Special Report Number IM-3
                     April 1963

              Public Health Service
  Division of Water Supply and Pollution Control
    Great Lakes-Illinois River Basins Project


                         TABLE OF CONTENTS

SUBJECT                                                  PAGE

INTRODUCTION                                               1


     Parameters                                            2

     Definitions and Significance                          2

LABORATORY PROCEDURES                                      9

     Sample Preservation                                   9

     Analytical Methods                                    9

RESULTS OF ANALYSIS                                       15

     Deepwater Studies                                    15

     Inshore Studies                                      20

     Harbor Studies                                       2.6

CONCLUSIONS                                               29

REFERENCES                                                30




                        LIST OP TABLES

Table              Title

  1     Average of Chemical Results by Seasons and Areas
        Lake Michigan^ 1962.

  2     Lake Michigan 1962, Dissolved Oxygen and Per Cent
        Saturation by Seasons and Areas.

  3     Lake Michigan 1962} Toxic Metals
        by Seasons and Areas.

                               LIST OF FIGURES
Figure         Title
   1    Ammonia  Nitrogen as N, Spring, Upper Lake Michigan
   2      "        "        "  "   "    , S.W. Quadrant of Lake Michigan
                                        O TB     II      II   tl    II
                                      , D..B.
                       II  II   II
k     "        "        "  " Summer,  S.W.    "      "   "
      511        ii        it  ii   ti      rs r>     ii      ii   ii    ii
                                  ,  D.ili.
6     "        "        "  "  Fall, S.W. Quadrant of Lake Michigan
7     "        "        "  "  Fall, S.E.     "      "   "
8     "        "        "  "  Fall, Milwaukee Harbor
9    Total Phosphate as PO. , Spring, Upper Lake Michigan
10   Total Phosphate as PO. , Spring, S.W. Quadrant of Lake Michigan
•I 1    It        If       II   It    II      « m   II       II   II    II
12    "        "       "   "   Summer, S.W.  "       "   ".   "
-|o    "        "       "   "     "     q T?   ii       "   "    "
Ik    "      "        "   "   Fall, S.E. Quadrant of Lake Michigan
15    "      "        "   "   Fall, S.W.    "       "   "
16    "      "        "   "   Fall, Milwaukee Harbor
17   Phenols, Fall,  Milwaukee Harbor
18   Alkyl Benzene  Sulfonate (Apparent), Fall,  Milwaukee Harbor



     This report presents the results of a physical and chemical
study of Lake Michigan water, conducted by the Great Lakes-Illinois
River Basins Project during the spring; summer, and autumn months
of 1962 (April 1962 to December 1962).

     The study was conducted through the collection of appropriate
samples during a series of eight cruises made on the Lake by three
laboratory-equipped vessels, the Cisco, Fitzgerald and Kaho.  Analyses
which required immediate attention were carried out aboard ship.
Other analyses were performed at the GLIRBP laboratories.  These
procedures are described later.  A detailed description of the vessels
and the cruises may be found in the special report LM-2, "Sampling

     The purpose of this report is to present the physical and
chemical findings of this study of Lake Michigan, in order to
establish present levels of chemical water quality and to describe
those areas of the lake which exhibit significant deviation from
the general quality of the entire lake.




     The parameters which were considered and reported in subsequent
sections of this report are: Ammonia Nitrogen; Total Phosphate;
Silica; Dissolved Oxygen; Phenols; Alkyl Benzene Sulfonate (ABS);
Biochemical Oxygen Demand (BOD); Hydrogen Ion Concentration (pH);
Dissolved Solids; Nitrate; Sodium; Potassium; Calcium; Specific
Conductance; Alkalinity; Magnesium; Sulphate; 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 by depth on all of the lake samples analyzed
to date, whereas others exhibited detectable changes in some areas
and seasons but not in the others.  The parameters showing significant
changes were Ammonia Nitrogen; Nitrate; Total Phosphate; Silica;
Dissolved Oxygen; Conductance; Phenols; and Biochemical Oxygen
Demand (BOD).  Of these, the first three cited appeared in 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 studies.

Definitions and Significance

                Nitrogen; Ammonia and Nitrate-Nitrite

     Nitrogen is necessary to the normal life cycle of aquatic life.
If it is present with phosphate in moderate concentrations, accelerated
growths of algae and plankton can result.   Ammonia in high concentrations,
above 2 to 2.5 mg/1 and under alkaline pH conditions (pH 8-8.5) (l> 2)
is a substance toxic to many forms of aquatic life (3J.  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 contribution in some industrial wastes.  Amines and cyanide
have toxicity 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 45 mg/1 of
nitrate (as nitrate) has been recommended in the U.S. Public Health
Service Drinking Water Standards (k).

                           Wotal Phosphate

     Phosphate,like nitrogen, is a necessary nutrient for biological
activity.  Its presence in the water will permit the processes of
organic decomposition to proceed at an optimum rate.  Its presence
in water is not considered harmful to human health.  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 operations,
increase taste and odor problems, cause unsightly scums and
decaying matter, and create problems due to fluctuations of dissolved
oxygen.  Concentrations 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).  The biological impact of phosphate is
discussed further in Special Reports LM-1, "Trends in Water Quality"
and LM-4, "Biological Investigations."

     Phosphate enters the water environment in treated sewage because
it is not removed by conventional treatment processes.  It is normally
present in human and animal waste products; synthetic detergent
formulations used in modern day washing practices contain high concen-
trations 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 industrial processes.


     Silica appears in water as finely divided or colloidal 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 strategic group of plankton.

     The presence of diatoms in large numbers interferes with water
treatment processes, especially the clogging of filters.

