIGAN BASIN, 1962-1963
Season
Spring
Summer
Fall
Depth
o-5
6-10
11-30
31+
o-5
6-10
11-30
31+
o-5
6-10
11-30
31+
DO*
Minimum
9.8
7.1
8.5
11
8.6
9.1i
9.0
11
9.0
9.0
8.2
8.3
(mg/1)
Maximum
17
111
111
15
12
111
15
111
12
12
12
13
Percent Saturation
Minimum
96
100
89
9U
98
103.
88
87
89
93
77
73
Maximum
152
110
109
115
115
119
128
108
112
102
10l|
100
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TABLE lla
CHEMICAL RESULTS
INDIANA AND CALIMET HARBORS
LAKE MICHIGAN BASIN, 1962-1963
AVERAGES, RANGES, AND NUMBER OF SAMPLES
No. of
Parameter Samples
DO
Percent
Saturation
BOD
NH3-N
N03-N
Organic -N
Total Sol.
POL
SiOg
Na
K
Dis. Solids
Spec. Cond.
(micromhos/cm)
pH (pH units)
Alkalinity
Ca
Mg
Cl
SO^
Phenols (micro-
grams per liter)
Phenols-Canal*
(micrograms per
liter)
Oil and Grease
30
22
12
U9
21
2
15
21
21
20
1U
2k
26
26
23
21
21
21
39
12
18
Indiana
Average
mg/1
2.7
29
3.5
I.It
0.16
0.72
0.05
2.5
10
2.6
225
355
-
110
liO
15
16
hi
33
159
h.h
Range
mg/1
O.L-10
U.2-99
1.9-5.1
0.10-2.3
0.01-0.81*
0.65-0.78
0.02-0.12
1.6-3.8
7.1i-l6
1.8-3.8
195-265
21*5-500
6.0-7.8
100-125
37-1*3
il*-i5
10-22
38-69
2.L--127
1*3-351*
O.k-29
No. of
Samples
32
32
15
53
16
2
15
19
20
20
15
30
21*
21*
20
111
21
18
52
NS
19
Calumet
Average
mg/1
8.5
90
1.3
0.23
0.12
0.1*9
0.05
1.6
1*.9
1.6
195
285
-
11C
35
13
7.6
21*
2
-
1.6
Range
mg/1
6.8-10
77-98
1.0-2.1
0.05-0.67
0.01-0.35
O.L8-0.50
0.01-0. Ill
1.0-3.0
k.1-6.1
1.1-2.0
165-230
2l|0-325
6.1i-8.1;
95-135
3L-37
11-lli
6.8-9.0
22-25
ND-12
_
0.1-3. li
K-Indiana Harbor Canal.
NS - not sampled.
OPO 806-484-6
-------
TABLE lib
CHEMICAL RESULTS OF TOXIC METALS
INDIANA AND CALUMET, HARBORS
LAKE MICHIGAN BASIN, 1962-1963
AVERAGES, RANGES, AND NUMBER OF SAMPLES
Metal
Copper
Cadmium
Chromium
Nickel
Zinc
No. of
Samples
8
8
8
8
8
Indiana
Average Range
mg/1 mg/1
<: 0.005*
<:o.oo5
^0.005
^0.005
O.Oltf 0.009-0.087
No. of
Samples
7
7
7
7
7
Calumet
Average
mg/1
<:o.oo5
^0.005
.-0.005
^0.005
0.0l|6
Range
mg/1
0.025-0
55-0.005 mg/1 limit of detection when using 1000 ml samples.
55
-------
TABLE 12
CHEMICAL RESULTS
CHICAGO AND RACINE HARBORS
LAKE MICHIGAN BASIN, 1962-1963
AVERAGES, RANGES, AND NUMBER OF SAMPLES
Chicago
Parameter
DO
Percent
Saturation
BOD
NH3-N
N03-N
Organic-N
Total Sol. P0}j
Si(->2
Dis. Solids
Spec. Cond.
( micromhos/cm)
pH (pH units)
Alkalinity
Ca
Mg
01
SO]^
Phenols (micro-
No, of
Samples
12
5
It
7
lit
6
lit
5
3
10
11
10
6
6
6
6
It
Average
mg/1
11
10U
0.8
0.07
0.10
0.20
o.oU
1.2
150
315
-
100
32
11
7.1
22
1 ND
Range
mg/1
7.8-13
86-110
0.6-1.6
0.02-0.16
0.05-0.11
0.09-0.32
0.01-0.15
0.75-2.0
il;5-i55
270-350
7.8-8.7
70-120
31-33
10-12
6.6-7.9
20-23
-
Racine
No. of
Samples
8
7
3
7
NS
6
-
7
1
8
8
10
7
7
7
7
7
Average
mg/1
11
96
0.7
0.06
-
0.29
0.07
1.6
155
305
-
110
3k
11
8.5
22
2
Range
mg/1
11-12
90-101
0-2.1
0.05-0.08
-
0.17-0.36
0.01-0.10
l.it-1.9
155-155
230-335
7.9-8.3
110-112
33-3U
10-12
6.8-9.1
18-21;
1-3
grams per liter)
NS - not sampled.
