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Dissertations Graduate College
4-1981
Storm-Sewer Input of Heavy Metals into an Urban Lake Environment
George A. Duba Western Michigan University
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Recommended Citation Duba, George A., "Storm-Sewer Input of Heavy Metals into an Urban Lake Environment" (1981). Dissertations. 2591. https://scholarworks.wmich.edu/dissertations/2591
This Dissertation-Open Access is brought to you for free and open access by the Graduate College at ScholarWorks at WMU. It has been accepted for inclusion in Dissertations by an authorized administrator of ScholarWorks at WMU. For more information, please contact [email protected]. STORM-SEWER INPUT OF HEAVY
METALS INTO AN URBAN LAKE ENVIRONMENT
by
George A. Duba
A Dissertation Submitted to the Faculty o f The Graduate College in partial fulfillment of the requirements for the Degree of Doctor of Philosophy Science Education
Western Michigan U niversity Kalamazoo, Michigan A p ril 1981
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. STORM-SEWER INPUT OF HEAVY METALS INTO AN URBAN LAKE ENVIRONMENT
George A. Duba, Ph.D.
Western Michigan University, 1981
T h e purpose of this study was to measure the concentration of
lead, cadmium, zinc and copper in runoff entering an urban lake
ecosystem and to measure the distribution of these metals in selected
tropic levels of the lake.
F - is k Lake was chosen as the study site and is located in East
Grand R a p id s, Michigan. Samples were collected of stormwater, rain
water a n d lakewater together with substrate, aquatic macrophytés
Peltandm a virginica, chironomid larvae, Chironomidae, snails
Phvsa» and eight species of fish, Ictalurus nebulosus, Esox lucius,
Lepomi s gibbosus, JL. macrochirus, Pomoxis nigromaculatus, Micropterus
sa lm o id e s , Catostomus coitmersoni, and Perea flavescens. A ll samples
were c o l 1 acted on the basis of being close to, or distant from, a
storm se w e r contaminated portion of the lake.
S a m p le s were prepared and analyzed using atomic absorption
spectrophotom etry (AA) and particle induced X-ray analysis (PIXE).
T h e results of this study suggested that:
1 - The metals did not show highest concentrations at highest
tropic levels.
2 . Lead? zinc aod copper were detected in stormwater.
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 3. Although some substrate was highly contaminated, the other
tropic levels need not show sim ilar contamination.
4. The benthic organisms, although shown to contain elevated
metal levels, do not seem to be passing these concentrations
along the food chain.
5. The two processes of analysis, PIXE and AA, give similar values,
6. In terms o f metal contamination, the fis h o f Fisk Lake
appear to present little toxic danger.
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. DEDICATION
To Mr. and Mrs. John C. Duba
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENTS
I would like to thank the members of my committee, Drs.
Clarence J. Goodnight, (Chairperson), W illiam B. Harrison I I I , George
G. Mallinson, Richard D. Brewer, and John D. Grace, for their
persistence, patience, and assistance throughout the three years
of this study. Dr. Julie Jones Medlin, Mr. Andy Davis, Ms. Sara
Cunningham, Ms. Margo Johnson, and Ms. Barb Leonard also have my
sincerest gratitude for their very special help in producing this
manuscript.
I would also lik e to thank the Graduate College along with
the Geology, Biology, and Physics Departments o f Western Michigan
University for their assistance in terms of finances and equipment
for this study.
The C o rva llis, Oregon Research Branch o f the Environmental
Protection Agency also helped immensely with further finances and
q u a lity control. Their work is g ra te fu lly acknowledged.
A final recognition must be given Mr. Jose Aizpurua and Ms. Linda
M iller, for their chironomid expertise, Mr. Mick Lynch, for his
superb surgical a b ility w ith frozen fis h , and Mr. and Mrs. Robert
Vander Veen, for allowing their boat to become a research vessel.
Special thanks must be given the Holm family. Bob, Carol, Liz,
John, and Amanda, whose warm house became a laboratory and whose warm
hearts encouraged this student.
George A. Duba i i
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D uba , G eorge Alexander
STORM-SEWER INPUT OF HEAVY METALS INTO AN URBAN LAKE ENVIRONMENT
Western Michigan University Ph.D. 1981
University Microfilms internetionsi 300N.ZeebKaad.AmiAibor.MI4il06
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Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS
ACKNOWLEDGEMENTS ...... i i
LIST OF TABLES...... v
LIST OF FIGURES...... v i i i
Chapter
I. INTRODUCTION AND LITERATURE REVIEW ...... 1
The Heavy Metal Problem ...... 1
Heavy Metals: Lead, Cadmium, Zinc, and Copper ...... 1
Heavy Metal P ollution ...... 4
Non-point Source Metal P o llu tio n ...... 7
Total Ecosystem A n a ly s is ...... 19
P u rp o s e ...... 23
I I . STUDY SITE, DESIGN, AND METHODOLOGY ...... 24
Study S i t e ...... 24
D e sig n ...... 29
Methodology ...... 31
I I I . RESULTS AND DISCUSSION...... 43
Prelim inary Survey ...... 43
Heavy Metals in Water ...... 43
Heavy Metals in Sediment ...... 47
Heavy Metals in Plants ...... 64
Heavy Metals in Chironomids ...... 70
Heavy Metals in Snails ...... 77
Heavy Metals in F is h ...... 81
i i i
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Heavy Metals throughout the Food Chain ...... 92
PIXE versus AA Methods o f Analyses ...... 93
Quality Control ...... 102
IV. CONCLUSIONS AND RECOMMENDATIONS ...... 106
Conclusions ...... 106
Recommendations ...... 107
BIBLIOGRAPHY...... 108
IV
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. LIST OF TABLES
