° ' ' “ ~ m 3““ " “"" «w ‘.‘.'*‘>‘~ -“4. ow~«a—J~§a'a‘fi§mm“nxu~nuvws . -.- A*~1'.t‘f'.’f‘cl‘——Ta

THE REIATIONSHIR BETWEEN THE BORON 2'
CONCENTRATION OF EAST IANSING MUNICIPAL
WASTEWATER AND RETENTION TIME THROUGH THE ; ~
MICHIGAN STATE UNIVERSITY WATER QUALITY
MANAGEMENT PROJECT UNDER CONTINUOUS FLOW
CONDITIONS .

Thesis for the DegreeOf M. S,
MICHIGAN STATE UNIVERSITY
PAUL EOMUNO OURANCEAU [ '
1976

THE RELATIONSHIP BETWEEN THE BORON CONCENTRATION OF EAST

LANSING MUNICIPAL WASTEWATER AND RETENTION TIME THROUGH THE

MICHIGAN STATE UNIVERSITY WATER QUALITY MANAGEMENT PROJECT
UNDER CONTINUOUS FLOW CONDITIONS

By

Paul Edmund Duranceau

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

1976

 

 

I \
I “’ \

"I“,

A J I '

ABSTRACT
THE RELATIONSHIP BETWEEN THE BORON CONCENTRATION OF EAST
LANSING MUNICIPAL WASTEWATER AND RETENTION TIME THROUGH THE

MICHIGAN STATE UNIVERSITY WATER QUALITY MANAGEMENT PROJECT
UNDER CONTINUOUS FLOW CONDITIONS A

By

Paul E. Duranceau

In recent years concern has risen over the increase in
boron concentration of sewage effluents and natural waters.

While industries are contributing part of the boron, most of

the problem is due to increased use of perborates and borax

in home laundry and hand cleaning products. It has been re-

Ported that boron is not removed by conventional sewage
treatment plants and is discharged directly into receiving

What effects this may have on aquatic life such as
Also the

Waters .

fish, algae, and plants has not been determined.

future uses of the water for drinking. irrigation, and in-

duStry may be effected by increased boron levels.

The purpose of this study was to determine the fate of

b°I‘on as it moved through the Water Quality Management

Project. The project is concerned with biologically treat-

ing sewage effluent by passing it through a series of four

InaI‘m-made lakes. The boron concentration was monitored at

the sewage plant and each of the lakes. Two small streams

Q0unected with the project were checked periodically for
boron levels. Wells of varying depth were dug on the site

a11d the boron levels of these were monitored. Algae. sedi-

Inent, and sludge samples were taken and the boron content

 

Paul E. Duranceau
determined.

The results confirmed the fact that conventional sewage
plants do not remove boron. The concentration was constant
through the plant and the load in Kg/day did not change. The
amount of boron ranged frOm 0.1 to 0.5 mg/l and was found to
be dependent on the precipitation and flow rate. The sewage
sludge contained from 28 to 8# ppm boron. There was no evi-
dence of any significant absorption of boron onto the sludge.
No significant change in boron occurred through the lakes.
The B/bl ratio was calculated to correct for flucuations
caused by precipitation and evaporation. The B/Cl ratio of
a given water mass did not change as it passed from lake to
lake. The stream which received discharge from Lake 4 was
found to have increasing levels of boron. The other stream
was not contaminated by effluents and the concentration re-
mained constant. During times of heavy rainfall, both streams
.showed evidence of contamination from poultry waste depos-
ited in the area. The boron content of the shallow wells
did not change. The deepest wells had very little boron
initially but over time increased to the levels of the shal-
low wells. The algae were found to contain 129 ppm boron.
The uptake of boron was not significant enough to change the
B/Cl ratio of the water masses. The organic matter and total
boron content of the sediments increased over time. The
available boron of the sediments increased during the growing

season but reached a constant value belore the next season.

To my parents

ii

ACKNOWLEDGMENTS

I wish to thank Dr. Frank M. D'Itri for his guidance and
suggestions during my graduate work. I would like to thank
Dr. Niles Kevern and Dr. Clarence McNabb for serving on my
graduate committee. I thank fellow graduate students Thomas
Ecker and Robert Glandon for their many interesting discus-
sions and ideas. I am indebted to Thomas Young for the sedi-
ment samples used in this study. I also must thank all
those people I have worked with in the laboratory, eSpecially
Charles Annett and Mary Jane Banas.

I would like to express my graditude to the Institute of
Water Research and the Rockefeller Foundation (#71-3038) for
their support during my graduate career.

Finally, a special thanks goes to Dr. Darrell King. His
many helpful discussions and suggestions made this thesis

possible and all worthwhile.

iii

TABLE OF CONTENTS

INTRODUCTION 0 O O I O O O O O O O O O O O O O

Geochemistry of Boron . .
Boron in Natural Waters .
Uses of Boron Compounds .
Boron in Waste Waters . .
Effects of Boron on Sewage Systems .
Role of Boron for Man, Animals, and Fish
Role of Boron for Algae and Aquatic Plant
Boron in Land Plants . . . . . . . . . .
Determinations of Boron . . . . . . . .

oomooocoo

SITE DESCRIPTION . o . . . . . . . . . . . .

METHODS AND MATERIALS . o . . . . . . .

sampling Methods 0 c c c o c c c a
sewage Plant 0 c o c c c
Lakes and Artificial Stream .
Herron Creek and Felton Drain
wellSococcccocooc
Sediments..........
Algae c c c c I c
Sewage Sludge c c o c c c 0

Chemicals, Reagents, and Equipment

Analytical Procedures . . . . . .
Total Boron in Water . . . .
Total Boron in Sediments . .
Available Boron in Sediments
Total Boron in Algae . . . .
Total Boron in Sewage Sludge
Organic Matter 0 c c o c c o

Cthéiae O O O I O O O O O O

O O O O C I D O O O O O O O C C O O
O O O O Q C O O O O I O O O O O O O
O O O O O C O O O O O O O O O O O O
O O O I O O O O O O O O O Q C O O O 0

RESULTS 0 C O O O O O O O O O 0 O O O O O

Sewage Plant . . . . . . . . . . .
Lakes and Artificial Stream . . . . . . .
Herron Creek and Felton Creek . . . . . .

iv

Wells . . . . .
Sediments . . .
Algaeoo...
Sewage Sludge .

DISCUSSION AND CONCLUSIONS

Sewage Plant .

Lakes and Artificial Stream .

Herron Creek and Felton

Sediments . . .
Algae c c c c 0
Wells 0 c c o c
Sewage Sludge .
SUMMARY 0 c c c o 0
LITERATURE CITED . c

APPENDICES . . . . .

0
Drain
O O O
O O I
0 0 o
O O O
O O O
O O O
O O O

Page
5h
55
56

105

105
107
109
110
112
113
11“

115
117
123

LIST OF TABLES

Table Page
1 The Boron Content of Rocks, Soils, and
Sediments . . . . . . . . . . . . . . . . . . . 3
2 The Boron Concentration of Natural
Waters in mg/l . . . . . . . . . . . . . . . . 9
3 Boron Concentration of Waste Waters in mg/l . . 13
u Boron (mg/l) Limits for Land Plants . . . . . . 23
5 Boron (mg/l) Limits for Irrigation Waters . . . 23
Appendices

A1 Storet Code and Location of Sampling Points . . 123

A2 The Boron Concentration, Flow Rate, and Kg
of Boron for East Lansing Sewage . . . . . . . 125

A3 Monthly Means and Standard Deviations for
EaSt LanSing Sewage Plant Data 0 c c c c c o c 139

A4 Boron (mg/l), Chloride (mg/l), pH, and B/Cl
Ratio for Sample Point UNLlIo . . . . . . . . . 141

A5 Boron (mg/l), Chloride (mg/l), pH, and B/Cl
Ratio for Sample Point UNLlEO . . . . . . . . . 1M6

A6 Boron (mg/l), Chloride (mg/l), pH, and‘B/Cl
Ratio for Sample Point UNLZEO . . . . . . . . . 155

A7 Boron (mg/l). Chloride (mg/l), pH, and B/Cl
Ratio for sample POint UNL3EO c c o c c c c c c 164

A8 Boron (mg/l). Chloride (mg/l). PH, and B/Cl
Ratio for Sample Point UNLUEO . . . . . . . . . 173

A9 Monthly Means and Standard Deviations for
Data from Sample Point UNLlIO . . . . . . . . . 182

vi

Appendices

A10

A11

A12

A13

A14
A15

A16

A17
A18

A19

A20
A21
A22

A23

A2“

A25

A26

A27

Monthly Means and Standard Deviations for Data
from Sample Point UNLlEO . . . . . . . . . . . .

Monthly Means and Standard Deviations for Data
from Sample Point UNLZEO . . . . . . . . . . . .

Monthly Means and Standard Deviations for Data
from Sample Point UNLBEO. . . . . . . . . . .,.

Monthly Means and Standard Deviations for Data
from sample POint UNLLAEO o c c c c c c c c c c c

Boron (mg/l) Data for Sample Point UNASOB. . . .

Boron (mg/1) Data for Herron Creek and
Felton Drain Sampling Points . . . . . . . . . .

Summary of Data from Herron Creek, Felton
Drain, and Artificial Stream . . . . . . . . . .

The Boron Concentration (mg/l) of Wells in 1975.

Total Boron, Available Boron, and Organic
Matter Data for Lake 1 Sediments . . . . . . . .

Total Boron, Available Boron, and Organic
Matter Data for Lake 4 Sediments . . . . . . . .

Data for Two Algae Samples from Lake 2 . . . . .
Boron and Organic Matter Data for Sewage Sludge.

Boron (mg/l), pH, and B/Cl Ratio Means and
Deviations for Water Mass 1 . . . . . . . . . .

Boron (mg/l). pH, and B/Cl Ratio Means and
Deviations for Water Mass 2 . . . . . . . . . .

Boron (mg/l). pH, and B/Cl Ratio Means and
Deviations for Water Mass 3 . . . . . . . . . .

Boron (mg/1). PH. and B/Cl Ratio Means and
Deviations for Water Mass #. . . . . . . . . . .

Boron (mg/l), pH, and B/Cl Ratio Means and
Deviations for Water Mass 5 . . . . . . . . . .

Boron (ms/1). pH, and B/Cl Ratio Means and
Deviations for Water Mass 6 . . . . . . . . . .

vii

Page

183

IBM

185

186
187

189

193
195

197

198
199
199

200

200

201

201

202

202

Appendices Page
A28 Interface Thickness of Sediment Samples . . . . 203

B1 Volumes and Retention Times for Lakes . . . . . 204
B2 Statistical Equations Used in Data Analysis . . 1205
BB Relation of Total and Available . . . . . . . . 206

B4 Relation of Available Boron and Organic
Matter in Sediments . . . . . . . . . . . . . . 207

B5 Relation of Total Boron and Organic Matter
inSGdimentScocoon-0000000000208

Bo Relation of Total Boron in Sewage Sludge
mdorgmicmatter0.000000000000209

B7 Relation of Total Boron in Sewage Sludge
and Boron Concentration of Water . . . . . . . 21°

viii

Figure

onmfloxmku

H
H

12

13
14
15
16
17
18

LIST

The structure of

The structure of
Rubrocurcumin .

OF FIGURES

Boric Acid and Borate . .

Curcumin, Rosocyanin, and

Page

Location of Water Quality Management Project . .

Location of surface water sample points .

Location of ground water sample points . .

Location of Lake
Location of Lake

Daily Boron data
Daily Boron data

Daily Boron data

Monthly means for Boron of Raw, Primary,

Secondary Sewage

1 sediment sample points
4 sediment sample points

for Raw Sewage c c c o o
for Primary Effluent . .

for Secondary Effluent .

Flow rate, Precipitation, and Boron data

for Raw Sewage .
Flow rate and Kg
Daily Boron data
Daily Boron data
Daily Boron data
Daily Boron data

Daily Boron data

of Boron/day data for Raw
for Lake 1 inlet . . . .
for Lake 1 outlet . . . .
for Lake 2 outlet . . . .
for Lake 3 outlet . . . .
for Lake 4 outlet . . . .

ix

27
33
35

37

41
43

58
60
62

64

66
68
7O
72
74
76
78

Figure
19
20

21

22

23

24

25
26

27
28

29

3O
31

Daily Boron data for Artificial Stream .

Monthly means for Boron, Chloride,

for Lake 1 inlet . .

Monthly means for Boron,

for Lake 1 outlet .

Monthly means for Boron,

for Lake 2 outlet .

Monthly means for Boron,

for Lake 3 outlet .

Monthly means for Boron,

for Lake 4 outlet .
Boron and 8/01 means
Boron and B/Cl means
Boron and 8/01 means

Boron and B/Cl means

for
for
for

for

Chloride,

Chloride,

Chloride.

Chloride,

and

and

water mass 1

water mass 2

water mass 3

water mass 4

B/Cl

B/Cl

B/Cl

B/Cl

Total Boron vs. Available Boron for Lake

Sediments . . . . .

B/Cl

Page
. 80
. 82
. 84
. 86
. 88
. 90
. 92
. 94
. 96
. 98

. .100

Available Boron vs. Organic Matter for Sediments.102

Total Boron vs. Organic Matter for Sediments .

, 104

INTRODUCTION

Geochemistry of Boron

The geochemistry of boron is covered in the texts by
Rankama (1950), Goldschmidt (1958), and Krauskopf (1967).
Boron occurs in the earth's crust at about 3-10 ppm. It
exists in the form of borates, boric acid, borax, and boro-
silicates. The most important and abundant boron mineral
is Tourmaline which contains about 3 per cent boron. Watanabe
(1967) has stated that the form of boron in minerals is very
complex and not well known. He also gives a detailed anal-
ysis of the several processes involved in the formation of
the different boron minerals.

One process which occurred extensively in this country
was the evaporation of sea water containing boron. Nemodruk
and Karalova (1965) have shown that boron is highly volatile
in steam as boric acid. Therefore in the past, volcanic ac-
tivity has been reSponsible for the release of boron from
the crust. The annual contribution of boron to the atmo-
sphere by this process was determined to be 7.3 x 10“ metric
tons by Bartel (1972). This atmospheric boron became con-
centrated in the sea through precipitation. The boron con-
centration of the sea has become constant over time and was
reported to be between 4.0 and 4.5 ppm by Matthews (1974)

and Afghan et al. (1972). Then as the climate become more
1

2

arid and the sea water evaporated, boron compounds such as
borax (Na20(8203)2. 10 H20) precipitated and were concen-
trated in basins. Therefore we have large amounts of boron
in California and other arid regions of the world which have
had volcanic activity.

The boron content of rocks and soils is variable de-
pending on origin. The results of several rock and soil
analyses are given in Table 1. Igneous rocks contain less
than 30 ppm but Sedimentary rocks contain much higher a-
mounts. The boron concentration can be as great as 300 ppm
in shales. This is confirmed by the high concentrations of
boron in marine sediments. Since there is a relationship
between rock source and boron in soils. the amount will vary
from place to place. Mitchell (1955) reported the mean for
U.S. soils to be 30 ppm. The mean for soils derived from
Igneous rocks was 14 ppm and from Sedimentary rocks it was
40 ppm as given by Bingham (1973). Higher concentrations
can be found in soils derived from marine sediments or in
arid regions where naturally high boron levels occur.

The boron present in soils comes from the organic mat-
ter, natural occurring minerals, and that adsorbed on soil
particles in equilibrium with soil solution. While the boron
in the organic matter is small, as it is mineralized it be-
comes part of soil-water system and available to plants.
Since plants respond to boron in soil solution, conditions
changing the equilibrium between adsorbed and soluble boron

are important. Factors which can effect the equilibrium are

3

 

 

 

 

 

 

Table 1. The Boron Content of Rocks, Soils, and Sediments.
Source Boron(ppm) Reference
IGNEOUS ROCKS
Granite 3.0 Goldschmidt (1958)
15.0 Krauskopf (1967)
Basalts 1.5 Goldschmidt (1958)
5.0 Krauskopf (1967)
Liparite 30.0 Goldschmidt (1958)
SEDIMENTARY ROCKS
Bauxite 3.0 Rankama (1950)
Limestone 3.0 Rankama (1950)
Carbonates 20.0 Krauskopf (1967)
Sandstone 35.0 Krauskopf (1967)
Shales 300.0 Rankama (1950)
100.0 Krauskopf (1967)
SEDIMENTS
Marine 300.0 Goldschmidt (1958)
SOILS
Total 4.0-98.0 Mitchell (1955)
Available 0.01-3.20 Goldsdhmidt (1958)

 

11

concentration of boron, pH, and the number of adsorption sites.
Hatcher and Bower (1958) and Singh (1964) have studied
the effects of increasing concentration on boron adsorption
of soils. Both concluded that over low concentration ranges
the behavior could be described by a Langmuir isotherm.1 At
higher concentrations of boron the number of sites available
for adsorption became limited. Banerji et a1. (1969) found
that the amount of boron adsorbed from solution increased with
increasing pH. It was postulated that this was due to the
formation of borate ions which were adsorbed more readily.
The type and number of adsorptive sites is covered extensively
in the series of articles by Sims and Bingham (1967, 1968a,
and 1968b). The processes are very complex and involve sev-

eral different kinds of minerals.
figgon in Natupal Waters

The weathering of rocks and soils is the main source of
boron occurring naturally in fresh waters. Boron in rocks
and mineral is found combined with oxygen usually in the
form of boric oxide (8203). When in contact with water,
these minerals slowly release boron in the form of boric

acid. The following reaction is a good example:
1.. + -
Na20(8203)2.10H20 + H20-—, 2Na + 2B(OH)u + 2B(0H)3 + 3H20 (1)

Therefore the chemistry of boron in natural waters is essen-

tially the chemistry of boric acid.

