ORTHOPHOSPHATE CONCENTRATION — g/l as P

2500 T T T T T T T

T
Abatement of
Domestic Pollution Orthophosphate in STONE LAKE

at Overturn

2000

°

1500

1000

Residual
Or thophosphate

Predicted by Washout
500 L y

fo) 1 J ! ! ! ! i !

ie) | 2 3 4 5 6 7 8
TIME — YEARS AFTER POLLUTION ABATEMENT

Figure 3: Washout vs. Overturn Orthophosphate in Stone Lake.


the appearance of filter-feeding zooplankton. The fact that the only green
algae which were present at this time were too large to be grazed by most

zooplankton suggests that the zooplankton had an impact on the rest of the

algal community.

Concurrently with the phytoplankton biomass increase, the macrophytes began

to die off. The decrease in weeds may have been due to shading from algae,
but, in any event, the macrophyte decline brought a simultaneous increase

in epilimnetic soluble phosphate. This event was not studied closely enough

to determine if the phosphorus regeneration was mainly due to nutrient pumping,
as suggested by Schults and Maluegl’, or to decay of the plants themselves.

As mentioned earlier, the green algae were the first to dominate the phyto-
plankton community. This dominance is probably due to their more rapid
growth and to the excess availability of all nutrients in the spring. At

the beginning of June the nitrate concentrations had become quite low (points
a, Figure 11) and ammonia was already zero in the surface water (Figure 10).
The low combined inorganic nitrogen provided a competitive advantage to the
nitrogen-fixing blue-green algae, which began to rise at the expense of the
green algal growth rate (Figures 12 and 13). The dominance and decline of
Anabaena and Aphanizomenon in late June and July brought a regeneration of
nitrogen in the epilimion. The nitrogen which they fixed appeared as
soluble nitrate due to their continual decomposition and the subsequent
nitrification of the ammonia released. The rapid decline of the nitrogen-
fixers could have been due to a number of reasons. Two plausible explanations,
however, are bacterial attachment -- blue-green algae are closely associated
with bacterial activity (Kuent ze1!®, Lange?) -- and the return of the
competitive advantage to the green algae because of the increased nitrogen
levels. Huang et a1.70 have used nutrient enrichment tests to show that
green algae, especially Chlorella, can more effectively compete with blue-

greens when phosphorus and nitrogen are added to a nutrient poor environment.

Green algae dominated again through August and again depleted the nitrate
in the water. This time blooms of Microcystis and a motile green alga shared

30


3
o
T

ro)
a
T

PHYTOPLANKTON DENSITY (Number/liter) (Log 19 scale)

Total a
All green algae

Nitrogen fixing
cyanophytes

Other cyanophytes

o db0

Figure 12:

J J A Ss 10) N
1973

Total Phytoplankton Density and Green, Nitrogen-
fixing Blue-green, and Non-nitrogen-fixing Blue-
green Phytoplankton Groups Densities in Stone Lake,
Michigan for May through October, 1973. Values
Represent a Composite of Upper 12 feet of Depth.

26


Te
TH, METERS
NM Dw WM - O
TOT TT TT TT

A

cS

DRQAC

DEP
B= 60 o
= TT
«fe
~~ °



Table 4 indicates the range of the macro-constituents of this substance.
It is composed primarily of silica, alumina, and variable amounts of
iron and calcium oxides. The lime brings about phosphate removal from
the overlying water and once in place fly ash displays sealing proper-
ties which effectively retard the release of phosphorus from the under-
lying sediments. Due to the variability of the lime content naturally
present in fly ash, some lime makeup may be required to bring about
acceptable levels of phosphate precipitation.

Table 4. TYPICAL RANGES OF THE CHEMICAL COMPOSITION OF FLY ASH

FROM PULVERIZED COAL FIRED PLANTS
(after Minnick?’)

Range

Constituent % by weight
Silica, $10, 34 - 38
Alumina, 41,0, 17 - 31
Iron Oxide, Fe,0, or Fe,0, 2 - 26.8
Calcium Oxide, CaO 1 -10
Magnesium Oxide, MgO 0O.5- 2
Sulfur Trioxide, SO, 0.2- 4

The effectiveness of fly ash in precipitating and retarding phosphate
release is illustrated in Figures 14 and 15. Depending on the fly ash,
a 5-20 gram/liter dose and a 2 to 5 centimeter layer should bring about
the desired effects.

To see if treated Stone Lake water was phosphorus limited, and perhaps
nitrogen limited also, an algal regrowth study was conducted on Stone

Lake water treated with 5 g/2 fly ash plus 150 mg/2 lime, and spiked

35


SECTION III

INTRODUCTION

GENERAL

This report contains information relating to two factors: (1) the effects

of domestic pollution abatement on a eutrophic lake, and (2) investigations

into methods of reclaiming such lakes especially through the use of particulate
materials which retard pollutant release from sediments. The study was for a
three year period supported by an Environmental Protection Agency grant (R-801245)
awarded for the period April 1, 1971 to May 31, 1974. It was an extension of

a previous grant from the Federal Water Quality Administration, the details

of which can be found in a previous report (Tenney et al.).
LOCATION AND DESCRIPTION OF PROJECT LAKE

The project lake was Stone Lake, located within the village limits of
Cassopolis, Michigan (pop. 3000) approximately 40 km northeast of the campus

of the University of Notre Dame. Between the years 1939-1966 it was used as

a receiving water body for the secondary wastewater effluent from the village.
In 1966 the residents of the village, concerned about Stone Lake's deteriorating
water quality, constructed a new wastewater treatment facility located outside
of the lake's natural drainage basin. Except for a few septic systems and

some storm drainage from the village, all domestic sources of pollution were
eliminated. Measurements indicated the total input of phosphorus to the lake

was reduced by 95%.

Stone Lake is a seepage lake with no natural surface inlets or outlets. A

hydrographic contour map is shown in Figure l.


11.

12.

13.

14.

15.

16.

17.

18.

19.

20.

21.

22.

23.

Soeder, C. J., Miller, H., Payer, H. D., and Schulle, H., "Mineral
Nutrition of Planktonic Algae: Some Considerations, Some Experi-
ments," International Association of Theoretical and Applied
Limnology, 19, p. 39 (1971).

Uhlmann, D., "Influence of Dilution, Sinking, and Grazing Rate on
Phytoplankton Populations of Hyperfertilized Ponds and Micro-
Ecosystems," International Association of Theoretical and Applied

Limnology, 19, p. 100 (1971).

Shapiro, J., "Blue-Green Algae: Why They Become Dominant," Science,
179, p. 382 (1973).

Azad, H. S., and Borchardt, J. S., "Variations in Phosphorus Uptake
by Algae," Environmental Science and Technology, 4, p. 737 (1970).

Round, F. E., "The Growth and Succession of Algal Populations in
Freshwaters," Mitt. Int. Ver. Limnol., 19, p. 70 (1971).

Mortimer, C. H., "Physical Factors with Bearing on Eutrophication

in Lakes in General and in Large Lakes in Particular," Eutrophication:
Causes, Consequences, Correctives, National Academy of Sciences,
Washington, D.C., p. 340 (1969).

Schults, D. W., and Malueg, K. W., "Uptake of Radiophosphorus by
Rooted Aquatic Plants," Proceedings of the Third National Symposium
on Radioecology, Oak Ridge, Tennessee (1971).

Kuentzel, L. E., "Bacteria, Carbon Dioxide, and Algal Blooms,"
Journal of the Water Pollution Control Federation, Vol. 41,
p- 1737 (1969).

Lange, W., "Cyanophyta~Bacteria Systems: Effects of Added Carbon
Compounds or Phosphate on Algal Growth at Low Nutrient Concentrations,"
Journal of Phycology, 6, p. 230 (1970).

Huang, V. H., Mase, J. R., and Fruh, E. G., "Nutrient Studies in
Texas Impoundments," Journal of the Water Pollution Control
Federation, Vol. 45, p. 105 (1973).

Bush, R. M., and Welch, E. B., "Plankton Associations and Related
Factors in a Hypereutrophic Lake," Water, Air, Soil Pollution, 1,
p. 257 (1972).

Hutchinson, G. E., A Treatise on Limnology, Volume 2, John Wiley
& Sons, Inc., New York, NY (1967).

Vinyard, W. C., "Growth Requirements for Blue-green Algae as Deduced
from their Natural Distribution," Environmental Requirements of
Blue-green Algae, (Proceedings of a Symposium) U.S. Environmental
Protection Agency, EPA-16010DXV10/67, p. 81, Corvallis, Oregon (1967).

63


The fly ash addition served to sink this Mat, and no signs of regrowth
or emergence of the mat occurred through the rest of the growing season.
However, the next summer portions of the mat reappeared with a grayish
tinge in color which suggests that gases produced through the winter and
early spring may have buoyed the mat up to the surface. Parts of the mat
were definitely green and viable indicating that the increased nutrients
due to runoff allowed for the development of an algal mat similar to that
Present before treatment. This occurrence indicates a potential problem
associated with applying fly ash over the macrophytes in Stone Lake and
their subsequent decomposition. It may be necessary to harvest any
macrophytes present in the lake prior to treatment. Another potential
Problem associated with macrophytes is their possible regrowth through
the fly ash in the littoral areas of the lake after treatment.

COMPARATIVE COSTS OF RECLAMATION

One drawback to the use of fly ash, or other particulate materials, as
aids to lake reclamation is the quantity of material involved. Based on
previously cited studies, amounts of up to 300 tons of fly ash per acre
are necessary. In spite of this, a cost analyses of various lake recla-
mation techniques, as applied to Stone Lake, found sediment sealing to
be competitive with most other methods and considerably less expensive
than some (Girman2?), The total cost of fly ash application to Stone
Lake was determined to be approximately $250,000. Table 7 indicates the
relative cost effectiveness of seven reclamation techniques weighted by

several factors onascale of 1 (least effective) to 5 (most effective).
SIDE EFFECTS

Unfortunately, fly ash imparts many water soluble species to an aqueous
solution. Table 8 is a partial list of these components and the
probable chemical form under which each would be likely to exist.

45


5cm
LAYER OF
FLY ASH

300 mg/l

Scm

LAYER OF FLY ASH
AND

150 mg/l LIME AS CoO

ie] 300m
—a es

STONE LAKE RESTORATION

Figure 18: Restoration Plan for Stone Lake (after Yaksich26),
43


64
DISSOLVED OXYGEN, mg/l

10.0

70

EFFECT OF FLY ASH No.2 ON
DISSOLVED OXYGEN IN A LAKE
COLUMN

40 g/l

1 i i 1

°

- PY PF ADA N ® oO
900000008

Figure 19:

2 3 4
TIME (DAYS)

Dissolved Oxygen Depletion and Subsequent Reaeration in an Isolated
Lake Column Following Fly Ash Addition.



10.0

a
7.0

T T T T T T U q v
RELEASE OF MERCURY IN LABORATORY -+ 90
AQUARIA. FLY ASH No.2 20g/1 .
— 4 8.0
o-Hg i”
4-pH
4 60
TT 5.0
8 9 10 IT 2 13 14 15 16

TIME (DAYS)

Figure 21: Mercury Release Patterns After Fly Ash Addition
to Laboratory Reactors.