Table Page Number T itle or Explanation Number
1 Lead in D irt o f 77 American C it ie s ...... 11
2 A Comparison o f PIXE and NBS Orchard Leaf Values .... 35
3 Physical, Chemical and Biological Parameters Measured in Preliminary Study o f Fisk Lake and Associated Stormsewer from Oct. 1978 to April 1979 ...... 47
4 Metals Detected in Three Sets o f Stormwater and Rainwater Samples Associated w ith Fisk Lake ...... 45
5 Metal Concentrations in Samples of Fisk Lake Substrate . 48
6 ftetal Concentrations in Samples of Fisk Lake Substrate . 49
7 Metal Concentrations in Samples of Fisk Lake Substrate . 50
8 Individual and Mean Metal Concentrations in Samples of Fisk Lake Substrate ...... 55
9 Individual and Mean Metal Concentrations in.Samples of Fisk Lake Substrate ...... 56
10 Individual and Mean Metal Concentrations in Samples of Fisk Lake Substrate ...... 57
11 Metal Concentrations in Substrate from United States Lakes ...... 63
12 Means and Standard Deviations of Metal Concentrations in Stems and Leaves o f Mature Peltandra V irginica Samples from Storm Sewer Affected and Non-Storm Sewer Affected Areas of Fisk Lake ...... 65
13 Means and Standard Deviations of Metal Concentrations in Stems and Leaves o f Mature Peltandra V irg in ica Samples from Storm Sewer Affected and Non-Storm Sewer Affected Areas of Fisk Lake ...... 66
14 Means and Standard Deviations of Metal Concentrations in Stems and Leaves o f Young Peltandra V irg in ica Samples from Storm Sewer Affected and Non-Storm Sewer Affected Areas o f Fisk L a k e ...... 67
V
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. LIST OF TABLES (continued)
Table Page Number T itle or Explanation Number
15 Means and Standard Deviations of Metal Concentrations in Stems and .Leaves o f Young P.. V irg in ica Samples from Storm Sewer and Non-Storm Sewer Affected Areas o f Fisk L a ke ...... 68
16 Heavy Metal Concentrations in Different Organs of Higher Water P la n ts ...... 69
17 Means and Standard Deviations of Metal Concentrations in Chironomid Larvae from Storm Sewer Affected and non- Storm Sewer Affected Areas o f Fisk L a k e ...... 76
18 Means and Standard Deviations of Metal Concentrations in S hell, Total Body, and Soft Body Samples o f Physa sp. from Storm Sewer Affected and Non-Storm Sewer Affected Areas o f Fisk L a k e ...... 78
19 Fish Sample Size,+N, Mean Weight, Wt, Weight Range, R, and Lead Content - Standard Deviation (ppm) for Selected Fisk Lake Species ...... 82
20 Fish Sample Size, N,+Mean Weight, Wt. , Weight Range, R, and Cadmium Content - Standard Deviation (ppm) for Selected Fisk Lake Species ...... 83
21 Fish Sample Size,+N, Mean Weight, Wt. , Weight Range, R, and Zinc Content - Standard Deviation (ppm) for Selected Fisk Lake Species ...... 84
22 Fish Sample Size, N, Mean Weight, Wt. , Weight Range, R, and Copper Content + Standard Deviation (ppm) for Selected Fisk Lake Species ...... 85
23 Metal Concentrations in 10 EPA Standard Samples .... 99
24 Metal Concentrations in 10 EPA Standard Samples .... 100
25 Metal Concentrations in Samples of Fisk Lake Substrate . 103
26 Metal Concentrations in Stems and Leaves of Peltandra Virginica from Fisk Lake ...... 104 vi
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. LIST OF TABLES (continued)
Table Page Number T itle or Explanation Number
27 Metal Concentrations in Selected Fish Tissues of Specimens Collected from Fisk Lake ...... 105
V I1
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. LIST OF FIGURES
Figure Page Number T itle or Explanation Number
1 Sources o f metal p o llu tio n in urban stormwater ...... 10
2 Hydrograph p o llu ta n t concentrations o f lead from storm sewers ...... 14
3 Reeds and Fisk Lake w atershed ...... 25
4 Land use in the Fisk Lake watershed ...... 26
5 Fisk Lake basin and storm canal ...... 28
6 Sampling stations (A-K) in Fisk Lake and storm c a n a l ...... 30
7 Typical PIXE spectrum for dried sample pellet ...... 33
8 Water, substrate, plant and animal sampling stations (A-K) in Fisk Lake and storm canal ...... 37
9 Comparison of lead concentrations in substrate samples using PIXE, AA(EDTA), and AA(HA) methods .... 51
10 Comparison o f cadmium concentrations in substrate samples using AA(EDTA) and AA(HA) methods ...... 52
11 Comparison of zinc concentrations in substrate samples using PIXE, AA(EDTA), and AA(HA) methods .... 53
12 Comparison of copper concentrations in substrate samples using PIXE, AA(EDTA), and AA(HA) methods .... 54
13 Comparison of mean lead concentrations in substrate samples using PIXE, AA(EDTA), and AA(HA) methods .... 58
14 Comparison o f mean cadmium concentrations in substrate samples using AA(EDTA) and AA(HCl) ...... 59
15 Comparison of mean zinc concentrations in substrate samples using PIXE, AA(EDTA), and AA(HCl) ...... 60
16 Comparison of mean copper concentrations in substrate samples using PIXE, AA(EDTA), and AA(HCl) ...... 61
v i i i
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. LIST OF FIGURES (continued)
Figure Page Number T itle or Explanation Number
17 Comparison of lead concentrations in plant tissues using PIXE and AA methods ...... 71
18 Comparison of zinc concentrations in plant tissues using PIXE and AA methods ...... 72
19 Comparison of copper concentrations in plant tissues using PIXE and AA methods ...... 73
20 Comparison o f mean zinc concentration in plant tissues using PIXE and AA methods ...... 74
21 Comparison o f mean copper concentrations in plant tissues using PIXE and AA methods ...... 75
22 Mean zinc, lead, cadmium, and copper concentrations in chironomid tissues from storm sewer and non-storm sewer areas ...... 78
23 Mean zinc, lead, cadmium, and copper concentrations in Physa sp. tissues from storm sewer and non-storm sewer a re a s ...... 23