5

Boric acid, B(0H)3, is a white. waxy solid which exists
as platelike crystals. It's solubility in water is 5.5 g /
100 g of solution at 25°C but increases with temperature to
28.7 g / 100 g of solution at 100°C. It is a very weak acid

and acts as a Lewis acid by accepting OH’:
13(0H)3 + H20 %B(OH); + H+ (2)

It has a dissociation constant of 5.8 x 10"8 (pK - 9.25) and
is essentially monomeric and undissociated in solution at
concentrations less than 0.1 M. At higher concentrations the
existance of polymeric species has been postulated and is
covered in the text by Adams (1964).

The structure of boric acid and the borate ion have been
determined by Muetterties (1967). By using spectroscopic
data it was confirmed that boric acid is planar and has ex-
tensive hydrogen bonding. The borate ion was found to be
tetrahedral and confirms the Lewis acid behavior of boric
acid. Both structures are presented in Figure 1.

As was shown in reaction (1) the solution of boron min-
erals results in the formation not only of boric acid but
borate ions as well. Therefore boric acid could act as a
buffer in natural waters. But at the low concentration it
is normally found. the buffer effect is negligible. It does
however become important in sea water where the concentra-
tion is much greater. A more detailed treatment of the chem-

istry of boron and it's compounds can be found in the texts

Figure 1. The structure of Boric Acid and Borate.

 

 

 

BORIC ACID

 

 

_ J

BORATE ION

8

by Meutterties (1967), Greenwood (1973), and Adams (1964).

The results of several boron analyses of natural waters
are presented in Table 2. Livingstone (1963) reported that
the mean value of boron for the lakes and rivers of the world
is 0.013 ppm. This value may be true for natural waters in
areas low in boron or waters uncontaminated by sewage or in-
dustrial wastes. The boron content of most rivers which flow
through urban areas are many times higher though. This is
confirmed by the data reported on American and English rivers
which flow through populated regions. Precipitation, although
usually very low in boron concentration, can contribute large
total amounts of boron over a period of time. It was post-
ulated by Odum and Parrish (1954) that the majority of boron
occurring in Florida waters may be of atmospheric origin. The
high concentrations of boron in the rain and snow of Japan
are due to the volcanic activity of that country. The fact
that the Great Salt Lake and Borax Lake are very high in boron
explains how the evaporation of saline waters can result in
boron deposits in arid regions. The increasing levels of
boron being found in natural waters is due to the industrial

and domestic use of boron compounds.

Uses of Boron Compounds

Boron compounds find wide use in many industries and the

pattern of use in 1968 was reviewed by MacMillan (1970). Boron

is used extensively in the manufacture of heat-resistant glass.

 

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11

About 34 per cent of the boron supply went into producing
glass and fiber-glass. The next highest demand for boron

(16 per cent) came from the use of borax and boric acid in
detergents and soaps. The mild alkalinity of these com-
pounds and germicidal prOperties also make them useful in
toothpaste, mouthwash, and eyewash preparations. Borax is
also used in fertilizers to supply boron poor soils. At

much higher concentrations it can be used as a herbicide.
Agriculture uses about 14 per cent of the demand for boron.
Another industry which uses 14 per cent of the boron supply
is the production of enamels. The enamel is used as a pro-
tective coating on many household and industrial appliances
(stoves, sinks, etc.). Boron compounds also make good flux-
ing materials and therefore find use in welding and solder-
ing metals. About 2 per cent is used in this manner. The
other 22 per cent of the demand is taken up by several smal-
ler industrial uses. It was found that the addition of small
amounts of boron to steels increased their hardness. Another
use for boron is in neutron absorber rods for atomic reactors.
This is due to the large absorption cross section of the boron
atom. Since borax is a good preservative it has found use

in dyeing leather and textiles, in cleansing hides and skins,
and in paints and plasters. Because boron compounds are non-
flammable they are used to fireproof wood and paper. Boron
compounds are also used as gasoline additives, in inks, and
as a fuel booster in jet and rocket engines. Although all

these industries do supply boron to our wastewaters, the

12

greatest amount comes from use of household detergents and
cleansers.

Boron compounds have found increased use in detergents
and soaps. In EurOpe the use of sodium perborate is quite‘
extensive. Davidsohn and Milwidsky (1967) reported that it
makes up about 8 to 17 per cent of the detergent. It acts
like a bleach by releasing hydrogen peroxide in solution:

NaB02.H202.3H20 é,- Na+ + Mon); + H202 + H20 (3)

Sodium perborate is not used in this country but other
boron containing compounds are. Borax is added as a builder
and gives a good buffering effect. Borax detergents have
bactericidal properties, easy solubility in water, and ex-
cellent water-softening properties which make them very use-
ful. The dissolution of borax is shown by:
Na20(13203)2.10H20f; 2Na+ + 2B(OH); + 21-3(OH)3 + 31120 (4)
The buffer is formed by the weak acid (boric) and it's salt
(sodium borate). The pH of a 0.1 M borax solution is 9.2
and therefore it finds use in hand cleaners because it will

not irritate the skin.
Boron in Waste Waters

The extensive use of boron compounds has resulted in an

increase in the load of this element to sewage plants. The

13

 

Anomav

 

 

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loamav one»: Hm.o onenaoom Henna .>mn: epepm nnem
Aommav nozsom om.o pcosamwm Henom esoufiu¢ .xflsoonm
moo.o pnosaMmm Hecflm
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H.m pnesammm Henflm
Amomav upommez H.m emezom gem oceamcm .emeso>opm
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monouowom souom meme: coopeooq
.H\me so muepez epmez Mo CowpeuPCoocoo Couom .m wanes

14

concentration of boron found in waste waters is given in
Table 3. The high concentration of boron in English sewage
effluents is due to the use of sodium perborate in detergents.
This is reflected in the high levels of boron found in English
natural waters reported earlier. The above normal concentra-
tions of boron reported from Luton and Newark are the result
of industrial wastes entering those sewage plants. In all
cases there is not a significnat difference between the con-
centration of boron in the raw sewage and final effluent.

This means that conventional waste treatment does not remove
boron and that all the boron which enters a sewage plant will
be discharged to receiving waters. This release of boron
could effect the aquatic environment and future uses of the
water. Therefore the needs, tolerances, and role of boron

for the biological community must be explored.
Effects of Boron on Sewage Systems

A few biological waste treatment systems have been stud-
ied relating to the effects of boron. Dawson and Jenkins
(1950) found that the oxygen uptake of activated sludge was
decreased by 20 per cent when 280 ppm was added as borate.
Hermann(1959) included boric acid in his study of the toxic
effects of various chemicals on the five day BOD test. He
tried to determine the ppm of a toxic substance which gave
50 per cent oxygen inhibition (T050). The TC50 given for

boric acid was greater than 1000 ppm (175 ppm as boron).

15

Doses of 500 and 1000 ppm of boric acid had little effect

on oxygen uptake. The small inhibition he got was probably
due more to lowered pH than to the boron. Banerji et al.
(1968) studied the effect of boron on the COD removal rate ,
and settling behavior of activated sludge. They reported
that the COD removal decreased exponentially with increased
boron levels. At 200 ppm boron there was a 90 per cent re-
duction in COD removal and as little as 10 ppm could cause

a 20 per cent reduction. In the settling test boron concen-
trations below 100 ppm had no effect on reduction of sus-
pended solids. Banerji et al. (1969) later looked at the
possibility of concentrating boron in sludge and also the
effects of boron on respiration. They found that at pH = 7.0
and a boron concentration of 1.0 ppm, that 0.025 mg of boron
was absorbed per gram of suldge. And at a boron concentra-
tion of 100 ppm the respiration was decreased 50 per cent.
But at 1.0 ppm there was actually an increase of about 1 per

cent.

figle of Boron for Man, AnimaISLAand Fish
Since man and animals use surface waters for drinking,
their needs for this element must be explored. The role of
boron in human nutrition has been reviewed by Underwood (1962)
and the World Health Organization (1973). Although boron
does exists in human tissue, no basic function has been found
in living cells which requires boron nor does it occur in

any enzymes. Forbes et al. (1954) determined the boron

16

content of several human tissues and found less than 1.0 ppm.
While the boron content of tissues is low, the levels in bones
are several times higher. Alexander et al. (1951) found the
average boron concentration in human bones to be 61.0 ppm.
This value has been questioned by Forbes et al. (1954) and

is probably too high. The levels in human bones is probably
about 5.0 ppm which is the value reported by the International
Commission on Radiological Protection (1964). Imbus et al.
(1963) reported the boron levels in blood and urine. The
concentration in the blood was less than 0.4 ppm but the urine
contained as much as 6.60 ppm with a mean of 0.90 ppm. The
high levels of boron found in the urine are due to the in-
take of the element in man's diet. Underwood (1962) reported
the daily intake by man to be between 10 and 20 mg, while

Zack and Lehmann (1965) determined the boron content of a
total daily diet to be from 3 to 5 mg. The amount taken in

is quickly absorbed by the body and excreted. This was

shown in the study by Kent and McCance (1941) in which 94

per cent of the boron administered to two subjects was re-
covered within a week.

Hove et al. (1939) reviewed the nutrition of other ani-
mals with respect to boron. It was found that the boron con-
tent of grazing animal's tissue was a little higher (per
unit body weight) than in humans. This is due to the high
intake of legumes which contain large amounts of boron (25 to
50 ppm). It was shown by Hove et al. (1939) that feeding

large amounts of boric acid to cows could increase the boron

17

content of their milk. The boron level in hen's eggs could
also be increased by addition of boric acid to the diet.

But in both cases the levels returned to normal given suf-
ficient time. And as with man the boron ingested is quickly
excreted by other animals as well. This was confirmed by
the study of Owen (1944) in which 100 per cent of the boron
added to a cow's diet was recovered.

Several studies have been done on test animals to deter-
mine toxic levels of boron. Pfeiffer et al. (1945) reported
the fatal level for humans to be between 5 and 6 grams for
infants and 15 to 20 grams for adults. This was based on
information from accidental poisoning from boron compounds.
They also reported that rats showed no effects from 175 ppm
boron in their drinking water. The World Health Organization
(1973) reported that amounts in excess of 100 mg/day can
produce toxic symptoms such as vomiting and nausea. But
little is known about repeated eXposure to lower levels.
Pfeiffer et al. (1945) determined that repeated doses could
result in accumulation of boron in the brain of test animals.
In extensive tests by Weir and Fisher (1972) it was found
that rats and dogs could tolerate boron concentration as
high as 350 ppm with no ill effects.

Sprague (1972) reported the results of several studies
concerning the effects of boron on fish. Rainbow trout and
Rudd were uneffected by a 30 minute exposure to 350 ppm of
boron. The safe limitations for bass and bluegill were set

at 30 ppm and 33 ppm respectively. A table is given concerning

18
the results of tests on minnows. The minimun lethal dose of
boric acid was 280 ppm as boron. The minimum for borax was

2000 ppm as boron.
Role of Boron_£or Algae and Aquatic Plants

Several authors have studied the effects of boron on
algae. They tried to determine if boron is required and at
what concentration. Also the concentration needed to bring
on toxic conditions was mentioned by some authors. The first
such study was carried out by Geigel (1935). He grew Chlorella
on media containing boron between 0.5 and 30 ppm. The best
growth was obtained between 5 and 10 ppm. With treatment up
to 140 ppm the Chlorella showed to ill effects. Eyster (1952
and 1958) showed a boron requirement for Nostoc muscorum. By
growing the algae on boron free media he obtained a reduction
in cell count and chlorosis. This could be corrected by add-
ing boron. He also determined that the optimum growth was at
0.1 ppm with concentrations greater than 1.0 ppm being toxic.
Cultures of Chlorella vulgaris were grown on boron free media
and then inoculated into media containing different amounts
of boron by McIlrath and Skok (1957 and 1958). They found
the optimum growth to be at 0.5 ppm but pointed out that
boron free cultures did not show chlorosis. Again work was
published concerning the boron requirement of Chlorella.
Bowen et al. (1965) used four different species which were

9. vannielii, Q. emersonii, Q. protothecoides, Q. vulgaris.

19

They measured the effects of adding different amounts of
boron to cultures already under ideal conditions. None of
the cultures were found to grow better at one boron concen-
tration than another and it became toxic above 50 ppm. A
study of boron requirements of fresh water diatoms was pub-
lished by Lewin (1966). Eight pennate species grown on media
with and without boron were tested. For all eight species a
requirement for boron could be shown. The culture with boron
contained 0.5 ppm. It was also shown that marine diatoms
require boron but at higher levels. This may be due to the
fact that sea water contains a higher concentration of boron.
Dear and Aronoff (1968) compared the growth rate of Scenedesggg
obliguus on media without boron and media with 0.1 ppm.

There was no difference between them and therefore they con-
cluded that boron was not required. The most extensive study
to date was carried out by Gerloff (1968). He not only looked
at green and blue-green algae but also determined the boron
content of the cells. He grew the algae on boron free media
and media containing 0.27 ppm boron. Of the three green
algae tested: Chlorella pyrenoidosa, Draparnaldia plumosa,
and Stigeoclonium 3233;; none showed a requirement for boron.
The cells of the green algae grown on boron free and boron
media contained 0.00 and 3.0 ppm boron respectively. But

when he tested the blue-green species; Calothrix parietina,

 

Nostoc muscorum. Anabaena cylindrica, and Microcystis

 

 

aeruginosa: he found that all showed significant increases

20

in growth on boron media. He also tested the blue-greens
with and without nitrate. In this case the algae grown on
boron media without nitrate gave the highest growth rate.
The Calothrix species was found to contain 225 ppm boron
when grown on nitrate free media with boron present. When
it was grown on nitrate media it was found to contain only
4.62 ppm. Boyd (1970) collected and analyzed for boron con-
tent thirteen genera of algae. He found values ranging from
3.4 ppm to 119.7 PPm with natural water concentrations of
0.1 ppm boron. Twelve of the species contained 11.0 ppm or
less of boron. This included both greens and blue-greens.
Two green species of gladophora and PithOphora contained
85.0 ppm and 65.0 ppm respectively. The highest boron con-
tent was in the Lyngbya species at 119.7 PPm.