Table 5
POLLUTIONAL POTENTIAL OF STONE LAKE SEDIMENTS

Soluble Retained on

Location Depth Orthophosphate |Total Soluole P cop NH3 Organic-N Organic Matter #200 sieve
Number ft. mg/l as P0g mg/l as P04 mg/lasO mg/lasN |mg/las N % dry wt. J Water % dry wt.
[ i
1AL 5 2.50 2.50 27 5.4 2.5 13,21 90.6 6.6

faz 8 7.16 8. 60 36 5.6 3.1 47.0 95.3 M4
AR 8 3.00 3.10 36 8.2 3.2 28.3 88.4 36.5
AS 8 3.75 3.95 40 5.5 3.2 44.2 93.8 8.1
AS 20 2.90 3.20 40 1.2 2.8 40.4 93.0 7.0

lat 20 5.70 5.70 48 8.5 2.2 12,3 76.2 72.3

1B2 42 7,30 8.10 63 35.0 3.9 32.3 92.8 2.5

~ [a3 44 6.10 7.10 16 39,2 3.6 22.8 93.0 3.3
= 1B4 35 8.60 8,84 55 23.7 - 28.1 91.6 12.6

BS 27 3.40 3.80 44 28.5 3.9 37.6 92.1 1.2
BG 50 4.85 6.00 55 43.2 4,2 33.9 92.0 10.4
BT 30 6.90 6.90 55 17.0 2.8 18,2 91.5 8.t
cL 18 1,70 1.70 55 2.6 3.9 2.5 41.8 94.6

ic2 5 1,25 - 72 1.6 - 1.7 27.7 99.0

{c3 16 1.40 - 45 1.8 - 1.5 36.8 98.6

;c4 9 1.70 - 86 2.0 - 0.7 22,2 99.5

cs 8 1,10 - 82 6.9 - 3.2 38.9 95.8

cé 7 45 - 91 1.9 - 0.5 18,7 99.4

c7 4 64 - 124 2.4 - 4.2 23.2 94.5

ca 12 1,32 - 107 2.4 - 0.3 23.1 98.8

DI 8 1.90 1,97 24 2.8 3.2 61.8 95.3 13.8

Ip2 4 3.92 4.70 34 1.5 2,2 20,2 96,2 27.5

jD3 18 3.25 3,47 38 5.7 17 29.2 94.4 23.1

i

1

* Concentration in interstitial water.


Coincidental with the macrophyte die-off in the first two weeks of June was
the beginning of the summer phytoplankton bloom conditions. Relatively
high suspended solids were attained in the surface waters by the end of
June and lasted at least through the fall circulation. There were at least
three individual peaks of suspended solids during this period (points d, e
and f) which will be seen to coincide with individual algal species blooms.
Also of interest is the gradual increase of solids in the thermocline region
throughout the stratification period. The contour lines roughly follow the
same deepening pattern as the thermocline, suggesting that some of this
material is possibly being trapped in the thermocline region. In addition,
the abrupt decrease in suspended solids with depth through this region
suggests that this material is being degraded as it settles. It could also
mean that the settled material has simply reached its buoyancy level, and

therefore, sinks no further.

The pH and dissolved oxygen variations in Stone Lake (Figures 6 and 7,
respectively) provide an indication of gross trends in photosynthesis and
respiration. While Stone Lake possesses a relatively hard water (total
hardness between 110-120 mg/1 as Caco.) and is well buffered (total
alkalinity between 120-140 mg/1 as CaCo,), the pH does show some variations
through the year. In contrast, the dissolved oxygen changes are quite
dramatic and highly significant. The interpretation of these parameters

is as follows. A rise in pH and a corresponding rise in dissolved oxygen
can be interpreted as an indication of high photosynthetic activity. The
photosynthetic uptake of co, (or co,*) results in an increase in pH, and
the oxygen released during photosynthesis causes a rise in dissolved oxygen.
Conversely, plant respiration and aerobic decomposition utilizes o, and
releases C043 therefore, these processes could cause a decrease in pH and
dissolved oxygen. These parameters vary diurnally; however, all Stone
Lake sampling was conducted between 10 A.M. and 12 noon on each sampling

date.

13


the productivity. A rise in these groups could possibly have been due to the
depletion of an essential nutrient other than phosphorus. Bierman’,
Shapiro 13 and Bush and wetch?+ have reported that blue-green algae, es-
pecially Microcystis, can out-compete other species for phosphorus when
external concentrations are low. Warmer water has been given as a possible
explanation for the development of blue-green algae (Hutchinson?*, Vinyard??)
and this may, in fact, be a contributing factor. It has been reported that
the op, imum temperature for growth of most blue-green algae is about 35°C
(Fogg” 4), however Stone Lake did not exceed 26°C during 1973 and most green

25
algae achieve maximum growth rates at about 25° C (Marre).

The motile green algal bloom could also have been a nutrient-depletion
Phenomenon. Being motile, these algae may be able to more efficiently

obtain an essential nutrient which is in low supply. Although it was not
investigated, they may have migrated into the lower epilimnion or thermocline
at night and thereby replenished their supply of a nutrient which is exhausted
at the surface. Also, this particular motile-green bloom consisted of
Euglenophytes. It happened to coincide with an increase in soluble organic
nitrogen in the surface water (Figure 9). Hutchinson2? has stated that

Euglenophytes dominate in water rich in nitrogenous organic compounds.

Depletion of combined inorganic nitrogen signaled the onset of a nitrogen-
fixing blue-green bloom (Anabaena, Figure 13) in late August and early
September. This time the domination was complete and the green algae suffered
a setback. The large decline in the green population (Figure 12) in this

case could be due to an inhibitory substance excreted by the Anabaena.
Hutchinson reported a number of studies on the effect of water collected
from lakes and ponds at the time of a large Anabaena bloom on the growth of
test organisms. The filtrate of this water was always algistatic to all
species studies. Again the blue-green bloom crashed as quickly as it came
about, with the corresponding nitrogen regeneration - this time as ammonia.

It is interesting to note this type of cyclic succession of green to nitrogen-
fixing blue-green and back to green which occurs during summer stratification

in Stone Lake. This successional pattern will probably be common in most

31


10.

SECTION VI

REFERENCES

Tenney, M. W., Echelberger, W. F., and Griffing, T. C., "Effects
of Domestic Pollution Abatement on a Eutrophic Lake," Partial
Report on FWPCA Demonstration Project Grant WPD 126, Dept. of
Civil Engineering, University of Notre Dame, Notre Dame, IN 46556
(September, 1970).

Stumm, W., and Morgan, J. J., Aquatic Chemistry, Wiley-Interscience,
New York, NY (1970).

Sawyer, C. N., "Some New Aspects of Phosphate in Relation to Lake
Fertilization," Sewage and Industrial Wastes, 24, p. 768 (1952).

Hutchinson, G. E., A Treatise on Limnology, Volume 1, John Wiley
& Son, New York, NY (1957).

Fogg, G. E., "Nitrogen Fixation," Physiology and Biochemistry of
Algae, R. A. Lewin, Editor, Academic Press, Inc., New York, NY,
p. 161 (1962).

Ogawa, R. E., and Carr, J. F., "The Influence of Nitrogen on Hetero~
cyst Production in Blue-green Algae," Limnology and Oceanography, 14,
p- 342 (1969).

Hutchinson, G. E., A Treatise on Limnology, Volume 2, John Wiley &
Sons, Inc., New York, NY (1967).

Bierman, V. J., "Dynamic Mathematical Model of Algal Growth in
Eutrophic Freshwater Lakes," unpublished Ph.D. dissertation,
Department of Civil Engineering, University of Notre Dame, Notre
Dame, IN 46556 (1974).

Payne, A. G., "Responses of the Three Test Algae of the Algal Assay
Procedure: Bottle Test," paper presented at the Thirty-Sixth Annual
Meeting of the American Society of Limnology and Oceanography,

Salt Lake City, Utah, June 12, 1973.

Morton, S. D., Derse, P. H., and Sernan, R. C., "The Carbon Dioxide

System and Eutrophication," U.S. Environmental Protection Agency,
EPA-16010DXV11/71, Washington, D.C. (November 1971).

62


FOREWORD

Effective regulatory and enforcement actions by the Environmental
Protection Agency would be virtually impossible without sound scien-
tific data on pollutants and their impact on environmental stability
and human health. Responsibility for building this data base has
been assigned to EPA's Office of Research and Development and its
fifteen major field installations, one of which is the Corvallis
Environmental Research Laboratory (CERL).

The primary mission of the Corvallis laboratory is research on the
effects of environmental pollutants on terrestrial, freshwater, and
marine ecosystems; the behavior, effects, and control of pollutants
in lake systems; and the development of predictive models on the
movement of pollutants in the biosphere.

This report describes the effects of controlling domestic pollution
on a eutrophic seepage lake in Michigan ard the control of nutrients
in water by using particulate materials which retard nutrient release
from sediments.

BO? /rb

A.F. Bartsch
Director, CERL

aii


36.

37.

38.

39.

40.

Oglesby, R. T., "Effects of Controlled Dilution on the Eutrophication
of a Lake," Eutrophication Causes, Consequences, Corrections,
National Academy of Science, Washington, D.C., pp. 482-493 (1969).

Hammer, U. T., "Eutrophication and Its Alleviation in the Upper
Qu Appele River Systems, Saskatchewan," presented at the Symposium
of Lakes of West Canada, University of Alberta, Edmonton (1972).

Larsen, D. P., Malueg, K. W., Schults, D. W., and Brice, R. M.,
"Response of Eutrophic Shagawa Lake, Minnesota, USA, To Point Source,
Phosphorus Reduction," Verk. int. Ver. Limnol, 19, 884 (Oct. 1975).

Cordiero, C. F., "Mathematical Modeling of Lake Systems with
Nutrient Cycling,” Ph.D. dissertation, University of Notre Dame,
Notre Dame, IN 46556 (1975).

DePinto, J. V., Bierman, V. J., Jr., and Verhoff, F. H., "Seasonal
Phytoplankton Succession as a Function of Species Competition for
Phosphorus and Nitrogen," Mathematical Modeling of Biochemical
Processes in Aquatic Ecosystems, R. P. Canale, Editor, Ann Arbor
Press, Ann Arbor, MI (1975).

65


24. Fogg, G. E., "The Comparative Physiology and Biochemistry of the
Blue-green Algae," Bacteriological Reviews, 20, p. 148 (1950).

25. Marre, E., "Temperature," Physiology and Biochemistry of Algae,
R. A. Lewin, Editor, Academic Press, New York, NY, p. 54 (1962).

26. Yaksich, S. M., "The Use of Particulate Materials to Control Phosphate
Release from Eutrophic Sediments," Ph.D. dissertation, University
of Notre Dame, Notre Dame, IN 46556 (1972).

27. Minnick, L. F., "Investigations Relating to the Use of Fly Ash as
a Pozzolanic Material and as an Admixture in Portland Cement Concrete,"
Proceedings of the American Society of Testing Materials, 54,
p. 1129 (1954).

28. Higgins, B. P. J., Irvine, R. L., and Mohleji, S. C., "Tertiary
Treatment of Industrial Waste and Lake Restoration: A Similarity
in Approach," Proceedings of the 30th Purdue Industrial Waste
Conference, Engineering Bulletin of Purdue University, Series 145,
West Lafayette, IN 47907 (1975).

29. Girman, S. T., "Cost-Benefit Evaluation of Various Lake Reclamation
Techniques," M.S. thesis, University of Notre Dame, Notre Dame, IN
46556 (1974).