24 Mean lead concentrations in tissues of selected Fisk Lake fish species ...... 86
25 Mean cadmium concentration in tissues of selected Fisk Lake fish species ...... 88
26 Mean zinc concentrations in tissues of selected Fisk Lake fish species ...... 89
27 Mean copper concentrations in tissues of selected Fisk Lake fish species ...... 91
28 Substrate pH values from Fisk Lake and storm canal . . . 94
29 Comparison of lead, zinc, and copper concentrations on selected snail and chironomid tissues using PIXE and AA methods ...... 96
30 Comparison of copper concentrations in fish tissue using PIXE and AA m ethods ...... 97
ix
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. LIFT OF FIGURES (continued)
Figure Page Number T itle or Explanation Number
31 Comparison of zinc concentrations in fish tissue using PIXE and AA methods ...... 98
32 Comparison o f lead, zinc, and copper in EPA samples using PIXE and AA methods ...... 101
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. CHAPTER I
Introduction and Literature Review
The Heavy Metal Problem
As long as humans have been using metals, there have been prob
lems with metal p o llu tio n . Metal p o llu tio n d iffe rs dram atically from
other types o f p o llu tio n . Schroeder (1974) states that "a ll organic
substances are eventually biodegradable except the great class of
plastics. Even if humans cover the earth with paper, sewage, garbage,
rubber, and wood products, bacteria and mold w ill slowly but inevitably
decay them and they w ill go back to the elements from which they were
made. Even the organic pesticides are biodegradable."
In contrast, the heavy metals being elements, are not degradable.
Therefore, they reside in the ecosystem fo r long periods o f time.
The basic problem is tha t humans now use great amounts o f d iffe re n t
metals. Metals are taken from dispersed and buried sources, brought
to the surface of the earth, and concentrated. Once a metal is used,
it eventually returns to an environment that has evolved without such
concentrations of these elements. The problem is that these metals,
in more than trace concentrations, are toxic to numerous life forms.
Heavy Metals: Lead, Cadmium, Zinc and Copper
Heavy metals are defined by Biddings (1973) as those metals having
a specific gravity greater than five. These include about sixty-eight
elements. Their common feature with respect to life is that in exces-
1
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. sive quantities, they are toxic. Because of the extensive use of
lead, cadmium, zinc, and copper, and the environmental problems th a t
have arisen, only these four metals w ill be addressed. Lead and
cadmium are generally considered more toxic than copper and zinc,
since harmful effects are caused by smaller amounts. Although lead
is introduced into the environment from a variety of sources, Corrin
(1977) states tha t the principal innut is from the combustion o f lead-
containing fuels such as gasoline, coal, and fuel o il. Hall (1972)
estimates tha t 300,000 tons o f lead are released annually in to the
atmosphere solely from in te rna l combustion vehicles. Lead mining and
refining also contribute to the release of lead into the environment.
According to Hall (1972), lead is not poisonous in the elemental form,
but becomes to x ic when ionized.
Cadmium as described by Mennear (1979) is a metal of great toxi-
cological importance. As Friberg et sHU (1971) point out, cadmium
in the air acts as an aerosol, and so far, has only been found as part
of inorganic compounds. Cadmium is found wherever there is zinc since
it is geochemically related to that metal. Generally cadmium is found
in most s o ils and minerals in Cd/Zn ra tio s from 1:1000 to 1:12000
(Bowen, 1966; Schroeder e t a ly , 1967). Forstner and Wittman (1979)
report ratios varying from 1:300 to 1:2900 in most soils; 1:35 in
seawater, and 0.6:1 in human kidneys. Cadmium is obtained as a bypro
duct in the refining of zinc and other metals. However, since it is
d iffic u lt to separate zinc and cadmium, the latter w ill often be found
in small amounts associated with zinc, even in commercially available
zinc compounds (Schroeder et a l., 1967). Friberg (1971) further
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 3 States that although copper, lead, and zinc have been known for thou
sands o f years, cadmium has been known fo r a re la tiv e ly short time.
Thus, man started cadmium p o llu tio n long before he knew the metal
existed. He reports that at present, cadmium enters the a ir and water
from mining activity, from lead, copper, and zinc smelting, and from
industries using c&dmium in batteries, alloys, paints and plastics.
The burning of o il and waste, along with scrap metal treatment, and the
use of chemical fe rtiliz e rs , sewage sludge, and some pesticides may
also contribute to a ir and water cadmium contamination. According to
McCaull, (1971) cadmium-containing fertilizers and pesticides are a
major source of contamination to the aquatic environment.
Zinc is a trace element essential for human and animal nutrition.
Sandstead (1974), Underwood (1971), the National Academy o f Sciences
(NAS) (1973) and others discuss this topic thoroughly. In fact, the
NAS (1974) reconriended d a ily allowances o f th is metal to be 10 mg./day
for growing children over a year old, and 15 mg./day for adults.
The NAS (1977) report further states that zinc is commonly found
in a sulfidic form in the mineral sphalerite, an important zinc ore.
Zinc may also replace iron or magnesium in many minerals. It may also
be present in carbonate sediments. In the weathering process, soluble
compounds of zinc are formed and are present in trace amounts in most
water bodies.
