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. THE INFLUENCE or MUNICIPAL AND
- ' AGRICULTURAL PRACTICES 0N
STREAM WATER QUALITY IN

’ 'I'HE GRAND RIVER BASIN
C_ Thesis for t Degree of M. S. . I . '

:.. MICHIGAN STATE UNIVERSITY
-' JAMES-R. wAYRRANT ' ' ’
1971

   

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ABSTRACT
THE INFLUENCE OF MUNICIPAL AND AGRICULTURAL

PRACTICES ON STREAM WATER QUALITY
IN THE GRAND RIVER BASIN

BY
James R. Waybrant

A study of phosphorus and nitrogen concentrations in
the Grand River watershed indicated that nitrate-nitrogen
fluqtuated significantly with changes in temperature and
photoperiod. A temperature—dependent shift in nitrogen-
form uptake took place at approximately 100 C. Above 100 C,
nitrate-nitrogen was preferentially absorbed, with an appar-
ent shift to ammonia-nitrogen as the ambient temperature was
reduced to less than 100 C.

Total phosphorus did not appear to fluctuate with changes
in biological activity. However, certain sites in the river
at times exceeded 100 times the 0.01 mg per liter concentra—
tion previously reported as a minimum phosphorus necessary
to stimulate nuisance algal blooms in lakes.

A study of nutrient concentrations in runoff from water-
sheds of predominantly urban, natural, or agricultural land
usages indicated significant differences: a) the natural

watershed runoff contained less nitrate-nitrogen than did

James R. Waybrant

runoff from either the urbanized or agricultural watersheds;
b) urbanized land runoff contained far greater concentrations
of phosphorus than did runoff from either natural or agri-
cultural watersheds, and c) natural and agricultural land
runoff did not containksignificantly different concentrations
of total phosphorus.

The Grand River frOm August, 1969, to August, 1970,
discharged an estimated 1,034,000 kg of total phosphorus into
Lake Michigan. This amount was estimated to be approximately
70 percent of the calculated input by drainage from the
entire watershed. Sewage treatment plant effluents along the
Grand River contributed amounts of total phosphorus equivalent
to the total discharge from tributary rivers.

Nitrate-nitrogen discharged by the Grand River into Lake
Michigan totaled 3,996,000 kg for the period August, 1969 to
August, 1970. This amount was estimated to be 33 percent of
the calculated input from all types of discharge.

Approximately 35 percent of the total nitrate-nitrogen
discharge was unaccounted for. It is suggested that this
may be due to action of nitrogen—fixing algae in the stream
system. Since about 67 percent of the nitrogen was apparently
extracted within the system and 35 percent of the final dis-
charge was unaccounted for, the Grand River indicated evidence

of possible nitrogen-limitation during the period of surveil-

lance.

THE INFLUENCE OF MUNICIPAL AND AGRICULTURAL
PRACTICES ON STREAM WATER QUALITY

IN THE GRAND RIVER BASIN

BYI

’ IA‘\

James RSRWaybrant

A THESIS

Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of

MASTER OF SCIENCE

Department of Fisheries and Wildlife

1971

I I. .I ”I :6] 5/

‘v. AJ'{.‘\J

ACKNOWLEDGMENTS

I wish to express my sincere thanks to Dr. Marvin E.
Stephenson for help in initiation of this study and for his
patience and guidance in development of results and prepara-
tion of this manuscript.

I also wish to thank Dr. Robert C. Ball for the Opportun-
ity to pursue advanced study and for financial aid. This was
extended from the Institute of Water Research, Michigan State
University, and the Michigan Agricultural Experiment Station
research assistantship. Thanks are also due him for his help
in editing this manuscript.

I am grateful to Dr. Niles R. Kevern, for his kindness
and generosity toward me. He was always willing to take time
out to discuss a problem with me.

I am indebted to my fellow graduate students, especially
Frank Tesar and David Jude, for many general and specific
discussions of limnology.

 

ii

TABLE OF CONTENTS

ON 000 U1 U1 00H |-'

Page
I. INTRODUCTION . . . . . . . . . . . . . . . . .
A. Need for Study. . . . . . . . . . .
B. Purpose and Scope of Study. . . . . . .
II. REVIEW OF PREVIOUS WORK. . . . . . . . . . . .
A. General Eutrophication Studies. . . . .
B. Biological Uptake of Phosphorus and
Nitrogen. . . . . . . . . . . . . . . .
C. Sources of Phosphorus and Nitrogen. . .
1. Precipitation. . . . . . . . . .
2. Nutrients Dissolved in Soil
Solutions. . . . . . . . . . . .
3. Surface water Runoff . . . . . .
a) Irrigated and Fertilized
Lands . . . . . . . . . . 9
b) Forested Lands. . . . . . 10
c) Urban Lands . . . . . . . 12
4. Pollution. . . . . . . . . . . . 13
D. Biological Nutrient Extraction in Flow-
ing Water . . . . . . . . . . . . . . . 14
E. The Importance of Nitrogen as a Func-
tion of Biological Activity . . . . . . 15
F. Phosphorus and Nitrogen Nutrient
Budgets on Large-Scale River Systems. . 16
III. FIELD STUDIES. . . . . . . . . . . . . . . . . 18
A. Description of Study Area . . . . . . . 18
1. General. . . . . . . . . . . . 18
2. Maple River Watershed. . . . . . l9
3. Red Cedar River. . . . . . . . 19
4. Looking Glass River Watershed. . 20
B. Sampling Sites. . . . . . . . . . . . . 22
C. Sampling Procedure. . . . . . . . . . . 22
D. Weather Data. . . . . . . . . . . . . . 26
E. Sewage Treatment Plants . . . . . . . . 27
F. Land Usage Data . . . . . . . . . . . . 27
G. Flow Rates. . . . . . . . . . . . . . . 27

iii

TABLE OF CONTENTS-—continued

IV.

V.

DISCUSSION OF RESULTS. . . . . . . . . . . . . .

A. Nitrate—Nitrogen. . . . . . . . . . . . .
B. Total Phosphorus. . . . . . . . . . . . .
§¢C. Nutrient Comparison of Urban, Natural and
Agricultural Watersheds . . . . . . . . .
éxp. Flow Contribution of Sewage Treatment
Plant Effluents to Rivers at Low—
Discharge Periods . . . . . . . . . . . .
E. Nutrient Budget . . . . . . . . . . . . .
1. Annual Nutrient Budget by Water-
shed . . . . . . . . . . . . . . .
2. "Flow-through" Nutrient Budget . .

CONCLUSIONS. . . . . . . . . . . . . . . . . . .

LITERATURECITED..................

APPENDICES. . . . . . . . . . . . . . . . . . . . . .

A.

Nitrate—Nitrogen Concentrations for Each
Sampling Site During the Period 8-21-69 through
8-1-70 . . . . . . . . . . . . . . . . . . . . .

Nitrate-Nitrogen Concentration Fluctuations at
Each Sampling Site Over the Period of Record . .

Total Phosphorus Concentrations for Each
Sampling Site During the Period 8-21-69 through
8—1-70 . . . . . . . .'. . . . . . . . . . . . .

Total Phosphorus Fluctuations at Each Sampling
Site Over the Period of Record . . . . . . . . .

Wastewater Treatment Plant Monthly Average Daily
Flow Rates During calendar Year 1969 . . . . . .

Analytical Procedures for the Determination of
Total Phosphorus and Nitrate-Nitrogen. . . . . .

Stream Flow Estimates at Sampling Stations
During the Period 8-21-69 Through 12-20-69 . . .

Dissolved Oxygen, Alkalinity, pH and Temperature
Data at the Mouth of the Grand River . . . . . .

iv

Page
28
28
35
38
47
48

48
53

59

61

66

66

71

78

84

92

94

97

99

TABLE OF CONTENTS--continued

I.

J.

Land Use Apportionment in the Grand River
Watershed. . . . ._. . . . . . . . . . . . . . .

Estimated Monthly Average Total Nitrogen Dis-
charge from Wastewater Treatment Plants in the
Grand River Basin During Calendar Year 1969. . .

Estimated Monthly Average Total Phosphorus Dis—
charge from Wastewater Treatment Plants in the
Grand River Basin During Calendar Year 1969. . .

Estimated Monthly Average Daily Total Phosphorus
Discharge at All Sampling Stations During the
Period August, 1969 Through December, 1969 . . .

Estimated Monthly Average Daily Nitrate-Nitrogen
Discharge at All Sampling Stations During the
Period August, 1969 Through December, 1969 . . .

Page

101

103

105

107

113

LIST OF TABLES

TABLE

1.

2.

Nutrients Discharged by Selected Land Use
Practices. . . . . . . . . . . . . . . . . .

Land Type and Population Comparisons Between
Three Subwatersheds in the Grand River Basin
(From U. S. Dept. of Agriculture). . . . . .

Sampling Sites Along the Grand River, with
Their Sampling Number, Description, and Dis-
tance in Miles from the River Mouth. . . . .

Comparison of Nitrate-Nitrogen Concentrations
at Selected Sampling Sites, with Average Week-

ly Temperatures in the Grand River Basin . .

Estimated Discharge Rates from Each Land—type

in Kg Mile-ZYear-l and for Sewage Treatment
Plants in Mg Liter.1 . . . . . . . . . . . .

Phosphorus and Nitrogen Balances in Surface

Runoff (Period of Surveillance: August 1969-

July 1970) . . . . . . . . . . . . . . . . .

vi

Page

11

21

23

32

51

54

FIGURES

1.

LIST OF FIGURES

A map of the Grand River and principle tribu-
taries. Also shown are major cities and the
thirty sampling sites . . . . . . . . . . .

Average nitrate-nitrogen concentrations at
each sampling site (August, 1969 to August,
1970) . . . . . . . . . . . . . . . . . . . .

Average total phosphorus concentrations at
each sampling site (August, 1969 to August
1970) . . . . . . . . . . . . . . . . . . . .

Comparison of nitrate-nitrogen concentrations
in three watersheds of different predominant
land usages . . . . . . . . . . . . . . . . .

Comparison of total phosphorus concentrations
in three watersheds of different predominant
land usages . . . . . . . . . . . . . . . . .

Comparison of mean nutrient differences from
different land usages (data from Sylvester,
1961) . . . . . . . . . . . . . . . . . . . .

Proportions of flow rate in the Red Cedar
River due to sewage effluents . . . . . . .

Nitrate-nitrogen concentration fluctuations
at each sampling site over the period of
record. . . . . . . . . . . . . . . . . . . .

Total phosphorus fluctuations at each
sampling site over the period of record . . .

Estimated monthly average daily total phos—
phorus discharge at all sampling stations
during the period August, 1969 through
December, 1969. . . . . . . . . . . . . . .

Estimated monthly average daily nitrate-
nitrogen discharge at all sampling stations
during the period August, 1969 through
December, 1969. . . . . . . . . . . . . . .

vii

Page

25

30

37

40

43

45

50

72

85,

108

114

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I . INTRODUCTION

A. Need forZStudy

Stream water quality depreciation by excessive fertil-
ization, as evidenced by undesirable odors and floating
algal scums, is very noticeable in the Grand River water-
shed. However, river-borne pollutants only recently were
recognized as being responsible for major quality changes
in the receiving Great Lakes. For example, Lake Erie has
undergone important overall ecological transformations.
These ecological changes have been attributed to introduc-
tion of large quantities of specific pollutants, primarily
the micro-nutrients.

In view of the widely publicized Lake Erie problem and
established reasons for that problem, people can no longer
concern themselves with only local stream conditions. They
must acknowledge that they are an element of a larger system
in which the totality of small influences may result in
almost irreversible change. Thus, the principle problem
now becomes one of halting excessive flows of pollutional
materials into the Great Lakes before the remainder suffer

damage similar to that of Lake Erie.