A boron requirement for aquatic vascular plants has not
been shown. Gerloff (1973) determined that Elodea occiden-
tglig had a critical concentration of 1.3 ppm (range was
0.3 to 11.2 ppm) boron. He arrived at this critical concen-
tration by growing the plants first on boron free media and
then adding different concentrations of boron. After four
weeks the plants were harvested and the boron content in the
terminal tissues determined. The boron concentration assoc-
iated with the maximum yield was called the critical concen-
tration. Plant samples from two Wisconsin lakes were also
analyzed for boron. Lake #1 had a range of 12 to 25 ppm and

Lake #2 had a range of 8 to 14 ppm. These lakes were in non

21

agricultural areas and low in nutrients but no concentration
of boron was given. The boron content of thirty species of
submersed and floating leaved and fifteen species of rooted
emergent aquatic vascular plantsof Pennsylvania were deter-
mined by Adams et al. (1973). The plants were taken from
three separated watersheds of the state. The submersed and
floating leaved plants had a range of 20 to 60 ppm, and the
rooted emergents contained 10 to 70 ppm. The ranges are
similar but the mean boron level in the submersed and float-
ing plants was greater. The authors found no correlation
between boron content and land use (urban, agriculture, forest,
etc.). Again no data was given on the boron concentration
of the waters where the plants were collected. The twenty-
two species of plants found.i1a.pond in the Southeastern U.S.
by Boyd and Walley (1972) contained between 1.2 and 11.3 PPm
boron. The concentration of boron in the water was 0.005
ppm and the available boron of the sediments was less than
0.1 ppm. They also found the boron content of Typha latifglig
and Juncus effusus ranged from 5.2 to 100.0 ppm and 4.6 to
51.0 ppm respectively. The plants were taken from several
different sites and the majority had boron levels below 20.0
ppm. No correlation could be found between the available

boron of the sediments and amount found in the plant tissues.
Boron in Land Plants

While the role of boron is uncertain in aquatic plants,

the fact that boron is needed for land plants has been known

22

for several years. The exact role of boron in plants is un-
known, but several different biochemical activities have been
supported experimentally. The possible roles for boron in
plants was reviewed by Gauch and Dugger (1954) and Dugger
(1973). It has been postulated that it is important in:
Organic translocation, enzymatic reactions, plant growth re-
gulation, nucleic acid biosynthesis, carbohydrate metabolism,
cell wall and membrane metabolism. It has also been reported
to be involved in pollen germination. Eaton (1944) carried
out extensive quantitative tests on the effect of boron on
plant growth. He determined the boron concentration for

best growth and that needed for injury. The plants were
separated into three classes: Sensitive, Semi-tolerant, and
Tolerant. The sensitive group included mostly fruits, Semi-
tolerant Species were mainly vegetables and cereal grains,
while the Tolerant species included beets and peas and cotton.
The results are summarized in Table 4. The data was collected
using known boron concentrations with plants grown on sand
cultures. The amount of boron available in normal soils will
depend on several factors. These factors, which include
organic matter content and pH, were discussed above. By de.
termining the toxic concentration of soluble boron in soils,
Bingham (1973) was able to classify several plants. The
toxic concentrations were found by using the saturation-extract
method which measures the boron in the soil solution. The
three classes: Sensitive, Semi-tolerant, and tolerant are

very similar to those of Eaton (1944). The toxic ranges are

23

Table 4. Boron(mg/l) Limits for Land Plants.

 

 

Class Best Growth Causes Injury
Sensitive Trace to 1.0 1.0 to 5.0,
Semi-tolerant Trace to 15.0 1.0 to 25.0
Tolerant 5.0 to 10.0 5.0 to 25.0

 

Table 5. Boron(mg/l) Limits for Irrigation Waters.

 

 

Class Critical Boron
Sensitive 0.30 to 1.00
Semi-tolerant 1.00 to 2.00

Tolerant 2.00 to 4.00

 

24

0.5 to 1.0 ppm; 1.0 to 5.0 ppm; and 5.0 to 10.0 ppm respectively.
Most soils contain soluble boron well below toxic levels.
The exception is in arid regions where leaching of boron has
not occurred. But problems can arise in using irrigation
waters which are high in boron. This is true of irrigation
waters which have been contaminated by sewage or industrial
effluents. These contaminated waters can cause toxicity by
increasing the amount of available boron in the soil. This
was shown by the study of Mathur et al. (1964). Irrigation
by high boron waters resulted in increasing the available
boron in the soil. The boron levels were as much as 20 times
higher than in soils which were not irrigation. The effects
will depend on the plant species, soil type, pH, climate,
etc. Therefore safe concentration limits have been placed
on the quality of irrigation waters. Table 5 gives the
critical boron concentrations relating to crop species. The
classifications were taken from Bingham (1973) and are ident-
ical to the ones which were mentioned above. The current
EPA (1972) Water Quality Criteria gives new recommendations.
The maximum values are as follows: 0.75 PPm for Sensitive,

1.0 ppm for Semi-tolerant, and 2.0 ppm for Tolerant.
Determinations of Boron
Boron can be determined by several different methods.

The most common methods are the colorimetric use of carmine

or curcumin. The carmine method of Hatcher and Wilcox (1950)

25
is usually preferred because the ions found naturally in water
do not interfere. But since it is not sensitive below 1.0
ppm, time consuming concentration steps are needed. Curcumin
is sensitive down to 0.01 ppm and Navone (1961) has shown it
to be a highly reproducable method. The only problem with
the ourcumin method is the interference of hardness salts re-
ported by Bunton and Tait (1969). With hardness values
above 100 ppm as Cacoa, the final solution is turbid. This
is because of the insolubility of the hardness salts in
ethyl alcohol. This hardness interference can be overcome
by passing the sample through a strong cation exchange resin
before the determination.

Spicer and Strickland (1952a, 1958b) have studied the
chemistry of boron and curcumin compounds. They found the
structure of curcumin to be the one found in Figure 2. The
'enolic B-diketone group in the middle is significant and is
present in all common reagents for boron. When a mineral
acid such as H01 is added to a curcumin solution in the
presence of boric acid, a red colored compound is precip-
itated. The product is called Rosocyanin and it's struc-
ture is given in Figure 2. It was also found that when
oxalic acid is added a red-orange compound will form. The
ratio of molecules was 1:1:1 for oxalate, boron, and curcumin.
The compound is formed during evaporation of the solution
and is soluble in ethyl alcohol. The compound is called
.Rubrocurcumin and the structure is presented in Figure 2.

The last reaction is the basis for the method most commonly

26

Figure 2. The structure of Curcumin, Rosocyanin, and
Rubrocurcumin.

27

MeO OMe
HOOCH:CH°C(OH)!CH-CO'CH:CHM//\OH
C URCUMIN
MeO CH OMe
Cl: +Ho=.<}CH -.CH :08/ \\c-:CH CH _©OH
\ B‘O/
fi<§:>_. .2: \8 OMe
HO OH: CH CH CH—C>=OH+
" \\CH/
R0 SOCYAN I N

OwCOCOCF—H '9

”)Im (I

H
H
/C— (WP-F N/O-O\
Hc/ °\e CH
\c_o’ \o—c=o7' E”\o—
H
[\H H
/
my I )0...
/ /
H+ H

RUBROCURCUMIN

28

The boron method for water samples involves the removal
of hardness followed by an evaporation in an oxalic acid-
curcumin solution at 55°C. The precipitate formed is taken
up in ethyl alcohol and compared to a group of standards
prepared by the identical procedure. The absorbance of the
solutions is measured using a spectrOphotometer at 540 mu.

Dible et a1. (1954) have applied the curcumin method to
the determination of boron in soils and plants. The boron
in soils is broken down into total and available. The total
boron content of a soil is determined by first fusing the
soil with sodium carbonate (Na2003). The melt is dissolved
in sulfuric acid (H2804) and the resulting solution is
analyzed for boron. The available boron content of a soil
is the measure of the amount of boron which can be used by
plants. The method involves a boiling water extraction
procedure using a 2:1 soil:water ratio. After boiling five
minutes the solution is filtered and the liquid analyzed for
boron. Plant material is ashed before analysis to destroy
organic material. Alkaline conditions must be maintained to
insure no loss of boron. A strong base such as NaOH is
added if needed. ‘

Another type of boron analysis done on soils is the
soluble boron content. This is a measure of the boron con-
centration of the soil solution. It is always less than the
available boron and is a better index for determining toxic-
ity to plants. It is found by allowing a 1:1 soil:water
sample to equilibrate for 24 hours. The liquid is vacuumed

off and the boron concentration determined.

SITE DESCRIPTION

The site under study was the Water Quality Management
Project at Michigan State University. The project consist
of biologically treating waste water which has undergone
primary and secondary treatment at the East Lansing Sewage
Plant. The Secondary Effluent is pumped through a 21 inch
asbestos-concrete pipe a distance of 4.5 miles to a series
of four man-made lakes at the southern edge of the campus.

The four man-made lakes have a total surface area of
40 acres and a mean depth of 8 feet. The volume of each
lake under design Operating conditions is given in Appendix
Bl. The site also includes three one acre marshes and 320
acres of land of which 150 are equipped for spray irrigation.
The lakes are designed to receive up to 2 million gallons
of effluent per day. During the study period in 1975 the
average amount of effluent pumped to the site was 0.5 mil-
lion gallons per day. This resulted in retention times in
each lake of 28 to 43 days. The retention time for each
lake is given in Appendix B1.

The Secondary Effluent moves sequentially through the
four lakes by gravity flow. The movement of water is shown on

Figure 4. The waste water is biologically treated by the

aquatic plants and algae present in the lakes. Nutrients

29

30
are removed and concentrated in the biological material which
can then be harvested and used for food. The nutrients can
also be removed by spraying the water on crops, pastures, and
trees located on the irrigation site. The excess water leav-
ing Lake 4 is channelled by an artificial stream to Herron
Creek. Herron Creek then empties into the Red Cedar River
near the campus. Running through the irrigation site is
Felton Drain which receives runoff from rain water and ir-
rigation water.

An intensive chemical and biological monitoring program
was set up to check for possible contamination of the sur-
rounding area. This includes 30 different chemical parameters
and several bacteriological and viral tests. Samples are
taken daily from the Sewage Plant, Lakes, and Artificial
Stream. Two sample points are located along Herron Creek
before it enters the Red Cedar River. Six concrete weirs
were constructed in Felton Drain to control and measure flows
and these plus several other points along the drain are con-
stantly monitored. The location of the sampling points for
the surface waters on the study site are shown in Figure 4.

In order to check for possible ground water contamin-
ation, a series of wells of varying depth were dug on the
site. Forty-one drift wells, fourteen shallow rock wells,
and four deep rock wells are positioned throughout the area.
The location of the wells is given in Figure 5. The drift
wells are 40 to 60 feet deep, the shallow rock wells average

85 feet, and the deep rock wells average about 180 feet. All

31
the wells are four inches in diameter and are equipped with
submersible pumps for sampling.

All sampling points have been given a storet code number
for data storage in a computer. The storet code for the
sampling points used in this study along with a description
of the location are given in Appendix A1. All data reported

in this study is presented by use of these code numbers.

32

Figur
93
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ater Quality Ma
nagemen
t Pro'
JQCte

33

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34

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METHODS AND MATERIALS

Sampling Methods

Sewage Plant

Raw Sewage, Primary Effluent, and Secondary Effluent
samples were collected on weekdays during 1975 from the East
Lansing Sewage Treatment Plant. The samples represented
composites taken during the proceeding day over a twenty
four hour period. The samples were stored in polyethylene

bottles and analyzed as soon as possible.

Lakes and Artificial Stream

Twenty four hour composite samples of the effluent from
each lake were taken weekdays between April and November of
1975. A composite of the influent to Lake 1 was collected
each weekday from July until November. Automatic samplers
were used and the samples were collected at approximately

the same time each day. The samplers were left operating

(D

C).

over the week n and therefore Monday's samples were com-
posites covering three days. The samples were stored in
polyethylene bottles and were analyzed as soon as possible.
('1 ~ ‘ 7 ' I r-

lne same procedures were used to collect a comp031te Sample
of the Artificial Stream each weekday. These samples were
taken only during times when water was being discharged

from Lake 4.

39

Herron Creek and Felton Drain

Periodic grab samples were taken from the two Herron
Creek sampling stations and the six Felton Drain weirs.
Herron Creek samples were taken only at times when water
was flowing. The Felton Drain samples were collected Only
when water was flowing over the weirs. The water samples
were stored in polyethylene bottles and were analyzed as

time permitted.

Wells

 

Water samples from the Shallow Rock, Deep Rock, and
Drift Wells were collected at various times during the study
period. Some of the wells were not operating and could not
be sampled. Many of the Drift wells were contaminated with
sand and gravel and the samples had to be settled for sev-
eral days before analysis. The samples were stored in poly-

ethylene bottles and analyzed as time permitted.

Sediments

Sediment samples representing the bed material in Lakes
1 and 4 were collected in 1973. The samples were taken
before the lakes were initially filled with water and the
sampling points are given in Figures 6 and 7. Then during
the Spring and Fall of 1975 core samples were taken from
the same two lakes. The points from which the cores were
taken are the same as in Figures 6 and 7. The coring tubes

were one and one quarter inches in diameter and the whole

#0

Figure 6. Location of Lake 1 sediment sample points.

1&1

290'

 

 

42

Figure 7. Location of Lake 4 sediment sample points.

W.

"I.

9.

:1.

V.

143

 

an

core was frozen intact immediately after sampling. At a
later date the cores were thawed and the interface separated
from the underlying material by sight. The thickness of the
interface material is given in Appendix A28 for each sedi-
ment. The sediment was dried in the oven at 100°C for sev-
eral days. The dried material was ground and passed through
a #35 screen (500 microns). The dried sediments were stored

in glass vials before analysis.

Algae

Two grab samples of algae were taken from Lake 2 during

July of 1975. Both samples were identified as Cladophora

 

species. All foreign material was removed from the samples
and they were dried at 100°C for several hours. The dry
algal material was ground and stored in glass vials prior

to analysis.

Sewage Sludge

Ten samples of sewage sludge were collected periodically
from the East Lansing Sewage Plant during February and March
of 1976. The sludge was collected as a slurry just prior
to entering the vacuum drum filters. Enough 1.0 fl NaOH
solution was added to bring the pH to 12 immediately after
sampling. The alkaline slurry was stored in glass vials and

analyzed as soon as possible.

45

Chemicals. Reagents, and Equipment

Anhydrous Sodium Carbonate (Na2C03)
Sodium hydroxide Solution (1.0 fl NaOH)
Sufuric Acid Sglgtion (h.0 3 H280“)

Ethanol (95% CH 0H)

3CH2
Qgrcumin Reagent

To prepare the reagent 0.100 gram of Curcumin (Eastman
#1179) and 12.5 grams of oxalic acid were dissolved in about
150 ml of 95% ethanol in a 250 ml volumetric flask. Then
10.5 ml of concentrated HCl was added and mixed, then the
flask was filled to the mark with 95% ethanol. This reagent
was then stored in polyethylene container in the refrigerator.
Stock Boron Solutigg

Dissolve 0.5716 gram boric acid (anhydrous H3B03) in de-
ionized water in a 1000 ml volumetric flask. Then dilute to
the mark. 1 ml = 0.1 mg B. The stock was stored in a poly-
ethylene container and refrigerated.
Stgpdard Boron Solution

Dilute 10 ml of stock boron solution to 1000 ml in a
1 liter volumetric flask with deionized water. ‘1 ml = 1.0
ug of boron.
Platinum Crucibles
Whatman Filter Pape;#u
Ion Exchange Column

The column was prepared using a glass column of 2 cm

diameter and 25 cm in length. At the bottom of the column

46

was a ground glass stOpcock used to control the flow rate.
Glass wool was placed in the bottom of the column and then
the volume of needed resin (15 ml) determined using water.
The resin used was DOWEX 50w-xa with ionic form H+. The
resin was stirred with deionized water in a beaker and then
added to the column. A small amount of water was in the
column to help with the transfer. After the right amount
of resin was added, the column was backwashed to remove any
air bubbles. After the resin has settled the water level
was lowered to just above the top of the resin. In order
to insure the resin was in ionic form H+, 50 ml of 1+5 HCl
was passed through the column. The column was now ready

for use.

Analytical Procedures

Total Boron in Water

A 25 ml sample to be tested is pipetted onto the ion
exchange column. Caution should be used not to disturb the
resin too much. The stapcock is Opened and the sample allowed
to move through the column at rate of 2 drops/sec into a 50
ml volumetric flask. When the liquid level nears the tap of
the column then it is washed with a small amount of deionized
water. CAUTION: never let the liquid level fall below the
resin because this will trap air and cause uneven flow rates
and poor ion exchange efficiency. Water is continued to be

added in small amounts until the flask is filled to the mark.

47

The flask is mixed and a 2 ml sample is pipetted into
a porcelain dish. The same size dish must be used for all
samples. Then # ml of the curcumin reagent is added, and
the dishes placed in a constant temperature bath at 55 t 2°C.
The liquid is evaporated to complete dryness (1 hour) and
then 15 minutes more. It is important that all the samples
are removed at the same time. The residue is dissolved in
10 ml of 95% ethanol and then washed into a 25 ml volumetric
flask and filled to the mark using 95% ethanol. Make sure
all the red residue is dissolved before adding to volumetric.

Various volumes of the standard boron solution (0.0, 0.2,
0.4, 0.6, 0.8, 1.0 ml) are added to the porcelain dishes and
diluted to 2 ml with deionized water. Then 0 ml curcumin is
added and the procedure continued the same as for the unknown
samples.