30. Hampton, T. K., “Evaluation of the Effects of Fly Ash and Lake
Restoration by Fly Ash on Aquatic Consumer Organisms," M.S. thesis,
University of Notre Dame, Notre Dame, IN 46556 (1974).

31. Palla, R. J., “The Effects of Fly Ash Addition on the Biological
Reduction of Sulfate in Eutrophic Sediments," M.S. thesis, University
of Notre Dame, Notre Dame, IN 46556 (1974).

32. Theis, T. L., "The Potential Trace Metal Contamination of Water
Resources Through the Disposal of Fly Ash," Proceedings of the
2nd National Conference on Complete Water Reuse, AICHE, EPA,
May 5-8, 1975 (in press).

33. DePinto, J. V., "Studies on Phosphorus and Nitrogen Regeneration:
The Effect of Aerobic Bacteria on Phytoplankton Decomposition and
Succession in Freshwater Lakes," Ph.D. dissertation, University
of Notre Dame, Notre Dame, IN 46556 (1975).

34. DePinto, J. V., "Design and Evaluation of a Portable Treatment
Plant for the Renovation of Water Bodies," M.S. thesis, University
of Notre Dame, Notre Dame, IN 46556 (1972).

35. Theis, T. L., "Side Stream Treatment for Phosphorus Removal from
an Eutrophic Lake," proposal #R803951-01, submitted to the Environ-
mental Protection Agency, Washington, D.C. (1975)

64


19

OEPTH, METERS

reweerere 1971

) Cee T Fe! T
[TF

aL 4
3L

4b 4
5E — -
6

TF 4
aL oS
oe _ 5 == |
nL —
12h oN,

| => L | | 1 !

M J J A s fe) N D


PHYTOPLANKTON DATA

In collecting the phytoplankton data an attempt was made to classify the
dominant algae encountered down to the genus level. Although a taxonomic
classification may be desirable in some instances, it was felt that the
important task in studying lake nutrient dynamics was merely to separate

the algae into broad functional groups. For the purposes of investigating
successional patterns, the phytoplankton were categorized into five functional
groups: (1) diatoms, (2) non-motile green algae, (3) motile green algae,

(4) non-nitrogen-fixing blue-green algae, and (5) nitrogen-fixing blue-green
algae. Each of these five groups have general differences in their nutritional
requirements, optimum environmental needs, susceptibility to predation,
competition, degradation, and sinking rates. A realization of what these

differences are can often be used to explain why one group succeeds another.

Table 2 contains a list of the dominant phytoplankton found in Stone Lake
between May and November of 1973. This list contains representatives of
four of the five groups discussed above. No dominant diatom genera were
encountered during this time span; however, the large February bloom may
have contained a significant diatom population. In the temperature zone,
eutrophic lake diatom blooms generaily occur in the early spring while the

water is cold and before the silicon is depleted’.

By grouping the phytoplankton into the four functional groups previously
mentioned, the successional pattern in Stone Lake becomes quite obvious.
Figure 12 presents a plot of the phytoplankton densities (on a log scale)
occurring in the lake through the sampling period. The values used are
an average of four depths counted. For the most part the non-motile green
algae were evenly distributed throughout the first twelve feet. On the
other hand, the blue-green and flagellates exhibited a slight decline in
numbers with depth. This is consistent with the fact that blue-greens
tend to float to the surface and flagellates are capable of diurnal

migrations to seek more light.

24


June 1 a fairly stable thermal stratification had developed which lasted
until the fall circulation period at the end of October (points b through c).
During the period from June through September a well-defined epilimnion
existed in Stone Lake the lower boundary of which began at about 3 meters
and progressively dropped to about 6 meters ag the summer proceeded. The
thermocline during this period can be roughly defined as that portion of
the water column between 4.5 and 7.0 meters with everything below this
depth being the hypolimnion. This study was concerned mainly with this
period of thermal stratification when very little mixing occurs between

the upper and the lower waters.

The suspended solids data for 1973 are presented graphically in Figure 5.
Since Stone Lake receives very little allochthnous suspended matter, the
suspended solids represent a relatively good indicator of the planktonic
biomass in the lake. It should be noted, however, that this parameter does
not separate living biomass from dead and decaying organisms, or other
detritus. For the most part, though, the filter pads used to measure sus-
pended solids were bright green for samples taken from the epilimnion,
indicating viable phytoplankton, and brown for samples collected from below
the photic zone, indicating decaying organisms. Using the suspended solids
data in this manner, one can make several observations about the trends

in total phytoplankton density in the lake. Although no actual algae data
exist for February, it was noted that a large algal bloom occurred in this
month (point a, Figure 5) beginning under the ice and persisting until
spring circulation. The increase in suspended solids in March between

10 and 25 feet is possibly a reflection of the sinking of this bloom but
more likely of the large Daphnia bloom which occurred at the end of March.
In either case the increase is probably a reaction to the February algal
bloom, No phytoplankton bloom conditions began to arise until stratification
started to appear around June 1. Between mid-April and June (points b
through c) the lake was dominated by macrophytes. A lake survey at the
end of May showed that approximately one-third of the lake bottom (to a

depth of 10-15 feet) was covered by rooted, submerged macrophytes.

10


From the pH and dissolved oxygen data for Stone Lake one can place the
February algal bloom (point a) and trace the steady depletion of CO, and

the correspondingly high dissolved oxygen in the surface water up to the
onset of summer stratification. At this time the oxygen in the hypolimnion
is rapidly used up, presumably by the stabilization of organic matter
raining down from the epilimmion. From the middle of June to fall circulation
the majority of the hypolimnion is anoxic. Also apparent from the dissolved
oxygen data is the rapid decrease in this parameter through the thermocline.
This seems to indicate that the oxygen in this region is being utilized as
rapidly as it diffuses down from above. It is also interesting to note

that the dip in the oxygen contour in mid-September (point b, Figure 7)
corresponds to an algal bloom occurring at the same time (point e, Figure 5)
which penetrates to deeper water as the thermocline drops. The subsequent
high uptake of oxygen in the thermocline region (point c, Figure 7) corre-

sponds to the crash and decomposition of this bloom.

Figure 8 traces the soluble orthophosphate concentration in Stone Lake
through 1973. The concentrations are given in mg/1 as PO, and are there-
fore approximately three times the concentrations as mg P/2. The data
reveal that the phosphorus concentration in Stone Lake is extremely high,
even in comparison with other eutrophic lakes. It is therefore highly
unlikely that phosphorus is limiting at any time in Stone Lake. This is
especially true in view of reports that a phosphorus concentration as low
as 0.01 mg/l at spring overturn might result in nuisance algal conditions
during the summer (Sawyer). It is possible, however, that changes in
phosphate, even at these levels, could favor one algal species over another.
In any event, it is likely that phytoplankton blooms and declines can be
reflected in the phosphate concentration in terms of nutrient regeneration

from algal decomposition.

In light of the above discussion, the phosphate data show some very inter-
esting fluctuations. It should be noted that any substantial increases

in phosphate in the surface waters are not likely to be the result of

16


ras

(m)

DEPTH

qa b ¢c d e fi
0 } { | i } {
7 V] TOMMY 7
re 10 12 12 14, 14
6 9 9
2 =
/ 4 3 5 6 8 8 o\ ut
sr 10
4r 8
8
aL V/
6h ile)
7 4
BE
or 2
10- NS 3 6
He 3 a
lar
%S
13
“ * 2
l4E
ibe) i j i 1 i it | i i
J F M A M J J A S io) N
1973
Figure 5: Suspended Solids Profile of Stone Lake, Michigan for 1973. Contours

are in Units of mg/f.


Table 2. DOMINANT PHYTOPLANKTON IN STONE LAKE (1973)

1. Diatoms

Present, but not found to be dominant

2. Non-motile green algae

Chlorphyta
Staurastrum
Cosmarium
Volvox
Scenedesmus
Pediastrum
Apatococcus
Quadrigula

Microspora
Unidentified coccoid

3. Motile green algae

Euglenophyta
Unidentified

Pyrrhophyta
Ceratium

Crytophyta
Unidentified
4. Non-nitrogen-fixing blue-green algae
Cyanophyta
Microcystis
5. Nitrogen-fixing blue-green algae

Cyanophyta
Anabaena

Aphanizomenon

25


SECTION IV

WATER QUALITY OF STONE LAKE

ELEMENTAL CYCLING

Inputs of pollutants to lakes can come from many sources. Direct discharges
of wastewater effluent, runoff, seepage, and rain water falling directly
on the lake have been shown to be significant sources. Once the intro-
duction of the pollutant has been made, the lake system relies upon internal
biogeochemical cycling to define its fate. Of great importance in this
yegard is the behavior of the lake sediments. Consider a simplified steady-

state model in a lake system as follows:

E in ~ E out +E sediments @

where E represents total amounts of a given element. The terms on the right
hand side of the equation refer to natural flushing (including atmospheric
exchange) and sediment interchange, respectively. Those mechanisms which
are operative for this latter term would include chemical precipitation,

sorption, ion exchange, and biological incorporation followed by sedimentation.

It is useful to compare the theoretical residence time of an element in a
lake with the hydraulic residence time of the water in the lake as a means
of determining the extent to which the last term influences specific lake
behavior. For a given element,

= avg.
te = EO (2)

in

where Te is the theoretical residence time of any element in the lake and
(Elayvg. is the average concentration of that element in the lake water.

For the water in the lake,


64

METERS

DEPTH,

SUSPENDED SOLIDS

1971

0) T T t T T

! SN od!

2 —_—— _
3 —w 40

4 0,) so 20 0 4
se) WA :
6 10 30

7 20 _
8

9 na a
10 0 10
WW 4
12 ite)

i | C\ LL | | | |
M J J A s oO N D

DATE


Figure
A-1

A~10
A-I1
A-12
A-13
A-14
A-15
A-16
A-17

A-18

APPENDIX

WATER QUALITY DATA 1971-72

Temperature 1971
Temperature 1972

Dissolved Oxygen 1971
Dissolved Oxygen 1972
Soluble Orthophosphate 1971
Soluble Orthophosphate 1972
Total Phosphorus 1971
Total Phosphorus 1972
Nitrate 1971

Nitrate 1972

Ammonia 1971

Ammonia 1972

Suspended Solids 1971
Suspended Solids 1972
Organic Nitrogen 1971
Organic Nitrogen 1972

coD 1971

CoD 1972

66

Page
67
68
69
70
71
72
73
4
75
76
7
78
79
80
81
82
83

84


log molar concentration

Figure 20:

Solubility of Various Heavy Metals
(free aqueous and mono-hydroxo species only).

51



TABLES

Morphological Characteristics of Stone Lake
Dominant Phytoplankton in Stone Lake (1973)

The Effectiveness as Lake Reclamation Tools
of Eleven Particulate Materials

Chemical Composition of Fly Ash
Pollut ional Potential of Stone Lake Sediments
Water Chemistry Data for Mishawaka Farm Pond
Cost-Benefit Table

Important Water Soluble Extracts of Fly Ash

Ranges of Trace Metals in Fly Ash

vili

25

34

35
41
44
46
47

50


(<4

{m)}

OEPTH

a
; .
ib yy]
ok 05
3 20 30 13
4
sr
et
L 23
7 0 \\ 20 O85
at
ot
10h
ue
12b
sr 44
ad 09 \n
15 ! i i 1 i aan fl \ 1 1
J FM A M J JA S$ fe) N
1973
Figure 11:

Soluble Nitrate + Nitrite Profile of Stone Lake, Michigan for 1973.
Contours are in Units of mg N/2.