                         Dissolved Oxygen

     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 oxygen 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
respiration.  It is replenished from the atmosphere try 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 consumption 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 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.
Organic pollution discharged into the lake may have an adverse
effect for considerable distances.  Persistent discharges of this
nature from tributaries would degrade large areas, affecting breeding
grounds of lake fish, and altering an otherwise favorable environment
for desirable aquatic life.

                 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 material, microorganisms accompanying it, and the natural
biota present in the receiving water.  Organic matter is rapidly
utilized as food by those organisms capable of converting it; 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 depletion potential of
wastes is necessary if adequate control measures are to be adopted.
The test commonly used for this purpose is the BOD test.

     The BOD test is 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.  The organic waste material supplies the
energy to effect this conversion.  Toxic substances, if present,
adversely influence this test.

     In general, high BOD values can be expected to result in low
dissolved oxygen levels in the receiving waters; this implies an
unsuitable environment to fish and other desirable aquatic life, •
greater need for chlorine and chemicals for water treatment, and a
deterioration of the quality of treated water because waste residues
are present.



     Phenolic material, whicli 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 areas, and
chemical plants may contain high concentrations.

     Lethal concentrations for fish are sonewhat related to the species,
time 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 chlorinated 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
addition of chlorine will have a more disagreeable taste and odor than
the parent substance.  Thresholds of taste and odor for chlorophenols
range 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.
Fortunately, phenols are decomposed by bacterial action in the
presence of dissolved oxygen, and their persistence from point of
entry is relatively short-lived.

            Alkyl Benzene Sulfonate (ABS) (Apparent)

     This test is a measure of the 3.arge, anionic-type molecules which
are representative of the synthetic organic detergents now contaminating
many surface and ground waters.  The ABS is that portion of a common
household or industrial cleaning compound that imparts foam and reduces
surface tension to aid in the removal of dirt particles by the cleaning
compound.  ABS compounds are new to the water environment.  They have
been used as substitutes for soap only in recent years.  They pass
through water and sewage treatment processes with only partial reduction
in concentration; moreover, they are not readily attacked by stream
purification processes.  Consequently, ABS can be found for many
miles below sources of waste water discharge.  ABS is believed to
be non-toxic to man (ll, 12) in the concentrations found in contaminated
waters; but it produces unsightly, persistent foams in water at points
of agitation.  The ABS content of drinking water used on interstate
carriers is limited to 0.5 mg/1 in the U»S. Public Health Service
Drinking Water Standards
                  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 times stronger than pH 1, 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.  Low
pH values (acidity) disrupt biological activity, cause corrosion of
steel and concrete, intensify the effect of toxic materials such as
sulfide and cyanide, interfere with water plant coagulation practices
and tend to add undesirable iron and manganese to the water.  High
pH values (alkalinity) also disrupt biological activity, precipitate
calcium and magnesium from water and increase the toxicity of ammonia
and other amines.

                        Dissolved Solids

     The dissolved solids test measures the concentration of dissolved
material present in the sample.  This includes both organic and
inorganic matter.  Excessive dissolved solids in water can be
unpalatable, and increase the cost of water treatment for many water
uses.  The Drinking Water Standards of the U.S. Public Health Service
recommend the rejection of sources providing water containing over
500 mg/1 of dissolved solids (if another water source is available)
because of a noticeable saline taste, and possible cathartic effect
on many individuals.


     Sodium is an alkaline base 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 is 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
is significant to those suffering from high blood pressure.


     Potassium, an alkaline metal, is abundant in the earth's crust,
yet its content in natural waters is usually small.  In low concen-
trations it is essential for plant development (l^), but must be
maintained in proper balance with phosphorus.

     Potassium stimulates plankton growth (l5)> but is otherwise
insignificant unless found in concentrations above 400 mg/1, a level
considered to be toxic to fish (l6).



     Calcivm, 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 transfer in heating and cooling systems
and because of increased soap consumption.  Research (17) has
demonstrated that there may be a relationship between the hardness
of drinking water and a reduction in cardiovascular diseases.


     Magnesium, like calcium, is a "hardness" producing mineral
and contributes to the hardness effects discussed under calcium.
It is not known to produce toxic effects, although in high concen-
trations 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 0.55 to 0.9 depending on dissolved
substances and temperature of water.

     Waters 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 organisms.  Wide variations in total salinity or in the
concentrations of individual salts can have far-reaching effects
upon water fauna, resulting even in the elimination of species (l8,19).


     Alkalinity is defined as the capacity of a water to neutralize
hydrogen ions and is expressed in terms of an equivalent aatunt of
calcium carbonate.  Alkalinity is caused by the presence of'carbonates,
bicarbonates, hydroxides, and to a lesser extent by borates, silicates,
phosphates, 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.




     The sulfate radical Is of significance only as it is
associated with calcium or magnesium.  When in combination with
these minerals a laxative effect is produced.  To control this
effect the drinking water standards suggest a maximum of
250 mg/1 as acceptable.


     This is a component of the dissolved ionized solids present
in most surface waters.  It is closely associated with man's
activities since it is a component of human waste and is also used
freely in many industrial processes.  Chloride can produce 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 250 mg/1 chloride if other water
of better quality is available.  It is not treatable 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 limit
the concentration of certain metals in drinking water because of
potential toxic properties to human beings.  These limits are as
follows:  Arsenic, 0.05 rag/lj Barium, 1.0 mg/1; Cadmium, 0.01 mg/1;
Chromium, 0.05 fflg/lj Lead, 0.05 mg/lj 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.  In addition, the standards list
tolerance limits for metals that, if exceeded, can constitute
grounds for rejection 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; 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 impor-
tant part in the biological makeup of the aquatic environment.  The
term toxic metals as used in this report refers to copper, cadmium,
nickel, zinc, lead and chromium.