ND - not detectable at the sensitivity of test.
See Table 2.
56
-------
TABLE 13
CHEMICAL RESULTS OF TOXIC METALS
CHICAGO AND MILWAUKEE HARBORS
LAKE MICHIGAN BASIN, 1962-1963
AVERAGES, RANGES, AND NUMBER OF SAMPLES
Metal
Copper
Cadmium
Chromium
Nickel
No. of
Samples
1
1
1
1
Chicago
Average Range
mg/1 mg/1
< 0.005*
<0.005
<:o.oo5
^0.005
Milwaukee
No. of
Samples
6
6
5
1
3
3
Average
mg/1
-------
TABLE Ik
CHEMICAL RESULTS
MILWAUKEE HARBOR AMD ADJACENT WATERS OF LAKE MICHIGAN
LAKE MICHIGAN BASIN, OCTOBER 1962-JUNE 1963
AVERAGES, RANGES, AND NUMBER OF SAMPLES
Harbor
Water Adjacent
No. of Average Range
Parameter Samples mg/1 mg/1
DO
Percent
Saturation
BOD
NH3-N
N03-N
Organic -N
Total Sol. POl,
Si02 ^
D.is. Solids
Spec. Conductance
( micr omho s/cm )
pH (pH units)
Alkalinity
Ca
Mg
Cl
SOjj
Phenols (micro-
1*8
26
60
35
35
ill
36
23
25
1*8
38
37
23
37
31
2k
63
11
116
3.U
1.1
0.15
0.37
0.1*1*
1.5
211*
393
125
39
15
19
29
3
5.3-15
77-139
1.5-8.1
0.28-2.7
0.0l*-0.2l*
0.30-0.67
ND-1.1*
0.98-2.1
135-285
21*5-585
7.1*-8.9
105-155
32-1*5
11-19
5.3-36
16-1*3
ND-10
to Harbor
No. of Average Range
Samples mg/1 mg/1
71*
27
25
71*
81
1*6
67
1*6
38
116
81*
82
1*6
82
81
50
118
12
117
2.5
0.18
O.ll*
0.27
0.07
1.5
160
310
105
33
10
8.3
22
1
8.7-15
108 -11*1*
0.3-6.7
ND-1.3
0.03-0.90
0.01-0.58
ND-0.70
1.2-2.8
130-225
220-1*85
7.1*-9.1
100-120
32-1*1*
8-19
5.3-23
16-53
ND-8
grams per liter)
ND - not detectable at sensitivity of test. See Table 2.
58
-------
TABLE 15
CHEMICAL RESULTS
AMMONIA AW NITRATE NITROGEN
LAKE MICHIGAN HARBORS,, 1962-1963
AVERAGES BY SEASONS
NH^-N (mg/l)
Harbor
Indiana
Calumet
Chicago
Milwaukee
Spring
0.11
0.19
NS
0.78
Summer
1.3
o.U?
0.08
NS
Fall
2.0
0.29
0.07
1.3
NO^-N (mg/l)
Spring Summer
0.06 0.17
0.07 O.llj
NS 0.10
0.10 NS
Fall
0.23
0.19
0.09
0.18
NS - not sampled.
-------
TABLE 16
CHEMICAL RESULTS
DISSOLVED 02TGEN AND TOTAL SOLUBLE PHOSPHATE
LAKE MICHIGAN HARBORS, 1962-1963
AVERAGES BY SEASONS
DO (rag/1)
Harbor
Indiana
Calumet
Chicago
Milwaidcee
Spring
3.3
9.6
NS
12
Summer
2.0
7.9
8.0
NS
Fall
NS
NS
12
8.7
Total Soluble PO^ (mg/l)
Spring
O.Oli
O.Oli
NS
0.21
Stunner
o.o£
0.06
O.Oli
NS
Fall
NS
NS
0.06
0.£9
NS - not sampled.