10.0 T T T T v
PCM © 1049-p/1

s 8.ob NCM = 6O0ypg-n/} 4
€

z

2

He 6.0F 7
4

e

=z

w

2

Z 4.0F 7
°

a

a

oO a

q 20r Chlorella 7

(No growth) Microcystis
° oh. 1 _L
April May June July August Sept
TIME
Figure 25: The development of Microcystis is limited by available

nitrogen when the initial nutrient concentrations are
10 ug-P/land 60 yg-N/1.

10.0 T T T T T
PCM = 10pg-p/1
S aol NEM = 300p9-071 a
€
Zz
2
& 6.0F 4
«
&
8 Microcystis
Z 4.0b 4
G
2
=
Z 2.0
< 2-0 _ chiorelto 4
\ (No growth }
n n
Aprit Moy June July August Sept
TIME
Figure 26: Microcystis uses virtually all of the available

phosphorus when the initial nutrient concentrations

are 10 ug-P/1 and 300 ug-N/1.
58


A second mathematical model, devised by Cordiero®?, made use of the

two step growth process mentioned previously in the dynamic modelling

of a lake ecosystem. The system included both nitrogen and phosphorus
limited situations and incorporated both upper (aerobic) and lower
(anaerobic) waters as a means of determining the degree of cycling of
these nutrients. The utility of the model was demonstrated by the simu-
lation of lake restoration control schemes. Results for the simultaneous
lowering of influent levels of phosphates, precipitation of phosphates
in the lake, and the sealing of bottom sediments (such as is proposed)

is shown in Figure 29 for algal populations in the overlying water.

60


19
CONCENTRATION (mg/£)

24,2

14.5 5

Treatment

9.69

4.855

0.0 n 1 t r =
0.0 1.0 2.0 3.0

. Time in Years
Figure 29: Effect of Reduction of H2P0,4 in Inflow and Lake, Algal and Lower Water Precipitation
at l-year on Concentration of Algae.



This build-up of phosphate also coincides with the rapid decrease of oxygen
in the hypolimion and the continued anoxic conditions until circulation.
Because of the lack of additional necessary information, it is impossible
to pinpoint the cause or causes for this increase. Based on the available
data, this phenomenon is probably the result of aerobic and anaerobic
decomposition of organic matter settling from the upper waters as well as
bacterially mediated release of phosphorus from the bottom sediments with

the latter most likely making the largest contribution.

The 1973 nitrogen data for Stone Lake are presented in Figures 9 (soluble
organic nitrogen), 10 (soluble ammonia-nitrogen) and 11 (combined soluble
nitrate plus nitrite). The soluble organic nitrogen did not appear to
show too much variation through the year. For this particular year there
seemed to be a progressive decrease in concentration from January through
August, although this type of trend has not been consistent from year to
year. Beginning in September, this parameter appeared to stratify somewhat

because of an increase in the upper water concentration.

The ammonia variations in the lake suggest some very interesting possibilities.
The rapid increase in ammonia at the end of February (point a, Figure 10)
coincides with the crash of the February algal bloom. The increase showed
up through the entire water column because of the complete mixing conditions
prevailing at the time. Hutchinson‘ noted that in most lakes, maximal
ammonia concentrations appear in the trophogenic zone at periods of full
circulation. This increase, however, is definitely not brought on by
mixing with deep water, since no ammonia is present in the entire water
column prior to the increase. From this peak there was a steady decline

of ammonia until the end of May when there was no ammonia left in the upper
waters (point b, Figure 11). The decrease of these nutrients from March
through May was most likely due either to uptake by macrophytes and green
algae, or nitrification (perhaps biologically mediated) of soluble

ammonia.

19


Te

DEPTH

METERS

°

nN

-OO0 AON Ooh Wn 7
\

SOLUBLE ORTHOPHOSPHATE 1971

La6/  \G A

L-— 3.5

| \

i \

24 2

(oe

2.0

NE

Ss
e

J

A

DATE

CTE


CONTENTS

Sections

I Conclusions

II Recommendat ions

IIt Introduction

Iv Water Quality of Stone Lake

Vv Studies on the Reclamation of Stone Lake
VI References

VII Appendix

Page

33
62

66


ABSTRACT

This report contains information relating to two factors: (1) the effects of
domestic pollution abatement on a eutrophic lake, and (2) investigations into
methods of reclaiming such lakes especially through the use of particulate
materials which retard pollutant release from sediments.

The study lake, Stone Lake, has been monitored for approximately ten years from
the time of pollution abatement. Results indicate that the sediments are major
pollutant sources during stratified periods and that for such lakes to achieve
meaningful improvements in water quality in a reasonable length of time, a
series of external manipulations is often needed.

Monitoring data indicated a cyclic pattern of phytoplankton succession within
the lake during growing season. This pattern included a steady base of green
algae with alternated dominance with different kinds of blue-greens (nitrogen-
fixing or non-nitrogen-fixing) - the available forms of nitrogen regulating
the cycle.

Certain types of fly ash, a particulate waste product of coal combustion, was
shown, in laboratory studies, to possess properties capable of precipitating
orthophosphate from overlying waters and subsequently "sealing" the phosphorus
within the sediments for long periods of time. A lake such as Stone Lake could
thus be made permanently, or semi-permanently, phosphorus limited thereby
altering the successional pattern previously indicated and significantly
reducing the overall standing algal crop.

This report was submitted in fulfillment of Grant Number R-801245, by the
Department of Civil Engineering of the University of Notre Dame under the
sponsorship of the Environmental Protection Agency. Work was completed as

of May, 1974.

iv


1. = Average Volume QB)
Ww = Inflows

where Tw is the mean hydraulic residence time. As indicated previously
by Stumm and Morgan”, the ratio Ty/ty becomes a useful parameter, If it
is less than one, specific elements are being stored in the sediments.
However, when this ratio is greater than one, the element is being cycled
within the lake and, thus, is present at higher concentrations than would
be predicted from external inputs alone. When the ratio is equal to one,

there is either no exchange with the sediments or the net exchange is zero.

Because of its naturally high reactivity, phosphorus, which is the limiting
nutrient for excessive algal productivity in many eutrophic lakes, has a
value of t/t, which is generally greater than one. Natural flushing with
waters having low phosphorus concentrations will reduce phosphorus levels

in such a system very slowly. This is illustrated in Figure 3 for Stone
Lake. Orthophosphate residual predicted by simple washout Cy It, =1) is
compared with the actual measurements made each year during circulation
periods. As is evident, the two curves have basically different shapes.
These differences are attributable to the influence of the sediments. That
portion of influent phosphorus which is initially incorporated into the
sediments is not lost entirely to the system and is available for subsequent
release under proper conditions. Accordingly, lake sediments can act as
sinks or sources of phosphorus at different stages within the lake's develop-
ment; and for some systems can act as both a sink and a source at various
times during a yearly cycle.

PHYSICAL AND CHEMICAL DATA FOR STONE LAKE

As a means of indicating the present status of Stone Lake, data for a specific
year, 1973, is presented in Figures 4-11. Data for 1971-72 are found in the
Appendix. Stone Lake is an example of a dimictic lake, the type most often
found in the north-central United States. Figure 4 graphically

illustrates the two periods of total mixing which regularly occur in a lake

of this type. The spring circulation period occurred in late March (point

a, Figure 4) with mixing conditions present until the middle of May. By


22

23

24

25

26

27

28

29

Mercury Release Patterns from Fly Ash in Laboratory
Reactors

Computer Simulation of Chlorella and Microcystis at
Low Phosphorus Levels

Computer Simulation of Chlorella and Microcystis
at Intermediate Phosphorus Levels

Computer Simulation of Chlorella and Microcystis at
High Phosphorus Levels

Computer Simulation of Chlorella and Microcystis at
Low Phosphorus and Nitrogen Levels

Computer Simulation of Chlorella and Microcystis at
Low Phosphorus and Intermediate Nitrogen Levels

Computer Simulation of Chlorella and Microcystis at
High Phosphorus and Intermediate Nitrogen Levels

Computer Simulation of Chlorella and Microcystis at
High Phosphorus and High Nitrogen Levels

Computer Simulation of the Effects of Reclamation
on Algal Concentrations

vii

57

57

58

58

59

59

61


SUSPENDED SOLIDS 1972

[— T T ar a if 4
oo
oO
+
L_ 4
g
0 2a
KO)
Se eS bod
I 4
fo} <s
\
‘ll
A as rm -
t +
pop oy ft py j} yy ft ft ft 4
o- NMUeseNOKRDAHO- A

SYy313W

“H1d30

80

DATE


1971

TOTAL PHOSPHORUS

i I I I | I
oo)
~~ * oO
m
eo
¢
ae 4
vt
4,
m
5 oases
A omen teen
mm —
i; fo)
O° st
+
LO
a Q
ea
fo}
aN
[et a DC SN
o-onmt © OF DOD MON

SYSLEW ‘Hid3a
73

DATE


9L

DEPTH, METERS
omn ouoanua

-o

NITRATE 1972
| | ) ) / |
! > !
J F M J A

DATE


4T

{m)

© on oo pawn

DEPTH

{e)

9.5

9.0
L 7.5
1

1 L i it 1 (Ce \.
J F M A M J
e733
Figure 6: pH Profile of Stone lake, Michigan for 1973.

Units.

Contours are in pH



EPA-600/3-76-106 ; ;
Sia 1976 Ecological Research Series



lL

DEPTH, METERS
© onNOU punw - O
T

AMMONIA - NITROGEN 1971

0.5 (-
{.



T T T T T T T T T T T T T T
ud 3.07 4
& A. Ocm FLY ASH |
x
o 2.0b Erupted 4
ro)
x 4
o
x 1.0 4
E
ie J
ro)
Oo
o Ff B. 2.0 cm FLY ASH 4
20} 4
aw”
() a 4
> Lob A
E 4
@) renner etgeen 2 en nN ene - O- oO.
I C. 5.0cm FLY ASH 7
2.0} 4
LOF 4
fe) mateeanoey Phe ptppnent- Ot creme nlrb 1
O 10 20 30 40 50 GO 7080 90 HO 130 15

Figure 15:

TIME (Days)

Effectiveness of Various Thicknesses of Fly Ash in
Retarding Phosphate Release from Stone Lake Sediments.
Experiments Performed in Laboratory Reactors (after
Yaksich2®) ,

37


SECTION I

CONCLUSIONS

In Stone Lake, Michigan, the lake sediments tend to act as nutrient sinks.
During periods of dissolved oxygen depletion in the hypolimnion large
amounts of phosphorus and nitrogen are released in the overlying water.
Insofar as Stone Lake is typical of many natural seepage lakes with
accelerated eutrophic conditions, the application of this finding to
other similar systems appears warranted.

A cyclic pattern of phytoplankton succession was observed in Stone Lake
auring summer stratification. The pattern consisted of green algae
followed by nitrogen - fixing blue-green algae followed again by green
algae with available forms of nitrogen regulating the cycle.

Particulate materials, especially certain clays and fly ash, were shown
to be potentially effective lake restoration tools for controlling
biogeochemical cycling of pollutants from eutrophic sediments. In most
cases a 2 to 5 cm layer of material was needed to control phosphate
release. Supplemental chemical addition, such as lime or alum, enhances
initial phosphate removal from the overlying water.

Sandy shoreline sediments low in water and organic matter have a low
pollutional potential and should not require covering with a particulate
layer in most instances.