All the solutions are now read on the DK-Z Spectrophoto-
meter for the absorbance using the blank as the reference
and a wavelength of 540 mu. A standard curve is drawn using
the standard solutions and the concentration of the unknowns
determined.
Total Boron in Sediments

A 0.5 gram sample of sediment is placed in a Platinum
crucible and 3 grams of anhydrous sodium carbonate (NaZCOB)
is added. A Platinum cover is placed on tOp and the crucible
contents are fused using a Meker burner. The crucible is

heated an additional 5 minutes and then removed. The contents

of the crucible are gently swirled to give a thin coating on

48

the sides. After the Platinum crucible has cooled, it is
placed into a 250 ml polyethylene beaker in which the bottom
is filled with water. A 4.0 3 solution of sulfuric acid is
added slowly. CAUTION: the reaction is vigorous and the acid
must not be added too fast. Small volumes of the acid are
continued to be added until the crucible is full. The beaker
is covered with a watch glass and set aside for several hours
until the reaction is complete.

The contents of the crucible are poured into the beaker
and the crucible is washed several times with deionized
water. Because the solution contains a precipitate it is
filtered through #U Whatman paper into a 100 ml polyethylene
volumetric flask. The beaker and precipitate are washed
with deionized water until a 100 ml sample is obtained. A
1 ml sample taken and the curcumin procedure for water samples
is performed. The final solution is cloudy and must be fil-
tered through #4 Whatman filter paper before reading the ab-
sorbance.

The above procedure is also carried out on a blank
using Na2C03 alone. The other standards are prepared the
same way as given under the water sample method.

Available Boron in Sediments

flgingoron-free glass and polyethylene must be used
throughout this procedure.

Depending on the amount of sediment sample, a 5.0 or
10.0 gram sample is placed into a 300 ml Erlenmeyer flask.

Then 10 or 20 ml of deionized water is added to obtain a

49
2:1 waterzsediment ratio for the extraction step. The flask
is connected to a condenser and using a hot plate the con-
tents are brought to boiling. The mixture is allowed to re-
flux for 5 minutes and then the hot plate is removed. EQTE:
It is important that all samples are refluxed for exactly the
same amount of time (5 minutes). The condenser is washed
several times with deionized water and when cooled the flask
is removed. The resultant slurry is filtered through #4
Whatman Paper into a 100 ml volumetric flask. The sediment
is washed several times with deionized water and the flask
filled to the mark.

A 1 ml sample of the filtered solution is taken and the
boron concentration determined by the method given for water
samples. If the final solution is cloudy it must be filtered
through #4 Whatman paper before reading.

Total Boron in Algae

A 0.5 gram sample of oven dried algae is placed into
a Platinum crucible. Two ml of a 1.0 fl NaOH solution is
added to make alkaline and prevent loss of boron upon heating.
The resulting slurry is dried in an oven at 100°C for 12
hours. The organic material of the algae was destroyed by
heating the crucible at 550°C for 12 hours in a muffle
furnace. To the ash was added 3 grams of anhydrous sodium
carbonate. The crucible contents were fused with a Meker
burner and then heated 5 minutes longer. The remainder of
the procedure is the same as that given under the method

for total boron in sediments.

50

A blank and set of standards ranging from 0 to 100 ug
of boron were prepared in Platinum crucibles. Five ml of
1.0 3 sodium hydroxide solution was added to the standards
and blank to insure alkaline conditions. All steps carried
out on the algae samples were performed on the blank and
standards also.
Total Boronvin Sewage Sludge

A 10 to 15 gram sample of the wet sludge, which had
been made alkaline (pH = 12) with NaOH to prevent loss of
boron, is weighed into a Platinum crucible. The water was
driven off by heating for 12 hours at 100°C in an oven. Then
the organic matter was destroyed by ashing the samples in a
muffle furnace for 12 hours at 550°C. To the ash was added
3 grams of anhydrous Na2C03 and the contents fused. The
rest of the method is the same as described under the total
boron in sediments section.

A blank and set of standards were carried through the
procedure by the same manner as outlined under the boron
in algae section.
Organic Matter

The organic matter content of the sediments and sewage
sludge was determined by calculating the weight loss upon
heating the samples at 550°C for 12 hours in a muffle furnace.
25

The measurement of pH was performed each day immediately

upon receiving the water samples. The measurement was done

51

with a pH meter using a calomel electrode.
Chloride

The Chloride analyses were performed by use of a
Technicon Auto Analyzer. The automated procedure depends
on the liberation of thiocyanate ion from mercuric thio-
cyanate (Hg(SCN)2) by the formation of unionized but soluble
mercuric chloride. In the presence of ferric ion, the
liberated thiocyanate forms a highly colored species (ferric
thiocyanate) proportional to the original chloride con-
centration. Ferric Nitrate (Fe(N03)3.9H20) is the source
of ferric ion and Sodium Chloride (NaCl) is used for the

preparation of standards.

RESULTS

Sewage Plant

The results of the boron analyses on the Raw Sewage,
Primary Effluent, and Secondary Effluent of the East Lansing
Sewage Plant for 1975 are given in Appendix A2 in mg/l.

Also tabulated in Appendix A2 is the flow rate1 in million
gallons for the Raw Sewage. The amount of boron entering
the plant each day was calculated in kilograms and is pre-
sented in Appendix A2. In Appendix A3 the sewage data are
summarized by giving the monthly means and standard devia-
tions for each of the reported results. The statistical
equations used to calculate the means and standard deviations
are given in Appendix B2. Included in Appendix A3 are the
means for the flow rate2 (MGD), precipitation (Inches), and
pH data collected from the sewage plant. Flow rate1 repre-
sents the flows on those days which the boron concentration
was determined while flow rate2 is the rate for all days of
a given month.

A graphical presentation of the daily boron data for
each sampling point of the sewage plant appears in Figures
8,9.and 10. In Figure 11 the monthly means of boron con-
centration for Raw, Primary, and Secondary sewage are

graphed. A graph showing the relationship between flow

52

53
ratez, precipitation, and boron concentration is given in
Figure 12. The monthly means and standard deviations for
the kilograms of boron per day entering the sewage plant

are plotted along with the flow rate1 in Figure 13.
Lakes and Artificial Stream

The boron concentration (mg/l) data for the Lakes
are presented in Appendix A4 through Appendix A8. The
chloride ion concentration in mg/l, pH, and calculated B/Cl
ratio is also tabulated. The Lakes data is summarized by
calculating the monthly means and standard deviations for
all the above parameters. These results are given in Appen-
dices A9 to A13. The results of the boron analyses on the
Artificial Stream are reported in Appendix A14. These data
are summarized in Appendix A16 with the monthly means and
standard deviations being given.

The daily boron data for the Lakes and Artificial Stream
are plotted in Figures 14 through 19. In Figures 20 through
24 the monthly means for boron concentration, chloride con-
centration, and B/Cl ratio are plotted for each lake sampling
point.

The retention time for each lake was calculated assuming
a constant input of 0.5 million gallons of effluent per day.
The calculations appear in Appendix B1 and are based upon
the volume of each lake at the designed Operating water ele-

vation. Using these data it was possible to follow the

54

changes of several water masses as they moved through the
lakes. Graphs showing what happened to the boron concen-
tration and B/Cl ratio of four of the water masses are given
in Figures 25 through 28. The first three graphs assume

no mixing occurred from lake to lake. In Figure 28 the
results from both the Lake 1 inlet and outlet are plotted
together, which would assume complete mixing. The data

used to draw Figures 24 through 28 and the data for two
additional water masses are given in Appendices A22 through
A27. Included are the data for chamges in pH for each water

mass as it moves through the system.
Herron Creek and Felton Drain
The boron data collected from the two Herron creek and
six Felton Drain sampling points are given in Appendix A15.
Monthly means and standard deviations were calculated and
appear in Appendix A16.

Wells

The boron concentration (mg/l) of the different wells

which were sampled are presented in Appendix A17.

55

Sediments

The total boron (ppm), available boron (ppm), and organic
matter (%) data for the sediments is given in Appendix A18»
and Appendix A19. Graphs of the total boron vs. available
boron, availalbe boron vs. organic matter, and total boron
vs. organic matter are given in Figures 29, 30, and 31.
Statistical methods were used to analyze the data from the
three graphs. Linear regressions were performed by the least
squares method and the calculated best fitting line for the
data is drawn on each graph. The coefficient of correlation
(r) was determined for each set of data and it appears on
the figure. All the statistical equations used in the anal-
ysis are given in Appendix B2. The results for each set of

data are summarized in Appendices B3, B4, and B5.

Algae

The boron data for the two algae samples is summarized
in Appendix A20. The boron concentration reported is the
average of three separate analyses. Data on the per cent
Carbon, per cent Nitrogen, and per cent Hydrogen for both

samples is also given.

56
Sewage Sludge

The total boron (ppm) and organic matter (%) data from
the sludge samples is given in Appendix A21. The data repre-
sent the average of four analyses for each sample. The
average boron concentration in mg/l of the water in the sewage
plant for the day the sludge sample was taken is also given
in Appendix 21. Statistical methods were used to determine
whether there is a relationship between total boron in the
sludge and boron in the water and also between total boron
and organic matter content. The results of the statistical
analyses are given in Appendices B6 and B7. This includes
the equation for the least squares line and the coefficient

of correlation (r).

57

r} ' o v
igure 8. Daily Boron data for Raw Sewage

— ¢u01u>oz L lu-OFUO

Anna: chOl

>431 —

 

 

 

 

 

5 § 3

'ONOO

3
(‘I/SW)

 

Fad

NOUOG

Figure 9. Daily Boron data for Primary Effluent.

6O

FIWUIIUOUO

— ¢0l1u>01

(alohoo

_¢u01uhaun

 

hm303(

_

.2... x53:

>435 —

uxaw

4.811

_

IONd

§

1
2

 

NOUOG

(1/9W)'0N03

Figure 10. Daily Boron data for Secondary Effluent.

62

_l (UOIuouo

— run-cu)»;

L

(mop—.8

.
b

Kw. !U h... um —

knaoac

_

“who; xrzcl

>439

_

U23...

p

_

4.14(

1014'

_

>¢<3¢Ouu —

>¢<32<1

16.6

 

63

Fi
gure
11
. Mon
th
Sec 1y
0 m
ndaryegns f
Sewagce)r Bor
. on
of R
aw
, Pr'
imar
y.
7 and

64'

Amsmsxezoz

a ._,

 

_ _

—_
~—
—

meemsm ....... .I
seemsm ........
«semen

IONO

10nd

 

 

'ONOO NOHOG NVEW

(T/SW)

'55

Figure 12. Flow rate, Precipitation, and Boron data for
Raw Sewage.

66

(new) 331%: MO'H man
0

 

T T I I T T
\
\
\
\
\
\

z

9

f-

(

L'
z E:
O O
m Ill
0 I
m 0.

— —-— —--FLow RATEZ

l L 13 (I)
Z";- i . a
("l/9N) NOHOG ONV (SBHONI)NOILV1Idl038d NVBW

 

 

APR. MAY JUN. JUL. AUG. SEPT. OCT. NOV. DEC.

JAN.

MONTH (ISTS)

6?

Figur
e 13
. Flow
rate a
nd K
g of Boron/day
data
for R
aw Sew
age.

68

(new) 'aivu MO'H wvaw

 

 

 

 

 

 

2 3 2’ 9. m (D
l
\ F
\
\
\
\
\
\
\
\
> /
a _ ,/
\ m l
f— \
z < \
o ‘\
s “‘ x
m g \\ L J
\
a? 3’. \ r I
I \
' \
' \
l /
l x
/
| /
/
/ l J
//’ T T
I
/
/
/
/
f
/
/
/
/
/
/
/
/
/
/
“\\‘
“\\

llll

Ill
sss~9mw

AVO/NOUOG 9)! NVEW

 

APR. MAY JUN. JUL. AUG. SEPT. OCT. NOV. DEC.

JAN.

MONTH (I975)

69

Figure 14. Daily Boron data for Lake 1 inlet.

7O

_|>zmmOFoo

_

mwmzwkamm

_

km303<

Anna: IFZOZ

>437

0:0

0N0

Omd

OQO

 

Cod

NOUOB

'ONOO

(T/OW)

‘J
p“;

Figure 15. Daily Boron data for Lake 1 Outlet.

72

r

mmmOPuo

—

mmmiwhamm

Fm3034

Anhm: IHZOE

>433

mzaa

><2

4354.

119.0

l
A
o'

l
1_
O
'0
O

 

nfiqao

(1/ew)‘ouoo NOUOG

73.

Fi
gure
16
. Dail
Y
Boron data
for
Lak
e 2
outle
t.

71.

«mockuo

_

mmmzmkawm

P

kmnma<

F

$5: 522..

>435

mzaa

><2

4:34

OZU

0N6

0nd

 

(1/9")'ONOO NOUOG

Figure 17. Daily Boron data for Lake 3 outlet.

mmmOkoo

_ mmmZukamm

Pmnond

$5: 520:

>435

mznj

><2

4Ea<

Ilofio

.IONO

liomd

 

L one

(W/OW)'ONOO NOUOG

77

Figure 18. Daily Boron data for Lake 4 outlet.

mmmOFoo

mmmZmPamm

_

hmaon<

”new: xezoz

>43a

NZDs

>42

.ima4

ORV

ONO

omd

OtO

 

Ono

NOBOB

'ONOO

(1/9w)

Figure 19. Daily Boron data for Artificial Stream.

$5: :50:

mmmoruo mmmEMPmmm B hm303< _ >433 — wZDm — >42 — n:ma<

P _

NOHOG

IIONd

'ONOO

(1/9")

IIOVO

 

ILOmd

Figure 20. Monthly means for Boron, Chloride, and B/Cl
for Lake 1 inlet.

NVBW

0mm 90: I! 13/8

Anna: :hzoz

 

 

 

FOO Plum .@D< .43..
_ _ _ _
llllll [0.6
0.. TI [ONO
[and
O.N I .IITQO
.\. 40\m...1.l.l.l
.\
.\
. \ MOE—0410 lllllll
.\
\
0.” Fl \. zomom

'I/OW NI (ca-OHBOIHOWHO ONV NOHOG NVBW

53

Figure 21. Monthly means for Boron, Chloride, and B/Cl
for Lake 1 outlet.

84

OLLVH £01 ‘ 'IO/E NVBIN

$.th 1.4.20!

 

 

Foo .Emm .03 >42, mzas >45 .54
4 4 4 4 4 4 4
\\\\\\\\\\\\\\\\\\ 2.0
o._ l 8.0
Ono
ON rI oto
..\ \ \ \ /././
\\.\\.
.\ a
.\ Orzo
.\
.\
.\ 40\@ I |||||
s\§
I I. .\
On... l.// x \ ”3:345 IIIIII

 

zomom

 

WISH NI (Q-O|)30lUO'IHO ONV NOBOB NVBW

85

Figure 22. Monthly means for Boron, Chloride, and B/Cl
for Lake 2 outlet.

86

OllVB QOIX 13/9 NVEH

$4.0: IP20:

 

 

 

.So .eemm .03 52. mzss :2 an:
4 4 4 4 4 4 a
I I IIIIIIIIIIIII .103
o._ .l .186
[Ono
\ /.
0:0. I \. loto
\. l../
\. ././
\. .I.
.\Q
s\.
.\ I. 00.0
.\.
\ .63 ...... I.
.\
o.» I . mSmosxo IIIIIII
.\
zomom

'I/sw NI (9.0”3GIUO1HO ONv noses uvaw

Figure 23. Monthly means for Boron, Chloride. and B/Cl for
Lake 3 outlet.

85*,

0.4

Ollva 20: x "IO/8 uvaw

0.m

350.414.2042

.._.00 Hamw .004 >401

mzns >42

.mad

 

 

.53 ....... I

w04m04z0 IIIIII

20100

04.0

0N0

0.10

 

00 .0

"I/ON NI (g-0|)30|80’1H0 ONV NOUOB NVEW

Figure 24. Monthly means for Boron, Chloride, and B/Cl
for Lake 4 outlet.

 

 

 

 

9O

OILVB EDI x '10/8 NVHW

0.4

0.N

0.m

$3: 5292

 

 

.So .eemm .03 52. mzss 22 .Eq
4 4 4 a 4 q 4
\.\ ‘‘‘‘‘‘‘‘‘ It, In
.53 ....... l
mascara IIIIII

20100

04.0

0N0

0 0.0

0.440

 

00.0

'T/ON NI (2-0” BOIHO'IHD ONV NOUOB NVBW

91

Figure 25. Boron and B/Cl means for water mass 1.