Human populations in the Grand River watershed are
increasing rapidly, producing a corresponding increase in
amounts of sewage and related pollution. The six major
cities totalling approximately 400,000 people utilize
secondary sewage treatment, while the remaining 157 employ
only primary or while the remaining 15% discharging directly
to the river system employ only primary or equivalent treat—
ment. In addition, no effective procedure for total nutrient
extraction from waste water has yet been develOped. Thus,
the Grand River is experiencing, and will continue to
experience, accelerated eutrophication. Lake Michigan is
consequently undergoing continuous enrichment which may
result in drastic ecological changes in the future.

About half of Michigan's phosphorus contribution to
Lake Michigan appears to result from flow contributions by
the Grand River. Thus, the importance of the Grand River
system on the state of the lake is clear. This study con-
stituted a first effort in the detailed examination of the
sources, sinks and mechanisms of nutrient transport. In
this manner, it was possible to determine amounts of nutrient
pollution discharged by a specific city. It also illustrated’
variations in phosphorus and nitrogen concentrations in
receiving waters immediately downstream from each sewage
effluent. Finally, concentrations and stream flow rates
together formed a phosphorus and nitrogen nutrient budget

for the Grand River watershed.

Few studies of this nature have yet been attempted,

although Park, Webster and Reid (1970) conducted a somewhat

similar survey on the Columbia River. However, no similar

study has been attempted on the Grand River watershed.
The Red Cedar River has been extensively studied in the
1958, Peters, 1959, Grzenda, 1960, Kevern,

past (Brehmer,

1961, Vannote, 1961 and 1963, King, 1964, Jensen, 1966 and

1969 and Hardgrove, 1969) , but little data other than

seasonal changes in nutrient concentrations are applicable

to the present study.

B- Purmse anQLSIcope of Study

The purpose of this study was to develop an overall
description of nutrient levels, total input to the system,
bio logical uptake and total discharge into Lake Michigan
from the Grand River Basin.

There were five major objectives in this project:

1. To analyze relationships between sewage treatment

p:Lant discharge and receiving water quality. Chief para-
rueters studied were total phosphorus and nitrate-nitrogen.
SaJl'lples were collected above and below discharges of major

Se“rage treatment plants along the Grand River or in and

1jelow major tributaries .

2. Relationships outlined in the first objective, when

Q0It‘tibined with flow rates throughout the watershed, formed

comprehensive phosphorus and nitrogen nutrient budgets
for the watershed.

3. The third objective of this project was to develop
comparisons between overall sewage effluents and total
stream flows during yearly low—flow periods.

4. An attempt was made to establish a significant
correlation between land usage practices and water quality
in terms of the measured parameters. For this purpose,
the watershed was divided into its subwatersheds and corre-
lations made between the nutrients, phosphorus and nitrogen,
and land usages. Subwatersheds studied consisted of:

a) predominantly agricultural, b) predominantly forested,
and c) predominantly urbanized land.

5. The fifth objective was to inventory several quality
parameters in the Grand River watershed. Three of these
parameters consisted of sewage treatment plants, their
degrees of treatment and their approximate daily outputs.
Tabulations were made (Appendix H) of water quality para—
meters at the Grand River mouth. These were dissolved

oxygen, pH, alkalinity and water temperature.

II. REVIEW OF PREVIOUS WORK

A. General EutroPhigation Studies

Extensive research has been conducted on phosphorus
and nitrogen uptake and ecological changes resulting from
excess nutrients. Hasler (1947) defined eutrophication of
lakes as the intentional or unintentional nutrient enrich-
ment of water. Hasler also indicated that increases in
phosphorus and nitrogen and decreases in dissolved oxygen
are acceptable indices of eutrophication. He described
37 lakes of varying size which showed eutrophication as a
result of domestic sewage. Hasler concluded with the
statement, "The problem is especially serious because
there is no way known at present for reversing the process
of eutrophy."

Beeton (1967) described the Lake Michigan pollution
situation as quite dismal, since net flow-through and

addition of water is only 1,492 m3 sec-1

and most of the
major tributaries are seriously polluted. Despite the fact
that polluted streams and rivers represent a source of
inflow for lakes and oceans, comparatively few workers

have studied the transport of nutrients in flowing water.

Mackenthun (1965) indicated a lack of research in this area.

B. Biological Uptake of Phosphorus and Nitrogen

Mackenthun, Ingram and Porges (1964) described nuisance
algal blooms and nutrient budgets for several lakes. They
concluded that fixed nitrogen entering a lake or reservoir
is incorporated into the biomass as an element of protein.
When an organism dies or excretes wastes, nitrogen is lib—
erated, but some is lost in lake effluents, by diffusion of
volatile nitrogen compounds into the atmosphere, by denitri-
fication in the lake and by precipitation by formation of
permanent sediments. Phosphorus, also assimilated into the'
biomass, is liberated by death or excretion. It may settle
with sediment, seston or fecal pellets or it may be re-

leased at the mud-water interface.

C. Sources of Phosphorus and Nitrogen

Mackenthun, Ingram and Porges (1964) stated that, as a
result of several studies, basic nutrient sources for lakes
and reservoirs were: a) tributary streams carrying land
runoff and waste discharges, b) the interchange of bottom

sediments, and c) precipitation from the atmosphere.

1. Precipitatigg.

Precipitation from the atmosphere contains significant
amounts of phosphorus and nitrogen. Since water itself
from the atmosphere should be uncontaminated, phosphorus
concentrations probably originate from atmospheric particu—

late matter (keup, 1967). Nitrogen, being the major

component of our atmosphere, is easily absorbed by rain-
drOps and thus provide lakes with a constant nitrogen
source. The equilibrium concentration of diatomic nitrogen
in water at 20°C is approximately 14.8 mg per liter under

a normal atmosphere. This, then, represents a reasonable
source for blue—green algae and other nitrogen fixing plant
life. Other commonly occurring compounds of nitrogen have
even higher solubilities.

Hutchinson (1957) found phosphorus concentrations in
rainfall ranging from trace amounts to a "very improbable"
value of 49 ug liter-1. However, that high value appears
possible, since Weibel et al. (1966) found concentrations
as high as 80 ug liter"1 in a Cincinnati suburb. Great
variation in rainfall concentrations probably results from'
changes in composition and quantity of atmospheric particu-
late matter in the area (Keup, 1967). After several assump-'
tions, Weibel (1967) estimated the direct rainfall
contributions to Lake Erie as two percent of its total sug-

gested load.

2. Nutrients Dissolved in Soil Solutions

Nitrate-nitroqen, because it is soluble in soil solu-
tions, is subject to leaching (Biggar and Corey, 1967).
Biggar and Corey concluded that rain dissolves nitrate
quickly and carries it into the soil before the soil becomes
water-saturated and forces water runoff. Thus, soil per-

colates contain considerably more nitrate than do surface

runoff waters. McGauhey et a1. (1963) stated that percola-
tion through soil effects only partial nutrient removal

and that percolation does not significantly reduce nitrate
concentrations.

Phosphorus concentrations in surface runoff and soil
percolates are just the reverse of the nitrate system
(Biggar and Corey, 1967). Phosphorus tends to saturate the
"fixing" sites at the surface, which are in close contact
with surface runoff water. Although some phosphorus
percolates into the soil, it is quickly extracted from
water by fixation of soil particles. Therefore, most soil—
related phosphorus reaches streams and rivers via erosional
processes created by surface water runoff. Juday and Birge
(1931) and other authors (Anon., 1966) described average
groundwater sampled as being relatively low in phosphorus,
which directly supports Biggar and Corey's assertions.

The above theories and conclusions are not applicable
to frozen soils. If soils are frozen, as during spring
runoffs, much of all soluble nutrients at the soil surface
is washed into the waterways. This is especially true for
manures and chemical fertilizers applied to frozen fields.

Groundwater contains significant concentrations of all
nutrients. Even though phosphorus is very low in soil
percolates, Corey et a1. (1967) stated that groundwater
contributed 42 percent of all Wisconsin surface water nutri-

ent concentrations. Biggar and Corey (1967) concluded that

there is often incomplete mixing between resident ground-
water and replenishment water, however, resulting in

occasional nutrient "caps" over the groundwater.

3. Surface Water Runoff

Nutrient concentrations in surface water runoff are
dependent upon (Keup, 1967):

1. Quantity of nutrients present in soils,

2. Topography.
3. Vegetative cover,

4. Quantity and duration of runoff,

5. Land use, and

6. Pollution.
Surface runoff from a watershed follows a general pattern
(Biggar and Corey, 1967). Most plots of surface discharge
versus time indicate a peak and then recession to a base

flow.

a) Irrigated and Fertilized Lands

Drainage from irrigated and fertilized land usually
contains significant amounts of nutrients. Eck et a1.
(1957) found that phosphorus losses on a 20 percent slope
were about 2 kg hectare-lyear"1, while an eight percent
slope lost only about 0.5 kg hectare-lyear'l. He also
found that significant amounts of nitrogen were lost from
both fields.

Total nutrient concentrations from irrigation return

—.1

drains (Sylvester, 1961) averaged 0.2 mg liter of phos-

Phorus, While subsurface irrigation drains alone averaged

1

1.3 mg liter- of nitrogen. Recent work by Erickson and

10

Ellis (1970) on four different tile drain systems located
on research farm areas in southern Michigan indicates a
seasonal fluctuation in nitrate-nitrogen with averages
ranging from 1.5 to 5.0 mg liter-1.

Johnston, Ittihadieh, Daum and Pillsbury (1965) showed
that filtration into drainage-tile effluent contained large
percentages of appliedlnitrogen while phosphorus losses
were not significant. Althoughnitrogen losses noted by
Sylvester were similar to those found by Johnston et al.,
much less phosphorus was apparently lost from non-irrigated
soils. This result is closely supported by Biggar and
Corey's (1967) assertions concerning phosphorus uptake.

Likens et a1. (1970) kept fields bare by regular appli-
cation of herbicides to simulate plowed-field conditions.
They concluded that large proportions of nutrients are
{lost from bared earth. Midgely and Dunklee (1945) found

[IRES manured field runoffs contained on the average 3 mg
L::::r-1 of nitrogen and 1 mg liter-1 of phosphorus. Sawyer
7) found that agricultural drainage near Madison,

Wisconsin contributed approximately 2040 kg of nitrogen and

10 kg of phosphorus mile—zyear'1.I Runoff from plowed and/or

 

fertilized fields therefore contribute significantly to)

stream enrichment. /j

«’d

b) Forested Lands
Forested lands lose considerably less nutrients by

runoff than do agricultural lands (Table l). Putnam and

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Olson (1959) and (1960) found that forested land runoff
averaged about 25 kg of phosphorus mile-zyear'l. These
results were taken from rivers in Minnesota, Wisconsin and
Michigan which discharged into Lake Superior. The rivers
all averaged higher in phosphorus than did Lake Superior,
Which indicates a gradual natural enrichment of the lake.
However, the rivers averaged lower in nitrate-nitrogen than
did the lake.

Ball and Hooper (1963) found even less nutrient enrich-
ment in the Sturgeon River, Michigan, since phosphorus
averaged about 17 kg mile-ayear-l. Because the drainage
basin was only about one—fifteenth the average basin size
in Putnam and Olson's studies, however, it probably contained
a more uniform soil structure and therefore fewer natural
enrichment possibilities.

Sylvester (1961) found much greater nutrient losses
from forested watersheds in Washington. Three rivers
averaged about 175 kg of phosphorus mile-zyear'l. However,
mean concentrations were quite low, so that only heavy rain—

fall and resulting large discharges produced the extensive

nutrient losses.

c) urban Lands

Sylvester (1961) investigated nutrient concentrations
of urban drainage, but he only included drainage from major
highways, arterial and residential streets in his study.