Available data indicates potentially harmful effects from other water
soluble extracts of fly ash, particularly sulfur (as $03-2) and various
heavy metals. Short term extremes of pH may also affect biota unfavorably.


ACKNOWLEDGMENTS

The support and cooperation of the citizens of Cassopolis, Michigan,
particularly Mr. Garrett Snyder, village superintendent, is gratefully
acknowledged.

To those individuals who performed the main portion of the research obtained
herein, Dr. Mark W. Tenney, Dr. Wayne F. Echelberger, Jr., Dr. Stephen M.
Yaksich, Dr. Victor J. Bierman, Dr. Cajetan F. Cordiero, Mr. Timothy J. Hampton,
Mr. Scott T. Girman, and Mr. Robert J. Palla, sincere appreciation is given.

ix


Table 9. RANGES OF TRACE METALS IN FLY ASH
2
{after Theis >”)

Avg. Crustal
Metal Concentration Range, ppm Abundance,
ppm

As 2 - 288 1.8

Pb 9.5 - 500 13

Cu 14 - 300 40

an 41 - 1000 50

Cd 0.6 - 11.2 0.2

Cr 18 - 500 100

Hg 0.08 - 0.32 0.06

Several factors will affect the availability and effects of toxic trace
metals on lake systems. These would include simple solubility controls,
pH, the ion exchange and adsorptive characteristics of local solid

phases (such as iron oxides and clays), complex formation, and biologi-

cal incorporation and transportation.

Figure 20 contains standard logarithmic concentration-pH solubility
diagrams for the various free metal ion and mono-hydroxo complexes of

all the metals in question except arsenic (which is generally very
soluble). In the normal pH range of natural waters, it is the hydroxide
of these metals which controls their solubility. At very high pH's and
high alkalinities, carbonate ion may control. It can be said from

Figure 20 that, in general, the trace metals display drastically decreased
solubilities with increasing pH. This factor would tend to keep most
metals insoluble at the elevated pH levels anticipated during fly ash
application,

50


SECTION V

STUDIES ON THE RECLAMATION OF STONE LAKE

INTRODUCTION

There is little doubt among most water resources experts that many of the
nation's freshwater inland lakes have deteriorated to a point where the
simple curbing of nutrient inputs is no longer enough to restore multiple
water uses. Numerous restoration techniques for these lakes have been
proposed and/or are being evaluated. Among them are the following:

(1) dredging, (2) harvesting, (3) nutrient inactivation/precipitation,

(4) total or hypolimetic aeration, (5) bottom sealing, (6) sediment
exposure, (7) ecological manipulations, (8) application of selected bio-
cides, and (9) artificial dilution or flushing. Each of these techniques
has advantages and disadvantages depending upon the particular system to
which they are applied. In this section, the potential use of particulate
materials to precipitate and seal phosphate in sediments will be presented.

PARTICULATE MATERIALS AS SEDIMENT SEALANTS

Several types of materials were investigated for their sealing properties
26
on eutrophic lake sediments including clays, sand, and fly ash (Yaksich” ).

A summary of these results is given in Table 3.

Although many of these materials showed promise in the restoration of lakes
through sediment sealing, particular attention was focused on the use of
fly ash, a common by-product of coal combustion. The United States pro-
duces 30 x 109 Kg of this material annually, with estimates of up to

90 x 10? Kg by the year 2000. Understandably there is a great desire
on the part of those concerned with its disposal for utilization in some

favorable manner.

33


1972

TOTAL PHOSPHORUS

\

Rol
6

s——

NT

aR
{ NU
L b 4
a
9)
J)
I. 3 4
Mm
Pop gy
o-NMOgnorOanorNn

SY3LaW ‘HidaG

74

DATE


TZ

(m)

DEPTH

Oo On oun £ WD
T

Figure 10:

Soluble Ammonia Profile of Stone Lake, Michigan for 1973. Contours
are in Units of mg N/2,


with nitrogen and phosphorus (Higgins et a1.78), The orthophosphate

level in treated water was 7.5 ug/£, while the filtered lake water had
101 wg/%. Figure 16 shows almost a ten-fold cellular growth increase in
filtered lake water spiked with 4 mg/2% of nitrogen (added by NaNO), as
compared to the unspiked control. Clearly, the lake water was nitrogen
deficient. Treated lake water showed the least growth, as it was
deficient both in phosphorus and nitrogen. Adding 4 mg/& of nitrogen
to treated water did not result in any significant increase because
growth was still phosphorus limited. Spiking the treated lake water
with both nitrogen and phosphorus to levels equivalent to the control
plus 4 mg/& of nitrogen did enhance algal growth significantly, but it
was much less than in the control spiked with 4 mgN/%. These data
suggest that the fly ash and lime treatment of polluted lake water
reduces the algal regrowth potential, not only by making it phosphorus
limiting, but also by either removing some additional growth factors
or by adding an inhibitory substance.

Available evidence indicates that within each yearly cycle the sediments
of Stone Lake act as a major pollutional source. Further research on

the sediments led to a delineation of four general sediment types shown
in Figure 17. These sediment types can be described as follows:

(1) shoreline sediments (C1-C8 in Figure 17), which comprise 25 percent
of the bottom of Stone Lake, are mostly sand, and possess little pollution
potential; (2) west bay sediments (D1-D3), which occupy 15 percent of the
bottom and are of an intermediate pollutional potential; (3) north bay
sediments (Al-A5), 19 percent of the bottom, are of a higher pollutional
potential; and (4) deepwater sediments (B1-B7), 42 percent of the bottom,
and have the highest pollutional potential. The precise parameters used
to define the pollutional potential are given in Table 5.

The characterization of Stone Lake sediments has led to a hypothetical
differential treatment scheme in which varying amounts of fly ash and lime
are added to Stone Lake reflecting the pollutional potential of the

38


02

(

oO on on om fs WN
T

DEPTH

ie)
T

ex)
L It 1.0 0.8 )
=e [ 0.7
‘a
IFL5 14 .
p-——_—*
l2-
13
os
4b \
15 } i 1 L109 |
F M A M

o

T

©)

1.2 7

0.8

)

1
J

0) 6 /
fe) is)
1.7
Lt
A S§ OO N

|
J J
1973

Figure 9: Soluble Organic Nitrogen Profile of Stone Lake, Michigan for 1973.
Contours are in Units of mg/L.


= 25.0 = T T T T 10.0
a .
Microcysils

2 feroeys
_
=z 20.0;—- 780 1
a ~
2 o
& €
Zz 15.0 L_ 46.0 z
a3 \ 5
Qa
Zo e
ey z
5 wor 440 8
8 s
Fa 3
2 F
8 5.0 s
S =
x
&
° ° °
4 =
a Aprit May June July August = Sept

TIME

Figure 23: Microcystis increases proportionately after phosphorus
concentration (dotted line) has been increased from
10 ug-P/1 to 25 ug-P/1.

3 50.0 = , t t t 10.0

Fy Microcystis

a

= 40.0}- 480 <

Fe é

#

5 z

Z 30.0} {6.0 6
- —

a3 :

ee g

5 20.0; 40 9

a 3°

3 2

8 a

B 10.0;- 420 5

& Chlorella <

°o

&

go ! somechon J 9

a April Moy dune July August Sept

TIME

Figure 24: Microcystis does not increase proportionately after
phosphorus concentration has been increased from
25 ug-P/1 to 50 pg-P/1.

57


10
11
12
13
14

15

16

17

18

19

20

FIGURES

Hydrographic Map of Stone Lake

Topographic Map and Tributary Drainage Area
of Stone Lake

Washout vs. Overturn Orthophosphate in Stone Lake
Temperature Profile of Stone Lake, 1973

Suspended Solids Profile of Stone Lake, 1973

PH Profile of Stone Lake, 1973

Dissolved Oxygen Profile of Stone Lake, 1973
Soluble Orthophosphate Profile of Stone Lake, 1973
Soluble Organic Nitrogen Profile of Stone Lake, 1973
Soluble Ammonia Profile of Stone Lake, 1973

Soluble Nitrate plus Nitrite Profile of Stone Lake, 1973
Phytoplankton Densities in Stone Lake, 1973
Phytoplankton Composition in Stone Lake, 1973
Effectiveness of Fly Ash in Removing Orthophosphate

Effectiveness of Fly Ash in Retarding Phosphate Release
from Stone Lake Sediments

Algal Regrowth Potential of Fly Ash-Treated Water
from Stone Lake

Sample Sites for Sediment Survey in Stone Lake
Restoration Plan for Stone Lake
Effect of Fly Ash on Dissolved Oxygen in a Lake Column

Solubilities of Various Heavy Metals

vi

11
12
14
15
17
20

21

26
28
36

37

39

40

43

49

51


IT

DEPTH

(m )

be —

LLLLA

: b
Ice cover {
|

2 Leen

2h
3h 3

es 4
4 9 20_~ 23

L 8 5
5 9
i | /
ab 12 15
SE
gt 12
10+
We lo
12- 3
13+
4p
15 1 | | { i i | it | {
mn) F M A M J J A Ss 0 N

1973

Figure 4: Temperature Profile of Stone Lake, Michigan for 1973.
in Units of °c.

Contours are



1971

NITRATE

|e De |

ican
- N

!
m

TOON
SYaLaW

75

o

1
oa

‘Hidaa

2 |
G=N

DATE


The effects of fly ash on zooplankton and benthos are less well known and

will be studied more extensively in the future.

Dissolved oxygen depletion occurs primarily due to the presence of water
2
soluble extracts of sulfite ion, S0, » a well known oxygen scavenger

according to the equation

2,21 . -2
So, +5 0, = SO, .
The effects of this reaction in an isolated lake column are shown in Figure
19. Dissolved oxygen is depleted rapidly under these conditions and

reaeration takes place gradually over a four day period.

Biological reduction of high levels of sulfate ion, 80, , (approximately
100 mg/1) have been shown to occur under the proper conditions. However
fly ash, at least initially, appears to inhibit most bacterial action
such that little reduction could be measured in laboratory reactors
(Palla3!), Ie should be noted as well that many eutrophic lake sediments
contain high levels of sulfide during stratified periods. The additional

amount due to fly ash may often be considered of minor importance.

The release of toxic trace metals to natural lake systems appears to be
the greatest potential drawback to the use of fly ash. Table 9 gives a
range of trace metals found in several different ashes as compared with

natural crustal abundances.

Of course the background metal concentrations in the specific lake
sediments are a more accurate indication of potential effects; however,

Table 9 gives evidence of a need for further study in this area.

48


1972

SOLUBLE ORTHOPHOSPHATE

2.5

2.0

l2e

DATE


gL

DEPTH, METERS

- oO

AMMONIA ~ NITROGEN 1972

M J J
DATE

I T Al T T T T
[ _ O.l |
2 A |
aN Xv KG Lo



TECHNICAL REPORT DATA

(Please read Instructions on the reverse before completing)

T. REPORT NO. 2.

EPA-600/3-76-106__

3. RECIPIENT'S ACCESSION NO.

ja. TITLE AND SUBTITLE

"Studies on the Reclamation of Stone Lake, Michigan."

5. REPORT DATE

November 1976
6. PERFORMING ORGANIZATION CODE

17. AUTHOR(S)
Thomas L. Theis, Joseph V. DePinto

|8. PERFORMING ORGANIZATION REPORT NO.