92

OIlVH SCI 1! 1o/e nvaw

~.N

0d

0.n

._.z 40; u4m1<m
0u¢423 0mm4z: 0u~4za 0m44z:

 

 

4 4 4 4

 

 

 

 

40\m IIIIIII

20100

04.0

0N0

 

('1/9”) 'ONOO NOUOB N‘v‘BW

93

Figure 26. Boron and B/Cl means for water mass 2.

we

NVBW

QOIX 13/8

OllVH

#4

0.4

N.N

0.~

0.m

>240a w4a2<m

 

 

 

 

 

 

332: 832: 832: omszs

4 4 4 4
2.0
H H 2.0

.4. H
one

4 I.

\. \ \ \. \ Lr I I IAV
.128

Im

 

40\m IIIIII

zomom

NOUOG NVBN

I1/9N)'0N03

Figure 27. Boron and B/Cl means for water mass 3.

96

OILVU gOl ! 'IO/B NVBN

b.2494 m4a2<m

 

 

 

 

 

 

Om'42: OanZD OwN4ZD Om4423
_ 4 4 4
¢._ fill
J41 41
S .l ]\
I44I 1T
.41
N.N...l. I!!! \\\\\\\IJVI lllllllll Av
lllll [GI \ I.
If lr
QN I
O.mrl 40\m nllllll

20100

04.0

ON .0

0nd

 

(l/sw)'3Noo Nuaoe Nvaw

97

Figure 28. Boron and B/Cl means for water mass 4.

90' at “13/6 wvaw

OILVU

4.2.0.. u4mE<m

0mm420 0u~423 0w4423 0H44ZD

 

c._ In

0.4 II

QM].

 

34'

4 4

4

 

 

H—I

"
I,
l
’
l
l
'

40\m IIIIII

20100

04.0

0N0

0nd

 

4.3

('l/SW)'ONOO NOBOB NVEW

99

Figure 29. Total Boron vs. Available Boron for Lake Sediments.

3.0—

h-
D
O
N
I!

l

0
N

('de) NOHOB

100

BWSVTIV/W

 

I.O'—

 

90

80

TO

60

50

4O

30

20

IO

TOTAL BORON (PPMJ

 

;
fin
5.
n.
f
u
A
c
‘b
....
. . .. .

101

Figure 30. Available Boron vs. Organic Matter for Sediments.

3.0

2.0

 

 

J l l I I I l 1

CD 0 ¢ I" N -

(%) a a 1mm omveao

IO"—
9

8

7

BORON (PPM.)

AVAILABLE

103

Figure 31. Total Boron vs. Organic Matter for Sediments.

 

 

 

In

(D

d

(I;
I I I I I I I I
g I» m t~ o In ¢ :0
(%)uaiivw omvseo

80

70

60

50

4O

30

20

I0

TOTAL BORON (PPM)

DISCUSSION AND CONCLUSIONS

Sewage Plant

Figures 8, 9, and 10 show that the boron concentration
of the sewage fluctuates from day to day. But at the same
time the concentration through the plant stays relatively
constant. This can seen by looking at the graph in Figure
11. Error bars were deleted to eliminate confusion but the
data show there is no significant difference between the
means for any given month. This confirms the Observation Of
Waggott (1969) that conventional sewage treatment systems
do not remove boron.

The amount of boron entering the sewage plant each day
is constant for most of the year. With the exception Of
November and December, the monthly means of Kg of boron/
day agree within t1 standard deviation as shown in Figure
13. This figure also shows that the boron is related to
the flow rate. This can be seen better by looking at Figure
12. During times Of high flow rate the boron concentration
is lowered and it increases with decreasing water flow. Ex-
ceptions occur at September and November where both the flow
rate and boron are increasing and May where the boron is
unchanged but the flow decreases. The precipitation data is

valuable to explain what happened during those months.

105

I‘ll-\"Ii"‘l‘1ll'!|l‘."lllillf

.[u‘ ( '1‘ .tllllnl..ill.l‘vll III I! [III ‘1 I

106

It was learned by cOnversations with the plant operator
that East Lansing has a 50 per cent sanitary and 50 per cent
combined storm and sanitary sewer system. Extensive ground
water infiltration of the sanitary sewers has been reported
as a problem. It was also learned that the flow rate at
the sewage plant is not measured but rather calculated from
influent data. In October a new addition to the plant was
Opened and the flow rates were continued to be calculated
instead Of measured. With this knowledge it is now possible
to explain the results presented in Figure 12.

In April the high precipitation caused the flow rate to
increase and the boron to decrease. The precipitation was
much lower in May but because Of high infiltration of the
sewers the flow rate remained high and diluted the boron.
June and July saw the precipitation level Off and as a re-
sult the flow rate decreased and the boron concentration
rose. August received the greatest amount Of precipitation
but it fell during the last week of the month. As expected
the flow rate increased and the boron decreased. But again
as in May the poor sewer system caused the flow rate to re-
main high intO early September even though the precipitation
dropped. The amount Of infiltration was not as great as
during April. This is probably due to the low summer rain-
fall which increased the ground's capacity to hold water.
The increased boron concentration was a result Of the low
precipitation for that month. The combination of high flow

rate and high boron caused the Kg Of boron/day to jump above

107
the levels found during most of the year. But the value is
still within :1 standard deviation Of the previous months.

In October the curves return to their expected patterns.
The precipitation increased in November but because of the
little rainfall received the previous two months, infiltra-
tion problems would not be expected. This is confirmed by
the increased boron concentration during the month. But
the flow rate data showed a large increase which does not
follow the pattern Of other months. Again in December the
high flow rate can not be explained by the precipitation.

As stated before the new sewage plant became Operational
during October. It appears that the new calculated flow
rates are tOO high. The plant operator expressed the opinion
that it is possible the new data is incorrect. This could
be attributed to unfamiliarity with the new system by the
personnel. The result is that the Kg Of boron/day values
for those two months fall out Of the range for the previous
eight months. The error seems to be constant because the
Kg Of boron/day calculated with available flow rates is the

same both months.

Lakes and Aritificial Stream

The daily boron data of Figures 14 through 19 show high
variability due to evaporation, precipitation, and movement
of water through the system. For this reason Chloride ion

was used as a index to compensate for natural changes in the

108
water level. Wetzel (1975) has pointed out that chloride ion

is not utilized in any form by the aquatic community. There-
fore the B/Cl ratio should be a good indicator of any changes
in boron by the lakes. Looking at Figures 20 through 24 a
definite trend is noticed in both the boron concentration
and B/Cl ratio. The values of boron and chloride for Lake 1
reflect the concentration in the sewage effluent. The other
lakes have curves similar to Lake 1 when the retention time
is taken into consideration.

Changes in the boron and B/Cl ratio Of a given water
mass as it moves through the system is shown in Figures 24
through 28. In each case no significant difference in the
B/Cl ratio occurs. This is evidence that boron is not re-
moved to any extent by the aquatic community. The data for
the first three water masses was calculated assuming no mix-
ing of the water masses. In Figure 28 both the Lake 1 inlet
and outlet data appear. The close agreement in B/Cl values
indicates that there is complete mixing Of water in the lakes.

NO B/Cl ratio was calculated for the Artificial Stream.
Flow data would be needed from the sampling point to make
any conclusions about the B/Cl ratio. The boron concentra-
tion data do support the evidence that the boron continues
to move through the water system unchanged.

The pH data was not plotted but appears in the Appen-
dices. The pH of a given water mass increases as it moves

through the lakes. The pH values reach as high as 10 later

in the year. At that pH the borate ion would dominate the

109
boric acid equilibrium. Banerji (1969) showed that borate
was adsorbed more readily onto clay materials at high pH's.
This may occur to some extent but the B/Cl data indicate that

it is not significant.

Herron Creek and Felton Drain

The boron concentration Of both Herron Creek sampling
stations slowly increased throughout the Spring. This was
due to the fact that water Of higher boron content was being
discharged from the lakes to Herron Creek via the Artificial
Stream. The discharge of water was stopped in July and the
boron concentration dropped. When discharge was continued
in August, it resulted in the boron concentration again
rising in the creek. The amount Of boron in Herron Creek
during the Fall was significant. Although the concentration
was lower than in the discharge water, the creek receives
runoff from a large area and this would tend to dilute the
boron. Complete flow data would be required to determine
for certain whether boron is being lost. It has already
been shown that boron is not removed by the lake community.
The boron concentration data gives evidence that boron is
also unchanged in Herron Creek.

The boron concentration of Felton Drain was consistent
through the study period. In the Spring there was no signif-
icant difference in boron from station to station. By June

water had ceased to flow over three of the weirs and by the

110
end of July there was no flow at any Of the weirs. Since
samples were taken only during periods of flow, only a few
samples were taken in the summer. During the last week of
August we received a large amount of rainfall. The drain
collected the runoff and water began to flow again. The
boron concentration was abnormally high during this period.
The source of the high boron may have been the poultry barns
located near UNFD01. The wastes from the chickens is spread
on the ground for drying. Hove et al. (1939) showed that
chickens excrete all the boron they ingest. With the heavy
rains the boron in the waste was probably leached out and
deposited in Felton Drain. This is supported by inspection
of the other chemical data. The chloride and ammonia concen-
trations were 2 to 3 times higher than during the Spring. As
before there was no significant difference in the boron be-
tween the sample pOints. This would confirm that the poultry

barns were the point source for boron.

Sediments

The total boron, available boron, and organic matter of
the sediments has increased over time. Figures 29, 30, and
31 show an excellent correlation exist between all three
parameters. It is postulated that as the aquatic plants and
algae grow they take up boron. It has already been shown
that boron is not significantly removed by the lakes. But

algae samples from Lake 2 were found to contain around 120

111

ppm. When the algae and plants die at the end of the season
they settle on the bottom. The plant material is broken
down by the microorganisms and born released back to the
water. The material which is not broken down will be incorp-
orated into the sediments. This has resulted in an increase
in the total boron and organic matter content of the sediments.

Additional data has been reported on the available
boron content Of the lake sediments. McNabb (1975) deter-
mined the amount in early Spring of 1974 to be 1.80 ppm for
two sites in Lake 1. Two sites from Lake 4 averaged 2.00 ppm.
The samples represent the interface material of each sedi-
ment. The sediments were taken before the first season of
full growth in the lakes. It is evident that boron must have
been adsorbed onto the clay bottom of the lakes initially.
Banerji et al. (1968) and Singh (1971) have shown that boron
is adsorbed by clay materials. It is interesting that the
available boron of the sediments did not change from spring
74 to Spring 75 but did increase over the 1975 growing sea-
son. It may be that when the sediments were sampled in the
Fall the plant material had not been completely broken down.
Analysis by the boiling water method for available boron
could have resulted in extracting some boron from the un-
decayed plant material. Giving the lake system one full
year to break down the plant material and reach equilibrium,
resulted in no increase in the available boron. If this
continues to hold true it would eliminate the threat of

toxicity to the aquatic plants from high available boron

112
levels. Eaton (1944) and Bingham (1973) have reported that
increasing the available boron to land plants can result in

toxicity to some Species.

Algae

Both algae samples had equivalent amounts for boron
(117 and 120 ppm). NO relationship could be found between
the amount of boron in the samples and the carbon. nitrogen,
or hydrogen content. Boyd (1970) found the boron content of
a Cladophora species to be 85 ppm. The water concentration
was reported to be 0.1 ppm or less. The boron concentration
Of the lakes is 2 to 3 times higher. This would suggest a
relationship between water concentration and amount in the
algae. Gerloff (1968) has shown that boron is not required
for growth by green algae. It is possible that boron is
being adsorbed on the algae surface. The pH at the surface
of algae cells can reach 9 to 10 during active photosynthesis.
At that pH the boron equilibrium would shift from boric acid
to borate. This could result in the precipitation of cal-
cium or sodium borate onto the algae surface. There is also
the chance that borate is adsorbed on the calcium carbonate
which will be precipitated at these pH's. These processes
would increase the boron content Of the algae without any

actual uptake Of the element.

113
Wells

NO significant change occurred in the boron concentra-
tion of the drift and shallow rock wells over time. An un-
usually high amount Of boron was found in the UNSR14 and
UNDW27 wells. As shown in Figure 5 these two wells are
located at the same point. A small natural pond and a few
homes are located in the adjacent area. Both Of these could
be sources Of boron to the gound water. The boron concentra-
tion in both wells is comparable, which would indicate that
boron is moving essentially unchanged through the ground.

It is possible that the boron concentration of the wells could
be used as a tracer Of ground water movements.

There was a significant increase in the boron concen-
tration Of all the deep rock wells. The boron concentration
was very low in the spring but by fall the amount was about
the same as in the shallow rock wells. This indicates a
definite movement of water through the ground. Upon inspec-
tion Of all the chemical data on the deep rock wells, it was
noted that several other parameters such as calcium and carbon
were also increasing significantly. This tends to confirm

the usefulness of boron as a tracer of ground water movement.

114

Sewage Sludge

The mean boron content Of the sludge ranged from 28 to
84 ppm. The standard deviation for many of the samples was
high. Large variations were also found in the organic mat-
ter analyses. A linear relationship between total boron and
organic matter in the sludge could not be found. The coef-
ficient of correlation was 0.5 and not significant at 5 per
cent. The high variability between samples was probably
due to the fact that sewage sludge is a very diverse mat-
erial. The relative amounts of types of organic and inor-
ganic material making up the sludge will vary from day to
day. Precipitation would be important here because it
will add solid matter to the sewage plant through runoff.

It was found by Banerji et al. (1969) that boron was
adsorbed by sewage sludge. At a water concentration of 1.0
ppm the sludge adsorbed 25 ug/g(ppm) boron. The adsorption
is concentration dependent and at 0.3 PPm only 5 ug/g of
boron was adsorbed. 0n the average this would represent
only about 10 per cent of the boron found in the East
Lansing sludge. No correlation could be found between boron
in sludge and the water concentration in this study. There
may be some adsorption of boron taking place but it is not

significant.

SUMMARY

The load Of boron to the sewage plant in Kg/day was
constant over the year. The concentration varied from 0.1
to 0.5 ppm and was dependent on the flow rate. Precipita-
tion was important because of the combined sanitary and storm
sewer system. It was found that the boron concentration did
not change through the plant. Boron was not being removed
by the sewage treatment process. There was no evidence of
boron adsorption onto the sewage sludge.

The concentration of boron in the lakes reached levels
found in the sewage effluent. The levels fluctuated due to
evaporation and precipitation. The boron was ratioed using
chloride ion data. The B/Cl ratio of a given water mass
did not change as it moved through the lakes. The boron
concentration of the Artificial Stream reflected the levels
released from Lake 4.

The boron concentration of Herron Creek increased during
times discharge from the lake system. Felton Drain did not
receive water from the lakes and the boron levels were found
to be constant. Boron did increase during periods Of heavy
rainfall in Felton Drain and Herron Creek. The source of

boron was probably the poultry waste deposited in the area.

115

116

The decay Of plant material has increased the total
boron and organic matter content of the sediments. The
available boron was found to increase during the growing
season but returned to a constant value over the Winter
months.

Algae samples of Cladophora had a boron content of
120 ppm. These levels were not high enough to effect the
B/Cl ratio of the water masses. The precipitation of boron
onto the algae at high pH's could explain the high tissue
concentration of boron.

The boron concentration of all but the deep rock wells
remained constant. The deep rock wells had boron concen-
trations approaching the shallow rock well levels. More
intensive sampling is needed before any definite conclusion

can be made.

LITERATURE C ITED

LITERATURE CITED

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Adams, R.M. 1964. Boron, metallO-boron compounds and
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Afghan, B. K., P. D. Goulden, and J. F. Ryan. 1972. Auto-
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APPENDICES

Appendix A1.

123

Storet Code and Location of Sampling Points.

 

ELSTPR-
ELSTPP-
ELSTPS-
UNLlIO-
UNLIEO-
UNLZEO-
UNLjEO-

UNL4EO-

UNASOj-

UNFD01-

UNFD03-
UNFDOS-

UN FDOfZ-

UNFDOB-

UNFDIO-
UNHCOl-

UNHCOZ-

Raw Influent Sewage from East Lansing Sewage Plant.
Primary Effluent from East Lansing Sewage Plant.

Secondary Effluent from East Lansing Sewage Plant.

Water sample taken just Off the inlet structure of
Water Quality Project Lake 1.

Water sample taken at the outlet structure Of Water
Quality Project Lake 1.

Water sample taken from the Outlet structure Of Water
Quality Project Lake 2.

Water sample taken from the outlet structure Of Water
Quality Project Lake 3.

Water sample taken at the outlet structure of Water
Quality Project Lake 4.

Sample station located at the diverter structure at

the junction of the artificial stream and Felton Drain.
Sample
behind

station located at the opening of Felton Drain
the University poultry barns.
Sample station located at Water Quality Project Weir 1.