Streets were sampled within 30 minutes to several hours

13

after a rainstorm had commenced. Results showed that runoff
immediately after rainstorms had commenced carried the
greatest amounts of nutrients, followed by a gradual return
to base flow. Street drainages averaged about 0.2 mg liter‘1~
of phosphorus and 0.5 mg liter'1 of nitrogen. If Sylvester
had included municipal wastes to get overall urban discharge,
however, his phosphorus values would have been much higher.

Weibel, Anderson and Woodward (1964) found that storm-
water runoff from a 10.9 hectare residential and light com—
mercial drainage basin contained 2.8 kg of phosphate

‘1 and 10 kg of nitrogen hectare-lyear’l.

hectare’lyear
Phosphates in storm runoff therefore comprised about nine
percent of calculated raw sanitary sewage phosphates, while
total nitrogen composed about 11 percent of the total

nitrogen in sewage.

4. Pollution

Stream enrichment by sewage effluent has been studied
extensively for many years. Keefer (1940), Rudolfs (1947)
and Buswell (1958) studied per capita nutrient contributions,
while Sawyer (1960) investigated nutrient concentrations in
raw sewage prior to extensive use of detergents. He found

'1 of phosphorus.

that raw sewage contained about 3 mg liter
Studies (Sawyer, 1947) also showed that biologically treated
sewage contributed approximately 2.73 kg of nitrogen and

0.55 kg of phosphorus per capita year‘l.

14

During the 1960's, detergents utilizing primarily
phosphate compounds as dispersing agents came into extensive
use in private homes. For example, Sherman (1966) stated
that phosphorus in detergents alone during 1965 amounted
to 1.45 kg person-lyear'l. With such a large increase in
.phosphorus discharge, our streams necessarily experience a

continuously increasing enrichment.

D. Biological Nutrient Extraction in Flowing Water

Researchers have found large proportions of nutrients
extracted from streams by biological activity (Davis and
Foster, 1958; Ball and Hooper, 1963 and Connell, 1965).
Although streams are capable of extensive nutrient extrac-
tion, however, they are not able to c0pe with the tremendous
amounts of nutrients thrust into their environment. For
example, a study conducted on the Sebasticook River in Maine
showed that a four-mile stretch of the river was capable of
assimilating only 29 percent of the phosphorus added as
municipal waste (Anon., 1966).

Biological assimilation was shown by Cummins (1966) to
occur in bottom plants rather than in phytoplankton. Ball
and HooPer (1963) also fixed major nutrient—extraction sites
as being in the periphyton. PhytOplankton are, therefore,
of minor importance in lotic environments, probably because
the constant turbulence affords little chance for develop—

ment of large plankton populations.

15

In addition to extraction by plants, nutrients are
removed by fixation to inorganic matter in water. Hepher
(1958) found that phosphorus was removed from water by
combination with soils. 'He further specified that soils
especially rich in calcium fixed the greatest quantities
of phosphorus. Hooper and Ball (1964) showed that phosphate
in a Michigan marl lake was probably fixed to colloidal marl
particles. Since Grzenda (1960) found striking differences
in nutrient extraction rates between summer and winter,
however, sorption to soils appears to play a minor role in
nutrient extractions. Brehmer (1958), Grzenda (1960) and
Kevern (1961) found large nutrient increases during March
and April, which were attributed to both melted snow runoff
and stream flushing of deposited sediments. Although the
increases should be due mainly to melted snow runoff, no
studies have yet shown just what proportion is actually due
to stream flushing.

E. The Importance ofANitrogen as aFunction
‘9; Biological Activity

Gerloff and Skoog (1957) indicated that, under normal
conditions, only nitrogen, phosphorus and iron required
consideration as possible limiting elements. Of the three,
nitrogen appeared the most critical indicator of biological
activity. Mackenthun, Ingram and Porges (1964) stated that
the biological productivity of a lake is a function of the

loading of inorganic nitrogen in the lake. In addition,

If

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16

Porges and Mackenthun (1963) found that nitrogen in waste
stabilization ponds fluctuated extensively between summer
and winter.

All of the above workers emphasized the importance of
nitrogen as a function of biological activity. Conversely,
Sawyer (1952) and (1961) maintained that productivity in
most aquatic areas is probably related largely to their
phosphorus budgets. Controversy exists as to which element
is the most critically important. However, it is reasonable
to assume that fluctuations in biological activity cause
corresponding fluctuations in both elements.

Korovin and Glyan'ko (1968) studied nitrogen uptake
in a hydroponic system. Their results indicated that nitro—
gen-form assimilation by plants was dependent upon tempera—
ture, since it shifted from primarily nitrate-nitrogen
uptake above 10°C to primarily ammonium—nitrogen below 10°C
Even though their results are significant only with a hydro—
ponic system, the temperature-dependency of nitrogen-form
assimilation may be true for natural systems as well.

F. Phosphorus and Nitrogen Nutrient Budgets
on Large-Scale Riverggystems

Few authors have studied nutrient budgets of large-
scale river systems. However, Park, Webster and Reid (1970)
studied the Columbia River watershed. Their study indicated
seasonal fluctuations in nutrient concentrations, with a

maxima during winter and a minima during summer. In addition,

17

they found that during May-August 1966, nutrients were
reduced 4 to 7 times through a 440 km section of the river.
During January-April 1966, both phosphate and nitrate were
within 10 percent of the total above the 440 km section.
However, although the workers also compared flow contribu—
tions of major tributaries with their nutrient concentra-
tions, they did not attempt a determination of contributions
by land usages and by sewage treatment plants.

MacCrimmon and Kelso (1970) attempted a "source-to-
mouth" investigation of nutrient changes in the Grand River,
Ont., watershed. However, although they sampled biweekly,
they only had five sampling sites for 3300 km2 of drainage
area. For this reason, the project did not adequately
describe nutrient fluctuations throughout the river length.

Many workers have developed nutrient budgets for given
sampling sites, such as Likens et a1. (1970), but they do
not analyze entire river lengths. Studies (e.g. Brehmer,
1958) have indicated ecological upsets resulting from
municipal waste discharges, but they did not discuss total

municipal impact on a whole river system.

III. FIELD STUDIES

A. Description of Study Area

1. General

The Grand River watershed is the major drainage basin
of Western Michigan. It is a warm-water system about 240
miles long, draining approximately 5,570 miles2 of predomi-
nantly agricultural land. The river originates in Hillsdale
County south of Jackson and empties into Lake Michigan at
Grand Haven, flowing through Jackson, Lansing and Grand
Rapids en route. Within the 13 counties, 29 cities, 43
villages and 158 townships that comprise the Grand River
watershed there resides approximately one million people.
Since 15 percent or more of any township or county's total
area lying within watershed boundaries warrants inclusion,
the list of counties and townships somewhat exaggerates the
basin size.

Seven major subwatersheds contribute to the Grand River
drainage. These include: the Rogue River, Thornapple River,
Flat River, Maple River, Looking Glass River, Red Cedar
River and Portage River. All have varying degrees of agri—
cultural urbanized and forested lands, but remain predomi-

nantly agricultural.

18

19

Three subwatersheds were selected and studied for
comparison of nutrient contributions by basins of different
land use practices. However, since all are predominantly
agricultural, basins were chosen by highest relative propor-
tions of urbanized and forested lands. Basins selected for
study were the Maple River (agricultural), Looking Glass
River (natural) and Red Cedar River (urbanized). The sub-
watersheds are grouped together, resulting from an attempt
to keep the basins within as similar a geological area as

possible.

2. Maple River Watershed

The Maple River basin contains about 974 milesz, which
includes about 82 percent cropland, 11 percent forest,
3 percent urbanized land, and about 4 percent "other" (U. S.
Dept. of Agriculture, unpublished data). Several small
towns are scattered throughout the basin, although most have
no sewage treatment plants and therefore no discharge. The
only towns with sewage treatment plants are St. Johns and
Fowler, totalling about 6,700 people and utilizing trickling
filter treatments. The basin houses about 12,000 people.
Since the high cropland percentage is combined with few
urban sewage effluents, the Maple River watershed was chosen

for the "agricultural" category of the comparison study.

3. Red Cedar River
The Red Cedar River contains about 57 percent cropland,

18 percent forest, 14 percent urbanized land, and about

20

11 percent "other". However, the upper section of the 473
miles2 watershed is predominantly agricultural with little
forested area. The stream passes through or near Fowlerville,
webberville, Williamston, Okemos, Michigan State University
and East Lansing before emptying into the Grand River in
Lansing. The Red Cedar River receives treated sewage from
about 74,000 people, with additions of industrial waste and
untreated sewage from urban residences along its course
(Kevern, 1961). Therefore, intense urbanization of the
basin's lower section was the basis for selection of the
Red Cedar watershed as the comparison study's "urbanized"

category.

4. Looking Glass River Watershed

The Looking Glass basin, about 296 milesz, includes
about 62 percent cropland, 22 percent forest, 4 percent
urbanized land, and about 10 percent "other". Much of the
"other" category is marshland and other non-forested, non—
tillable land types. Much cropland in this basin resides
in the soil bank and is untilled. Dewitt, a town of about
1,240 people, discharges primary-treated sewage, while the
whole watershed encompasses about 2,800 people. This basin,
although statistically agricultural, is therefore in actur'
ality a very natural watershed and is categorized as such
for the comparison study. Table 2 summarizes the land usage

and population comparisons between these watersheds.

21

Table 2. Land Type and Population Comparisons Between Three
Subwatersheds in the Grand River Basin (From U. S.
Dept. of Agriculture).

 

Rivers
Maple Red Cedar Looking Glass

 

Total Area (mi?) 974.3 473.4 296.4
Agricultural (miz) 795.0 268.1 182.7
Forest (mi’) 105.8 84.9 63.8
Urbanized land (miz) 31.2 68.3 12.3
”Other” (miz) 42.3 52.1 28.6
Population (total) 12,000 ~I90,000 2,800
Population (discharging 6,700 74,000 1,240

wastes through
sewage treatment
plants)

 

22

B. Spmpling;§iteg

Sampling sites (Table 3, Figure l) were selected so
that one sample was taken above a sewage treatment plant
outfall and one below the outfall, or else so that one was
taken in the major tributary and one in the Grand River
after confluence. In this manner it was possible to
approximately determine the extent of phosphorus and
nitrogen contribution by specific tributaries or sewage
treatment plants. Buck (unpublished) found variations
greater than 50 percent in a cross-section profile of the
Red Cedar River. Because of his results, all sampling
sites in the present study were continually sampled at the
same spot on a given bridge. Such consistent sampling spots
should theoretically have negated all but actual phosphorus

fluctuations.

C. Sampling Procedure

A routine water sample collection trip was conducted
every second weekend, for a year's duration beginning August
21, 1969 and ending August 1, 1970. Each sampling trip
lasted a total of approximately twelve hours and covered
about 440 miles. Because of the long time on the road, the
collection trip was sometimes extended to two days, but
efforts were made to collect all samples within a twenty-
four hour period. During each sample-collection trip a

total of thirty water samples were collected.

23

Table 3. Sampling Sites Along the Grand River, with Their
Sampling Number, Description, and Distance in
Miles from the River Mouth.