                     LABORATORY PROCEDURES

Sample Preservation

    After samples were collected as described in Special Report
LM-2, "Sampling Surveys", each sample was divided (on shipboard)
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$ 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 collection 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
published 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 reproducible
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 repetitive 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 herein the 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.

                  Nitrogen-Ammonia 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 3°5-3°7»

                  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 ninety-six 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 acid medium.  The following procedure was followed:

1.  Apparatus used:

     Technicon Auto Analyzer. (20)

2.  Reagents used:

     a.  Sodium Acetate Solution: 34 g. per liter.

     b.  Sodium Acetate Hydrochloric Acid Buffer Solution: (100 ml
of hydrochloric acid (l : 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 hydroehloride, 10 ml of concentrated hydrochloric
acid and 500 ml of 95$ ethyl alcohol per liter.  (This reagent
eventually becomes slightly discolored and may form a slight
precipitate.  If discoloration occurred it was removed "by mixing
with nitrate free activated carbon and filtering.)

     e.  Color Reagent:  Equal volunes 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 potassium
nitrate per liter.  This solution contained 1 mg of nitrate nitrogen
per ml.
     h.  A series of working standards from 0.05 to 3»0 ra
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

     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 analysing ninety- six 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



                          Total Phosphate

     This test was performed in accordance with procedures described
in "Standard Methods/' Method C, Total Phosphate and Polyphosphate,
pages 204-206, on samples filtered to remove suspended matter.


     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
Winkler Method, pages 309-311.


     Phenols were determined as described on pages i|-0^-^08, using
the Aminoantipyrene Method.

                     Alhyl-Benzene Sulfonates

     The methylene blue procedure for determining alkyl-benzene
sulfonate (ABS) as described in "Standard Methods," pages 2k5-25I}
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
     eliminated 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 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 MS.S extracted two times with 10 ml portions
     of chloroform and filtered through a pledget of cotton"in the" tip
     of the separately 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 650 millimicrons.

                    Biochemical Oxygen Demand*

     The procedure for biochemical oxygen demand was the same as
described on pages 318-23 in "Standard Methods."

                  Hydrogen Ion Concentration (pH)*

     This test was performed by the Glass Electrode Method as
described on page 194.

                          Dissolved Solids

     Dissolved solids were measured by the method described on
pages 326-330 of Standard Methods titled "Piltrable Residue."

                        Sodium and Potassium

     So6ixan_and potassium content were measured by the Flame
Photometric Method as described on pages 231-232.


     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 114-116.

                         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 45-4-7.


     This test was performed by the Photometric Method as described
in "Standard Methods" on pages 153-154.

         The Turbidimetric Method was used as described on pages



     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.  The instrument used was the Sargent Model XV.  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$«

     A detailed description of procedure has been given



                       RESULTS OF ANALYSES

     Samples of Lake Michigan water were subjected to a large number
of physical and chemical analyses to establish base line water
quality, to identify those parameters likely to provide the best
index of water quality, and to determine areas or zones of water
quality variability.  The parameters studied were those listed on
page 2 of this report.  In general, the bulk waters of Lake Michigan
were found to be of good chemical quality, in that the concentrations
of the constituents present would be acceptable to the present water
uses and to anticipated future uses of these waters.

     The parameters showing appreciable variability and likely to
provide the greatest threat to satisfactory water quality management
were found to be ammonia nitrogen, total phosphate, silica, phenol
and dissolved oxygen.  These and other findings will be discussed
with respect to the study area in subsequent paragraphs.

Deepwater Studies

                         Ammonia Nitrogen

     The deepwater study in the northern sector of the lake was
conducted in the spring.  Figure 1 represents the ammonia nitrogen
levels found in this area.  The range was from less than 0.01 mg/1
to 0.12 mg/1 for all depths.  The averages (shown in Table la) for
surface, middle and bottom depths were 0.03, 0.05 and 0.05 mg/1.respec*
tively.  There appears to be no particular pattern in the distribution
of these results, since they vary from station to station with respect
to maxima and minima in relation to depth.  A similar condition
exists geographically in that high and low values are at random
throughout the sector.  The highest value was found l6 miles out from
Sheboygan.  The second highest value was found in Green Bay.

     Figures 2 and 3 show the southern portion of the lake which was
also studied during the spring season.  The surface concentrations
ranged from less than 0.01 mg/1 to 0.20 mg/1.  The two highest con-
centrations, 0.20 mg/1 found at the surface, and 0.10 mg/1 found at
bottom, were located along the same longitude in the southern end of
the lake about 20 miles apart.  The overall averages for all depths
for the southern sector are not appreciably different from those
observed in the northern sector for the spring period.  The recorded
averages for the southern sector were 0.05, 0.05 and 0.0k milligrams
per liter.



     Additional sampling for ammonia nitrogen in the southern sector
of the lake was conducted during the summer season.  These results
are presented in Figures k and 5.  The levels of concentration range
from 0.01 to 0.20 mg/1, with an average of 0.06, 0.07 and 0.08
milligrams per liter for surface, middle and bottom depths respectively.
The data show a slight increase in concentration of ammonia nitrogen
occurring in the area when compared with the results reported for
the spring season (Figures 2 and 3)»  The highest concentrations in the
southern sector were found in the area off Hammond and East Chicago,

     With the exception of the two high results of 0.18 mg/1 and
0.20 mg/1 found in the south basin during the summer, and the high
results of 0.13 mg/1 and 0.12 mg/1 found in the north basin, the
deepwater ammonia nitrogen results indicate no water quality deterio-
ration with respect to this parameter.