Sample station located at Water Quality Project Weir 2
just north of the main work road in the spray area.

Sample station located at the earthen dam slightly
northwest Of Water Quality Project Weir 3.

Sample station located at Water Quality Project Weir 3.

Sample station located at Water Quality Project
Weir 4 on Felton Drain.

Sample station located at the intersection of Bennett
Road and herron Creek.

Sample station located at the intersection of Mt.
Hope Road and Herron Creek.

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-- -- oom.o o5m.o -- m
M5.0H m.mH omm.o mom.o oHN.o w
mH.HH m.m oom.o nmm.o on.o 5
o5.m m.m m5m.o O5N.o oom.o o
mamas

couom mo mm spam 30Hm mmemqm mmemqm mmemqm mama

 

.A.U.pcOov N< xfipcmmm<

128

 

No.5 m.NH mmN.o ONm.o omH.o HN
Hm.NH s.NH oom.o mmN.o m5N.o ON
m5.oH :.NH mNN.o oHN.o omN.o 0H
mm.HH m.mH osN.o omH.o mmN.o mH
mm.m m.HH osN.o oHN.o OON.o 3H
Ho.oH m.NH mNN.o moN.o mom.o mH
mo.mH o.mH mmN.o mNN.o mmN.o NH
-- .. mom.o .. u- m
-- -- omN.o -- -- m
-- -- ONm.o -- -- 5
-- -- on.o -- u- o
-- -- moms -- -- m
m:.HH N.mH mmN.o omN.o omN.o H
2mm

Hs.HH 5.mH ONN.o OON.o QNN.o om
NN.oH o.mH 05H.o me.o owH.o mN
couom No ms mpmm 30Hm mmemqm mmamqm mmamqm mums

 

. A 00.9COOV N4 XHUzmanAw

129

 

 

s5.w H.m mHN.o osN.o ONN.o mH
No.oH m.m osm.o ONm.o 05N.o 5H
Hm.m 5.5 on.o mHm.o osm.o 0H
mN.m s.m omN.o o5N.o ooN.o mH
mm.oH o.HH omN.o omN.o omN.o m
ms.HH N.HH mmN.o O5N.o 05N.o s
5m.HH N.HH omN.o omN.o omN.o m
5m.5H m.MH nmN.o onm.o m:m.o N
om.m s.m nHm.o omN.o omN.o H
mash

-- -- osN.o mmN.o -- mN
mm.m m.m owH.o -- ooH.o mN
no.5 N.HH omN.o m5N.o owH.o 5N
H5.5 5.m m5N.o ooN.o oHN.o sN
mo.oH m.HH mHN.o msN.o mmN.o mN
Hm.m 5.HH m5N.o onN.o ONH.o NN
couom No ms spam zOHm mmemHm mmemqm mmemqm mama

 

.H.e.pcoov N< ancmma<

130

 

00.0H 3.0 000.0 030.0 0N0.0 5H
35.5 5.0 000.0 000.0 00N.0 0H
03.0 0.0 030.0 000.0 000.0 0H
53.0 5.5 0H0.0 000.0 0N0.0 3H
00.0 H.0 030.0 000.0 00N.0 0H
-- -- 0N0.0 0H0.0 000.0 5
-- -- 000.0 030.0 00N.0 0
50.0 0.5 030.0 000.0 000.0 N
50.0 0.0 030.0 000.0 0H0.0 H
0400

0H.0 0.3 030.0 0N0.0 030.0 00
00.5 0.5 0H0.0 0N0.0 000.0 0N
0H.0 0.0 00N.0 05N.0 05N.0 0N
H3.5 5.0 0N0.0 000.0 0NN.0 3N
00.0 0.5 0H0.0 .. 000.0 0N
N5.5 0.0 05N.0 05N.0 00N.0 NN
souom 00 00 0000 30H0 mmamqm mmemHm mmamqm 0900

 

.H.0.pcoov N0 xH02000<

131

 

0N.0 0.0 00N.0 00N.0 000.0 5
00.5 3.5 000.0 00N.0 00N.0 0
30.0 0.5 0H0.0 030.0 00N.0 0
0H.0H N.0 00N.0 000.0 00N.0 3
NN.0H 0.0 000.0 00N.0 000.0 0
.000

00.0 5.5 000.0 030.0 0H0.0 H0
NN.HH 3.0H 000.0 0N0.0 00N.0 00
00.0 0.0 000.0 000.0 00N.0 0N
00.0 0.0 0H0.0 000.0 0N0.0 0N
03.0 0.5 0N0.0 000.0 0N0.0 5N
00.0 H.0 000.0 000.0 0N0.0 3N
HN.0 0.0 000.0 0H0.0 00N.0 0N
00.0 0.0 000.0 000.0 00N.0 NN
HN.0H 5.0 0H0.0 000.0 0H0.0 HN
0N.0 0.5 000.0 000.0 0H0.0 0N
00000 00 00 0000 :0H0 000000 000000 000000 0000

 

.A.v.p:oov m< xflvaag<

132

 

0N.NH 0.0H 030.0 0N0.0 000.0 0N
H3.5H N.0 000.0 050.0 000.0 5N
00.0H 5.NH 000.0 050.0 030.0 0N
NN.0H 0.HH 05N.0 00N.0 00N.0 0N
30.HH 5.NH 00N.0 000.0 03N.0 3N
00.0 0.0 00N.0 03N.0 05H.0 HN
50.5 5.5 00N.0 00N.0 05N.0 0N
00.0 0.0 0N0.0 0N0.0 05N.0 0H
0H.0 0.5 00N.0 00N.0 0H0.0 0H
00.0 3.0 05N.0 05N.0 03H.0 5H
05.0 0.0 0HN.0 0HN.0 00N.0 3H
00.0 0.0 00N.0 0NN.0 0HN.0 0H
3N.5 0.0 0H0.0 0H0.0 00N.0 NH
5N.0 0.0 05N.0 00N.0 03N.0 HH
00.0 N.0 000.0 030.0 00N.0 0H
00000 00 00 0000 3000 000000 000000 000000 0000

 

.A.U.pcoov N< xfiusmmm<

133

00.0

0.0

 

0H0.0 00N.0 00N.0 NN

35.0H 0.0 030.0 03N.0 000.0 0H
N0.NH 0.0H 0N0.0 000.0 0H0.0 5H
00.0 0.0 050.0 033.0 000.0 0H
33.NH 0.0H 030.0 030.0 0H0.0 0H
30.5 0.0 000.0 0H0.0 03N.0 3H
NH.0H H.HH 000.0 00N.0 000.0 HH
05.NH 3.HH 000.0 00N.0 00N.0 0H
30.0H 0.0 000.0 00N.0 00N.0 0
03.0H N.0H 00N.0 00N.0 000.0 0
00.NH 5.NH 00N.0 00N.0 05N.0 5
00.NH 0.3H 00N.0 03N.0 00N.0 3
NH.0H 0.NH -- 00N.0 05N.0 0
30.5H 0.0H 00N.0 000.0 00N.0 N
05.5H 0.0H 0NN.0 03N.0 00N.0 H
.mmwm

00000 00 00 0000 2000 000000 000000 000000 0000

 

.0.0.00000 N0 00000000

134

 

00.0 H.0 00N.0 000.0 050.0 0H
0N.0H 0.0 030.0 003.0 030.0 NH
00.NH 0.HH 05N.0 000.0 05N.0 0
00.0H N.0 00N.0 05N.0 0N0.0 0
00.0 0.0 000.0 000.0 00N.0 5
50.HH N.0 000.0 0H0.0 000.0 0
00.5 0.0 0H0.0 03N.0 000.0 0
0H.0H H.0 0H0.0 00N.0 00N.0 N
30.0 0.0H 000.0 000.0 00N.0 H
. 00

00.HH 0.0 0H0.0 0HN.0 0H0.0 00
H5.0 0.5 000.0 000.0 00N.0 0N
00.0 0.5 0H0.0 0H0.0 00N.0 0N
00.HH 0.0H 000.0 03N.0 00N.0 0N
H0.0H 0.0H 000.0 00N.0 000.0 3N
H0.NH 3.HH 0N0.0 000.0 00N.0 0N
00000 00 00 0000 3000 000000 000000 000000 0000

 

.0.0.0:000 N0 00000000

135

 

00.00 0.00 000.0 0N0.0 000.0 0
00.00 0.0 00N.0 000.0 000.0 N
.>oz

00.00 0.0 00N.0 00N.0 000.0 00
N0.00 N.00 00N.0 00N.0 00N.0 0N
00.00 0.0 000.0 0N0.0 0N0.0 0N
00.N0 0.0 0N0.0 000.0 000.0 0N
00.00 0.0 000.0 0N0.0 000.0 0N
00.00 0.00 000.0 000.0 000.0 0N
N0.N0 0.00 000.0 000.0 000.0 mN
00.0 0.0 .. 000.0 000.0 0N
00.0 0.0 000.0 000.0 000.0 0N
No.00 N.0 -- 000.0 000.0 00
00.00 0.0 000.0 00N.0 000.0 00
0N.0 0.0 00N.0 00N.0 000.0 00
00.0 0.0 000.0 00N.0 000.0 00
00000 00 00 0000 2000 000000 000000 000000 0000

 

.0.0.00000 N0 00000000

136

 

N0.00 0.00 000.0 000.0 000.0 0N
00.00 0.0 000.0 000.0 000.0 0N
00.00 0.0 000.0 000.0 000.0 0N
00.00 0.0 000.0 000.0 00N.0 0N
00.00 0.00 000.0 000.0 000.0 00
00.00 0.00 000.0 000.0 000.0 00
00.00 0.00 000.0 000.0 000.0 00
00.00 0.00 0N0.0 000.0 000.0 00
00.00 0.00 000.0 000.0 000.0 00
00.00 0.0 0N0.0 0N0.0 000.0 00
00.00 0.N0 000.0 000.0 000.0 00
0~.N0 0.N0 000.0 000.0 00N.0 00
00.00 0.0 000.0 000.0 000.0 0
00.00 0.00 000.0 000.0 000.0 0
00.00 0.00 000.0 000.0 000.0 0
00.00 0.00 000.0 000.0 000.0 0
00000 00 00 0000 3000 000000 000000 000000 0000

 

.A.U.Pcoov N< xNUCme<

137

 

00.00 0.00 .. 000.0 000.0 00
00.00 0.00 000.0 000.0 000.0 00
00.00 0.00 -- 000.0 000.0 00
00.00 0.00 000.0 000.0 000.0 00
00.00 0.00 000.0 000.0 000.0 00
00.00 0.00 000.0 000.0 000.0 00
00.00 0.00 000.0 000.0 000.0 00
00.00 0.00 000.0 000.0 000.0 00
00.00 0.00 000.0 000.0 000.0 0
00.00 0.00 000.0 000.0 000.0 0
00.00 0.00 000.0 000.0 000.0 0
00.0 0.00 000 0 000.0 000.0 0
00.00 0.00 000.0 000.0 000.0 0
00.00 0.00 000.0 000.0 000.0 0
00.00 0.00 000.0 000.0 000.0 0
.omQ

00000 00 00 0000 3000 000000 000000 000000 0000

 

.0.0.00000 00 00020000

 

138

00.00 0.00 000.0 000.0 000.0 00

 

00.00 0.00 000.0 000.0 000.0 00
00.00 0.0 000.0 000.0 000.0 00
00.00 0.00 000.0 000.0 000.0 00
00.00 0.0 000.0 000.0 000.0 00
00.00 0.00 -- 000.0 000.0 00
00000 00 00 0000 3000 000000 000000 000000 0000

 

.0.0.00000 00 00000000

139

 

0.0 H 0.00 000.0 0 000.0 000.0 0 000.0 000.0 0 000.0 00000000
0.0 0 0.00 000.0 0 000.0 000.0 0 000.0 000.0 0 000.0 00000>0z
0.0 0 0.0 000.0 0 000.0 000.0 0 000.0 000.0 0 000.0 0000000
0.0 0 0.00 000.0 0 000.0 000.0 0 000.0 000.0 0 000.0 000000000
0.0 0 0.0 000.0 0 000.0 000.0 0 000.0 000.0 0 000.0 000000
0.0 0 0.0 000.0 0.000.0 000.0 0 000.0 000.0 0 000.0 0000
0.0 H 0.0 000.0 0 000.0 000.0 0 000.0 000.0 0 000.0 0000
0.0 H 0.00 000.0 0 000.0 000.0 0 000.0 000.0 0 000.0 000
0.0 0 0.00 000.0 0 000.0 000.0 0 000.0 000.0 0 000.0 00000
0.0 0 0.0 000.0 0 000.0 - 000.0 0 000.0 0000000
0000 3000 000000 000000 000000 00000

 

.000Q 0:000 0mmzom 0:00:00 000m 000 0:00000>0Q 0000:00m 0:0 0:002 0000:02

.m< 000:mamd

1&0

 

 

0.0 00.0 0.00 000 0 00.00 00000000
0.0 00.0 0.00 00.0 0 00.00 00000>0z
0.0 00.0 000 00.0 0 00.00 0000000
0.0 00.0 0.00 00.0 0 00.00 000000000
0.0 mm.o 0.m :m.m H 0w.m pmsm3<
0.0 00.0 0.0 00.0 0 00.0 0000
0.0 00.0 0.0 00.0 0 00.0 0000
0.0 00.0 0.00 00.0 0 00.0 000
0.0 00.0 0.00 00.0 0 00.00 00000
0.0 00.0 0.0 00.0 0 00.0 0000000
ma :000000000000 000m 3000 :000m 00 mm 00:02

 

.0.0.00000 00 00000000

141

 

00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 on
00.0 00.0 000 000.0 00
00.0 00.0 00 000.0 00
00.0 0m.0 0m0 00m.0 mm
00.0 00.0 000 000.0 00
00.0 00.0 0M0 mmm.0 mm
00.0 00.0 000 000.0 mm
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 0m0 00m.0 00
00.0 00.0 000 000.0 00
0000

000 x 00\m :0 00000000 00000 0000

 

.000020 00000 000000 000 00000 00\0 000 .00 .00\00V 00000000 .00\00v 00000

0:4 x00:mam<

142

 

0m.m 00.0 000 00m.0 mm
00.m 00.0 m00 00m.0 mm
00.m 00.0 000 00m.0 0m
00.0 00.0 000 m0m.0 om
00.0 00.0 000 mmm.0 00
00.0 00.0 000 00m.0 00
00.0 00.0 000 mmm.o 00
00.0 00.0 0m0 0mm.0 00
00.0 00.0 000 00m.0 00
00.0 00.0 mm0 00m.0 00
00.0 00.0 000 000.0 0
No.0 no.0 mm0 00m.o 0
00.0 00.0 mm0 0mm.0 m
00.0 -- 000 0mm.0 0
mm.m 00.0 NMO onm.o 0
.000

m00 x 00\m. mm 00000000 00000 0000

 

.A.u.pcoov 3< vaCmmm<

143

 

00.0 00.0 mM0 mmm.o 00
mm.m 00.0 000 000.0 00
00.0 00.0 000 m0m.o N0
mo.m 00.0 000 mom.0 00
00.0 00.0 000 mmm.o 00
mm.m 00.0 000 o:m.o 0
00.m .. 00 oom.o w
mm.0 00.0 00 00m.0 m
mm.m om.m 0m omm.o 0
00.m o:.w mm mmm.o m
0m.m mm.m mm omm.o m
.mmmm

0m.m 00.0 000 00m.0 mm
00.0 00.0 000 00m.0 mm
00.m 00.0 m00 000.0 00
mm.m 00.0 000 00m.o mm
000 x 0o\m :0 00000000 00000 0000

 

.A.0.p:oov 3< xflvaQm<

um

 

00.0 00.0 000 000.0 0
00.0 00.0 000 000.0 0
00.0 00.0 000 000.0 m
00.0 00.0 00 000.0 m
00.0 00.0 mm 000.0 0
. 00

00.m om.m mm 0mm.o 0m
00.m_ 00.0 00 000.0 00
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 mm
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 mm
00.0 00.0 000 000.0 mm
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
000 x 00\0 00 00000000 00000 0000

 

.0.0.pcoov :0 x000000<

145

 

 

00.0 00.0 000 000.0 on
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 mm
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 mm
00.0 00.0 000 mmm.0 mm
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 0
m00 x 00\m 00 00000000 00000 0000

 

.0.0.00000 00 00000000

146

 

00.0 -- 000.0 00

00.0 00.0 000 000.0 mm
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 mm
00.0 00.0 000 000.0 mm
00.0 00.0 00 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 0
00.0 00.0 00 000.0 0
00.0 00.0 00 000.0 0
04000