 

Number Miles Description

 

1 0 South Wall below Corps of Eng. Grand Haven
2 20 Eastmanville Bridge

3 25 Grand Valley, M-45 Bridge

4 34 Grandville, M—ll Bridge

5 55 U. S. 131 Bridge

6 62 U. S. 21 Bridge at Ada

7 62 Grand River Ave. in Ada (Thornapple River)
8 70 Railroad Bridge in Lowell (Flat River)

9 70 M-91 Bridge at Lowell

10 78 Bridge at Saranac

11 89 M-66 Bridge at Ionia

12 94 Bridge at Muir (Maple River)

13 96 Bridge at Lyons

14 107 Goodwin Road Bridge

15 112 Lost Bridge, Portland (Looking Glass River)
16 112 U. S. 16 Bridge at Portland

17 126 Charlotte Highway Bridge

18 135 State Road Bridge

19 145 Webster Road Bridge at Delta Mills

20 148 Waverly Road Bridge in Lansing

21 152 Seymour Ave. Bridge in Lansing

22 154 Cedar St. Bridge in Lansing (Red Cedar River)
23 155 Logan St. Bridge in Lansing

24 165 Bailey Road Bridge near Dimondale

25 174 Bunker Road Bridge

26 181 Smithville Road Bridge

27 192 Thompkins Road Bridge

28 205 Berry Road Bridge

29 212 Parnell Road Bridge near Jackson

30 220 Brooklyn Road Bridge south of Jackson

31 218 High St. Bridge

 

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Each sample was taken from a bridge in approximately
the main current of the river and below the water surface
to exclude floating debris. Two types of samplers were
used, a two liter Van Dorn bottle and a 1200 m1 Kemmerer
Sampler. However, during the winter, ice prevented use of
these samplers, and samples were taken by hand through the
ice. A 500 m1 polyethylene bottle was filled at each
sampling site and, upon return to East Lansing, immediately
refrigerated until analysis. Methods of analysis are
described in Appendix F. During warm summer months, samples
were stabilized with mercuric chloride at the sampling site.

These were again refrigerated upon return to East Lansing.

D. Weather Data

Since heavy rains would be so indicated in flow rates
per sampling date, only average temperatures and cloud-
cover indexes were collected. This data was all available
in monthly reports at the U. S. Weather Bureau in East
Lansing. Information from three weather stations in or near
the Grand River watershed area; Lansing, Grand Rapids and
Muskegon, was collected and averaged into weekly means for
each location. A Friedman non-parametric test for two-way
analysis of variance indicated no significant difference
between the three sites. The sites were subsequently averaged

into one set of data for the whole watershed.

27

E. Sewage Treatment Plants

All sewage treatment plants in the basin are listed
by the U. S. Department of Health, Education and Welfare.
Several treatment plants have been recently developed, but
they are all aerated lagoons which to date have not yet
discharged effluents (Appendix E). Treatment types listed
in the appendix have been updated to present, but p0pu1a-

tions served by individual plants are only estimates.

F. Land Usage Data

Percentages for each land use practice in the three
studied subwatersheds were developed from two week's
research by Soil Conservation Service employees of the
U. S. Department of Agriculture. Acreages per land usage
were not included in the description however, they are

shown in Table 2 and Appendix I.

G. Flow Rate;

All flow rates from August, 1969 to December, 1969
were obtained from the U. S. Geological Survey. At this
time, flow rates for January, 1970 through July, 1970
have not yet become available. These rates were estimated
by graphing flow data from 1963 to 1969, and then extrapo-

lating from these figures.

IV. DISCUSSION OF RESULTS

A. _§trate—Nitrogen
Nitrate-nitrogen concentrations in the Grand River
were characterized by several consistent zones with high
values on route from Jackson to Lake Michigan. Appendix A
lists all values obtained during the study by date and
location. South and upstream from Jackson, the Grand
River is a fairly clean warm-water stream, but addition of
Jackson sewage effluent during 1969 increased nitrate
concentrations to usually well over 2 mg liter-1 (Figure 2).
From Jackson until the river entered Greater Lansing,
averaged nitrate concentrations continued to decrease,
probably by biological uptake and some dilution. Lansing
industries, residential areas and sewage effluents, in
addition to Red Cedar River contributions, then sharply
increased nitrate concentrations. These concentrations
continued to increase in the river until just upstream from
Portland, and then gradually decreased until it reached Ada.
From Ada until Lake Michigan, the river again experienced
increasing nitrate concentrations. Increases, however, were

not nearly as large in concentration as those indicated

further upstream.

28

29

Figure 2. Average nitrate-nitrogen concentrations at
each sampling site (August, 1969 to August,

1970).

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31

Nitrate-nitrogen appeared to fluctuate seasonally in
correspondence with biological activity (Appendix B).
Although nitrate concentrations were always measurable, low
river velocities downstream from Ada and wyoming and
several upstream impoundments enabled macr0phytes to extract
large amounts of total nitrates during the growing season.
Through September and October, nitrate concentrations in
lovaelocity river sections increased gradually with a
gradual lowering of average weekly temperature (Table 4).
After November 1, nitrate concentrations increased rapidly
and average weekly temperatures decreased quickly. Although
this correlation is one of nitrate concentration with
temperature, it is indirectly one of nitrates with biological
activity. However, daily photoperiod is probably as im—
portant as temperature in determining biological activity,
and may have a considerable, although unknown, influence in
this correlation.

Nitrate fluctuates significantly with seasonal changes
in biological activity. Such close correlation is indica-
tive that it is somewhat critical as a limiting or almost-
limiting element in the Grand River drainage system.

Gerloff and Skoog (1957) found that nitrogen was the most
critical element for growth opriprocystis aeruginosa in
southern Wisconsin lakes. Through algal counts and nutrient
correlation, Mackenthun, Ingram and Porges (1964) found that

biological productivity is a function of the loading of

32

Table 4. Comparison of Nitrate-Nitrogen Concentrations at
Selected Sampling Sites, with Average Weekly
Temperatures in the Grand River Basin

m

Average of

 

 

 

Week Average Weekly Stations 1-6 Station 23
Temperature OF (mg liter-1) (mg liter-1)
August
1-7 70
8-14 71
15-21 73 0.13 0.10
22-28 72 0.14 0.11
29-31 79
§eptember
1-7 74
8-14 62 0.19 0.15
15—21 62
22—28 57 0.16 0.26
October
1-7 62
8-14 , 53 0.21 0.37
——————————————— h—————— ~10 0 C____————————————————————————————
15-21 47
22-28 39 0.67 0.77
29-31 39
November
1—7 42 0.65 0.68
8-14 38
15-21 32 0.83 0.71
22-28 32
December
1-7 29 0.95 0.90
8-14 32
15-21 26 0.82 0.71
22-28 16

29-31 26

 

33

inorganic nitrogen in lakes. These conclusions agree with
results from the present study. Allen (1955) concluded
that, due to a relatively unlimited phosphorus supply, the
most severely limiting element in raw sewage was nitrogen.
Since phosphorus concentrations in the Grand River are
relatively large, seasonal nitrate fluctuations in the
system appear to indicate excessive enrichment.

Several authors have verified the fact that nitrate
concentrations increase during winter months. For example,
Porges and Mackenthun (1963) concluded that nitrate removal
in waste stabilization ponds fell to as low as 6 percent
in winter and rose to as high as 80-90 percent in summer.
Table 4 indicates similar results from the present study.
Average nitrate values are shown for several low water-
velocity sampling sites (sites 1-6), while site 23-presents
a description of nitrate concentrations in an impoundment
in Lansing. Lackey and Sawyer (1945) also found that
nitrate concentrations increased with decreasing biological
activity during winter.

A further reason for fluctuating nitrate concentra-
tions was propounded by Korovin and Glyan'ko (1968) from
hydroponic studies. They found that ammonium and nitrate—
nitrogen form uptake was temperature-dependent, and that
plants appeared to absorb nitrate-nitrogen better at
temperatures above 10°C, while ammonium-nitrogen was

absorbed better at temperatures below 10°C. This temperature

34

division is marked on Table 4 and indicates a statistically
significant shift in nitrate concentration. The results
found by Korovin and Glyan'ko for a hydroponic system
therefore appear applicable to the Grand River drainage
system. Also implied in Table 4 is a gradual decrease in
biological activity through decreasing temperatures and
seasonal fluctuation in photoperiod.

Nitrate concentrations increased significantly during
March and April. This increase is probably a combination
of runoff from melting snow and spring rains with down-
stream flushing of silt and organic matter by the large
discharges. Nutrient surveys of the Red Cedar River water-
shed (Brehmer, 1958; Grzenda, 1960 and Kevern, 1961) have
found similar fluctuations, indicating that the increase is
normal for Spring discharges. The large increase in nitrate
concentration fluctuated similarly with phosphorus, except
that nitrates remained higher throughout the flood period.
These results are also similar to those found by Kevern
(1961) and Grzenda (1960).

Sampling sites 17 and 18, upstream from Portland con-
sistently had the highest nitrate concentrations of any
site on the Grand River downstream from Lansing. They thus
present something of an indeterminate, since no recognized
pollution source is known to discharge into that river
section. The city of Grand Ledge discharges about 0.3 MGD

of primary treated sewage upstream from site 18, however,

35

since Grand Ledge contributes only about 0.2 percent of the
total Grand River discharge, its nutrient contribution is
not a sufficiently accurate explanation of the large

nitrate increases.

B. Total Phosphorus

Averaged total phosphorus concentrations showed several
consistent peaks in the Grand River enroute to Lake Michigan
(Figure 3). Generally, all peak values of total phosphorus
coincided with those of nitrate concentrations. Appendix C
lists the results of all phosphorus determinations by
station and sampling date.

Phosphorus did not fluctuate significantly with changes
in temperature and season. Sawyer (1968) emphasized that
nutrient removal should relate primarily to phosphorus,
since it is most often limiting. His earlier work (Sawyer,
1947) indicates that algal blooms can be stimulated by
inorganic phosphorus concentrations in excess of 0.01 mg
liter-1. Total phosphorus concentrations at certain sites
along the river at times exceed 100 times that minimal
amount for nuisance algal blooms (Figure 3). The river
system therefore appears to require extensive nutrient con-
trols in order to curb cultural enrichment.

Sawyer (1947) indicated that urbanization is responsible
for a very large proportion of total phosphorus in rivers.
Brehmer (1958) verified this assertion with his study at

Williamston along the Red Cedar River. Since wastewater

36

Figure 3. Average total phosphorus concentrations at
each sampling site (August, 1969 to August

1970).

37

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own com 09 om. 9.. ON. 00. or om or. on o .
_L__+________e_____e__ooo

 

 

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38

treatment plants discharge at a relatively stable flow rate
throughout the year (Appendix E), little seasonal fluctua—
tion in the amount of phosphorus discharged is expected to
occur from changes in river discharge. If most of the
phosphorus was contributed by sewage effluents, increased
river discharge would serve only to dilute the concentration.
C. Nutrient Comparigon of Urban, Natural
and Agricultural Watersheds

Comparisons of nutrient concentrations in runoff from
watersheds reflecting principally EEEEE_£EEE,EE§3£.§EXE;I’
natural (Looking Glass River),_Endfiag:ifgltufglfl(Maple River)
land usages produced significantly different results.

- Runoff from the urbanized and agricultural watersheds
contained approximately equal concentrations of nitrate-
nitrogen through the annual cycle, while surface runoff
concentrations from the natural watershed were generally
lower (Figure 4). The appearance of high nitrate-nitrogen
values during the April-May period is coincident with the
high spring flow and results largely from the rapid appear-
ance of interstitial surface soil water in the stream
channel. Since the biological productivity in the stream
is still relatively low (ambient water temperature less than
10°C) these nitrate levels are not incorporated into the
stream biomass. The scouring action of these high flows
also destroys the existing periphyton crops which serve as
a principal trophic level for the extraction of nitrate

from the stream flow.

39

Figure 4. Comparison of nitrate-nitrogen concentrations
in three watersheds of different predominant

land usages.

Nos-N, mail as N

a
1
35" (N '-
3.0L 5'. j
I /Rea Cedar
E 1 (urban)
2.5- ': 4
20r- 53‘ E: ‘7"
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s-ao.9-27.Io-25. ll'22,|2°20.|'|6. 2'I3, 3'13. am, 5-8, 6-5 , 7-2. M

Calendar Date l969 - 70

41

Comparisons of total phosphorus (Figure 5) indicated
that urbanized watershed runoff consistently contained
greater than five times the phosphorus concentration of
either natural or agricultural land runoff. The linearly
decreasing trend in phosphorus levels in the Red Cedar River
at its confluence with the Grand River is related to the
City of East Lansing's wastewater treatment plant operation.
Over the period of study values of phosphorus content
recorded upstream of the plant usually ranged between 0.2
0.3 ml/l. The maximum difference recorded was approximately
18 times greater than values obtained from the other water-
sheds. Phosphorus levels in the agricultural and natural
watershed runoffs were not significantly different from each
other.