60
-------
TABLE 17
CHEMICAL RESULTS
DISSOLVED OXYGEN AND PERCENT SATURATION
LAKE MICHIGAN HARBORS, 1962-1963
AVERAGES BY SEASONS
DO (mg/1)
Percent Saturation
Harborte
Indiana
Calumet
Chicago
Racine
Milwaukee
Season
Spring
Summer
Fall
Spring
Summer
Fall
Spring
Summer
Fall
Spring
Summer
Fall
Spring
Summer
Fall
Minimum
2.2
o.U
NS
9.2
6.8
NS
NS
7.8
9.0
NS
NS
11
8.2
NS
5.3
Maximum
10
3.k
NS
10
8.8
NS
NS
8.1
13
NS
NS
12
15
NS
11
Minimum
22
U.2
NS
89
77
NS
NS
86
9k
NS
NS
90
77
NS
kl
Maximum
99
39
NS
97
95
NS
NS
89
110
NS
NS
101
138
NS
96
NS - not sampled.
61
-------
TABLE 18
CHEMICAL RESULTS
PHENOLS
LAKE MICHIGAN HARBORS 1962-1963
AVERAGES BY SEASONS
Phenols (micrograms per
Harbors
Indiana
Indiana Harbor Canal
Calumet
Chicago
Racine
Milwaukee
Milwaukee River
Spring
23
NS
1
NS
NS
2
5
Summer
16
£0
2
ND
NS
NS
NS
liter)
Fall
19
163
2
ND
2
3
NS
NS - not sampled.
ND - not detectable at the sensitivity of test. See Table 2.
62
OPO 800-484-3
-------
LEGEND
Quadrant Average(mg/l)
Not Sampled
iiil 0.02-0.08
0.09-0.14
0.15- I.I
10 Mile Zone (Boundary Line
Between Inshore and Offshore Areas)
GREAT LAKES ILLINOIS
RIVER BASINS PROJECT
AMMONIA-NITROGEN
LAKE MICHIGAN
1962-1963
US. DEPARTMENT OF THE INTERIOR
FEDERAL WATER POLLUTION CONTROL ADMIN
Great Lakes Region Chicago,Illinois
FIGURE i
-------
LEGEND
Quadrant Average(mg/l)
I I Not Sampled
SI NO-0.03
0.04-0.07
0.08-0.36
ND - Not Detected
10 Mile Zone (Boundary Line
Between Inshore and Offshore Areas)
GREAT LAKES ILLINOIS
RIVER BASINS PROJECT
TOTAL SOLUBLE PHOSPHATE
LAKE MICHIGAN
1962-1963
US DEPARTMENT OF THE INTERIOR
FEDERAL WATER POLLUTION CONTROL ADMIN
Great Lakes Region Chicago,Illinois
FIGURE 2
-------
LEGEND
Quadrant Average(mg/l)
Not Sampled
0.8-1.9
10 Mile Zone (Boundary Line
Between Inshore and Offshore Areas)
GREAT LAKES ILLINOIS
RIVER BASINS PROJECT
SILICA
LAKE MICHIGAN
1962-1963
US DEPARTMENT OF THE INTERIOR
FEDERAL WATER- POLLUTION CONTROL ADMIN
Great Lakes Region Chicago,Illinois
FIGURE 3
-------
GREAT LAKES ILLINOIS
RIVER BASINS PROJECT
GREEN BAY
SAMPLING STATIONS- 1963
U S.DEPARTMENT OF THE INTERIOR
FEDERAL WATER POLLUTION CONTROL ADMIN
Great Lakes Region Chicago,Illinois
FIGURE 4
-------
I-4QOOO
LE GE N D
I Img/l
GREAT LAKES ILLINOIS
RIVER BASINS PROJECT
GREEN BAY S TRIBUTARIES
AMMONIA NITROGEN
March,l963-April,1964
U S DEPARTMENT OF THE INTERIOR
FEDERAL WATER POLLUTION CONTROL ADMIN.
Great Lakes Region Chicago,lllinois
67
FIGURE 5
-------
T;OOO
0.50
LEGEND
r~Ug/l
Kbs/DAY
GREAT LAKES ILLINOIS
RIVER BASINS PROJECT
GREEN BAY & TRIBUTARIES
TOTAL SOLUBLE PHOSPHATE
March,l963-April, 1964
U.S.DEPARTMENT OF THE INTERIOR
FEDERAL WATER POL LUTION CONTROL ADMIN.
Great Lakes Region Chicago,Illinois
68
FIGURE 6
-------
FIGURE 7
-------
Beaver
Island
AKE
MICHIGAN
GREAT LAKES ILLINOIS
RIVER BASINS PROJECT
TRAVERSE BAY AREA
SAMPLING STATIONS
U.S DEPARTMENT OF THE INTERIOR
FEDERAL WATER POLLUTION CONTROL ADMIN.