000 x 00\0 00 00000000 00000 0000

 

.000020 00000 000000 000 00000 00\0 000 .00 .00\000 00000000 .00\msv 00000

.00 x000000<

 

 

 

[It {all t F ‘0 II

147

 

00.0 00.0 000 000.0 mm
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 0
00.0 00.0 000 000.0 0
00.0 00.0 000 000.0 0
00.0 00.0 000 000.0 0
00.0 00.0 000 000.0 m
00.0 00.0 000 000.0 m
00.0 00.0 00 000.0 0
00mm

00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 00
000 x 0p\0 00 00000000 00000 0000

 

.0.0.00oov m0 x0000000

1#8

 

 

00.0 00.0 000 000.0 mm
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 m
00.0 00.0 000 000.0 m
00.0 00.0 000 000.0 m
00.0 00.0 000 000.0 m
0030

00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
000 x 00\0 00 00000000 00000 0000

 

.0.0.00000 00 00000000

149

 

00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0. 00.0 000 000.0 0
00.0 00.0 000 oom.o 0
00.0 -- 000 000.0 m
-- -- -- 000.0 0
m0.m nu mw0 ommé 0
.000

00.0 00.0 000 000.0 00
00.0 -- 000 000.0 mm
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 mm
000 x 00\0 00 00000000 00000 0000

 

.0.0.00oov 00 00000000

150

 

00.0 00.0 000 000.0 0
00.0 00.0 000 000.0 0
00.0 00.0 000 000.0 m
00.0 -- 000 000.0 0
00.0 00.0 000 000.0 0
.000

00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 mm
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 mm
00.0 00.0 00 000.0 00
00.0 00.0 000 000.0 mm
00.0 00.0 000 000.0 mm
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
m00 x 00\m m0 000,000.00 Couom mpma

 

.0.0.00oov 00 00000000

151

 

00.0 00.0 000 000.0 0
.000m

00.0 00.0 000 000.0 00
-- 00.0 -- 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 .mmm.0 mm
00.0 00.0 000 000.0 mm
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
000 x 00\0 00 00000000 00000 0000

 

.0.0.00000 00 00000000

152

 

00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 mm
00.0 00.0 00 000.0 mm
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 0
00.0 n. 000 000.0 0
00.0 00.0 000 000.0 m
00.0 00.0 00 000.0 0
00.0 00.0 000 000.0 m
000 x 00\0 00 00000000 00000 0000

 

.0.0.00oov 00 00000000

153

 

00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 m0.m 000 omm.o M0
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 0
00.0 00.0 000 000.0 0
00.0 00.0 000 000.0 0
00.0 00.0 000 000.0 m
00.0 00.0 00 000.0 N
00.0 00.0 00 000.0 0
.100

00.0 00.0 00 000.0 on
00.0 00.0 00 000.0 mm
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 mm
000 x 00\0 00 00000000 00000 0000

 

.0.0.0000v 00 00000000

CJ

 

 

0m.m no.0 000 mmm.c 0m
0m.m om.m 000 mmm.o om
mm.m no.0 000 omm.o mm
mw.m 00.0 000 30m.o mm
wo.m 00.0 000 mmm.o mm
mn.m 00.0 000 oom.o 0m
m0.m 00.0 000 oom.o mm
mm.m 00.0 000 mmm.o NN
00.m 00.0 000 0mm.o 0m
mo.m om.m Q00 0mm.c om
m00 x 0p\m xa 000000co :000m 000:

 

.A.c.p:oov m4 xflbcwam<

155

 

00.0 00.0 :00 000.0 mm
00.0 om.0 000 000.0 mm
00.0 o~.w ~00 000.0 00
00.0 00.0 000 000.0 mm
00.0 00.0 000 000.0 mm
00.0 00.0 00 000.0 00
00.0 00.0 000 000.0 00
00.0 om.0 000 000.0 00
mm.m om.0 N00 000.0 00
00.0 00.0 00 0mm.o 00
00.m 00.0 mm onm.o 00
00.0 00.0 mm 000.0 00
00.0 00.0 00 000.0 0
-- 00.0 -- 000.0 0
00.0 0.0 m0 000.0 0
44000

000 x 0p\0 00 00000000 00000 0000

 

.000000 00000 000000 000 00000 0p\0 0:0 .00 .00\msv 00000000 .00\wsv 00000

.04 xflqu00<

156

 

00.0 00.0 «0 000.0 mm
00.0 00.0 000 000.0 om
00.0 00.0 m00 000.0 00
00.0 00.0 00 000.0 00
00.0 00.0 mm 000.0 00
00.0 00.0 00 000.0 m0
00.0 00.0 00 000.0 0
00.0 00.0 00 000.0 0
0N.0 00.0 000 000.0 0
00.m 00.0 00 000.0 0
00.0 00.0 00 000.0 m
00.0 00.0 00 000.0 m
00.0 00.0 00 000.0 0
Nag

00.0 0.0 m0 00N.0 om
-- 00.0 00 -- 0m
m00 x Ho\m x0 wufluoano Couom mpmm

 

.A.n.pcoov o< xflquamx

157

 

 

00.0 00.0 000 000.0 mm
00.0 00.0 00 000.0 00
00.0 00.0 000 000.0 00
no.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 N0
00.0 00.0 00 000.0 0
00.0 00.0 000 000.0 m
00.0 00.0 000 000.0 m
00.0 00.0 N00 000.0 m
isu

00.0 00.0 000 000.0 on
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 mm
00.0 00.0 00 000.0 00
m00 x 00\0 00 00000000 00000 0000

 

.A.U.P:oov ©< xqumam<

158

 

00.0 00.0 000 000.0 mm
0N.0 00.0 :00 000.0 00
no.0 00.0 0m0 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 o0~.o 00
00.0 00.0 000 000.0 00
00.0 mo.0 00 000.0 00
00.0 o0.0 000 o0m.o o0
oo.~ 00.0 000 o0~.o 0
00.0 00.0 000 000.0 0
00.0 -- 000 o0~.o m
0000

00.0 o0.0 000 000.0 on
00.0 -- 000 o0m.o mm
00.0 00.0 000 omm.o 00
00.0 o0.0 000 000.0 mm
m00 x Hp\m :0 00000000 Couom ovum

 

.0.0.00000 00 00000000

159

 

00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 o0.0 000 m0m.o 00
00.0 00.0 000 000.0 0
00.0 00.0 000 000.0 0
00.0 00.0 000 o0m.o m
00.0 -- 000 000.0 0
00.0 00.0 000 omn.o 0
.000

00.0 om.o 000 mom.o 00
00.0 00.0 000 000.0 on
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
mn.m 00.0 0m0 m:m.o 0m
om.m 00.0 000 00m.o mm
000 x 00\0 00 00000000 00000 0000

 

.A.0.PcOov o< x0UCmaa<

160

 

mm.m om.0 mad 00m.0 n
00.m no.0 odd 0mm.0 0
00.0 00.0 0HH onm.0 m
m0.m 00.0 on” nflm.0 m
.mmmm

00.N 0H.m HNH mmm.0 0m
om.~ 0H.0 00H 00m.0 mm
«0.0 00.0 mmfl mmm.0 mm
H0.m n0.m Hmfi mmm.o om
00.0 «0.0 NHH 0mm.0 mm
00.0 00.0 00H 0mm.0 mm
00.0 00.0 «Ma 00m.0 Hm
mm.m 00.0 0mH 0mm.0 om
00.0 00.0 0mH mmm.o 00
00.0 00.0 and 00m.0 ma
0m.~ 00.0 00H 0mm.0 ma
mofl x H0\m ma 00000Hco couom 0009

 

.A.c.p:oov o< xHUCmmm<

161

 

mo.m om.m :m omm.o mm
00.m m0.0 m0 mwm.o om
mH.n 00.0 00 mom.0 mm
mo.m mn.m om mmmoo 0N
00.m 00.0 00 mwm.0 mm
00.m 00.0 mm 000.0 mm
0m.m 00.0 HNH 0am.o 00
00.0 00.0 000 000.0 00
00.N 0000 000 m0m.0 0H
00.m 00.0 mmfi ,mm.o 0H
0m.m 00.0 Hmfi 00m.0 0H
0m.m 00.0 0mH 0mm.o NH
m0.m 00.0 0m0 0mm.0 00
2m.m om.w omfi 0mm.o OH
mn.m 00.» 0mg m0m.0 m
00.m -- 00H nmm.0 m
M00 x Hu\0 00 00000H00 couon 0003‘

.«.o.pcoov o< xwucmmmd

162

 

00.m m0.0 m0 om~.o mm
mmom mH.m mm oam.o Hm
0~.m .. mm 00m.0 om
0H.m mm.m mm mom.o 0H
mm.m 00.0 mm oom.o 0H
:0.m 00.0 mm omm.o 0H
mm.m 00.0 mm 0mm.0 ma
mo.m mn.m no oom.o oH
mm.m 00.0 mm mom.0 0
Hm.m 00.0 mm m0m.o 0
mfl.m 00.0 mm 00N.0 0
Hm.m 00.0H mm mam.o m
mm.m m0.o om omm.o N
om.m mm.m om mflm.o H
. 00

fio.m 00.0 mm 00N.0 on
m0H x H0\m m0 00000H00 00000 0000

 

.A.U.pcoov m< xflUCmmn<

163

 

 

00.m -- m0 0mm.0 Hm
00.N 0m.0 m0 0mm.0 on
mm.m mm.m am omm.o mm
Ho.m 0m.0 m0 00N.0 mm
00.m 0m.0 m0 00N.0 0m
00.m no.0 m0 000.0 00
00.m mH.m m0 mmm.o mm
mofi x Hp\m 00 00000H00 couom 090o

 

.A.U.Pcoov o< xflucmmaa

16h

 

m0.m 00.0 000 m0m.0 00
00.0 00.0 000 mmm.0 mm
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 mm
00.0 00.0 000 000.0 mm
00.0 00.0 00 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
mm.m 00.0 000 00.0 00
mm.m 00.0 00 000.0 00
00.0 0m.0 00 000.0 00
m0.m 00.0 mm 000.0 00
00.m 00.m ow 000.0 m
0m.m 00.0 00 000.0 0
mm.0 00.0 mm mmm.0 0
00:00

m00 x Hp\m mm 0000000o 000om 000m

.00m020 00000 000000 000 00000 0p\m 000 .00 .00\000 00000000 .00\000 00000

.00 00000000

165

 

00.0 -- 000 000.0 mm
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 0
00.0 00.0 00 000.0 0
-- 00.0 .. 000.0 0
00.0 00.0 00 000.0 0
00.0 00.0 00 000.0 m
00.0 00.0 00 000.0 m
00.0 00.0 00 000.0 0
0.0.0.00

00.0 00.0 00 000.0 on
00.0 00.0 00 000.0 00
m00 x 00\0 00 00000000 00000 0000

 

.0.0.00oov 00 00000000

166

 

00.0 o0.0 00 m0m.o mm
00.0 00.0 00 000.0 00
No.0 00.0 0o0 000.0 00
00.0 00.0 000 omm.o 00
no.0 00.0 oo0 mom.o 00
00.0 00.0 000 o00.o m0
mo.m om.0 oo0 mom.o 00
00.0 om.m m0 ocm.o 0
no.0 00.0 00 000.0 m
0o.m 00.0 000 000.o m
00.0 om.0 mo0 o00.o 0
0:00

00.0 o0.0 00 000.0 on
00.0 00.0 00 000.0 00
00.0 o0.0 mm 000.0 00
00.0 00.0 00 mmm.o mm
000 x 00\0 :0 00000000 00000 0000

 

 

.A.o.pcoov m< xflucmqat

167

00.0

 

000 o0m.o mm

00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
.00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 mom.o 0
00.0 00.0 000 000.0 0
00.0 .. 000 000.0 m
-- -- -- omm.o 0
00.0 -- 000 omm.o 0
0000

00.0 00.0 000 000.0 on
00.0 -- 000 000.o 00
00.0 00.0 000 000.0 00
00.0 00.0 00 000.0 00
M00 x 00\0 00 00000000 00000 0000

 

.0.0.00000 00 00000000

168

 

o0.m 00.0 000 000.o 00
00.0 00.0 000 000.0 00
0o.m 00.0 000 000.0 00
00.0 om.0 000 mmm.o 0
00.0 00.0 000 m00.o 0
00.0 00.0 000 000.0 m
00.0 .. 000 omm.o 0
00.0 .. 000 owm.o 0
.000

00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 om
00.0 00.0 000 000.0 00
00.0 o0.0 000 000.0 00
00.0 00.0 000 m0m.o mm
00.0 00.0 on0 m0m.o 00
0o.m 00.0 000 mmm.o mm
000 x 00\0 00 00000000 00000 0000

 

.0.0.00000 00 00000000

169

 

00.0 00.0 00H 0mm.o m
00.m ma.m 00H omm.0 0
om.m nfl.m :NH ofim.0 m
:m.m om.m 0mH mom.o m
.mmmw

m:.m mm.m :NH oom.o mm
:H.m 00.0 00H mam.0 mm
00.0 0m.m Hmfi 00N.0 mm
mm.m 00.0 mmfi 00m.0 00
00.0 00.0 00H omm.o mm
om.m 00.0 NNH mom.o mm
00.0 00.0 000 00m.0 Hm
0H.m 00.0 mmfl 000.0 om
Hm.m 00.0 0mH 00m.0 0H
00.0 00.0 0MH mom.0 0H
00.0 0m.0 mmfl mmm.o ma
mcfi x Hp\m 00 00000a00 cogom 000a

 

.A.0.00000 m< xfl0c000<

170

 

00.0 00.00 000 mom.o 00
0m.m m0.0 MHH omm.0 0m
m0.m 00.0 :00 oom.o mm
0m.m 00.0 000 000.0 :m
00.0 00.0 000 00m.0 mm
00.0 00.0 000 mom.o mm
mm.m 00.0 HNH onm.o m0
mm.m 00.0 000 0mm.o 00
wm.m 00.0 mmfi mfim.o 00
00.0 00.0 000 00m.0 00
mm.m 00.0 mmfi 00N.0 00
mm.m 00.0 000 mmm.0 00
00.0 00.0 000 mmm.o M0
0m.N 00.0 000 m:m.0 00
00.m mm.m NMO m:m.o m
mm.m -- mmfi omm.o m
m00 x Ho\m ma 00000000 00000 000:.