A land usage comparison in the Pacific Northwest
(Sylvester, 1961) indicated somewhat different results,
which are shown in Figure 6. Average annual total phos-
phorus concentrations showed those derived from urban areas
equivalent to those of agricultural land and greater than
forested land concentrations. Furthermore, annual nitrate—
nitrogen averages indicated that agricultural lands dis-
charged four to six times the urban concentrations, and 15
to 25 times the forested concentrations.

Sylvester's urban drainage study contained samples
taken only from highway and residential street drains,

anywhere from 30 minutes to several hours after a rain

42

Figure 5. Comparison of total phosphorus concentrations
in three watersheds of different predominant

land usages.

NOa-N, mq/l as N

43

 

2.00

 

 

 

 

 

 

 

 

 

 

TTTITWIIITIITII TTrTTI IITI
I.75- R
l.50"
7
/Red Cedar
) (urban)
LOO
0.75-
I
0.50
Looking Glass 9 fig
Maple _;_.'\ ,4:
0'25 (agricultural) (natural) '5‘ '1 \ p a‘. n
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8‘2l 9'l3 IO'II ”'8 I?!) l'3 l’30 2'28 3'30 4'25 5'22 6'22 7‘I9

30 9'27 IO'25 "‘22 IZ'ZO l'l6 2'l3 3‘l3 4'”

Calendar Date l969 - 70

5‘8 6'5 7'2

 

44

Figure 6. Comparison of mean nutrient differences
from different land usages (data from

Sylvester, 1961).

Concentration, mg /l

3.0

2.5

2.0

(.5

I.O

0.5

0.0

45

 

 

P = Total Phosphorus
N = Nitrate- nitrogen

 

 

IE...

Urban
street
drains

as EA.

Urban

street

drains
(median)

Runoff
from
forested
areas

 

 

Subsurface
irrigation
drains

 

 

EU

Surface
irrigation
drains

 

 

46

storm had commenced. His data did not include sewage
effluent, a major component of urbanized land discharge.
Since the Red Cedar River at times contained about 50 per-
cent sewage effluent, one would expect it to contain
greater amounts of phosphorus than did Sylvester's urban
samples.

The agricultural data in Sylvester's (1961) study
was derived from samples taken directly from irrigation
drains. These samples, being consistently closer to sites
of actual fertilization, would be expected to contain
higher nitrate values than those from receiving streams.

Natural lands used by Sylvester's comparison studies
were forests with some logging operations and no human
habitation. However, the streams also contained large
natural reservoirs which probably extracted large propor-
tions of nutrients by biological uptake. Sylvester's forest
drainage data may have been modified by the reservoirs and
lower-unimpounded in nutrient runoff than that from water-
sheds. The Looking Glass River watershed encompassed about
2,400 people and contained approximately 50 percent fallow
cropland. Because it is not entirely natural, its nutrient
drainage should be greater than drainage from an unculti-
vated watershed.

It must be emphasized that this comparison did not
produce generalized results. Although efforts were made to

select these study areas near each other to ensure uniform

47

soil structure, close uniformity could not be assured.
.However, slight differences between results from the present
study and results of Sylvester's study all were apparently
related to differences in watershed and sampling locations.
However, rational explanations for these releases can be
made if sufficiently detailed analyses on nutrient inputs,
storage and releases are available.

It therefore appears reasonable to justify an equivalence
between this study's urban and agricultural watersheds in
terms of nitrate levels and an equivalence between the
agricultural and natural-watersheds in terms of phosphorus
levels.

Finally, it appears that each watershed is somewhat
inimitable with respect to phosphorus and nitrogen releases
over an annual cycle.

D. Flow Contribution of Sewage Treatment
Plant Effluents to# Rivers at Low-
Discharge Periods

Average stream and river discharge rates (Appendix G)
varied greatly between seasonal high and low-water periods.
Sewage effluent rates varied little in comparison (Appendices
J and K) so that their discharges comprised different propor-
tions of total flow through the seasons. For example,
sewage effluents during August, 1969 contributed about 16
percent of the total Grand River discharge, while September,

1969 contributions were approximately 19 percent.

48

Sewage effluents comprised a larger proportion of total
flow in an urban watershed. For instance, the Red Cedar
River discharged about 55 percent as sewage effluent in
September (Figure 7). This percentage does not consider
contributions by small towns such as Webberville, private
industries or by residences along the river. It also does
to consider volume changes by stream loss through groundwater

replenishment.
E. Nutrient Budget

1. AnngglNutrient Budget by Watershed

To obtain reasonable approximations of total phos—
phorus and nitrogen inputs to the Grand River system, total
areas of each land usage were multiplied by the estimated
discharge from each classification. Table 5 summarizes
nutrient discharges per year per square mile for each land
usage.

The determination of total areas for different land
use practices in both the Grand River basin and its sub-
watersheds appear to be reasonable approximations. Areas
of various land usages per county were available from
Kimball (1969), and were reapportioned to tributary water—
sheds.

Estimated nutrient discharge rates per year per mile2

(Table 5) were multiplied by total area of miles2 of each

land classification for all basins. For example, the

Figure 7.

49

Proportions of flow rate in the Red Cedar

River due to sewage effluents.

is

C

l‘low,

Volurrlasrtrtc

Volumetric Flaw, cfs

60

50

40

30

20

IO

50

 

 

 

 

 

 

 

 

 

 

55.!
FL!
42.0
_1.
24.9 24.6
Aug. Sept. Aug. Sept.
I969 I969

River Flow Sewage Effluent
Discharge

 

 

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g 2 c2
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0.7 0.9
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Sept. I969

Sewage Effluent
Discharge

 

 

51

Table 5. Estimated Discharge Rates from Each Land-type in

Kg Mile‘zYear-1 and for Sewage Treatment Plants
in Mg Liter-1

 

 

 

Total Total

Land-type Phosphorus Nitrogen
Agricultural land A) 95 B) 2045
Urbanized Land C) 727 D) 2500
Forested Land E) 25 F) 897
"Other“ land uses ‘ G) 45 H) 1363
Sewage Treatment Plants

Primary 7 35

Secondary. 5 15

A)
B)
c)
D)
E)
F)
G)

H)

Sawyer (1947)

Sawyer (1947)

Weibel, Anderson and Woodward (1964)

Weibel, Anderson and Woodward (1964)

Averaged from Table l in Keup (1967)

Sylvester (1961)

Approximation relative to rates from agriculture and
forest

Approximation relative to rates from agriculture and
forest

 

52

Grand River Basin, from Appendix I, contains about 3102
miles2 of agriculture, 586 miles2 of urbanized land, 1113
miles2 of forest and 762 miles2 of "other“ land-types.
These totals, when added together, comprised most of the
total nutrient drainage into the Grand River system per
year. The remaining portion of the total is contributed
by sewage treatment plants, industries, private residences,
and the small portion of land draining directly into the
Grand River throughout its length.

Although sewage treatment plants in general do not
discharge appreciable amounts of nitrate-nitrogen, their
effluents contain large quantities of ammonia and organic
nitrogen. They also vary in their total nitrogen concen-
trations, but Sawyer (1952) gave a rough estimate of 15-35
mg liter'l. His limits then, for this study, became
averages of 15 mg liter"1 for secondary treatment, and 35
mg liter‘1 for primary treatment. Total phosphorus con-
centrations in sewage effluents are normally found at
present to be about 5 mg liter‘1 for secondary treatment
and 7 mg liter'1 for primary treatment.

River flow data are measured values for the months of
August through December, 1969. Because the Uhited States
Geological Survey did not have flow rates at this writing
for January through July, 1970, these rates were estimated
by graphing previous rates from years 1963 through 1969.

Values for 1970 were then extrapolated from curves drawn for

given sampling sites.

 

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53

Results from this study are shown in Table 6. The
data indicate that the overall nutrient discharge is a
unsteady-state system, since actual river discharges are
only a fraction of calculated inputs to the system. It
should be recognized that the mass discharges per land
classification were derived from studies on other river
basins. Calculated values can therefore only approximate
actual nutrient drainage into the river system. In addi-
tion, the actual discharge factors were derived from samples
taken biweekly. Thus, total nutrient discharge releases
could be quite different from derived estimates.

When values given in Table 6 are examined in view of
such approximations, estimated phosphorus discharges are
remarkably similar to actual discharge values. Nitrate-
nitrogen discharges are considerably less than calculated
values, but they still agree reasonably well. The Grand
River system therefore appears to discharge amounts of
nutrients per unit area of each land classification equiva-
lent to discharges from other areas of Michigan, Ohio, and

Wisconsin.

2. jglpw-through" Nutrignt Budget

The flow—through nutrient budget is a monthly average
nutrient discharge, given in kg day-1. However, at this
writing, flow rates were available only for months of

August through December, 1969. The yearly nutrient budget

54

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57

into Lake Michigan was calculated by extrapolating flow
rates for months of unavailable flow data. Similar averages
for upstream sites were not estimated due to larger flow
variations in smaller catchment areas.

Although the phosphorus budget should theoretically
increase throughout the length of the river, it decreased
consistently from Portland until just upstream from Grand
Rapids. Not only did this decrease occur in the summer, it
also occurred during November and December.

During August and September, sewage treatment plants
(Appendix K) discharged about three times the total amount
discharged into Lake Michigan. This is evidence of con-
siderable removal by soil*fixation and plant activity. In
December only did final discharge exceed total sewage treat-
ment discharge, indicating that plants had exerted a notice—
able effect during the growth period.

Total nitrogen discharges fluctuated in correspondence
with seasonal changes in biological activity (Appendix M).
August and September average discharges were minimal for
the five-month period. The October average final discharge
at Lake Michigan was about five times those of August and
September, showing a gradual increase in discharge with the
decrease in temperature. November and December final dis-
charges averaged about twelve times those of August and

September.

58

Although the nitrogen budget does not increase in the
summer beyond about 60 miIes from the river headwaters,
colder months produced expected increases. Much fluctua-
tion occurs even during November and December, but the
budget shows a gradual increase from source to mouth.

Nitrogen was continually utilized by plants, since the
final discharge in December was only one-half of the total
contributed by sewage treatment plants alone (Appendix J).
Even so, a considerable decrease in utilization was shown,
because the final discharge during August was only one-
twentieth the total contributed by sewage treatment plants.

Assuming that the river system is in a long term
"steady state" position with respect to nutrient discharge,
a very large nutrient load must be flushed downstream during
spring floods to compensate for such retention in the sys-

tem.

V . CON CLUS IONS

1. Nitrate-nitrogen concentrations appeared to fluctuate
significantly with changes in temperature and photo-

period.

2. A temperature-dependent shift in nitrogen-form uptake
by plants apparently takes place at approximately 10°C.
Above 10°C, nitrate-nitrogen is preferentially absorbed.
with a shift to ammonium—nitrogen as the ambient tempera-

ture is reduced to less than 10°C.

3. Total phosphorus did not appear to fluctuate signifi—
cantly with changes in biological activity. However,
certain sites in the river at times exceeded 100 times
the 0.01 mg liter”1 previously reported as the minimum
phosphorus concentration necessary to stimulate nuisance

algal blooms in lakes.

4. A study of nutrient concentrations in runoff from water—
sheds of predominantly urban, natural, or agricultural
land usages indicated significant differences:

a) The natural watershed discharged less nitrate-nitrogen
than did either the urbanized or the agricultural

watersheds.