9. PERFORMING ORGANIZATION NAME AND ADDRESS
Department of Civil Engineering
University of Notre Dame

10. PROGRAM ELEMENT NO.

1BA031
11, CONTRACT/GRANT NO.

Notre Dame, Indiana 46556 EPA R-801245

12. SPONSORING AGENCY NAME AND ADORESS 13. TYPE OF REPORT AND PERIOD COVERED

Final - 4/71-5/74

U. S. Environmental Protection Agency
Corvallis Environmental Research Laboratory
200 S. W. 35th St.

Corvallis, Oregon 97330

14, SPONSORING AGENCY CODE

EPA/OR&D

15. SUPPLEMENTARY NOTES,

16. ABSTRACT

This report contains information relating to two factors: (1) The effects of domes-
tic pollution abatement on a eutrophic lake, and (2) investigations into methods of
reclaiming such lakes, especially through the use of particulate materials which
retard pollutant release from sediments.

The study lake, Stone Lake, has been monitored for approximately ten years from the
time of pollution abatement. Results indicate that the sediments are major pollutant
sources during stratified periods and that for such lakes to achieve meaningful im-
provements in water quality in a reasonable length of time, a series of external
manipulations is often needed.

Certain types of fly ash, a particulate waste product of coal combustion, was shown,
in laboratory studies, to possess properties capable of precipitating orthophosphate
from overlying waters and subsequently "sealing" the phosphorus within the sediments
for long periods of time. A lake such as Stone Lake could thus be made permanently
or semi-permanently, phosphorus limited, thereby altering the successional pattern
previously indicated and significantly reducing the overall standing algal crop.

17. KEY WORDS AND DOCUMENT ANALYSIS.

a. DESCRIPTORS b.IDENTIFIERS/OPEN ENDED TERMS {c. COsaATI Field/Group
lakes* models 08H
limnology nitrogen O6F
phosphorus* aquatic biology 078
fly ash* bioassay
sediments*
renovating *Major descriptors

algae
18, DISTRIBUTION STATEMENT

19, SECURITY CLASS (This Report) 21. NO, OF PAGES

Release unlimited Unclassified 94
20. SECURITY CLASS (This page) 22. PRICE
Unclassified

EPA Form 2220-1 (9-73) 85

tt U.S. GOVERNMENT PRINTING OFFICE: 1976—796-498/ 23 REGION 10



For the two-species case in which phosphorus is the regulating nutrient,
it was shown that a slower-growing alga with a high phosphorus transport
efficiency can dominate a faster-growing alga with a low phosphorus
transport efficiency when the concentration of available phosphorus is low.
This is shown in Figures 22 through 24 for a mixture of Chlorella, a
green alga, and Microcystis, a blue-green specie. Nuisance blue-green
algal blooms frequently coincide with elevated summer temperatures and
low concentrations of dissolved nutrients in eutrophic lakes. In the
example presented, species differences in phosphorus uptake efficiencies
are sufficient to explain these correlations and it is not necessary to
invoke a causal relationship between elevated temperatures and assumed

higher growth rates for blue-green algae as compared to other species.

For the cases in which both phosphorus and nitrogen regulate algal growth,
it was shown that the availability of nitrogen in relation to a given
amount of phosphorus, especially the form of the nitrogen, can greatly
affect total algal crop as well as relative species abundance. Figures

25 through 28 indicate these findings. On this basis, a need is recog-
nized to include nitrogen dependence, especially nitrogen-fixation, as
part of any algal growth model that is to be applied to field conditions.

The final set of applications considered various external inputs from
diffuse and point sources such as surface runoff, direct precipitation,
and nutrient loads from assumed secondary~ and tertiary-treated waste-
water. Use was made of the physical basin characteristics of Stone Lake.
Generally, these chronic, low-level inputs significantly enhance the size
and duration of the algal crops in the lake and, during the summer months
when dissolved nutrient concentrations are lowest, these inputs prefer-
entially stimulate the more efficient blue-green species. Urbanization
has a very significant effect on these same parameters and, for the
assumed nutrient loadings in the examples, surface runoff from the urban
land in the basin was more stimulatory than if all of the wastewater
Produced in the basin had been tertiary-treated and directly discharged
to the lake.

55


87

PERCENT COMPOSITION BY NUMBER

oO

Non-motile Green

E3 Non-nitrogen-fixing Blue-green

{1 Motile Green Nitrogen - fixing Blue-green
100 —_—
104A 4a F im 1 i
rT if Z
80- | !
Z
(4
60 a
| il
40F
L
20 Zz
fe) ! 1 \ LZ !
May June July Aug Sept Oct Nov
1973
Figure 13: Composition of Phytoplankton in Stone lake, Michigan from May through

Cetover, 1973. Relative Numbers of Each of the Four Major Groups are

Normaiized to 100 percent,


89

DEPTH, METERS

ON ourbuan —- O

oo

pn =

TEMPERATURE 1972

XN \ \ Ad
20 “ \Y

2 —= ;
—

i | 1 |

M J J A


behind the non-motile green algae. The third and final summer peak was
caused by this green algae resurgence, with Microspora being the dominant
genus in the bloom. A final algal sample taken on November 12 (during
circulation) revealed qualitatively that this final green algal bloom had
been distributed through the entire water column. Also, a great deal of
detritus was observed at all depths - and much more in the upper waters than

before complete mixing conditions had existed.
SEASONAL SUCCESSION AND NUTRIENT REGENERATION

By comparing the time variation of nutrients in the upper waters of Stone
Lake with the phytoplankton succession, one can postulate several causal
relationships to explain the lake dynamics. These relationships are important
to the concept of lake management and/or restoration. It is desirable to be
able to predict a priori if a given set of environmental conditions will tend
to favor a stable (non-blooming) or an unstable (frequent blooms) system.
Based on the common definition of an algal bloom being about 5-20 mg/1 (dry
wt.) (Azad and Borchardt‘), it can be stated that Stone Lake supports a
continuous bloom throughout the summer stratification period. Often, however,
the only objectionable blooms are those of blue-green algae. Knowledge of
nutrient dynamics and how they affect algal dominance can perhaps lead to

the prevention of these nuisance conditions.

It was noted earlier that the phytoplankton in Stone Lake began to bloom
with the onset of thermal stratification. Prior to this the macrophytes

in the lake were by far the dominant biomass. There are two probable
explanations for the macrophyte dominance during the months of April and
May. First, the complete mixing conditions in the lake at this time corres-
pond to one of the "stress points" suggested by Round!?, Tt is possible
that the average residence time of the algae in the illuminated zone was

not long enough to effectively compete with the macrophytes for light.
Mortimer?® has stated that a high ratio of stirred depth to illuminated
depth can impose a condition of "morphometric oligotrophy". The second

disadvantage which the phytoplankton faced at this time of the year was

29


"4

Table 6.

SUMMARY OF WATER CHEMISTRY

DATA FOR MISHAWAKA FARM POND

Datet Before treatment After treatment
*
Parameter’ May 15, 1972 | July 6, 1972 | July 10, 1972 | Aug. 2, 1972] July 2, 1973
pH 8.75 8.80 210.90 9.00 9.30
Suspended solids 15.0 17.5 25.0 10.0 10.5
(mg/2)
Alkalinity 84 70 181 66 45
(mg/2 as CaC03)
+
Ca"* hardness 66 45 278 173 54
(mg/& as CaC03)
80%, (mg/% as $0,) 20.1 19.2 178 166 25.1
Soluble orthophosphate| 0.086 --- 0.013 0.084 0.110
(mg/2 as PO,)

* Treatment of pond took place on July 7-9, 1972.
+ values given are an average of 4 horizontally located points in the pond.



LT

(m)

© aM9N ow fF w NY

DEPTH

fe}

Figure 8:

a b
, 4
WW
| i5\ hl
L 13
' 14
L 20 15
/.,
1 L \ t/a iia
MAM J JA Ss. Oo N

1973

Soluble Orthophosphate Profile of Stone Lake, Michigan for 1973.
Contours are in Units of mg/% as PO).



Table 8. IMPORTANT WATER SOLUBLE EXTRACTS OF FLY ASH

Specie Major Chemical Form(s)
+2 +
Ca, Mg cat? g*?
Na, K Nat, xt
Fe, Al Fe(ou)*TM, aicony'TM, ete.
Co, Ni, Cu, Zn, Cd Various hydroxylated forms
2 2 +n
Cr cro, > cr,0, ’ Cr (OH),
As 430,77
Pb ppt?
+
Hg ug? Hg’
-2 ~2
s $0,~*, so,
-2
Si Si0,
Alkalinity HCO,” co,”

Not all of these aqueous extracts can be considered harmless. Several
adverse effects of fly ash addition can be noted as follows: (1) high

pH effects, (2) dissolved oxygen depletion, (3) biological reduction of
high sulfate levels to sulfide, (4) heavy metal accumulation and toxicity,
and (5) physical clogging and crushing of aquatic organisms.

In laboratory aquaria tests, 10-20 grams/liter of fly ash was found to

be toxic to fish indigenous to Stone Lake (Hampton?”), The cause of death

was attributed to clogging of gills and subsequent impairment of oxygen

transfer. The applicability of these conditions to an actual lake, however, is
questionable since the addition of fly ash would be to local areas over an extended

time period allowing fish to avoid extreme conditions of pH or turbidity.

47


PHOSPHORUS CONCENTRATION IN EXTERNAL MEDIUM

BQ-p/t

10.0 =,
x T T T T
8.0
\
6.0 \
\
4.0b \ Microcystis
2.07 _chioretta
\e growth)
° L
April Moy June duly August Sept
TIME
Figure 22; The slower-growing Microcystis

dominates the faster growing
Chlorella at low phosphorus
concentrations (dotted line).

56

10.0

8.0

6.0

4.0

2.0

mg ft

ALGAL CONCENTRATION,


DISCLAIMER

This report has been reviewed by the Corvallis Environmental Research
Laboratory, U.S. Environmental Protection Agency, and approved for
publication. Approval does not signify that the contents necessarily
reflect the views and policies of the U.S. Environmental Protection

Agency, nor does mention of trade names or commercial products con-
stitute endorsement or recommendation for use.

ii


3.0

ORTHOPHOSPHATE mg/L as PO,

© EXPERIMENTAL
@ THEORETICAL SOLUBILITY

A. FLY ASH No. |!

10 20 30 40 50

C. FLY ASH No.3

10 20 30 40 50
FLY ASH gm/t

B. FLY ASH No.2

O 10 20 30 40 50
FLY ASH gm/l

0. LIME

0 50 100150 200250300
mg/l Cad

Figure 14, A-C: Effectiveness of Different Fly Ashes in
Removing Orthophosphate from Solution.
D: A Similar Plot for Lime (after Yaksich?®).