Fertilizers applied each year in the United States contain approx
imately 22,000 tons of zinc. The extent to which this zinc enters fresh
water bodies from agricultural runoff is not known. Likewise, no con
sequential body of data dealing with the runoff of zinc into streams
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. from dumps and m étallurgie wastes has been gathered (NAS, 1977).
Smelting operations also can contribute to zinc concentrations in the
environment according to Friberg et (1974). Forstner and Wittman
(1979) found that because of human activity,zinc levels are increasing
in the environment and may adversely affect metabolic pathways of many
organisms.
Copper compounds are commonly found in most ecosystems. Accord
ing to Kopp and Kroner (1967), copper was detected in 74.4% of more
than 1500 river- and lake-water samples in the United States at con
centrations up to 280 pg./liter. Ackermann (1971) reported similar
results from analyzing water from 27 Illin o is streams, with a maximum
of 260 pg./liter.
Sources of copper contamination include various types of piping
used for domestic and industrial water transport. Copper is also
used for various brass and bronze alloys. Therefore, smelting opera
tions could introduce large amounts o f copper in to various ecosystems.
Oxides and sulfates of copper are used for pesticides, algacides, and
fungicides. Its compounds are also used in paints and wood preserva
tives to inhibit algal and invertebrate organisms (EPA, 1976). All
these are sources o f copper contamination.
Heavy Metal Pollution
Brown (1971) defines pollution as a term "widely applied to sub
stances introduced into an environment which are potentially harmful
to, or which interfere with, man's own use of his environment". He
further categorizes the pollutants as those that are increasing the
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 5 concentrations of material already in the water and those that are not normally present in the environment. Two of the metals, copper and
zinc, belong in the firs t category as they are usually present in small
amounts. The other two, lead and cadmium,fall into the second cate
gory. This difference between the two sets o f metals, lead-cadmium
versus copper-zinc, is reflected in the EPA (1976) criteria for •
drinking water. Copper and zinc have lim its of 1.0 mg./I. and 5.0 mg./I.,
respectively whereas those fo r lead and cadmium are 50 fig ./I. and
10 pg./l. respectively. Thus two orders of magnitude of difference
are evident. As noted by Schroeder (1974), metals such as zinc and
copper, that are common in the material on the earth's surface, are those
with which li f e has evolved. Lead and cadmium, however, have been
brought to the surface and concentrated, thus their previous influence
on the evolution o f ecosystems was minimal. Because o f th is and th e ir
exchangeability with other metals, toxicity occurs at a much lower
concentration, although all four of the metals are toxic at high
concentrations (Schroeder, 1968).
Metal p o llu tio n can occur in e ith e r a ir or water. Lead, cadmium,
zinc, and copper were a ll found by Schroeder (1968) in the lungs o f
urban Americans and Europeans from ten c itie s . When a ir contains
foreign substances, rainfall carries them to the ground. According
to Schroeder (1968), i f these substances are soluble they may appear
in the water supply. Therefore metals in the atmosphere may contribute
to aquatic contamination.
Sources of metal pollution may be divided into two categories,
point sources and non-point sources. Point sources include those
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 6 sources that can be identified as releasing pollutants at a single place
such as from a pipe or canal opening. The Federal Water P ollution
Control Administration (1969) refers to municipal sewage and indus
tria l wastes as point sources. Surface runoff from farms, rural roads,
and urban-suburban settings would then be considered non-point sources.
Classic cases of point-source mercury and cadmium pollution have
occurred in Minamata Bay in Kyushu, Japan and in the Jentsu River,
Toyama Prefecture, Japan. According to F u jik i (1972), victim s o f thé
"Minamata" disease had eaten contaminated fish and shellfish during
the early 1950's. The methyl-mercury was traced back to the Chisso
Company, a chemical firm that had dumped methyl-mercury in to a channel
that leads to Minamata Bay. This was apparently the firs t identified
case of point-source mercury pollution. The cadmium pollution was
associated with zinc mine drainage into the Jentsu River. The Makioko
Company had discharged untreated flotation sludge for several years
after World War II. The rice fields of the area were flooded by down
stream Jentsu River water. The people who ate the rice showed skeletal
deformities along with experiencing much pain. The resulting "ita i-
ita i" disease ("ouch-ouch") was later shown to be cadmium related
(Hagino and Yoshioka, 1961). Numerous episodes of point-source metal
pollution have been described. Roskano (1972) studied marine pollution
by copper and Lewin et (1977) provided a description of lead, zinc
and arsenic mine drainage in mid-Wales, England. Point sources can
be easily identified. Non-point sources for metal pollution present
another problem. Since th e ir origins cannot be narrowed to a single
source, the sources are extremely d if f ic u lt to measure, regulate or
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. perhaps even id e n tify . Non-point sources include rural and urban
runoff. The runoff its e lf contains at least some of the materials
humans apply, intentionally or unintentionally, to the surface of the
land.
Non-point Source Metal P o llution
According to McElroy et , (1975), 97% of the total land area
of the United States is essentially rural in nature, much of which
is cultivated. This cultivation may be responsible for 95%-99% of
soil erosion. The resulting sediment is recognized as the largest
single pollutant affecting water quality. Forstner (1979) says that
this eroded soil may become enriched with heavy metals due to the land
application o f plant nutrients and crop protective measures. Rock
phosphates and phosphate fe r tiliz e r s may contain high levels o f heavy
metals, especially cadmium and zinc. Studies by Stenstrom and Vahter
(1974) and Williams and David (1973) show th a t levels o f cadmium vary
V between 18 ppm and 91 ppm in commercial f e r t iliz e r o f Sweden and
Australia. Thus, rural runoff may potentially be a "distributor" of
heavy metals.