     The average phosphate concentrations found in each area of the
lake in each season are presented in Table 1.  The phosphate results
are also presented graphically in Figures 9 through 16.  A study of
Table 1 shows that phosphate levels in deepwater samples, during
the spring, averaged 0.01 mg/1 at the surface, middle depths and
bottom depths.  During the summer the average phosphate levels at
the surface increased to O.Olj- mg/1, and the average at middle and
bottom depths remained constant at 0.01 mg/1.

     Figure 9 present the phosphate results in the northern basin
of Lake Michigan.  All sampling in the upper half of Lake Michigan
was in the spring.  Only two results above 0.03 mg/1 were found
in this part of the lake.  One was about mid-lake at Mf0UO' north,
86°30f west and the other was found in Green Bay.

     Figures 10 and 11 show the phosphate levels found in deepwater
in the lower half of Lake Michigan in the spring season.  A study of
these figures reveals that two results were above 0.03 mg/1.  One
of these was at mid-lake between Milwaukee and Muskegon, and the
other was 1? miles out from Ludington, Michigan.

     Figures 12 and 13 show the phosphate results in the summer in
both deepwater and inshore samples.  The summer deepwater samples
were found to be higher than the spring samples, with seven values
above 0.03 mg/1, and two of these as high as 0.73 and 0.20 mg/1.



     Although there was found to be a substantial increase in deep-
water phosphate between the spring and summer periods, with the
exception of the few high results cited above, phosphate levels of
the surface, mid-depth and bottom samples were below that considered
necessary to produce high concentrations of algae (22).


     The average silica concentrations found in each area of the lake
in each season are presented in Table 1.  A study of this table shows
the silica results in deepwater samples during the spring to average
3.3> 2.6 and 2.8 mg/1 in the surface, middle and bottom samples
respectively.  The average silica results in the deepwater samples
during the summer were essentially the same as during the spring in
the mid-depth and bottom values (2.7 and 3*2 mg/l), but the average
surface value dropped from 3«3 mg/1 in the spring to 1.5 mg/1 in
the summer.

     Thirteen samples were found with silica results greater than
U mg/1.  Four of these were surface samples which were all found in
the spring.  Nine of these were found at the bottom depth and all
nine were found during the summer.  The geographical distribution of
the high results was random in both the spring and summer sampling.

     The variations found in silica concentration serve to demonstrate
its uptake by biological life during multiplication.  Since silica
forms the skeletal structure of diatoms, its removal indicates
significant biological activity.  It could be a limiting factor in
population explosions of diatoms where other growth factors are at
optimum levels (23) (2*4-).

                       Dissolved Oxygen (DO)

     Table 2 shows the dissolved oxygen and related temperature
results of samples collected in Lake Michigan in 1962.  This table
presents the average, maximum and minimum DO, the associated
temperature, and the maximum and minimum per cent saturation values.
These results are presented together because temperature is necessary
to determine the per cent saturation values presented.  The per cent
saturation calculation is made assuming a standard sea level
barometric pressure of 760 mm of mercury.  One hundred and ninety-five
deepwater samples were collected in the spring and summer of 1962
for dissolved oxygen analysis.  The results are summarized in the
first two groups of results in Table 2.  With the exception of a
few bottom samples collected in the spring, the results were between
91 and 118.  The minimum per cent saturation figure for these few



bottom results was 71 per cent.  The minimum DO result was 7.1 mg/1.
This sample was collected from a station located in Green Bay at
1&045' N 87°50' W.  Other than the few values indicated above, .the
dissolved oxygen levels in deepwater all were near 100 per cent

             Alkyl Benzene Sulfonate (ABS) (Apparent)

     As expected, ABS concentrations found in all deepwater samples
were below the level of accuracy of the method used.  Therefore no
water quality significance is attached to the levels (0.01 to 0.05 mg/l)

                         Nitrate Nitrogen

     Nitrate nitrogen results are presented in Table 3»  The results
in deepwater sampling in the spring ranged from 0.03 to 0.25 mg/1
at the surface, 0.06 to 0.26 mg/1 at mid-depth and 0.02 to 0.21 mg/1
at the bottom depth.  The average values were 0.14, 0.14 and 0.11 mg/1
at the surface, mid-depth and bottom respectively.

     Results of deepwater sampling in the summer had approximately
the same ranges of values but slightly lower averages.  The average
values were 0.09 at the surface and 0.11 at the mid-depth and bottom.
The maximum concentration in each sampling period was found in the
bottom depth.  The difference between spring and summer results is
minimal and no appreciable difference is found in geographical

                           Toxic Metals

     Toxic metals were measured in a number of lake samples from
each area of the lake to ascertain if any one of them might be
found in sufficient concentration to be significant.  The metals
were found in detectable amounts but the quantities were quite low
and are important only from the standpoint that the laboratory has
established that they are not present in sufficient quantity to
have any effect on human or aquatic life.

     Table 3 shows the frequency of occurrence in any one area and
season and the concentrations found.

     Zinc was found in measurable amounts, ranging from 0.005 " 0,021 mg/1,
over the entire northern half of the lake during the spring sampling.
Copper, cadmium and lead were found between Charlevoix and Manistique
in the range of 0.005 - 0.008 mg/1.



     In the summer sampling, nickel was present in the center of the
lake at a level of 0.005 mg/1 opposite North Side Chicago and 0.009 mg/1
of lead was found twenty miles out from Waukegan.  Lead, in a concen-
tration of 0.009 mg/1 was found near Muskegon, chromium was found
all the way across the lake between Muskegon and Milwaukee, in the
range of 0.005-0.008 mg/1.  Copper and chromium were present in the
center of the lake opposite Manitowoc in the range of O.OOT-0.008 mg/1.

                         Other Parameters

     In the deepwater study of the lake, other parameters showed results
of some variability but of little water quality significance.  The
analyses performed and the ranges found are briefly discussed below:

     pH; range 8.0 to 8.9.  There was no difference between
         spring and summer.