59

60

b) Urbanized land discharge contained far greater quanti-
ties of total phosphorus than either natural or agri-

cultural land discharges.

c) Natural and agricultural lands did not discharge

significantly different quantities of total phosphorus.

The Grand River from August, 1969 to July, 1970 discharged
an estimated 1,034,000 kg of total phosphorus into Lake
Michigan. However, this amount was only 69 percent of

the calculated input from the overall watershed.

Sewage treatment effluents along the Grand River contrib—
uted amounts of total phosphorus equivalent to the total

discharge from tributary rivers.

Nitrate-nitrogen discharged into Lake Michigan totaled
3,995,821 kg for the year of August, 1969 to July, 1970.
This amount, however, was only 33 percent of the calcu—

lated input.

Tributary rivers contributed about 43 percent of the
total nitrate-nitrogen discharge. However, they contained

only 35 percent of the total calculated nitrate input.

Approximately 35 percent of the total nitrate-nitrogen
discharge was unaccounted for. It was suggested that
that prOportion might be due to action of nitrogen—fixing

algae.

LITERATURE CITED

LITERATURE CITED

Allen, M. B. 1955. General features of algae growth in
sewage oxidation ponds. California State Water Polu—
tion Control Board, Sacramento, California. Pub. No.
13, pp. 11-34.

Anon. 1966. Fertilization and algae in Lake Sabasticook,
Maine. Tech. Advisory and Investigations Activities
Federal Water Pollution Control Admin. Cincinnati,
Ohio. 124 pp.

Ball, R. C. and F. F. Hooper. 1963. Translocation of phos-
phorus in a trout stream ecosystem. In Radioecology
(Ed. by Schultz, V. and A. W. Klement, Jr.), pp. 217-
228.

Beeton, A. M. 1967. Changes in the environment and biota
of the Great Lakes. In Eutrophication: Causes,
Consequences, Correctives (Proceedings of*a Symposium)
National Academy of Sciences, washington, D. C., pp.
150-188.

Biggar, J. W. and R. B. Corey. 1967. Agricultural drainage
and eutrophication. In Eutrophication: Causes, Conse—
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404-446.

Brehmer, M. L. 1958. A study of nutrient accrual, uptake,
and regeneration as related to primary production in
a warm-water stream. Unpub. Doctor's thesis, Mich.
State Univ. Lib., 97 pp.

Buswell, A. M. 1958. The chemistry of water and sewage
treatment. The Chemical Catalog Co., New York.

Connell, C. H. 1965. Phosphates in Texas rivers and
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Research Council, Fort Worth, Texas.

Cooper, C. F. 1967. Nutrient output from managed forests.
In Eutrophication: Causes, Consequences, Correctives
(Proceedings of a Symposium) National Academy of Sciences.
Washington, D. C., pp. 446-464.

61

‘1
UV‘

 

 

 

Corey, R. B., A. D. Hasler, G. F. Lee, F. H. Schraufnagel
and T. L. Wirth. 1967. Excessive water fertilization.
In Proceedings of Conference/Pollution of Lake Michigan
and its tributary basin. Federal Water Pollution
Control Administration. 6:3050-3107.

Cummins, K. W. 1966. A review of stream ecology with
special emphasis on organism-substrate relationships.
In Oganism-Substrate Relationships in Streams. pp.
2-51. Spec. Publ. No. 4. Pymatuning Laboratory of
Ecology, Univ. of Pittsburg.

Davis, J. J. and R. F. Foster. 1958. Bioaccumulation of
radioisotopes through aquatic food chains. Ecology
39: 530-535.

Eck, P., M. L. Jackson, 0. E. Hayes, and C. E. Bay. 1957.
Runoff analysis as a measure of erosion losses and
potential discharge of minerals and organic matter
into lakes and streams. Summary Report, Lakes Investi-
gations, Univ. of Wisconsin, 13 pp.

Erickson, A. E. and Boyd G. Ellis. 1970. The Nutrient
Content of Drainage Water from Agricultural Land in
Michigan, Michigan Water Resources Commission.

Gerloff, G. C. and F. Skoog. 1957. Nitrogen as a limiting
factor for the growth of Microcystis seriginosa in
southern Wisconsin lakes. Ecology 38:556-561.

Grzenda, A. R. 1960. Primary production, energetics, and
nutrient utilization in a warm-water stream. Unpub.
Doctor's thesis, Michigan State Univ. Libr., 99 pp.

Hasler, A. D. 1947. Eutr0phication of Lakes by domestic
drinage. Ecology 28:383-395.

Hepher, B. 1958. On the dynamics of phosphorus added to
fishponds in Israel. Limnol. Oceanog. 3:84-100.

Hooper, F. F. and R. C. Ball. 1964. Responses of a marl
lake to fertilization. Trans. Amer. Fish. Soc.

Hutchinson, G. E. 1957. A treatise on limnology. Vol. 1.
geography, physics and chemistry. J. Wiley and Sons,
New York.

Juday, C. and F. A. Birge. 1931. A second report on the
phosphorus content of Wisconsin lake waters. Wis.
Acad. Sci. Arts Lett. 26:261-275.

63

Johnston, W. R., F. Ittihadieh, R. M. Daum and A. F. Pills-
bury. 1965. Nitrogen and phosphorus in drainage tile
effluent. Soil Sci. Soc. Amer. Proc. 29(3):287—289.

Keefer, C. E. 1940. Sewage treatment works (lst ed.).
McGraw-Hill Book Co., New York.

Keup, L. E. 1967. Phosphorus in flowing waters. Water
Research 2:373—386.

Kevern, N. R. 1961. The nutrient composition, dynamics,
and ecological significance of drift material in the
Red Cedar River. Unpubl. M. S. thesis, Mich. State
univ. Lib., 94 pp.

Kimball, W. J. and G. Bachman. 1969. County and district
land use patterns in Michigan. Dept. of Resource
Development, Coop. Exten. Service, Mich. State Univ.

Korovin, A. I. and A. K. Glyan'ko. 1968. Ammonium and
nitrate nitrogen uptake by plants as a function of
temperature in the root zone. Dokl. Akad. Nauk.
SSSR 180(6):l495-l496.

Lackey, J. B. and C. N. Sawyer. 1945. Plankton produc-
tivity of certain southeastern Wisconsin lakes as
related to fertilization. I. Surveys. Sewage Work
Journal 17(3):573-585.

Likens, G. F., F. H. Bormann, N. M. Johnston, D. W. Fisher
and R. S. Pierce. 1970. Effects of forest cutting
and herbicide treatment on nutrient budgets in the
Hubbard Brook Watershed-ecosystem. Ecological Mono-
graphs 40(1):23-47.

MacCrimmon, H. R. and J. R. M. Kelso. 1970. Seasonal
variation in selected nutrients of a river system.
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Mackenthun, K. M., W. M. Ingram and R. Porges. 1964.
Limnological aspects of recreational lakes. U. S.
Public Health Serv. Publ. No. 1167, 176 pp.

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Health Service, Div. Water Supply and Pollution Con-
trol, PHS Publ. No. 1305.

I):

‘0'

”-1

\V.

V?!

.,.~

.
ta
‘4

 

\l~

.,_‘

1

64

McGauhey, P. H., R. Eliassen, F. Rohlich, H. F. Ludwig
and E. A. Pearson. 1963. Comprehensive study of the
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through controlled waste dispoasl. Prepared for the
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Tahoe, Calif., 157 pp.

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losses from manure spread during the winter. Vermont
Agr. Exp. Sta. Bull. 523, 19 pp.

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and carbon dioxide in the Columbia River. Limnol. and
Oceanog. 15(1):70479.

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McGraw-Hill Book Co., New York.

Sawyer, C. N. and A. F. Ferullo. 1961. Nitrogen fixa—
tion in natural waters under controlled laboratory
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(Oct. 12).

65

Sylvester, R. O. 1961. Nutrient content of drainage water
from forested, urban and agricultural areas. In Algae
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Engr. Center, Cincinnati, Ohio. 162 pp.

Weibel, S. R. 1967. Urban drainage as a factor in
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National Academy of Sciences, Washington, D. C., pp.
383-404.

Weibel, S. R., R. J. Anderson and R. L. Woodward. 1964.
Urban land runoff as a factor in stream pollution.
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1075-1084.

APPENDICES

APPENDIX A

NITRATE-NITROGEN CONCENTRATIONS FOR EACH
SAMPLING SITE DURING THE PERIOD

8-21-69 THROUGH 8-1-70

66

67

Table A.--- Nitrate—nitrogen concentrations (mg/1) for each
sampling site.

 

 

 

Sampling Date of Collection

Site 8/21 8-30 9-13 9-27 10-11 10/25
1 0.13 0.13 0.17 0.17 0.24 0.56
2 0.18 0.22 0.19 0.15 0.68 0.76
3 0.15 0.18 0.18 0.14 0.23 0.70
4 0.12 0.15 0.08 0.27 0.74 0.49
5 0.10 0.07 0.13 0.09 0.21 0.59
6 0.07 0.11 0.35 0.32 0.11 0.72
7 0.07 0.10 0.12 0.25 0.24 0.43
8 0.16 0.11 0.11 0.18 0.21 0.41
9 0.09 0.11 0.12 0.17 0.38 _ 0.86
10 0.35 0.13 0.41 0.52 0.42 1.29
11 0.43 0.18 0.52 0.20 0.33 0.85
12 0.20 0.25 0.22 0.17 0.24 0.48
13 0.30 0.11 0.50 0.39 0.50 1.33
14 0.25 0.36 0.75 1.05 0.76 1.87
15 0.09 0.15“ 0.13 1.02 0.62 0.25
16 0.33 0.70 0.80 0.90 0.99 1.53
17 0.80 0.88 0.83 1.30 1.01 1.28
18 1.43 1.78 0.80 1.40 1.42 0.94
19 1.44 0.88 0.68 1.30 0.52 0.89
20 0.48 0.50 1.05 0.66 0.48 0.68
21 0.20 0.24 0.23 0.46 0.27 0.71
22 0.53 0.74 0.50 0.20 0.04 0.28
:23) 0.10 0.11 0.15 0.26 0.37 0.77
.24 0.71 0.40 0.70 1.03 0.58 0.55
25 0.63 0.68 1.14 0.80 0.62 0.74
26 0.61 1.00 1.00 1.30 0.95 0.54
27 0.95 1.60 1.90 1.78 1.40 0.82
28 1.63 1.35 1.44 1.43 0.86 1.33
29 2.30 2.80 3.60 3.40 2.86 2.32
30 0.12 0.12 0.13 0.12 0.06 0.12

continued

Table A-—continued

m

68

 

 

Sampling Date 9; Collection

Site 11-8 11-22 12-6 12—20 1-3 1—16
1 0.68 1.00 0.91 1.01 0.73 1.01
2 0.76 1.02 1.06 0.82 0.93 0.82
3 0.66 0.80 1.03 0.95 0.94 0.84
4 0.49 0.84 0.96 0.55 0.83 ----
5 0.72 0.79 0.92 0.98 0.80 0.99
6 0.59 0.52 0.81 0.62 0.79 1.01
7 0.54 0.51 0.55 0.71 0.73 0.72
8 0.49 0.48 0.39 0.70 0.66 0.81
9 0.83 0.95 1.06 1.12 1.12 1.20
10 1.30 1.47 1.47 1.69 1.23 1.64
11 0.96 1.02 1.56 1.43 1.46 1.25
12 0.33 1.13 1.50 0.93 0.92 1.05
13 1.75 1.15 1.67 1.71 1.41 1.53
14 1.15 1.24 2.07 1.27 2.27 1.92
15 0.25 0.28 0.47 0.82 0.63 0.72
16 1.67 1.73 2.28 1.25 1.91 1.60
17 2.19 1.51 2.54 1.51 1.44 2.19
18 2.81 1.52 1.70 1.95 1.57 1.29
19 1.54 0.86 1.32 0.70 0.95 1.84
20 2.15 0.84 1.13 0.70 0.77 0.75
21 0.80 0.98 1.12 0.72 0.56 0.75
22 0.29 0.91 1.08 0.32 0.84 0.69
23 0.68 0.71 0.90 0.71 ---- 0.50
24 0.89 0.86 1.13 1.05 0.50 0.59
25 0.29 0.74 1.15 1.14 0.48 0.48
26 0.63 0.71 1.38 0.93 0.44 0.43
27 0.79 0.89 1.06 1.38 —--- 0.39
28 1.36 0.84 1.84 1.03 0.27 0.29
29 2.20 0.72 1.52 2.49 0.59 0.32
30 0.19 0.10 0.18 0.16 0.19 0.29

continued

69

Table A—-continued

 