Great Lakes Region Chicago,Illinois
GPO 8O64844
70
FIGURE 8
-------
FIGURE 9
-------
FIGURE 10
-------
-------
FIGURE 12
-------
FIGURE 13
-------
GREAT LAKES ILLINOIS
RIVER BASINS PROJECT
AMMONIA NITROGEN
RACINE HARBOR
1962-1963
U.S. DEPARTMENT OF THE INTERIOR
FEDERAL WATER POLLUTION CONTROL ADMIN.
Great Lakes Region Chicago,Illinois
76
FIGURE 14
-------
GREAT LAKES ILLINOIS
RIVER BASINS PROJECT
TOTAL SOLUBLE PHOSPHATE
RACINE HARBOR
1962-1963
U.S.DEPARTMENT OF THE INTERIOR
FEDERAL WATER POLLUTION CONTROL ADMIN.
Great Lakes Region Chicago.lllinois
77
FIGURE 15
-------
\floqt R.
GREAT LAKES ILLINOIS
RIVER BASINS PROJECT
PHENOLS
RACINE HARBOR
1962-1963
U.S.DEPARTMENT OFTHE INTERIOR
FEDERAL WATER POLLUTION CONTROL ADMIN.
Great Lakes Region Chicago,Illinois
GPO 806-484-3
78
FIGURE 16
-------
0 15- 0 49
0 50-099
I 00-2 20
SCALE IN MILES
Sampling Station
ND-Not Detected
GREAT LAKES ILLINOIS
RIVER BASINS PROJECT
MILWAUKEE HARBOR
AMMONIA NITROGEN.I962-I964
US DEPARTMENT OF THE INTERIOR
FEDERAL WATER POLLUTION CONTROL ADMIN
Great Lakes Region Chicago,Illinois
GPO 8O6-4042
79
FIGURE 17
-------
LEGEND
mg/1
ND- 0.02
0 03 - 0 14
O.50-I.3
Sampling Station
ND- Not Detected
2
SCALE IN MILES
GREAT LAKES ILLINOIS
RIVER BASINS PROJECT
TOTAL SOLUBLE PHOSPHATE
MILWAUKEE HARBOR
1962-1964
US DEPARTMENT OF THE INTERIOR
FEDERAL WATER POLLUTION CONTROL ADMIN
Great Lakes Region Chicago,Illinois
80
FIGURE 18
-------
LEGEND
ug/l
NO
Sampling Station
NO- Not Detected
2
SCALE IN MILES
GREAT LAKES ILLINOIS
RIVER BASINS PROJECT
MILWAUKEE HARBOR
PHENOLS ,1962- 1964
US DEPARTMENT OF THE INTERIOR
FEDERAL WATER POLLUTION CONTROL ADMIN
Great Lakes Region Chicago,Illinois
81
FIGURE 19
-------
-------
-------
EF.EATA
The following corrections should "be made in the "Lake Michigan Basin
Report of Fnysical and Che-oical Quality Conditions."
1. Page 17 - 3rd paragraph - change (Table'5) to (Tat>le 3).
2. " 1? -lith " " ' 2.7 Kg/1 to 2.5 ng/1.
3. " 18 - 1st " " Table 2 to Table 3.
4. " 18 -last " " 0.03 Kg/1 to 0.04 Eg/1.
" 0.01 Eg/1 to 0.02 mg/1.
5. " 19 - 2nd " . " 72 microgra-as per liter to 32.
6. " 21 - 2nd " " 0.06 as/1 to 0.07 mg/1-
0.15 mg/1 to 0.14 eg/1.
7. " 21 - 3rd " " 23 tons to 123 tons.
8. " 24 - 5th " " 156 raicrograrns per liter to 159.
9. " 24 - 6th " Delete the words "lead, and" in last sentence
and change "were" to "vas."
10. " 26 - 1st " Delete the vords "lead, and" in first sentence
and change "were" to "was."
11. " 27 - 4th " Change 1ID-0.05 Eg/1 to KD-0.04 mg/1.
12. . " 27 - 5th " " 0.49-1.3 rrg/1 to 0.50-1-3 mg/1.
13. " 27 - last " " 0.49-1.3 mg/1 to 0.50-1.3 mg/1.
" KD-0.03 ng/1 to lffi-0.02 ing/1.
14. " 38 - last line " 0.02 to 0.002.
15. " 45 - Table TO Menistique River - MBAS - Change O.l8 to 0.08
820 to 364
Cu, Ni, Zn - Change US to 0.08-0.08
January 31, 1968
------- |