     Alkalinity; range 100 to 125 mg/1.  There was no difference
         between spring and summer.

     Dissolved Solids; spring; range 98 to 258 mg/1.  No results
         above 150 were found in the upper third of the lake.  In
         summer samples, the range was 1^0 to 160 mg/1.

     Conductance (specific); spring; range 2l6 to 298 micromhos
         per cm.  In summer samples, the range was 192 to 272
         micromhos per cm.  The variation with changes in depth
         at each station was less than 20 micromhos per cm.

     Sodium; range 3.5 to 4.9 mg/1.  Results were very low and
         nearly constant.  Analysis for sodium was discontinued
         in the fall because of uniform results.

     Potassium; range 0.9 to 1.3 mg/1.  Results were very low and
         nearly constant.  Analysis for potassium was discontinued
         in the fall because of uniform results.

     Calcium; range 30 to 35 mg/1.

     Magnesium; range 9 to 11 mg/1.

     Sulfate; range 19 to 23 mg/1.

     Chloride; range 4.5 to 8 mg/1.



Inshore Studies

     Inshore studies of Lake Michigan were made in the summer and
fall of 1962.  The inshore studies comprised sampling at one mile,
four miles, seven miles and ten miles from the shore with samples
collected at several depths at each station where indicated.  In
addition to the parameters which were found significant in the
deepwater studies (Ammonia Nitrogen, Total Phosphate, Silica,
Dissolved Oxygen and Nitrate), Phenols were found in significant
quantities in some of the inshore samples.  Greater variations
were found in the parameters in the inshore studies than in the
deepwater studies.

                         Ammonia Nitrogen

     Ammonia nitrogen determinations on inshore stations of
Lake Michigan were conducted during the summer and fall  seasons.
The results are presented graphically according to areas and
seasons in Figures ^, 6, and 7> and are summarized in Table 1.

     Figure 4 represents concentrations found during the summer
period in the southwest quadrant of the lake.  The range of
values according to sampling depths are from 0.01 to 0.37 mg/1
at the surface; 0.01 to 0.20 mg/1 at mid-depth and 0.01 to
0.12 mg/1 at the bottom.  The higher values tend to distort the
average because they are found in only two or three locations for
each depth, yet it is observed that the greater number of high
concentrations, particularly from surface samples, are found in
the southern end of the lake between Chicago and Gary.  The other
points, with the exception of several stations near Waukegan
and Milwaukee, which rise as high as 0.12 and 0.13 mg/1 respectively,
tend to be fairly uniform throughout.  The averages for surface,
middle and bottom were 0.05, 0.0*)-, and 0.0^ mg/1 respectively.

     The southwest quadrant comprising approximately the same
stations selected in the sunner was also studied in the fall season.
The overall results are shown in Figure 6.  When comparing this
chart with Figure 4 it is observed that, although several individual
stations show a higher concentration of ammonia nitrogen during the
summer (Figure 4), the average values for the fall period are
distinctly higher, (Table Ib).  The concentrations during this period
are 0.06, 0.0*J- and 0.09 milligrams per liter for top, middle, and
bottom depths respectively.  The figures indicate that the bottom
concentration is slightly higher than at the other two measured
depths, and is double the value found for the same depth during the
summer (Table la).  The increased overall concentration for the



fall period is probably due to colder temperatures which reduce the
rate of oxidation of ammonia to nitrates.  Similarly, the bottom
level may be higher because of cooler temperatures.  Also apparent
from the figure is that the higher concentrations tend to occur in
the southern tip of the lake as was reported for the summer period
of study.

     The inshore stations in the southeast quadrant of Lake Michigan
were studied during the fall season«,  The graphical picture is
presented in Figure 7»  Concentration ranges of ammonia nitrogen are
from 0.01 to 0.08 mg/1 for surface samples and from 0.01 to 0.10 mg/1
for both middle and bottom depths„  The averages are 0.04, O.Olj-,
and 0.05 mg/1 for surface, middle and bottom respectively (Table la).
These figures would indicate no significant differences with respect
to vertical depths, but do show slightly higher values geographically
for the points between Michigan City and Benton Harbor as compared
with the results from points immediately north of this area.  There
is again a slight increase in average concentration at the extreme
northern sector of this quadrant around Muskegon where values reach
around 0.10 mg/1 and are comparable to those in the extreme southern
sector.  An interesting observation is noted when comparing Figure 6
and Figure 7> the southeast and southwest quadrants respectively.
Both studies were conducted during the fall season but concentrations
were significantly higher on the west side.  This is probably due
to the more heavily populated areas adjacent to the west shore.

     It is apparent from this study of ammonia nitrogen concen-
trations that the inshore areas of the lake, particularly in the
southwest sector, carry higher levels than the deeper water.  These
increased levels indicative of deteriorating water quality can be
attributed to the heavy population concentration of the adjacent
land area.  However, with the exception of the several extreme values
noted above, the levels found do not represent serious degradation
at this time.

                           Total Phosphate

     The average phosphate concentrations found in each inshore study
area in each season are presented in Table 1.  These results are
also presented graphically in Figures 12 to 15.  A study of Table 1
shows average phosphate results in inshore samples during the summer
to be 0.01, 0.10 and 0.27 nig/1 respectively at the surface, middle
and bottom.  This table reveals further that the average phosphate
concentration in inshore samples in the fall was only 0.01 mg/1 at
the surface and middle, and only 0002 mg/1 in the bottom sampling
depth.  This was a marked decrease from the concentrations found in
the summer samples.