 

 

Sampling Date of Collection

Site 1-31 2-13 2—28 3-13 3-30 4-11
1 0.87 1.03 0.94 0.96 0.94 2.31
2 1.09 0.89 0.92 1.44 0.91 1.69
3 0.85 1.13 0.93 2.18 1.02 1.77
4 0.90 1.16 0.92 1.80 1.01 2.18
5 1.07 1.16 0.92 1.98 0.83 2.57
6 0.87 1.13 0.97 1.41 0.82 2.31
7 0.72 0.78 0.78 2.05 0.87 2.20
8 ---- 0.70 0.66 0.73 0.45 0.53
9 —--- 1.31 0.91 2.22 0.95 2.82
10 -—-— 1.71 1.24 1.47 0.85 2.91
11 ---— 1.39 1.45 1.48 0.71 3.17
12 ---— 1.06 1.27 1.42 0.70 3.72
13 ---- 1.83 1.79 1.83 0.94 3.20
14 ---— 1.41 1.76 1.83 1.28 3.82
15 -——— 0.70 0.69 1.75 0.88 2.07
16 —--- 2.05” 2.01 2.24 2.24 3.94
17 ---- 1.56 2.25 2.28 1.93 2.01
18 --—— 1.38 1.40 2.22 1.45 2.14
19 —-—— 0.89 1.21_ 1.49 1.12 2.01
20 --—- 0.79 1.00 1.37 0.87 1.85
21 ---— 0.80 0.91 1.42 0.83 2.25
22 1.05 1.06 1.18 1.73 1.59 3.47
23 0.52 0.56 0.56 0.87 0.64 1.71
24 0.93 0.56 0.97 0.95 0.52 2.14
25 0.60 0.57 0.76 0.82 0.71 1.34
26 0.38 0.46 0.53 0.67 0.57 1.39
27 0.82 0.48 0.65 0.94 0.57 1.64
28 0.67 0.43 0.66 1.18 0.70 1.38
29 0.44 0.74 0.58 0.35 0.15 0.38
30 0.31 0.33 0.28 0.37 0.32 0.19

continued

70

Table Aj—continued

 

 

 

m
Sampling Date of Collection
Site 5—8 5-22 6—5 6-22 7-2 7-19 8—1
1 0.83 1.05 1.59 1.25 1.32 0.24 0.15
2 0.92 1.25 1.38 1.30 1.51 0.55 0.13
3 0.82 1.27 1.28 1.11 1.25 0.25 0.19
4 0.75 1.25 1.27 1.14 1.09 0.54 0.11
5 0.73 1.36 3.09 0.98 0.85 0.54 0.11
6 0.72 0.94 0.78 0.75 0.82 0.23 0-11
7 0.51 0.85 0.74 0.66 0.70 0.05 0.13
8 0.08 0.22 0.37 0.14 0.16 0.04 0.06
9 0.50 1.50 1.64 1.37 1.13 0.30 0.78
1.27 1.58 1.64 1.65 1.60 1.96 0.75
0.77 1.00 1.75 0.57 0.67 0.87 0.50
0.35 0.50 1.77 0.80 0.66 0.68 0.49
1.16 1.58 1.36 1.13 1.02 1.67 0.41
0.99 1.67 1.37 1.28 0.83 1.60 0.41
0.41 0.55 1.55 0.45 0.56 0.26 1.02
1.27 2.31 1.57 1.33 1.40 1.50 0.75
1.47 2.04 1.72 1.59 1.39 1.26 0.82
1.26 1.37 1.24 1.24 1.32 1.11 1.00
0.86 1.01 0.72 0.70 0.85 0.82 0.61
0.73 0.82 0.50 0.50 0.45 0.58 0.50
0.58 0.77 0.53 0.53 0.48 0.50 0.41
1.35 1.21 0.63 0.99 0.81 0.66 2.00
0.44 0.55 0.56 0.45 0.42 0.25 0.25
0.55 0.57 0.59 0.48 0.44 0.69 0.79
0.42 0.54 0.58 0.53 0.48 0.80 0.71
0.30 0.73 0.47 0.31 0.39 0.71 0.57
0.39 0.79 0.37 0.36 0.34 0.80 0.70
0.40 0.72 0.25 0.39 0.30 0.71 0.22
0.19 0.26 0.15 0.14 0.11 1.52 1.05
0.16 0.14 0.11 0.17 0.16 0.17 0.12
0.20 0.25 0.05 0.12 0.12 0.26 0.12

 

APPENDIX B

NITRATE-NITROGEN CONCENTRATION FLUCTUATIONS AT
EACH SAMPLING SITE OVER THE PERIOD

OF RECORD

71

I ‘1 II II
I\a-II fiI-a)\vhhu,u 1. Ail-idlhu’u

 

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77

 

 

 

 

 

 

 

 

 

 

 

 

Calendar Date

APPENDIX C

TOTAL PHOSPHORUS CONCENTRATIONS FOR EACH
SAMPLING SITE DURING THE PERIOD

8—21-69 THROUGH 8-1-70

78

79

Table C«—-— Total phosphorus concentrations (mg/l) for each
sampling site.

 

 

 

Sampling Date of Collection
Site 8—21 8/30 9/13 9—27 10—11
1 0.27 0.28 0.33 0.24 0.35
2 0.46 0.47 0.40 0.44 0.37
3 0.45 0.45 0.56 0.47 0.45
4 0.40 0.45 0.38 0.32 0.33
5 0.21 0.15 0.21 0.16 0.20
6 0.14 0.21 0.27 0.08 0.08
7 0.07 0.12 0.11 0.08 0.07
8 0.15 0.15‘ 0.14 0.11 0.11
9 0.25 0.12 0.15 0.14 0.33
10 0.26 0.25 0.33 0.28 0.38
11 0.22 0.18 0.32 0.25 0.26
12 0.19 0.18 0.18 0.11 0.14
13 0.28 0.22 0.40 0.42 0.48
14 0.50 0.59 0.64 0.65 0.75
15 0.15 0.14 0.10 —.06 0.07
16 0.66 0.57 0.89 0.73 0.69
17 1.19 0.78 0.91 0.80 0.76
18 0.46 0.63 0.64 0.70 1.03
19 0.63 0.65 0.86 0.74 0.80
20 0.53 0.44 1.36 0.62 0.72
21’ 0.46 0.49 0.55 0.52 0.75
22 0.82 1.16 0.91 1.09 1.77
23 0.25 0.24 0.30 0.30 0.33
24 0.29 0.44 0.32 0.34 0.32
25 0.32 0.33 0.41 0.41 0.39
26 0.41 0.33 0.41 0.44 0.36
27 0.75 0.52 0.64 0.67 0.48
28 0.92 0.60 0.95 1.04 0.92
29 1.35 1.87 1.82 1.55 1.30
30 0.11 0.11 0.12 0.13 0.12

continued

80

Table C-—continued

 

 

 

 

Sampling Date of Collection

Site 10-25 11-8 .11—22 12-5 12-20
‘1 0.28 0.37 0.32 0.83 0.28
2 0.90 0.34 0.33 0.48 0.25
3 0.41 0.37 0.35 0.45 0.28
4 0.37 0.33 0.29 0.27 0.21
5 0.22 0.21 0.33 0.14 0.31
6 0.20 0.25' 0.25 0.11 0.08
7 0.08 0.10 0.08 0.06 0.10
8 0.08 0.13 0.10 0.10 0.10
9 0.42 0.35 0.39 0.17 0.28
10 0.43 0.42 0.49 0.34 0.35
11 0.31 0.31 0.28 0.26 0.27
12 0.09 0.12 0.13 0.10 0.05
13 0.41 0.41 0.40 0.45 0.42
14 0.63 0.59 0.68 1.39 0.91
15 0.06 0.08 0.10 0.11 0.07
16 0.61 0.66 0.53 0.50 0.62
17 0.56 0.63 0.60 0.95 0.61
18 0.52 0.79 0.80 0.67 0.67
19 0.84 0.66 0.49 0.70 0.76
20 0.76 0.59 0.40 0.47 0.39
21 0.57 0.48 0.42 0.52 0.75
22 1.09 0.95 0.77 1.09 0.93
23 0.29 0.33 0.36 0.26 0.28
24 0.34 0.35 0.35 0.36 0.32
25 0.30 0.29 0.25 0.36 0.25
26 0.38 0.35 0.25 0.40 0.27
27 0.53 0.36 0.51 0.56 0.50
28 0.60 0.62 0.61 0.86 0.49
29 1.16 0.94 0.88 0.86 0.85
30 0.06 0.07 0.05 0.05 0.08

continued

Table C-—continued

‘
—__fi

81

 

 

Sampling Date 9; Collection

Site 1—3 1—16 1—30 2-13 2-28
1 0.30 0.33 0.41 0.20 0.24
2 0.30 0.44 0.29 0.22 0.42
3 0.34 0.35 0.36 0.31 0.31
4 0.30 0.43 0.39 0.25 0.24
5 0.33 0.45‘ 0.30 0.18 0.30
6 0.13 0.47 0.14 0.14 0.11
7 0.11 0.08 0.11 0.20 0.07
8 0.07 0.27 —--- 0.15 0.13
9 0.30 0:50 ——-- 0.29 0.36
10 0.47 0.51 ---- 0.30 0.33
11 0.30 0.68 -——— 0.26 0.24
12 0.07 0.11 ——-— 0.10 0.19
13 0.37 0.70 -—-- 0.30 0.33
14 1.00 0.59 ———- 0.30 0.59
15 0.10 0.05 ---— 0.09 0.08
16 0.72 0.67 ---- 0.56 0.47
17 0.54 0.81 —--— 0.47 0.34
18 0.71 0.88 -—-— 0.39 0.49
19 0.80 0.67 —-—- 0.56 0.75
20 0.53 0.55 -——- 0.34 0.37
21 1.45 0.60 -—-- 0.26 0.26
22 0.55 0 75‘ 0.74 0.83 1.33
23 0.21 0.35 0.41 0.19 0.20
24 0.45 0.27 0.31 0.16 0.23
25 0.20 0.23 0.34 0.23 0.22
26 0.30 0.38 0.43 0.18 0.45
27 0.55 0.36 0.49 0.29 0.23
28 0.55 0.58 0.35 0.37 0.47
29 0.90 0.93 0.57 0.65 0.86
30 0.05 0.09 0.05 0.03 0.04

continued

Table C--continued

82

 

 

 

 