 

.A.0.0:00V m< x000000<

171

mn.w

 

00.0 000 000.0 mm

00.0 00.0 000 000.0 00
00.0 .. 000 00N.0 om
m0.m 00.0 ~00 000.0 00
00.0 mm.0 000 oom.0 00
00.0 00.0 000 00m.0 00
00.0 00.0 N00 00m.0 m0
m0.m 00.00 ~00 mom.o 00
00.0 00.0 000 oomoo 0
mm.m 00.0 N00 ommoo 0
00.0 00.00 ~00 000.0 0
00.0 mm.00 N00 mom.0 m
0m.m m0.00 00 mom.o m
m0.m 00.0 000 mom.o 0
. 00

00.m m0.00 N00 oom.o on
m00 x Hp\m IQ mvfinoano Couom mpma

 

.0.0.0:000 00 x000000<

172

 

 

00.m 00.0 N00 mmm.0 on
00.0 00.0 ~00 000.0 mm
00.0 00.0 000 000.0 mm
No.0 00.0 000 omm.o mm
00.0 00.0 000 000.0 0m
0m.m 00.0 000 000.0 mm
mo0 x 0p\m 00 00000000 00000 0000

 

.0.0.00000 0< 0000000<

173

mm?“

 

00.0 00 000.0 00

00.0 00.0 00 000.0 mm
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 mm
00.0 00.0 00 000.0 mm
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 00
mm.m 00.0 00 000.0 00
00.0 0m.0 00 000.0 00
00.0 00.0 00 000.0 00
-- 00.0 -- 000.0 0
m0.0 00.0 00 000.0 0
00.0 00.0 00 000.0 0
40000

000 x 00\0 00 00000000 00000 0000

 

000020 00000 000000 000 00000 00\0 000 .00 .00\000 00000000 .00\000 00000

.00 00000000

174

0:.N

 

00.0 00 000.0 00

00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 00
mm.m 00.0 00 000.0 00
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 0
00.0 00.0 00 000.0 0
00.0 00.0 00 000.0 0
00.0 00.0 00 000.0 0.
00.0 00.0 00 000.0 m
00.0 00.0 00 000.0 m
00.0 00.0 00 000.0 0
000

00.0 00.0 00 000.0 on
00.0 00.0 mm 000.0 mm
00 x 00\0 00 00000000 00000 0000

 

.A.0.0000v m0 x0000000

175

 

 

00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 M0
00.0 00.0 00 000.0 00
mm.m 00.0 00 000.0 0
00.0 00.0 00 000.0 m
00.0 00.0 00 000.0 m
00.0 00.0 00. 000.0 0
0:30

00.0 00.0 00 000.0 on
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 00
00.0 00.0 00 000.0 00
00.0 -- 00 000.0 mm
000 x 00\0 00 00000000 00000 0000

 

.A.n.pcoov m< xficcmmm<

176

 

00.0 00.0 000 000.0 00
00.0 0m.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 000 000.0 0
00.0 00.0 000 000.0 0
00.0 -- 000 000.0 m
-- -- .. 000.0 m
00.0 -- 000 000.0 0
0000

00.0 00.0 000 000.0 om
00.0 -- 000 000.0 00
00.0 00.0 000 000.0 00
00.0 00.0 00 000.0 mm
00.0 00.0 00 000.0 mm
000 x 00\0 00 00000000 00000 0000

 

.A.0.0:oov m0 x0usmma<

177

00.0

m©.m

 

NNH nom.o m

mm.fi om.m mHH 0HN.0 m
mm.H 00.0 0H0 mam.o m
m0.fi .. 0HH mom.o 0
0H.N om.m 0H0 omm.o H
.mm«

mH.N 0H.m 0HH mmm.0 Hm
mo.m om.m mfifi 00N.0 om
00.m 0N.0 BHH 00N.0 0m
00.H no.0 mHH mmm.o mm
0m.H 00.m mHH 0HN.0 mm
00.0 0m.m mHH omm.o 0m
mH.m 00.m mHH 00N.0 mm
00.m 00.w 0H0 0mm.o mm
m0.m 00.0 MOH omm.0 Hm
om.H oo.m moH mmH.o m0
mofi x Hp\m x0 00000H00 couom 000a

 

.A.U.PCO0V m< xflucmmm<

178

 

:md 0:6 doe mmmé N
.mmmm

mm.~ mm.m ONH mmm.o mm
mo.m 0m.0 00H mmm.o mm
mm.m 00.0 0NH 00N.0 0m
mo.m m0.m mmfi 00N.0 0N
mm.m m:.m NHH 00N.0 mm
mm.m 0N.0 mHH 00N.0 mm
0m.m mm.0 0H0 00N.0 Hm
H0.H 0H.m mmfi m0m.0 0m
0m.fi om.m 0NH mmm.o 0H
00.m 00.0 0NH 00N.0 ma
m0.m 00.0 0NH mmm.0 ma
mm.H 00.0 0mH 00N.0 0H
mw.H mm.0 0NH 0mm.0 NH
00.H 0m.m mmfi 00N.0 HH
mofi x H0\m x0 00000H00 :000m mpmo

 

.A.U.pcOoV m< xflUCmam<

179

 

0H.m 00.0 mHH 00N.0 0m
00.H om.0H 0NH 00N.0 mm
mH.N 0N.00 0NH 00m.0 mm
oo.m 00.0 00H omm.o 0H
0o.m m0.0 00H 00N.0 ma
00.m 00.0 mmfl 00N.0 0H
0H.m 00.0 0mH 00N.0 0H
0m.m m0.m 0NH mmm.o ma
00.0 00.0 00H mmm.0 NH
mm.H 00.0 mmfi mwm.0 HM
0m.H mm.m 000 00N.0 00
mH.m mm.m mmfi 00N.0 0
N0.m -- 0NH 00m.0 w
mm.m 00.0 000 00N.0 m
m0.m 0N.0 mHH 000.0 0
0m.m mm.m mflfl 00N.0 m
mofl x Hp\m :0 00000Hno couom 090a

 

.A.n.pcOov m< xflvc®mmc

180

 

sm.m 00.0 nmfi 000.0 0H
00.0 00.0 00H nmm.o 00
00.0 n0.0 000 nwm.0 0H
00.0 n0.0 000 000.0 00
00.N n0.0 00H 00N.0 0H
00.0 n0.0 000 n0m.o 0
00.H 00.0 00H onm.o 0
00.0 nn.0 000 000.0 0
mm.m n0.0H an 000.0 0
mm.m 00.00 an nmm.0 N
mm.m no.0 00H n0m.0 H
. 00

00.0 0n.0 000 n0m.0 00
0N.0 0n.0 000 00N.0 00
00.0 nn.0 an onm.o 0N
0m.m n0.0 000 000.0 nm
000 x Ho\m 00 00000000 00000 0009

 

.A.U.pcoov m< xflUCmaa<

181

 

00.0 00.0H 00H nmm.o 00
n0.H 00.0 00H o:m.o 0m
mo.m 00.0 00H onm.o mm
00.0 00.00 000 n0m.0 00
00.0 n0.0 an nom.o 00
00.0 00.0 0m0 000.0 mm
0H.m nn.0 000 o0m.o mm
00.0 00.0 00H n00.o Hm
00.m -- 00H 000.0 om
moH x Hoxm ma mnflhoaso couom mpma

 

.A.0.p:000 0< x00c000<

182

 

+l
+l
o

 

 

00.0 00.0 00.0 \0.0 0.0 H 0.000 000.0 + 000.0 0000000
0n.0 H 00.0 0n.0 H 00.0 0.00 H 0.000 000.0 m 000.0 000000000
00.0 H 00.0 0n.o w 0n.0 0.00 H 0.000 000.0 w 000.0 000000
n0.0 H 00.0 00.0 0 00.0 n.m 0 0.000 000.0 0 000.0 0000
000 x 00\0 00 00000000 00000 00000

 

.000020 00000 000000 0000 0000

000 0200900>mo vHNUQMpm 0:0 0:002 00:0:o2

.00 00000000

183

 

+u

 

30.0 + om.m 30.0 00.0 m.m H m.000 m0o.o H mom.o hmnopoo
00.0 0 00.0 n0.0 H 00.0 0.0 H 0.000 000.0 0 000.0 000000000
00.0 H 00.0 00.0 H 00.0 0.0 H 0.n00 000.0 0 000.0 000000
00.0 H 00.0 00.0 H 00.0 0.0 H 0.000 n00.0 0 000.0 0000
00.0 0 00.0 n0.0 H 00.0 0.00.0 0.000 000.0 0 000,0 00:0
00.0 H 00.0 00.0 H 00.0 0.00 0 0.000 000.0 0 000.0 002
00.0 H 00.0 00.0 0 00.0 0.00 0 0.00 000.0 0 000.0 00000
000 0 00\0 00 00000000 00000 00000

 

.OM0023 9:000 m0050m 8000 0003 000 0:00000>0Q 0000:00m 0:0 0:00: 00:»:02 .004 x00:mmm<

181+

 

 

00.0 + 00.0 00.0 + 00.0 0.0 + 0.00 000.0 0 000.0 0000000
00.0 H 00.0 00.0 H 00.0 0.00 H 0.000 000.0 0 000.0 000000000
00.0 m 00.0 00.0 H 00.0 0.0 H 0.000 000.0 0 000.0 000000
00.0 H 00.0 00.0 H 00.0 0.00 H 0.000 000.0 0 000.0 0000
00.0 H 00.0 00.0 0 00.0 0.00 0 0.00 000.0 H 000.0 0000
00.0 H 00.0 00.0 H 00.0 0.0 u 0.00 000.0 0 000.0 000
00.0 0 00.0 00.0 0 00.0 0.0 0 0.00 000.0 0 000.0 00000
m00 x 00\m x0 00000000 £0003 £0003

 

.000020 00000 000000 0000 0000 000 0000000000 00000000

000 00002 0000000

.000 00000000

185

 

 

am.o H :o.m :m.o H mw.m m.: w n.0HH mmo.o + mmmoo umpopoo
om.o w mm.m mm.o u mm.m 5.NH H «.mNH mHo.o w :Hm.o “magmpamm
mm.o w mfi.m mm.o w :m.m m.o u m.mmH «No.0 H nmm.o pmzms<
mm.o w mo.fl m:.o w om.m 2.0 H u.wma mmo.o w g:m.o masa
om.o w ao.m mfi.o H mm.@ n.mfi w m.oofl omo.o w mam.o mesa
mm.o w mm.m mm.o H om.w o.m M :.2m mmo.o w mmm.o has
am.o w mm.m mm.o w om.m o.m u 5.30 amo.o u mHN.o Hflua<
moH x ao\m :Q muwuoaco Couom :pcOs

 

.omqu: pcflom maaemm sou% «pan u0% mcoflpmfl>mq nuancmpm new mama: aazpcos

.NH< xflvcmga<

186

 

 

om.o u 5H.m mm.o H 55.0 H.H + 5.:NH omo.o w 5cm.o umnopoo
mm.o w ofi.m o:.o H 53.5 0.HH w 0.05H 0H0.0 u N5m.o “magmpgmm
Hm.o H mo.m 05.0 + 50.5 m.5 w :.NNH omo.o u 5:~.o pmsms<
mm.o u m5.H «0.0 + m5.m 0.0H u H.HHH mmo.o w amm.o masw
am.o w :H.m No.0 + :m.m 5.mH u 5.55 Hmo.o u 005.0 mczw
:m.o w Nm.m Ho.o u H:.m :.m u 5.0m Nmo.o H Hmfi.o 5mg
mm.o w NH.N w:.o + mm.5 w.5 u N.0w Hmo.o w omfl.o aflum<
mofi x ao\m za ocflpoaso couom syncs

 

.omaqz: pcflom maasmm aou5 «pan go“ mQOflpmH>ma unau:muw cam madms mangcoz

.mH< xflucmmm<

Appendix A14.

187

Boron (mg/l) Data for Sample Point UNASOB.

 

 

Date Boron Date Boron
April Max

7 0.180 29 0.225
8 0.185 30 0.195
9 0.200 M2

10 0.190 2 0.215
11 0.200 3 0.185
21 0.165 5 0.215
22 0.165 9 0.205
23 0.175 12 0.180
29 0.175 13 0.230
25 0.185 16 0.185
28 0.195 17 0.225
29 0.185 18 0.220
30 0.190 19 0.215
MEX 23 0.220
1 0.160 25 0.215
2 0.180 26 0.235
5 0.190 27 0.220
6 0.180 JELX

7 0.195 1 0.220
8 0.195 2 0.210
9 0.210 3 0,205
12 0.180 525.

13 0.195 0 0.200
10 0.200 5 0.190
15 0.195 7 0.210
19 0.185 8 0.215
23 0.205 11 0.220
27 0.235 12 0.230
28 0.205 10 0.250

Appendix A10 (cont'd.).

 

 

Date Boron Date Boron
{Lg- E22.-

15 0.225 22 0.265
18 0.195 23 0.250
19 0.175 24 0.245
20 0.195 25 0.235
21 0.185 26 0.235
22 0.195 29 0.285
25 0.240 30 0.265
26 0.260 Qg_.

27 0.255 1 0.275
28 0.255 2 0.270
29 0.255 3 0.275
§§2§ 6 0.260
2 0.260 7 0.250
3 0.255 9 0.260
4 0.265 10 0.255
5 0.250 13 0.250
8 0.270 14 0.275
9 0.275 16 0.235
10 0.265 17 0.200
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18 0.265 22 0.280
19 0.280

 

189

 

 

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199

Appendix A20. Data for Two Algae Samples from Lake 2.

 

 

Sample Total Boron(ppm) %C %N %H
1 116.72 t 5.75 28.5 3.40 3.81
2 119.6/5L :- 12.15 22.9 2.79 2.62

Appendix A21. Boron and Organic Matter Data for Sewage Sludge.

 

 

Date Total Boron(ppm) Organic Matter(%) B0ron(mg/l)
2-13-76 28.142 t 2.759 50.61 t 1.86 0.264
2-18-76 26.996 t 3.385 --- 0.309
2-20-76 53.292 t 11.798 --- 0.241
2-23-76 32.664 t 3.898 --- 0.176
2-24-76 45.581 1 5.963 50.03 t 0.90 0.205
2-26-76 84.332 t 33.637 50.99 t 2.87 0.202
3-8-76 83.356 t 8.222 49.37 t 0.62 0.206
3-15-76 82.522 1 19.860 44.02 t 2.12 0.203
3-23-76 79.338 t 11.386 45.71 t 0.42 0.304
3-24-76 81.407 t 11.219 45.06 t 0.50 0.303

200

 

 

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203

Appendix A28. interface Thickness of Sediment Samples.

 

 

Lake Date Sample Thickness(cm)
1 5/3/75 A 5-50
F 2.00
C 2.00
L 3.00
M 2.00
1 9/16/75 A £1.50
F 1.60
C 2.20
L 1.10
M 2.00
4 5/9/75 A 1°70
F 1.50
C 0.75
L 1.75
M 1.00
4 10/9/75 A 1.00
b 1.20
C 1.80
L 2.00

M 1.50

 

204

Appendix Bl. Volumes and Retention Times for Lakes.

 

VOLUMES
Lake 1 53.54 x 106 Liters
Lake 2 53.87 x 106 Liters
Lake 3 70.16 x 106 Liters
Lake 4 81.20 x 106 Liters

RETENTION TIMES

 

Assume constant input of 0.5 MGD of effluent.

0.5 M00 x 3.785 Liters/Gallon a 1.893 x 106 Liters/hay

Lake 1) 53.5“ x 106 / 1.893 x 106

28.29 days

Lake 2) 53.87 x 106 / 1.893 x 106 a 28.u6 days

Lake 3) 70.16 x 106 / 1.893 x 106 a 37.06 days

Lake #) 81.20 x 106 / 1.893 x 106 “2.89 days

 

205

Appendix BB. Statistical Equations Used in Data Analysis.

 

MEAN

Zx's

XI
11
3 [H

STANDARD DEVIATION

S z/nz - (2x2)./n
n - 1

 

 

 

 

 

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A = Zyixd - inxy
9 2
nzx“ - (2X)
SLOPE
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nix“ - (2x)2

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206

Appendix 83. Relation of Total and Available Boron in Sediments.

 

 

y = Available Boron X y
X = Total Boron 0 -1.16
10 -0.66
_ - 20 -O.16
y = 1'2“ P8” 30 0.34
E = “8.68 ppm 40 0.85
50 1.35
’ 60 1.85
A = -1.16 (Intercept) 70 2.35
B = 0.05 (Slope) 80 2.86
90 3.36
100 3.86
y = —1.16 + 0.05x (Equation of Line)
r2 = 0.76
r = 0.87

Significant Correlation at 0.01 (r - 0.463)

207

Appendix Bu. Relation of Available Boron and Organic Matter
in Sediments.

 

 

y 2 Available Boron x y
x = Organic Matter 0 -0'27
1 0.07
2 0.41
§ 2 1028 ppm 3 0075
51 1.42
6 1.76
A = -0.267 (Intercept) 7 2.10
B = 0.338 (Slope) 8 2-44
9 2.78
10 3.12

y = -O.267 + 0.338x (Equation of Line)

I‘ = 0073

r = 0.85

Significant Correlation at 0.01 (r = 0.h63)

 

 

208

Appendix B5. Relation of Total Boron and Organic Matter
in Sediments.

 

y = Total Boron x y

x = Organic Matter 0 21'9”
1 27.78
2 33.62

5 = 48.68 ppm 3 39.46

E = 4.58 % a “5'30
5 51.14
6 56.98

A = 21.94 (Intercept) 7 62.82

B = 5.84 (Slope) 8 68'66
9 74.50

10 80.33

y = 21.94 + 5.84x (Equation of Line)

r2 = 0.72

r = 0.85

Significant Correlation at 0.01 (r 2 0.463)

 

 

209
Appendix B6. Relation of Total Boron and Organic Matter
' in Sewage Sludge.

 

 

y = Total Boron x Ag

x = Organic Matter 0 258'0
20 179.3
40 100.6

E" = 69.24 ppm 50 61-3

i- : 47.97 ya 60 2109

A = 258.0 (Intercept)

B = -3.9 (Slope)

Y = 258-0 + -3.9x (Equation of Line)
r2 = 0026
r =3 0051

Not Significant at 0.05 (r = 0.75)

 

216

Appendix 8?. Relation 0: Total Boron in Sewage Sludge and
:oron Scncentration of Water.

 

 

y = Total Boron x y
x z Boron Concentration in Sewage Water 0'0 67'82
0.1 64.48
0.2 61.1“
g = 59:70 ppm 0.3 57.80
i = 0.261 ppm 0'“ 54.46

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i.

0.005

Not Significant Correlation at 0.05 (r = 0.75)

p