     Figure 12 shows the geographical distribution of the inshore
results in 'the summer.  All of these samples were collected in the
southwest quadrant of the lake.  Of a total of one hundred and
twenty-nine samples, twenty-two were greater than 0.03 mg/1
(including five between 0.10 mg/1 and 1 mg/l, and six above 1 mg/l).
Fourteen of the twenty-two high results were in the vicinity of
Milwaukee, including an six which were above 1 mg/1 and four of the
five others above OdO mg/1.  These showed a fairly even distribution
between middle and bottom samples«  Six high results (greater than
0.03 mg/l) in these inshore samples weie distributed between Racine
and Waukegaru  One of these rasultn was greater than 0.10 mg/l.
The remaining two results above 0C03 mg/l were between Waukegan and

     Figures lU and 15 illustrate the inshore phosphate results in
the fall of 1962*  Figure 14 shows the southeast quadrant and
Figure 15 shows the southwest quadrant of the leke.

     Twelve out of two hundred thirty-seven fall samples had phosphate
results greater than 0.03 mg/l«  In the southeast quadrant two of
these high results were at the surface, six at mid-depth and one
at the bottom depth0  1'he remaining three were in the southwest
quadrant»  A comparison by depth in the southwest quadrant in fall
samples is not of any value because all of the samples except
nine were collected at the surface. the high phosphate results occur with greatest
frequency in two general areas: inshore between Milwaukee and
Kenosha. Wisconsin  on the west shore; and inshore between Muskegon
and Benton Harbor, Michigan on the east shore.

     The extremely high levels found in the Milwaukee area are
logically attributed to the discharge of waste effluents from those
cities.  The low concentrations found at the surface during the
summer study may be the result of uptake by planktonic organisms.


     The average silica concentrations found in each inshore area
in each season are presented in Table 1,,  This table shows average
silica results in inshore samples during the summer to be 1.5, 2«0
and 2.5 mg/l respectively for the surface, middle and bottom samples.
All of these samples were collected in the southwest quadrant of
the lake.  The average silica results in inshore samples during the
fall in the same quaoraiyfc of the lake were somewhat less, being
1.4, 1.8 and 1,5 ng/1 respectively for the surface, middle and bottom
samples.  The average silica results during the fall in the southeast



quadrant of the lake were nearly the same as in the southwest quadrant,
that is, 1.7, 1.8, and 1.9 mg/1 at the surface, middle and bottom
respectively.  A review of these averages, deepwater and inshore,
indicates that the surface results are highest in the spring, the
bottom results highest in the summer and a nearly uniform distribution
occurs in the fall.  The top to bottom variations noted in these
observations are paralleled by the findings in the deepwater study,
namely that this variation can be attributed to biological uptake.
The above averages reflect a range from 0,02 mg/1 to ij-.O mg/1 in the
areas studied.

                       Dissolved Oxygen (DO)

     Table 2 shows the dissolved oxygen levels and related temperatures
of samples collected in Lake Michigan.  Included are both the maximum
and minimum DO values, the corresponding temperatures and the maximum
and minimum per cent saturation values.

     Five hundred eighty-one inshore samples were collected for
dissolved oxygen analysis in the summer and fall of 1962.  The con-
centrations on the southwest side during the summer range from a
maximum 99 per cent saturation on the surface to a minimum 77 per cent
saturation at the bottom.  Samples from this same area in the fall
range from Bk to 107 per cent saturation at the surface, 9^ to
100 per cent saturation at mid-depth, and from 78 to 105 per cent
saturation at the bottom.  The minimum DO value was obtained in the
summer and was 6.7 mg/1.

     No inshore samples were collected from the southeast side of
the lake during the summer but the samples collected during the
fall range from 96 to 106 per cent saturation at the surface.  A
minimum of 93 per cent saturation at the middle depths and 75 to 87
per cent saturation at the bottom depths.  Little geographical
variation was noted.

     Dissolved oxygen concentrations in Lake Michigan do not appear
to be of serious concern with respect to the water quality of the
inshore waters.


     Since phenolic compounds are not likely to persist at distances
far removed from the source of entry, except during low temperature
periods, the samples analyzed for these materials were taken from the
three principal harbors on the western shore of the lake and at
inshore sta'tions near industrial complexes in the southeast and
southwest quadrants of the lake.



     The inshore study for phenols in the southeast quadrant includes
sampling stations extending from Michigan City, Indiana northward
to a point above Muskegon, Michiganc  The range at Benton Harbor
was from less than 1.0 to about 2,0 micrograms per liter.  Results
from Saugatuck and Grand Haven areas range from 1.0 to 5.0 M-g/1,
and 0 to 5»0 HS/1 respectively,,  No indication of phenols was found
in the Muskegon area.  The sampling stations for the southwest
quadrant extend from inshore at Gary, Indiana northward to Milwaukee.
The range of values reported at Gary is from 1.0 to 9,0 ng/1 at
Chicago from less than 1,0 to 5.0 n.g/1; Racine 2.0 to 3.0 i^g/1; at
Milwaukee and Kenosha from lass than 1,0 to 3°0 p.g/1 and 1.0 to
2.0 M-g/1 respectively.  In the southwest quadrant it is observed that
the maximum values tend to increase from the north to the south,
while in the southeast quadrant the reverse is true.  This is probably
due, in. part, to the nature of the industries located around or near
the selected sampling points.  The observed levels of phenols found
in the southwest inshore area may at times affect the quality of
municipal water supplies by Imparting disagreeable tastes following

                         Nitrate Nitrogen

     Nitrate nitrogen sampling was conducted at inshore stations
of the lake during summer and fall seasons..  The results are summarized
in Table 3.