Sampling Date of Collection

Site 3-13 3-30 4-11 4-25 5—8
1 0.17 0.35 0.31 0.20 0.24
2 0.23 0.43 0.19 0.27 0.30
3 0.25 0.47 0.26 0.27 0.26
4 0.27 0.39 0.29 0.22 0.26
5 0.30 0.32 0.21 0.17 0.21
6 0.24 0.16 0.19 0.11 0g17
7 0.09 0.09 0.13 0.18 0.19
8 0.17 0.20 0.17 0.10 0.12
9 0.28 0.14 0.20 0.19 0.22
10 0.19 0.38 0.16 0.30 0.24
11 0.35 0.26 0.21 0.28 0.26
12 0.30 0.08 0.10 0.13 0.22
13 0.22 0.39 0.28 0.25 0.32
14 0.35 0.44 ' 0.33 0.36 0.34
15 0.06 0.32 0.14 0.18 0.15
16 0.25 0.56 0.35 0.56 0.30
17 0.26 0.41 0.41 0.28 0.43
18 0.34 0.38 0.37 0.18 0.37
19 0.30 0.63 0.27 0.26 0.38
20 0.26 0.71 0.21 0,37 0.34
21 0.15 0.28 0.22 0.35 0.34
22 0.43 0.93 0.24 0.66 0.76
23 0.19 0325 0.15 0.18 0.23
24 0.09 0.09 0.13 0.22 0.29
25 0.13 0.17 0.24 0.15 0.26
26 0.20 0.49 0.11 0.18 0.25
27 0.25 0.41 0.17 0.11 0.21
28 0.24 0.28 0.17 0.15 0.41
29 0.56 0.98 0.25 0.45 0.78
30 0.18 0.22 0.12 0.14 0.13

continued

83

Table C--continued

 

 

 

Sampling Date of Collection
Site 5—22 6-5 . 6-22 7-2 7—19 8-1

1 0.30 0.16 0.25 0.22 0.33 0.30
2 0.32 0.15 0.30 0.31 0.43 0.33
3 0.29 0.24 0.32 0.29 0.35 0.36
4 0.23 0.14 0.21 0.27 0.31 0.19
5 0.31 0.12 0.22 0.18 0.21 0.14
6 0.13 0.11 0.13 0.12 0.16 0.09
7 0.10 0.09 0.11 0.06 0.11 0.07
8 0.13 0.19 0.14 0.10 0.27 0.12
9 0.28 0.14 0.26 0.28 0.18 0.24
10 0.34 0.14 0.24 0.18 0.29 0.24
11 0.32 0.16 0.20 0.16 0.20 0.18
12 0.27 0.14 0.15 0.13 0.20 0.13
13 0.32 0.15 0.26 0.20 0.25 0.23
14 0.45 0.23 0.31 0.44 0.33 0.31
15 0.21 0.09 0.16 0.14 0.10 0.09
16 0.37 0.30 0.42 0.42 0.39 0.32
17 0.47 0.49 0.26 0.37 0.51 0.29
18 0.44 0.46 0.22 0.35 0.37 0.27
19 0.70 0.38 0.37 0.53 0.47 0.26
20 0.53 0.69 0.49 0.79 0.39 0.26
21 0.35 0.35 0.21 0.27 0.36 0.30
22 0.47 0.77 0.26 0.32 0.53 0.35
23 0.20 0.13 0.14 0.23 0.08 0.21
24 0.23 0.21 0.27 0.27 0.50 0.25
25 0.25 0.14 0.16 0.23 0.32 0.22
26 0.21 0.25 0.24 0.22 0.39 0.23
27 0.31 0.24 0.20 0.32 0.44 0.37
28 0.51 0.28 0.36 0.32 0.46 0.25
29 0.64 0.49 0.95 0.96 0.89 0.51
30 0.16 0.05 0.04 0.06 0.05 0.06

 

APPENDIX D

TOTAL PHOSPHORUS FLUCTUATIONS AT
EACH SAMPLING SITE OVER THE

PERIOD OF RECORD

84

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STATION l I

 

 

 

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Calendar Date

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Date

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s o N o J F M A M J J A
I969 I970
Calendar Date

t

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I970
Calendar Date

I969

E‘s-f. P‘l «I aknufl‘. Egan“,

APPENDIX E

WASTEWATER TREATMENT PLANT MONTHLY AVERAGE

DAILY FLOW RATES DURING CALENDAR YEAR 1969

92

93

 

 

 

 

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APPENDIX F

ANALYTICAL PROCEDURES FOR THE DETERMINATION OF

TOTAL PHOSPHORUS AND NITRATE-NITROGEN

94

,5 .

 

o-

95

LABORATORY ANALYSES OF TOTAL PHOSPHORUS

AND NITRATE-NITROGEN

a) Nitrate-Nitrogen

Either a ten—ml water sample or an aliquot diluted to
ten ml was placed in a large test tube and emersed in a
cool water bath. To each sample was then added 2 ml satu—
rated salt solution, 10 ml strong acid solution and 0.05 ml
brucine—sulfonilic acid.

The test tube rack was then placed in a hot water bath
of not less than 95C for exactly twenty minutes. After
return to room temperature, the samples were analyzed for
absorbance at 410 mu in a Beckman DK—2A spectrOphotometer.

‘1 of nitrate—nitrogen

Values obtained were read in ug sample
on an absorbance curve drawn from processed nitrate standards.
Processed standards were analyzed with every set of thirty

water samples.

b) Total Phosphorus

A 50-m1 water sample was placed in a boiling flask and
4 ml of 3.6 N sulfuric acid and 0.5 ml concentrated nitric
acid added to it. The sample was then digested On a hot
plate until sulfuric acid fumes evolved.

Samples were analyzed for total phosphorus according
to modifications by Kolter (unpublished) and D'Itri (unpub-

lished) of the method employed by Sugawara and Kanamori

96

(1961). After addition of distilled water and neutraliza-
tion, samples were placed in 500—ml separatory funnels

and the flasks rinsed with 4 ml concentrated hydrochloric
acid and distilled water. The rinses were placed in the
same separatory funnel. Fifteen ml N-butyl alcohol and 15
ml of 3:7 chloroform-butanol were added, the funnel then
shaken for five minutes and the organic layer drawn off
and discarded. Butanol-chloroform was again added and the
extraction process repeated. After these steps to remove
interference, 10 ml butanol-chloroform and 3 ml of 10 per—
cent ammonium molybdate were added and the funnel again
shaken for five minutes. The extracted bottom layer was
drawn off and read for absorbance at 310 mu in a Beckman
DK-ZA spectrophotometer. Values obtained were read in pg

—1

sample of total phosphorus on an absorbance curve drawn

from processed phosphorus standards.

APPENDIX G

STREAM FLOW ESTIMATES AT SAMPLING STATIONS
DURING THE PERIOD

8—21-69 THROUGH 12-20-69

97

J” 5| 30M

4......‘chu

JmQ-zpi 2‘

98

 

 

 

mm 00 00 00 00 00 00 00 00 00 00
00 00 000 00 00 00 00 00 00 00 00
m0 000 000 00 00 00 .00 00 00 00 00
000 000 000 000 000 000 00 000 000 000 00
000 000 000 000 000 000 000 000 000 000 00
N00 000 000 000 000 000 000 000 000 000 00
000 000 000 000 00m 00m 000 000 000 000 00
000 000 000 000 000 000 000 000 000 000 00
00 000 000 000 000 000 00 00 00 00 mm
000 000 000 000 000 000 00m 00m 000 000 00
000 000 000 000 000 000 000 000 000 ~00 00
000 000 000 000 000 000 000 00m 00m 000 00
000 000 000 000 000 000 000 000 000 000 00
000 000 000 000 000 000 000 000 000 000 00
000 000 000 000 000 000 000 000 000 000 00
00 00 000 00 00 00 00 00 00 00 00
000 000 0000 000 000 000 000 000 000 000 00
000 000 0000 -000 000 000 000 000 000 000 00
00 000 000 00 00 00 00 00 00 00 m0
000 000 0000 000 000 000 000 000 000 000 00
0000 0000 ,0000 0000 000 000 000 000 000 000 00
0000 0000 0000 0000 0000 000 000 000 000 0000 0
00m ~00 000 000 000 000 000 000 000 N00 0
000 000 000 000 000 000 000 000 00m 000 0
0000 0000 0000 0000 0000 0000 000 000 000 0000 0
0000 0000 0000 .0000 0000 0000 000 .000 000 0000 0
0000 00mm 0000 0000 0000 0000 0000 0000 0000 0000 0
0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0
000m 0000 0000 0000 0000 0000 0000 0000 0000 0000 m
0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0
00-00 0-00 mm-H0 0-00 00-00 - 00-00 00-0 00-0 00-0 00-0 0000000
-mwu .3000 00000 000020000 00000200

 

 

.0000 00000800 £000 How 0000 000 00000 00000 3000 sluyw 00909

.1vlnlkiul. . I! ‘2... 3.0%

APPENDIX H

DISSOLVED OXYGEN, ALKALINITY, pH AND
TEMPERATURE DATA AT THE MOUTH

OF THE GRAND RIVER

99

100

 

 

 

Total
Dissolved Alkalinity Tempera-

Date . Oxygen as CaC03 Sure

(1968) Time mg/l mg/l F pH
6-25 1200 11.8 183.0 64 .
7—2 1900 6.2 '150.0 66 .
7-11 1500 7.0 216.0 74 .
7-16 1730 9.8 275.0 81 .
7-24 1330 7.7 306.0 77 8.0
7-30 1000 12.5 261.0 72 8.2
8-7 1630 13.7 318.0 80 8.5
8-14 1230 11.8 230.0 75 8.
8-19 1715 9.6 235.0 79 8.
8-26 1730 6.6 226.0 72 7.9
9-5 1230 8.7 252.0 72 .2
9-10 1000 6.7 225.0 67 .0
9-17 1330 9.0 187.0 71 8.0
10-5 1220 9.7 188.0 59 8.
10-19 1120 8.9 221.0 62 8.2

 

APPENDIX I

LAND USE APPORTIONMENT IN THE

GRAND RIVER WATERSHED

101

. . w'fifilxw l. 1.1....
#3.” 3 . p I." jwkb.‘

102

 

 

2

 

Basin Designation Area, mi
Grand River Agriculture 3102
Urban 586
Forested 1113
"Other" 762
Total 5563
Red Cedar River Agriculture 268.1
Urban 68.3
Forested 84.9
"Other" 52.1
Total 473.4
Looking Glass River Agriculture 182.7
Urban 12.3
Forested 63.8
"Other" 28.6
Total 287.4
Maple River Agriculture 795.0
Urban 31.2
Forested 105.8
"Other" 42.3
Total 974.3
Flat River Agriculture 312.0
Urban 31.2
Forested 143.0
"Other" 93.0
Total 579.2
Thornapple River Agriculture 504.1
Urban 60.3
Forested 174.7
"Other" 110.4
Total 849.5

 

APPENDIX J

ESTIMATED MONTHLY AVERAGE TOTAL NITROGEN
DISCHARGE FROM WASTEWATER TREATMENT
PLANTS IN THE GRAND RIVER BASIN

DURING CALENDAR YEAR 1969

103

104

 

 

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0.00 c.0n m.~m 0.0m 0.HOH 0.Vma 0.0¢H 0.Hma ~.00H 0.00 0.Haa 0.0HH .039 drama
m.m~ m.mq m.mH m.ma m.ma 0.ma v.04 c.0N N.H~ 0.0H c.0a ¢.0L una3mo
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>m0\mna

d«mumflumfia hawmo ommuw>¢ Manage:

 

 

JPN... r $1; I.

APPENDIX K

ESTIMATED MONTHLY AVERAGE TOTAL PHOSPHORUS
DISCHARGE FROM WASTEWATER TREATMENT
PLANTS IN THE GRAND RIVER BASIN

DURING CALENDAR YEAR 1969

105

1C)6

 

 

 

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APPENDIX L

ESTIMATED MONTHLY AVERAGE DAILY TOTAL PHOSPHORUS
DISCHARGE AT ALL SAMPLING STATIONS DURING

THE PERIOD AUGUST, 1969 THROUGH DECEMBER, 1969

107

108

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APPENDIX M

ESTIMATED MONTHLY AVERAGE DAILY NITRATE-NITROGEN
DISCHARGE AT ALL SAMPLING STATIONS DURING

THE PERIOD AUGUST. 1969 THROUGH DECEMBER, 1969

113

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