Helsel e t , (1979) made s ta tis tic a l comparisons o f several
land uses - fo re s t, a g ric u ltu ra l, re s id e n tia l, and commercial - in
terms of 7 metals found in that runoff from the Occuquam watershed,
in eastern Virginia. A total of 1337 sanples were collected from
260 station visits. Lead, zinc, and copper levels were higher in
the urban station as compared with those of the rural station samples.
Excluding the sediment fra c tio n , urban ru n o ff is considered to be a
major source of pollution containing more types and amounts of pollu-
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 8 tants than other forms of runoff including agricultural.
General studies of urban runoff probably begin with three studies
done in the early 1950's. Akerlinch (1950) from Sweden, Shigorin
(1950) in the Soviet Union, and Palmer (1955) from the United States
worked with various standard chemical and b iolog ical parameters such
as biological oxygen demand (BOD), suspended s o lid s , and coliform
content. They found that the shock load to a receiving water by
various pollutants in urban stormwater runoff could be 100 to 1000
times as great as that from secondarily treated wastewater. These
appear to signal the firs t consequential attention given on the sub
ject. Most of the early reports involved analyzing the water only
and the particulate matter in it.
Later reports, such as those of Weibil (1964), Geldreich (1968),
Bryan (1970), and Dharmadhikari (1970), sought to id e n tify the types
and amounts of pollutants coming from specific types of urban water
sheds.
Two studies examined closely quantities of pollutants as they
were related to landuse. The American Public Works Association
(APWA) (1969) in Chicago and the AVCO Economic Systems Corporation
study (1970) in Tulsa, Oklahoma studied accumulation rates of dust and
d irt on streets and related them to land uses and pollutant loadings
from urban watersheds, respectively. These studies involved the use
of trace metals as part of their pollution parameters. Research
related to stormwater p o llu tio n was summarized by Bradford (1977)
up through 1972. He reported that trace metals only became of analy
tical interest during the late 1960's and early 1970's. Among the
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. metals that were regularly identified in the summarized research
reports were lead, cadmium, zinc and copper.
Research reports on trace metals in urban runoff can be divided
into four groups, those dealing with (1) sources, (2) material on
the street such as dust and d irt, (3) material in the stormwater
runoff, and (4) the eventual fate of the trace metals themselves.
Figure 1. (p. 10) contains information summarized by Malmquist
(1975) concerning the sources of trace metals in stormivater runoff.
In urban areas lead, cadmium, zinc and copper enter ru n o ff in several
different ways mentioned previously.
Wilber and Hunter (1979) collected stre e t sweepings from urban
watersheds near Lodi, New Jersey. Only p a rticle s less than 63 pm.
were collected to eliminate possible size-related variation. These
samples were digested using a nitric-hydrochloric acid total metal
digestion. The digests were then analyzed using atomic absorption
spectrophotometry. Metal concentrations contained in road dust from
in d u stria l areas were generally higher than those from reside ntia l
areas. Lead was greatest in sweepings obtained at intersections.
Howell (1978), Spring (1978), and Anderson (1978) analyzed dust and road
d irt and emerged with sim ilar results. Lead again tended to be higher
in heavily used road areas implying deposits from auto emissions.
Table 1 (p.11) contains information provided by the Environmental
Protection Agency on lead concentrations in street d irt in 77 American
c itie s . Lead levels appear to be sim ila r throughout the urban areas
of the United States.
Stormwater analyses have received much attention especially from
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. CD ■D O Q. C g Q.
■D CD FIGURE 1. C/) C/) SOURCES OF METAL POLLUTION IN URBAN STORMWATER (after Malmquist, 1975) 8 Independent ■D Dependent variables parameters
Polluted air City planning T ra ffic Industrialization Topography 3"3. CD Geology
CD Climate/season "O O R ainfallDustfall Corrosion Land usage Q.
3O "O O Polluted urban storm water
CD Q.
■D CD
(/)C/) n TABLE 1
LEAD IN DIRT OF 77 AMERICAN CITIES. (FROM SCHROEDER, 1974)
LEAD IN DIRT OF STREETS
STATE NO. OF RESIDENTIAL AREAS COMMERCIAL AREAS CITIES (PARTS PER MILLION)
Arkansas 1 1,163 2,775
Colorado 3 1,741-2,974 2,843-4,065
Illin o is 9 656-3,067 1,774-3,549
Indiana 8 290-9,972 942-6,597
Iowa 5 849-2,525 1 ,127-3,790
Kansas 3 865-1,558 1,498-2,080
Kentucky 4 1,945-2,702 1,350-5,089
Mi chigan 9 1,041-3,042 2,524-4,722
Minnesota 3 1,265-2,563 1,650-4,681
Mi ssouri 3 1,566-4,681 2,086-4,639
Nebraska 2 1,891-2,603 2,256-4,464
North Dakota 1 958 2,522
Ohio 12 206-2,639 352-2,933
Oklahoma 2 1,683-1,950 2,272-4,935
Tennessee 4 1,010-4,416 2,677-20,667
West V irg in ia 5 1,084-2,045 375-6,979
Wisconsin 3 912-1,993 1,895-3,331
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 12 1974 to 1980. Sartor (1974) attempted to develop an accurate descrip
tion of stormwater using his own analyses of sampling, literature
review, and surveys. Among his several generalizations about storm
water were that: (1) runoff is highly contaminated with metals such
as. chromium, copper, zinc, n ic k e l, mercury, lead, and cadmium; (2)
major pollutants were inorganic particulates sim ilar to sand and s ilt;
(3) the quantities of all pollutants were highly variable; (4) the
amount of pollutant was time dependent; (5) amounts of pollutants
differed with different storm events, and (6) present street cleaning
methods are in e ffic ie n t. Randall e t , (1979) agreed as a re s u lt
of analyses of urban runoff in tv/o sub-basins in northern Virginia
th a t showed th a t amounts o f zin c, lead, chromium, and copper, war
ranted further investigation.