     The average values found in the southwest quadrant during the
summer were 0.10, 00lU and 0.16 mg/1 for surface, middle and bottom
depths respectivelye  The ranges were 0.02 to 0.18 mg/1 at the
surface, 0.08 to Oo22 mg/1 at mid-depth, and 0.03 to 0.27 mg/1 at
the bottom.  The same geographical area studied during the fall
season reveals results that are in comparable ranges: from 0.05 to
0.19 at the surface, 0.08 to 0,lo at mid-depth and 0.07 to 0.19
at the bottom.

     The southeast quadrant of the lake was  sampled for nitrate
nitrogen during the fallo  The average concentrations found were
0.10, 0,12 and 0.13 mg/1 for surface, mid-depth and bottom samples
respectively.  The ranges were from 0.08 to 0.13 mg/1 at the
surface, 0.08 to 0.32 mg/1 at mid-depth and 0005 to 0.36 mg/1 at the
bottom o

     These figures show a slightly higher value at bottom than at
surface or mid-depth, but average values are not appreciably
different.  In fact there is a fairly uniform distribution of nitrate
nitrogen in all areas of the lake studiedo



                   Biochemical Oxygen Demand (BOD)

     BOD analyses on inshore samples in the summer season ranged
from 0.5 to 2.6 mg/1.  BOD analyses on inshore samples in the fall
ranged from 0.2 to 2.5 mg/1.

     Although these results are not high when compared to BOD levels
found in flowing streams below sources of pollution, they do indicate
some evidence of deteriorated water quality.

                            Toxic Metals

     On inshore samples collected during the summer in the southwest
quadrant of the lake, nickel, chromium,  lead and zinc were found
to be present only in close proximity to major cities in the range
of 0.005-0.025 mg/1.

     On inshore samples collected during the summer on the south end
of the lake, copper, chromium, lead, nickel and zinc were found to be
present in the immediate vicinity of the major cities in the range
of 0.005-0.032 mg/1.

                          Other Parameters

     Other parameters were considered in the inshore studies of the
lake.  Some were studied which had values of some variability but
of little water quality significance.  These results have importance
in establishing that these parameters are not present in sufficient
quantity to have any apparent effect on human or aquatic life.  The
parameters examined and the range found are briefly discussed below:

     Alkyl Benzene Sulfonate (ABS) concentrations were below the
         level of accuracy of the method used.  Therefore no
         water quality significance is attached to the levels
         (0.01 to 0.03 mg/l) reported.

     pH values ranged from 8.0 to 9.0 in the summer, and
         6.8 to 9.3 in the fall.

     Alkalinity ranged from 100 to 115 mg/1 in the summer and
         87 to 136 mg/1 in the fall.

     Dissolved solids ranged from 1^0 to l6o mg/1 in the summer;
         119 to 172 mg/1 in the fall.

     Conductance (specific) varied from 256 to 3^0 nmho/cm
         in the summer and from 220 to 380 mnho/cm in the fall.



     Sodium and Potassium results were very low; sodium ranged from
         3.5 to ij-,9 mg/.l and potassium ranged from 0.9 to 1.3 mg/1.

     Calcium results were also low, varying from 25 to 33 mg/1.

     Magnesium results ranged from 9 to 11 mg/1.

     Sulfate results ranged from 19 to 22 mg/1.

     Chloride results ranged from 5 to T»l mg/1.

Harbor Studies

                          Chicago Harbor

     Ihe analyses performed and the ranges found were as follows:

     Ammonia Nitrogen, average concentration 0.07 mg/1; range,
         0.02 to Oal6 mg/1.

     Total Phosphate, average concentration 0.01 mg/1; range
         up to 0.05 mg/1.

     Dissolved Oxygen, average concentration 12.0 mg/1; range
         11.6 to 12.6 mg/lo

     Phenols, range up to 2.0 jig/1.

     Nitrate, range 0.05 to 0.1 mg/1.

     ABS, less than 0.1 mg/1.

     BOD, range 1.0 to 1.5 mg/1.

     Other parameters - None of the other parameters measured
         showed significant differences when compared to
         analyses of inshore waters taken in the vicinity.

     The results of the analyses presented above compare very
closely with results obtained in the inshore study, southwest
quadrant, fall season.  This is to be expected since the movement
of water in this vicinity is toward the harbor, rather than away
from it.  OIherefore, can be concluded that the waters'adjaceftt to
the inlet of the Chicago River were representative of the inshore
waters of the southwest quadrant with respect to the chemical



                           Racine Harbor

     The analyses performed and the ranges found were as follows:

     Ammonia Nitrogen, average  0,06 mg/1, max. 0.10 mg/1.

     Total Phosphate, average 0.02 mg/1, max. 0.10 mg/1.

     Dissolved Oxygen, average 11»7 mg/1, range 11.1 to 12.7 mg/1.

     Phenol, range up to 5'° M-g/1-

     Nitrate, range 0.05 to 0.17 mg/1.

     ABS, less than 0.1 mg/lo

     BOD, 1.0 to 2o5 mg/1.

     Other parameters.  Of the parameters measured, only chloride
         shoved a slight increase in concentration when compared
         to the results obtained in the inshore study, southwest
         quadrant, fall season.

     Racine Harbor receives the flow of the Root River, which is
a small tributary draining the immediate area.  Any drainage from
the Root River would include the overflows of storm sewers and
surface runoff but not the effluent from the sewage treatment plant,
the outfall of which is located two miles south of the harbor.

     With the exception of very minor differences in DO and phenol
levels, the chemical quality of these waters compares favorably
with the levels found for inshore waters in this area.

                         Milwaukee Harbor

     Because considerable variation in chemical quality was observed
in these waters when compared with the inshore waters of the southwest
quadrant, this harbor study will be reported in greater detail.