36



Table 3

Summary: The Effectiveness as Lake Restoration Tools of Eleven Particulate Materials,

‘Ability to contral —T

Compatability Settling proper- | phosphate relea Avitity to resist | Commenta:
Effect with chemicals ties, time for 99. | from sediments resuspension elfectiveness in
on water used to Improve | percent to settle | under anaerobic veloctty needed | a take restoration
Material quality water quality 20 feet conditions to disrupt barrier | project
Kaolinite Adtorbed phos- | Alum could be used | Good 5..0.¢m layer Vary Good Gould be used if alum
Clay phate but addi- | to precipitate phos ifective wan added first to pre
tonal chemicals cipitate phosphate and
may be needed 40 em/ece ter added to reduce
turbidity caused by the
chy
r
Bentonite Very poor Atum could be used Ineffective, it Vary Good Should not be ured,
Clay phorphate to precipitate phos Increased rate of Ht would increase tate
Sdrorption phate and reduce phosphate releace of phosphate release
turbidity >40 days 40 em/eec
Georgie Exhibited some | Alurn could be used | Fair 5.0 em layer Barely Acceptable | Could be used on deep
cay Phosphate to precipitate phos- water sedimente if ata
Adsorption, addi. | phate and reduce wan added first to pre
tlonal chemleale | turbidity 22 hours 18 em/ cipitate phosphate cag”
would be needed Inter added to reduce
turbidity caused by the
clay
Tennessee Adsorbed phos- | Alum could be used | Very Good 5.0 em layer Good Alum coutd be used
chy phate, but addi- | to precipitate phor- sttective first to precipitate
a | phate 12 houre 30 cm/sec Phosphate, then clay
added to cover sedi~
mente
——
Minot Adsorbed phos- | Alum could be used | Poor 5.0 om layer Good Coats be used in ehary
chy piute, butacat- | to preciltate phos Sitecive Whee ifelny wan oes
onal chemicals | phate and reduce lirat to precipitate pie
needed | turbidity 28 days 30 cm/sec phate acd later addeq s~
Feduce taristy con te
by the clay

sur Adsorbed phos- | Alum could be used | Good Sank below sedi- Weald be an ineffective
phate, but addi- to precipitate phos ments and did not barrier on floceulang

Tional chemicals | phate and reduce phosphate tedimente
a | Lurbicity 24 hours release 20 em/aee,
‘Sand Did not absorb Alum could be used | Excellent $,0 em layer Very Good Not recommended
phosphate te precipitate pho titective ana barrier on Stong
pute Lake sediments b
18 minutes 40 cm/sec. caure of difficulty
in forming a stable
barrier
Fiy Ash No.1 | Precipitated | precipitated phot- | Very Good Sank below seci- | Good Would be an inettectivg
phate in combinatio rents und kd nat barrier on Moceuiane
With alum oF lime Telard phosphate tedimente
6 hour release
Fly Ash No.2 | Exfectively Precipitated phos. | Good 2,0 em layer Fair Could be weed by ie.
precipitated | phate? excellent sitactive fell, oF with alum cy
Phoephate with Ilene, good lime to precipitate
with alum 24 houre 20 em/sec. phosphate, Effective,
Feterced hope “TY
Fiy Ath No.3 | Precipiuted | Precipitated phos. | Very Good Inatfective BarelyAcceptabie | Not recommended
phosphate, but | phater excellent because of lailare
Galdonal chera= | with lime, good te ttop phosphate
eats needed. | with alum Shout 15 em/oee rele
. . © Most etfective
Fly Ath No.4 | Very effectively | Precipitated phos- | Good 2.0 em layer Fat
7 precipitated phat eltective particularly tested 1,
Phosphate with lime, good precipitating phoca
with slum 24 howra 20 em/ace. and retarding phos ate.

phate release. Efte
ively precipitated “*>
phosphate and settig,

fp elt column study
Hiself ene in combi, bY
ton with lime ~



Figure 27:

ALGAL CONCENTRATION, mg/I

Figure 28:

ALGAL CONCENTRATION, mg/1

0.0 “T T T T ‘

POM = SOpg-p/t

NOM © 300 p9g-n/1
8.0 4

6.0 4

Chlorella

Microcystis

° 1
Aprit Moy June July August Sept
TIME
Chlorella can exploit its faster growth rate at a
phosphorus concentration of 50 ug-P/1 and it utilizes
most of the limited supply of nitrogen, 300 yg-N/1,
before Microcystis.
10.0 T T T T u
PCM = SOpg-p/t
NCM = 1S00p9-n/1
8.0F no Microcystis
6.0F 7
4.0 7
2.0b Chlorella 4
\ : ! 1 1
Aprit Moy June July August Sept
TIME
There is enough nitrogen in the system, 1500 ug-N/1,

for both Chlorella and Microcystis to utilize the
initial phosphorus concentration of 50 yg-P/1 to the
best of their capabilities.

59


HYDROGRAPHIC SURVEY

STONE LAKE
CASSOPOLIS, MICHIGAN
MARCH 1968

SCALE {"=200' A +150 ACRES|

Figure 1: Hydrographic Map of Stone Lake.
4


oF

2

Table 7. COST-BENEFIT TABLE (after Girman )
Ease in Fishery 3
criteria cost handling Time of resources Reroval Potential for Aesthetic Torat out of a
& application | application after tt “i tivit. Se value 1b. int!
of technique treatment nutrients ac es points
Multi-factor 5 3 1 1 4 2 4
4
1) Fly ach (20) 5s) 4a) 20) “a6 48) “a6 Bt
2) Fly ash & lime | 4 (29) Sar 5¢5) 20) * (6) *¢a) * (6) a
3) Nutrient inacti- 2 2 3 3 4 4 4 62
eae meer | 710) (6) (3) @) a6) (8) (a6)
sealing (clay)
4) Nutrient inacti- | 1 a 2 4 5 5 5 64
terient 4 “) @) @ (oy (20) (19) (20)
dredging
- 2 2
5) Nutrfent tnactix | 5 (25) 5 (15) tay a) 2a) () (8) 65
aeration
1 5 2
O Meltevesting & | C25) Sas) @ @) mc) hay 1) 6
aeration
7) Replacing lake 1 1 3 1 4 5 5 58
water with @) @) @) @ a6) (0) (20)

higher quality
& a soil &
plastic barrier

Note: Numbers in parenthesis denote the rating times the multiplication factor.


Of course localized adsorption, complex formation, or biological incor-
portation, could functionally circumvent the relationships expressed in
Figure 20. This is illustrated convincingly by the behavior of mercury
from fly ash in laboratory aquaria shown in Figure 21. Two peaks of
mercury release were noted, the first within a few hours of addition at
an elevated pH, the second several days later at a lower pH. Although
no corroborative evidence could be gathered, it is reasonable to postu-
late the action of a combined chemical/biological mechanism to explain
the observations. The initial release, which is enhanced by the high
pH, is essentially a desorption of mercury, probably in the elemental
form. As conditions become more favorable for bacterial activity, it
appears plausible that some of the mercury is biologically converted to
an organo-mercurial, perhaps methyl mercury. The rapid disappearance of
mercury is not unexpected since the reactors were at all times open to
the atmosphere and many mercurial forms, particularly the two noted, ard

notoriously volatile.
SIDE STREAM TREATMENT

One further method of lake reclamation which was considered was the side-
stream treatment of the water for selective removal of phosphorus.
DePinto>! investigated this method initially and performed laboratory
bench scale studies to demonstrate its feasibility. He calculated the
total cost of a 1 MGD portable treatment plant utilizing chemical precipi~
tation to be approximately $100,000. A further analysis by Theis35
suggested the use of activated alumina columns as selective phosphate
adsorbents. A portable plant could be made significantly larger without a
proportionate increase in cost. Another advantage of this method is that

few, if any, undesirable constituents are added to the lake.

Of great importance in the technical evaluation of this method of treatment
are the size of a plant necessary to bring about phosphorus removal in a
reasonable length of time and the contribution of phosphorus from the
sediments once treatment has begun. While this method itself has not been

treated on a large scale, other flushing-type projects have been performed

52


SCALE Ite 440"
CONTOUR WITERVAL 20 FECT
10 FOOT CONTOUR - DASHED LINES

ORAINACE AREA

AGRICULTURAL +18 acres
onexe 310 gees REEX OAAINAGE AREA OUTLINE

FORESTED - BB ecren

CONSTRUCTED FROM US. GEOLOGICAL SURVEY ~ CASSOPOLIS: K4I45-WE600/15 - 1945

VILLAGE

S oF
CASSOPOLIS

UNIVERSITY OF KOTRE DAME
DEPARTMENT OF CIR CAGIMEE RING
TOPOGRAPHIC MAP
ORAINAGE AREA
STONE LAKE
CASSOPOLIS, MICHIGAN
MARCH 1968

Figure 2: Topographic Map and Tributary Drainage Area of Stone Lake.

6



EPA-600/3-76-106
November 1976

STUDIES ON THE RECLAMATION OF STONE LAKE, MICHIGAN

by

Thomas L. Theis
and
Joseph V. DePinto

University of Notre Dame
Notre Dame, Indiana 46556

Grant No, R-801245

Project Officer

Donald W. Schults
Marine & Freshwater Ecology Branch
Corvallis Environmental Research Laboratory
Corvallis, Oregon 97330

CORVALLIS ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CORVALLIS, OREGON 97330


Three peaks in the total phytoplankton are evident in this graph. The first
peak occurred in the first week of July, and was followed by maxima in the
middle of September and the middle of October. The population peaks correlate
exactly with the suspended solids maxima in the surface waters of the lake
(Figure 5). A further observation from this graph is that Stone Lake appears
to be dominated by green algae. While the blue-green groups come and go,

the green algae seem to be always present (though different genera within

the group may dominate) and continually increasing (except for a drop in
September). Several authors (Bierman®, Payne’, Morton?” et al.) have

stated that green algae in general have higher maximum growth rates than
blue-green algae. On the other hand, the minimum phosphorus requirement

for green algae is considerably higher than that for blue-greens (Soeder , et al.,
Uhimanit?, Shapiro’), The fact that green algae generally dominate in a
eutrophic lake where phosphorus is never limiting is consistent with these
findings.

The successional pattern of the phytoplankton groups is more easily visual-
ized in Figure 13, which presents a bar graph of the percent composition

of each algal group at each sampling date normalized to 100 percent. In
mid-May the phytoplankton in Stone Lake were largely non-motile green
species. Throughout June the nitrogen~-fixing blue-green algae (Anabaena and
Aphanizomenon) began to occupy a larger and larger percent of the population.
During July the nitrogen-fixers disappeared and once again the green algae
returned to dominance, although a small, short-lived bloom of Microcystis
(the only non-nitrogen-fixing blue-green alga found in Stone Lake) occurred

in early August.

In contrast to the earlier green algae dominance, the August green algae
consisted roughly of equal parts of the motile and non-motile groups. In
mid-September the second summer maximum was caused by another nitrogen-fixing
blue-green bloom (Anabaena). In this case Anabaena completely dominated

the total phytoplankton population (99 percent). Again, however, the greens
recovered fairly rapidly and again the motile green algae lagged somewhat

27


1971

DISSOLVED OXYGEN

}

Nio
We

:

Se, 7 Nos

mo ohontTmn

6
5

] I ] I

I) NL

7 I

ie)

(

!
m

0
at

nn

ee! |
+O O % OD CO a

SYH3BLEW ‘Hid3a

69


ST

DEPTH (m)

° Noe7 [
i
8
2b 9 J
10
bE 4
5 fi
4h
5L 6
6h 4 a
Te
3
8 =
gk
1OF
He
12
I3F
14 Es 2
15 M i ] I |
J F M A fe) N
Figure 7: Dissolved Oxygen Profile of Stone lake, Michigan for 1973. Contours

are in Units of mg/2.


RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into five series. These five broad
categories were established to facilitate further development and application of
environmental technology. Elimination of traditional grouping was consciously

planned to foster technology transfer and a maximum interface in related fields.
The five series are:

Environmental Health Effects Research
Environmental Protection Technology
Ecological Research
Environmental Monitoring

5. Socioeconomic Environmental Studies
This report has been assigned to the ECOLOGICAL RESEARCH series. This series
describes research on the effects of pollution on humans, plant and animal
species, and materials. Problems are assessed for their long- and short-term
influences. Investigations include formation, transport, and pathway studies to
determine the fate of pollutants and their effects. This work provides the technical

basis for setting standards to minimize undesirable changes in living organisms
in the aquatic, terrestrial, and atmospheric environments.

fon>

This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.


"8

DEPTH,

METERS

On Ou ds wUNnN - O

———~
ee
ip
Ds
“RA.

N\ 20
\\

10

SON\ 30 \
{

M

TOW
i

coD \972

q T
7

| {

J 4A


NUMBER OF CELLS /‘ml

T TT T TT T7 T
-_ o-
CONTROL + 4mgN/1
lo” ~ Filtered
CONTROL (Lake Water )
5 TLW + 95,19 P/L
ie) + 4:0 mg N/1
4 TIWW+4 mg NZL
10 4
TLW
(Treated Lake Water)
10° Z [ee es OR OS |
0) 4 8 l2 I6 20
DAYS
Figure 16: Algal Regrowth Study on Stone Lake Water Treated

with 5 g/? Fly Ash and 150 mg/2 Lime.

The Top Two Curves (open and closed circles)
Indicate the Lake Water is Nitrogen Limited.
The Bottom Curves Show the Same Water to be
Phosphorus Limited After Treatment (after
Higgins et a128),

39


In the beginning of June it would appear that nitrogen is limiting in

Stone Lake yet, at this same time, a large algal bloom begins to develop.

The apparent anomaly is explained by the theory that nitrogen-deficient
conditions provide a definite competitive advantage to nitrogen-fixing
blue-green algae??®, As will be seen in the next section, the June algal
bloom (point d, Figure 5) was in fact a nitrogen fixing bloom. Of further
interest is the increase of nitrate in the surface waters (points b to c,
Figure 11), which coincides with the wane of this algal bloom. The activity
and decay of the nitrogen-fixing algae replenished the supply of inorganic
nitrogen in the lake. Although ammonia is an end-product of organic nitrogen
breakdown, the nitrogen regeneration appeared only as nitrate. This suggests
that a rapid nitrification of the released ammonia was taking place in the
surface water. There was a rapid build-up of ammonia in the hypolimnion,
however, and this regenerated inorganic nitrogen remained as ammonia because
of the anoxic conditions in those waters. As Hutchinson suggests, the rise
of hypolimnetic ammonia is caused by decomposition of falling plankton as
well as deamination of organic nitrogen compounds in the sediments.

From August 1 to fall circulation the inorganic nitrogen fluctuations become
difficult to interpret. There was a gradual decrease in nitrate from August
1 through the middle of September (point c to d), which corresponds to a
gradual increase in suspended solids. During this time period there was
little change in the epilimnetic ammonia concentrations, except perhaps

some invasion of ammonia from the hypolimnion due to vertical entrainment.
About the middle of September both the epilimnetic nitrate (point d to e,
Figure 11) and ammonia (point c to d, Figure 10) showed an increase again.
This increase corresponds quite closely with the wane of the second summer
bloom (point e, Figure 5), but it is masked somewhat by the nitrogen uptake
associated with the third bloom (point f, Figure 5). As the fall mixing
did not occur until about November 1, these variations are not likely to be
explained by this event. These variations may be explained in terms of
biological nutrient cycling with the aid of the phytoplankton data.

23


stratified lakes with excess phosphates and a tendency toward nitrogen

limitation.

The nitrate regeneration associated with the second nitrogen-fixer bloom

was somewhat masked by the rapid nitrate uptake as the green algae regained
their previous status. In contrast to previous green dominations, this late
September - early October bloom was dominated by one species (Microspora).
Apparently Microspora is an opportunistic variety, which outgrew other greens
when conditions were favorable. Subsequent to the Microspora peak, a
planktonic Cryptomonad emerged. Practically all Cryptophyta require vitamin

B
12
may possibly have been the result of a vitamin excretion by Microspora or

or thiamin, usually both, for optimal growth. The Cryptomonad appearance

stimulated bacterial activity. Organic growth factors can be an important
reason for the decline of alloauxotrophic phytoplankton. As noted earlier,
this fall bloom terminated rather abruptly with the fall circulation. Fall

circulation represents another of Round's "stress points".

32


ze

DEPTH,

METERS

-o

COON OU PWD

ORGANIC NITROGEN 1972

T T wy \ TG T
\ 13 |
> 12 |
—s _
aA | | | |
J F M A M J J A

DATE


allochthonous inputs. The only significant nutrient input to Stone Lake at
the time of this study was surface runoff. Based on rainfall data and
estimates of total phosphorus concentrations in the runoff, it was estimated
that the increase in total phosphorus in the epilimnion over the six month
period from mid-April to mid-October would be approximately 0.05 mg/l as
PO,- It would seem then, that the phosphorus time-variations in the
epilimnion of Stone Lake can safely be attributed to biological and thermal
cycling. Looking at the upper waters, several features stand out. First,
the February algal bloom causes a rather dramatic decrease in phosphate
(point a, Figure 8) only to be followed by what appears to be a phosphorus
regeneration after the bloom (point b). Since no large algal population
appears in April and May, this recycled nutrient remains as soluble ortho-
phosphate. The macrophyte growth which took place at this time apparently
did not require phosphate from the open waters of the lake; however, it
appears that their die-back had a significant effect on the epilimnetic
phosphate concentration. During the macrophyte withdrawal (points c and d),
the orthophosphate concentration in the epilimnion and the thermocline rose
0.30 mg/1 as PO,.
The phosphorus dynamics through the summer stratification period are difficult
to interpret. It is clear that the three sequential algal blooms during the
period (points d tog) continually reduced the phosphate concentration in

the epilimnion from 1.7 mg/1 as PO), to 1.0 mg/l as PO, + Any regeneration
which might have taken place in this region is masked by phytoplankton uptake.
It is interesting to note that the second bloom (points e to £) reduced

the phosphate concentration by only 0.10 mg/1 as PO,- This fact leads one

to postulate that there was an additional phosphate source during this

bloom. The source may very well have been phosphate regeneration from

aerobic algal decomposition in the lower epilimnion and thermocline region.

Also of note is the steady increase in soluble orthophosphate in the
hypolimnion which begins with the onset of rapid phytoplankton growth at
the surface (point d) and continues to the fall circulation (point h).

18


C

W
=
2 . 6
x
a 7 es

TS :

24
J

——
Ss



SECTION IL

RECOMMENDATIONS

Particulate materials should be field tested on 4 large scale to
determine their effectiveness as lake restoration tOols. As part
of this effort further information on the costs and harmful effects
(if any) should be obtained.

A more intensive field investigation of phosphorus and nitrogen cycling
in eutrophic lakes should be undertaken. Such 4 stUdy should focus on
an evaluation of aerobic vs. anaerobic regeneration of these nutrients.

A mathematical model of a lake ecosystem should be developed which will
combine nutrient regeneration with other important aspects of lake
systems such as sediment-water interchange and algal and bacterial
growth and decay.

Investigations into other methods of lake reclamation, such as side-
stream treatment, should continue.


(Lake Washington36, Buffalo Pound Reservoir3?, Shagawa Lake?®) which
indicate the potential of this approach as applied to lake reclamation.

MODELING EFFORTS ON STONE LAKE

The techniques of mathematical modeling can provide a systematic basis
for a research approach to the complex problem of cultural eutrophication
and can be extremely valuable in comparing management options for control
and/or restoration. The general advantage of a mathematical model in
algal growth studies is that such a model can synthesize data from many
different experiments, each with its own particular scope of inquiry,

and present the results in a dynamic and comprehensive manner

A model devised by Bierman® focused primarily on the kinetics of algal
growth in eutrophic lakes and utilized a two-step process involving
Separate nutrient transport and cell synthesis mechanism at the species
level. This model included carrier-mediated transport of nutrients,
using a reaction-diffusion mechanism, and allowed for intermediate

nutrient storage in excess of a cell's immediate metabolic needs.

Applications involved one- and two-species systems where phosphorus is
the regulating nutrient and two- and three-species systems where both
Phosphorus and nitrogen are important regulating nutrients. Effects of
atmospheric nitrogen fixation as well as combined nitrogen were included.
For purposes of simplicity, growth simulations were confined to aerobic
surface waters and were extended only through the course of a single
growing season. However, in order to make the model as realistic as
possible, temperature variation, cell sinking, cell decomposition,

nutrient recycle, and predation by higher animals were included.

Because of luxury phosphorus uptake, the proposed model predicts a lag
between the removal of phosphorus from solution and the subsequent algal
growth, and the specific growth rate predictions of the model were not
compatible with the same predictions of Monod kinetics for the single-

species example presented.

54


Wigan
(A
RAN \.



SEDIMENT
SAMPLE SITES
STONE LAKE

Figure 17: Sample Sites for Sediment Survey of Stone Lake (after Yaksich26).
40


sediments. This is shown in Figure 18, A similar approach could be
used for other eutrophic lakes to which this treatment technique is

applied.

FARM POND STUDY

In the summer of 1972, a one acre farm pond in Mishawaka, Indiana was
treated with fly ash. The main purpose of the treatment was to evaluate
fly ash application methods and to aid in the development of an appli-
cation method for Stone Lake. In this respect, the treatment was a
success and helped lead to the current method proposed for fly ashing

eutrophic lakes.

In addition to the above studies, some monitoring of the pond was performed
before and after treatment to help evaluate the effect of the treatment

on water quality and biota. The pond was not an ideal test case for the
long term effects of fly ash in reducing productivity because the con-
stant enrichment from high nutrient runoff and direct input of cattle
wastes could not be curtailed following treatment. In any event data

were taken and visual observations made which did shed light on the

technique of treating natural waters with fly ash.

The water quality data in Table 6 show that the fly ash treatment was
effective in reducing the phosphate concentration in the pond. However,
it can be seen from the chemical data that the pond one year later is
very similar to its pretreatment state. The relatively high suspended
solids can be explained by noting that the ground water well which
feeds the pond is high in colloidal clay material (20 mg/1). The
significant phosphate increase over the immediate post-treatment level
was due to nutrient runoff from the heavily fertilized drainage area.

A significant increase in the combined inorganic nitrogen concentration
from July 10, 1972 to August 2, 1972 corroborates this hypothesis.

Before treatment, this pond was approximately one-half covered with a
thick, filamentous algal mat, which was not skimmed off prior to treatment.

42


Pertinent morphological data are given in Table 1.

Table 1. MORPHOLOGICAL CHARACTERISTICS OF STONE LAKE

Surface area 60 ha (150 acres)
Depth
Maximum 18 m (60 feet)
Average 6 m (20 feet)
Volume 3.4 x 10° 2 (2876 acre-feet)
Drainage area 176 ha (435 acres)
Urban 128 ha (319 acres)
Forest 40 ha (100 acres)
Agricultural 6.4 ha (16 acres)

The total watershed of Stone Lake is relatively small. As indicated in
Table 1 the total drainage area is 176 hectares. Figure 2 illustrates the
approximate boundaries of the drainage basin. Previous calculations had
indicated a hydraulic retention time of approximately 11 years. However
this was prior to the discovery of storm sewers from the village. The
present calculated hydraulic retention time of Stone Lake is approximately
5.5 years. Further details regarding the climatological and geological

characteristics of the lake can be found in Tenney et al,