Whipple et ^ . , (1977) tried to evaluate the relationship between
storm frequency and pollutant loading. Samples of stormwater were
taken after 10 storm events of different intensities. Intervals
between storms varied from less than one day to 13 days. Zinc and
copper were at highest levels after storms preceded by only two or
three days of dryness. The conclusion of these researchers suggests a
slight tendency for pollutant loadings to increase with the passage
of time. They expressed serious doubt as to whether a mathematical
progression could be established by comparing time intervals between
storms with amounts of pollutants in urban stormwater.
Helsel et (1979) collected numerous stomwater samples to
determine whether there were differences in pollution loading of
lead, cadmium, zinc, and copper associated with different land-use
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 13 patterns. Runoff from forested sites contained the lowest concentra
tions of all metals. Lead, zinc, and copper were significantly higher
in runoff from other land-use areas when compared to that from the
forested site, with lead having the highest concentrations (1 ppm-1.5
ppm) in the runoff from commercial areas. Only cadmium fa ile d to
show a difference, possibly due to the levels of detectibility. Lead,
zinc, and copper levels all increased with increasing tra ffic volumes.
The authors state that gasoline, motor o il, tires, and brake linings
could be possible sources of these metals. They concluded that metal
loadings in runoff from similar land-use categories are highly variable
and thus forecasting metal loads would be d iffic u lt. They also found
that metal concentrations in stormwater were three orders of magnitude
higher than those found in wastewater from secondary sewage treatment.
Whipple and Hunter (1977) sampled urban stormwater from two sub
basins near Lodi, New Jersey. Samples were taken at 5 to 10 minute
intervals during storms. Using atomic absorption analysis, the heavy
metals found were lead, zinc, and copper. All metals show a charac
teristic "first flush" effects (Fig .2, p.14). Effects of rapid loading
occurred within the firs t 30 minutes of the storm event. Analyses were
made for 24 different storm events. The metal concentrations were
highest from the commercial and industrial land-use areas. The amount
of copper in runoff from these areas v/as three times the amount found
in runoff from any of the other areas.
Alley and Ellis (1978) reported on trace metals in rainfall and
snowmelt ru n o ff in the Denver area. Their re s u lts , as well as those
o f Randall (1978), support the " f ir s t flush " idea proposed by Whipple
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 14
g
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Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 15 and Hunter (1977). They also found that most of the trace metal content
is associated with the particulate matter in the stormwater, not in
solution.
P itt and Field (1977) used existing information and devised a
hypothetical case study to demonstrate potential problems with urban
stormwater runoff. Their model was based on hypothetical inputs and
loading descriptions of metals and other pollutants, hydrologie infor
mation, q u a lity comparisons o f sanitary m te r and stormwater, and the
effects on receiving waters. The study involved a hypothetical city
with a population o f 100,000. Worst case storms were delineated as
0.25 inches/hour since greater amounts of water would add a dilution
factor and lesser amounts would not move the pollutants. The pollution
levels were postulated as 1800 ppm fo r lead, 3.4 ppb fo r cadmium,
370 ppm for zinc, and 110 ppb for copper in road particulates. From
their results, it was concluded that urban runoff should be treated
as is secondary waste water. When a 20-day bioassay was conducted
on stickleback fish, no physiological effects were registered, although
the need for more long-term effect studies v/as indicated.
Once stormwater enters a repository, such as a stream or lake,
pollutants quickly leave the water column and enter other portions of
the ecosystem. Whipple (1976) and Wilber and Hunter (1977) showed
that the metals are generally associated with the less than 80 um.
suspended particles in the water and are likely to be deposited at
areas near the point of discharge into a lake or stream.
In terms o f fin a l metal destinations, sediment studies dealing
with urban runoff are the most numerous, probably because o f the ease
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 16
of sampling and the stationary nature of the material. The total
number o f studies is s t i l l small when compared with the number o f other
sediment studies related to point-source p o llu tio n conducted mostly in
the 1970's (Ruch e t (1970), Copeland and Ayers (1972), Walters et
(1974), Thomas e t al^. (1976), Farmer (1978), and many others).
Sartor e t (1974) has said th a t most trace metals are assoc
iated with the smaller size fraction of the particles in urban storm
water runoff. The very fine, silt-like material ( 43 um.) accounts
for only 5.9% of the total solids although it accounts for one-fourth
of the oxygen demand and one-third to one-half of the algal nutrients.
It also accounts for over one-half of the heavy metals and three-
fourths of the pesticides. This is the material that becomes part of
the sediment of lakes and streams and may be directly attributable to
urban stormwater runoff.
Nightingale (1975) showed tha t the sediments o f holding ponds
in California, b u ilt to hold increasing amounts of urban runoff, have
high accumulations of lead. Since these basins are often used for
recreation, the metals could become a health hazard. Nakamura et al.
(1974), Satake e t (1975), and Tatekawa e t , (1975) show that
metal concentrations, including lead, cadmium, zinc, and copper, are
enriched in lake bottoms, most likely due to industrialization, urban
ization, and land development.
In the U.S., Wilber and Hunter (1979) sampled sediments from
the Saddle River near Lodi, N.J. Samples were taken in , and upstream
from, the urban area of Lodi, N.J. They found lead concentrations
ranging from 14.0 ppm in upstream areas to 70.7 ppm in the urban area.
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 17 zinc ranging from 23.9 ppm to 69.4 ppm, and copper ranging from 5.2
ppm to 32.6 ppm in s im ila r areas. The urban areas showed a 67% en
richment fo r lead and 350% and 310% enrichment for zinc and copper,
respectively.