     Figure 8 presents the findings with respect to ammonia nitrogen.
Inspection of this figure reveals significantly high concentrations,
both within and outside the breakwater.  The overall average for the
study area was 0.6 mg/1.  The highest values, (max. 2.73 mgA) were
observed within the breakwater, but several values above 0.5 mg/1
were found outside, near the breakwater openings.

     The concentrations found outside the breakwater form a pattern
indicating a southward movement of the water in that vicinity.



     The phosphate levels found in this study of Milwaukee Harbor
are presented in Figure 16.  Levels as high as 1.^ mg/1 were observed,
with an overall average of 0.27 mg/1.  Concentrations of phosphate
outside the breakwater form a pattern similar to the ammonia nitrogen

     Dissolved oxygen levels in the harbor averaged 10.0 mg/1.
One values ranged from II.k to 5.3 mg/1 with the corresponding
saturation values between 98 and 52 per cent.  These values are con-
siderably lower than the comparable levels found in the inshore,
southwest quadrant, fall survey.

     Phenols ranged up to 11.0 ng/1 within the harbor area and may
be compared in Figure 17.

     Nitrates ranged from 0.08 to 0.27 mg/1 ^n the harbor and
averaged O.l6 mg/1.  This average was higher than the average value
for deepwater and inshore samples.

     ABS levels (see Figure 18) were as high as 0.3 mg/1 and BOD
was found to be as high as 4.5 mg/1.

     Other parameters of interest were; pH, which was lower than
adjacent waters, and chloride, as high as 37»9 mg/1.

     In contrast to the other harbor areas studied, the Milwaukee
Harbor and adjacent areas showed significant evidence of degradation
of chemical wa'ter quality.  Low DO and high BOD values indicated
severe water quality deterioration.  The high ammonia nitrogen and
phosphate levels which are typical of polluted streams may be expected
to stimulate algal growth.  Phenols and ABS levels were further
evidence of this degradation.  Because all the wastes of the Milwaukee
area, including treated domestic sewage, surface runoff and storm-
water overflow are discharged through the harbor into the Lake, it
is riot difficult to understand why the beaches of Milwaukee are
frequently closed to bathers.

     It may also be presumed, subject to further confirmation by
current measurement studies, that most of the subtle differences
observed in chemical quality of the western inshore area are the
result of the waste discharges from the Milwaukee area.




     Studies of chemical water quality were undertaken in specific
areas of Lake Michigan,  Of the chemical parameters considered,
Ammonia Nitrogen, Biosphate, Silica, Phenol and Dissolved Oxygen
were found to be significant with respect to the differences

     Ihe deepwater studies provided little or no evidence of water
quality deterioration, in the areas studied.  Considerable uniformity
was displayed between surface and depth samples for most parameters
measured.  The low silica levels observed on surface samples during
the summer study are believed to be due to uptake by plankton.

     The inshore studies provide information which points to some
water quality deterioration in areas adjacent to populated sectors
of the lake.  Ammonia nitrogen levels were highest in the southwest
sector; phosphate was also highest at depths other than the surface.
The low concentrations found at the surface may be due to uptake
by planktonic organisms<»  Phenol, in sufficient concentrations to
affect municipal water supplies, was detected.

     Of all areas studied, Milwaukee Harbor was found to be most
degraded with respect to chemical quality of the water.  Significant
degradation was evidenced by the high concentrations of ammonia
nitrogen, phosphate, ABS, phenol and BOD, and the low concentrations
of DO observed.  Some of the tests also revealed evidence of
southward movement of waters from this harbor.

     An illustration of the probable effects of returning Chicago's
sewage effluents to the lake may be obtained by observing the
Milwaukee Harbor results*  Although this may be an extreme example
of the conditions which might occur, nevertheless the return of any
large portion of Chicago's effluents would be expected to have some-
what similar effects on the surrounding waters as those observed in
the Milwaukee Harbor area,,  Among these expected effects would be an
accelerated increase in nitrogen and phosphate levels which are
already approaching critical levels in the Southwest inshore quadrant
of the lake.




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10.  Warrick, L.F.  Relative Importance of Industrial Waste in Stream
     Pollution,  Sewage Works Journal, 6: 158 (193*0.

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. ^63,
     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.  Gastroenterology• 4:  332-3^3



13.  Bills, C.E., et al.  Sodium and Potassium in Food and Water.
     Journal American Dietetic Association, 25:  304 (1949).

14.  Wilcox, L.V.  Agricultural Uses of Reclaimed Sewage Effluent.
     Sewage Works Journal. 20: 592 (1948).

15.  Lackey, J.B. and Sawyer, C.N.  Plankton Productivity of Certain
     Southeastern Wisconsin Lakes.  Sewage Works Journal. 17: 573

16.  Brandt, H.J.  Intensified Injurious Effects on Fish, Especially
     the Increased Toxic Effect Produced by a Combination of Sewage
     Poisons.  Chemical Abstracts, No. 42 (1948).

17.  Muss, D.L.  Relationship Between Water Quality and Deaths
     From Cardiovascular Disease.  Journal American Water Works
     Association. 54:  1371-1378 (1962).

18.  Ellis, M.M., Westfall, B,H. and Ellis, Marion D.  Determination
     of Water Quality.  Department of Interior Research Report 9

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 AAl.  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.  Sawyer, C.N. and Lackey, J.B.  Investigation of the Odor Nuisance
     from Madison Lakes*  Report to the Governor's Committee, Madison,
     Wisconsin (1945).

23.  Hutchinson, G. Evelyn.  A Treatise on Limnology.  John Wiley
     & Sons, Inc., New York (1957^pT 797»

24.  Lund, J.W.G.  The Seasonal Cycle of the Plankton Diatom.
     Journal Ecology 42:  151-179, 734-797 (1954).


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