Few studies go beyond the sediment in so far as investigating
metal concentrations is concerned. According to Forstner (1979)
"the greater part of the dissolved heavy metals transported by natural
water systems is under normal physiochemical conditions, rapidly
adsorbed onto the p a rticu la te m aterial. However, heavy metals immo
bilized in bottom sediments do not necessarily stay in that condition,
but may be released as a result of chemical changes in the aquatic
mileau". Thus the metals could become available for the aquatic fauna
and flora of the area.
Numerous studies have been undertaken on accumulation and toxicity
of zinc, lead, copper, and cadmium with respect to a variety of types
of fauna and flora. Knauer and Martin, (1973), Stenner and Nickless
(1975), Lei and and McNurney (1974), Heydt (1977), and others, a ll
studied metal enrichment in terms o f lead, cadmium, zinc and copper
in various plants from phytoplankton and macroalgae to higher plants
such as Potamogeton species, a typ ica l pond weed. Knauer and Martin
(1973), investigated to zinc concentrations in zooplankton but two
groups of fauna, mollusks and fish, received the most attention in
terms of toxicity and accumulation of lead, cadmium, zinc and copper.
This is probably due to the economic value of both these groups, along
with the benthic habits of the mollusk group. These habits keep the
mollusks in close proximity to major metal concentrations.
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 18 Bivalves, being filter-feeding organisms and only slightly mobile,
can reflect the heavy metal composition in a relatively small region.
Bryan (1973), Phillips (1976), Bloom and Ayling, (1977), and Forstner
(1979) are among those who have undertaken studies in bivalve accumu
lation and toxicity of the previously mentioned metals. The crusta
ceans receive some attention probably for reasons sim ilar to those
given for the mollusks. Bryan (1971), Leiand and McNurney (1974),
and Prosi (1977) investigated the accumulation and toxicity of various
metals in fresh- and salt-water crustaceans and found high concentra
tions of zinc in the exoskeleton of the various crustaceans.
Fish receive great attention in the literature probably because
o f th e ir high economic value. Forstner and Wittman (1979) state three
reasons fo r using fis h as a subject fo r heavy metal research, namely
(1) they can be used as an indicator organism for heavy metal pollution
of a specific environment, since some species are more tolerant to the
metals than others; (2) they are advanced enough to study physiological
behavior of heavy metals; and (3) they are generally the end consumer
"top of the food pyramid" and can be used as an indicator of heavy
metal enrichment (Note: Forstner, (1979) uses the phrase "heavy metal
enrichment" in the same manner that the phrase "biological magnifica
tion" is used in this study. Biological magnification is the tendency
of heavy metals or any non-biodegradable toxin to increase in concentra
tion as one moves up the food chain from producer to end consumer.)
Lucas et a j., (1970), Uthe and Bligh (1971), Muller and Prosi (1977)
investigated the accumulation and distribution of the metals (Pb, Cd,
Zn, and Cu) in a variety of freshwater fish with which this study is
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 19 concerned. They found low accumulations o f the metals mentioned in a ll
fish analyzed.
Total Ecosystem Analysis
As stressed by Forstner and Wittman (1979), "many investigations
have demonstrated tha t in order to determine the overall heavy metal
pollution of a biotope (ecosystem), it is necessary to determine the
heavy metal concentrations in as many trophic levels as possible in
the aquatic system." The conclusion that high metal concentrations
in the sediment would lead immediately to an ecosystem with high heavy
metal concentrations throughout the floral and faunal tissues of all of
the trophic levels is not valid. Potter et (1975) further suggest
that numerous trophic levels should be simultaneously investigated,
since the metal concentrations within a certain trophic level can
fluctuate considerably with different dietary habits.
Few analytical studies have been done that concern the whole food
chain. A m ajority o f these concern the metal mercury (Cumbie (1975),
Fagerstrom e t aly (1975), and others). Even these studies involve
only a few trophic levels.
If the principle of bioaccumulation does hold for the heavy
metals, one could expect the follow ing in terms o f degree o f metal
concentration:
Water < sediment < algae < invertebrates < fish
This ordering assumes that all metals are available throughout the
trophic levels and are transported through the food chain. As w ill
be shown, th is does not seem to be the case in natural ecosystems.
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. I 20 Stenner .and Nickless (1975), for example, found high concentrations of
zinc in barnacles from southwest Spain and southern Portugal but the
concentrations of these metals (Pb, Cd, Zn,Cu ) were low in the end-
consumer fish. Bohn (1975) showed an increase in arsenic along the
food chain in a west Greenland mining area. The concentration values
for zooplankton were determined to be 6.0 ppm, for seaweed 35.5 ppm,
fo r mussels 14.1 ppm-16.7 ppm, fo r prawn 62.9 ppm-80.2 ppm, and fo r
different fish species 88.4 ppm.
Mathis and Cummings (1973) undertook one of the earlier studies
in ecosystem analysis o f concentrations o f heavy metals in the Illin o is
River. Eight metals were detected including lead, cadmium, zinc and
copper. They made collections at industrial and non-industrial sites
of the Illinois River near Peoria, Illinois. Their findings indicate
that the pattern of metal concentrations for all metals were:
Water < carnivorous < omnivorous < clam < worms < sediment fis h fis h
Their study implies, as subsequent studies do, that sediment metals
are not totally available to aquatic organisms and, if available, are
not necessarily transferred to, and accumulated at, higher trophic
levels. They mention that the higher levels in the benthic organisms
could be due to the fact that gut sediment in the clams and tubifiscid
(worms) could falsely elevate the metal concentrations in their samples.
Namminga and Wilhm (1977) examined a stream ecosystem affected by
municipal and industrial waste. They obtained 8 water samples, 12
sediment samples and 0.5g chironomid samples (a f ly larva known to
be pollution tolerant) at five stations along Skeleton Creek between
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 21
Enid and Guthrie, Oklahoma. These were analyzed using standard acid
digestion and atomic absorption techniques. The researchers found
that the concentrations of lead, zinc, and copper varied through the
trophic levels with:
water < sediment < chironomid
whereas the metal hierarchy fo r chromium was:
water < chironomid < sediment
Mixed results in terms of food chain enrichment are evident although
lead, zinc, and copper did show tendencies towards possible bioaccumu
lation. Too few trophic levels and gut contamination may have influ
enced the stucty resu lts.
Prosi (1977) investigated different regions on the Elsing River
in West Germany. Lead, cadmium, zinc, and copper concentrations were
measured in samples o f fis h , invertebrates, including sludgeworms,
isopods (small crustaceans), and leeches and in sediments and water
from urban-affected and rural areas. The researcher found that sediment-
dependent benthic organisms had highest metal concentrations o f the
organisms analyzed with fis h having the,lowest. The metal concentra
tions increase with increasing dependency upon the ingestion of sedi
ment.
Rabe and Bauer (1977) obtained results sim ilar to those of Prosi
(1977) in a study o f water, sediment, benthic organisms, and fis h
tissue from nine lakes of the Coeur d'Alene River valley in Idaho.
Metal concentrations were measured in samples from lakes receiving
mine drainage and compared with those concentrations obtained for
samples collected from a control lake mine drainage. The substrate
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 22 had the highest metal concentrations with zinc ranging from 240 ppm
to 6800 ppm, copper from 8 ppm to 160 ppm, lead from 100 ppm to 4600
ppm and cadmium from 2 ppm to 130 ppm. The control lake showed zinc
ranging from 52 ppm to 110 ppm, copper from 4 ppm to 9 ppm, cadmium
<2 ppm, and lead from 30 ppm to 300 ppm. A metal concentration hier
archy for the samples from the substrate was established with
water < fish < chironomids < sediments
The metal content in benthic organisms was s im ila r to sediment concen
trations in terms of copper but was generally less with the other
three metals. The researchers conclude th a t the sediments represent
a storehouse of metals that are potentially toxic to aquatic organisms.
The pH o f the mine lakes however, is 7.0 or higher and therefore, the
metals are essentially trapped in the sediments and do not enter the
water column. Heavy metals are more soluble in water at lower pH
values and decrease in solubility at higher pH values. These authors
conclude that high metal values in sediment concentrations are not
necessarily indicators of polluted ecosystems.
Enk and Mathis (1977) record s im ila r findings in stream ecosystems.
The levels of cadmium and lead follow a sim ilar pattern
water < fish < sediments < aquatic invertebrates
They concluded th a t heavy metal enrichment does not occur in the same
way as do the classic "pesticide" residues such as DDT in the food
chain of fish and birds.
There appears to be minimal study designed to associate the metals
in urban stormwater runoff to concentrations found in various trophic
levels of aquatic ecosystems. Of this work, most involved rivers.
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 23 Few studies were involved with lake ecosystems and those concerning
urban lakes were even more scarce. Thus, th is seems to be a fr u itfu l
area fo r in ve stig a tio n .
Purpose
In light of previous discussion, this study was undertaken to
measure the concentrations of lead, cadmium, zinc and copper in runoff
entering an urban lake ecosystem and to measure the d is trib u tio n o f
these metals in various trophic levels of the lake.
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 24
CHAPTER I I
Study S ite , Design, and Methodoloqy
Study Site
Fisk Lake Is a small urban lake located in the western portion
of the Lower Peninsula of Michigan, within the city lim its of East
Grand Rapids in Kent County. I t is part o f a larger Coldbrook Creek
watershed (Fig. 3, p.25) draining parts of East Grand Rapids and the
city of Grand Rapids into the Grand River, the largest of the Michigan
rivers entering Lake Michigan.
The City of East Grand Rapids is basically a residential commun
ity with a population of 12,782. It is a suburb of Grand Rapids, a
city with a metropolitan area population of 427,074. The total com
munity o f East Grand Rapids comprises an area o f 3.4 square m iles.
Roughly one-fourth of East Grand Rapids area consists of parks and
lakes. The area near Fisk Lake is urbanized area with a shopping
center, schools, apartments and much impervious ground surface. A
map of landuse for the area appears in Figure 4 (P-26) together with the
drainage area fo r Fisk Lake. East Grand Rapids receives, on the
average, 33.18 inches of precipitation per year through rain and
snowfall as measured by the Kent County A irp o rt Meteorological
Station over the past 45 years. The climate is mild with a mean
annual temperature of about 48.5° Fahrenheit.
The study site is located within the shoreline of Fisk Lake and
a large associated storm canal draining into the lake. Fisk Lake
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 25
puei/jpw
l/l oc I innoüiXid ■-I
ro :>c «t
es to
o
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| b I *aAtf uo)S|Aia
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 26
§ £ c e LU
tn uo ce
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_ l
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 27 lies approximately 2,000 feet northwest of Reeds Lake, a 283-acre
lake that drains into Fisk Lake on the eastern side. Fisk Lake is
an open system th a t drains in to the Coldbrook Creek toward the Grand
River. The lake is approximately 28 acres with depths of 80 feet in
the central area (Fig. 5, p.28). The lake is oval-shaped being 1,610
feet long and 1,140 feet wide. The mean depth of the lake is 26.6
feet giving Fisk Lake an estimated storage capacity of 745 acre-feet.
The total volume of water entering Fisk Lake via overland runoff is
approximately 940 acre-feet per year. This represents a water exchange
ratio of 1.26 times the lake volume per year, or a possibility of total
water exchange every JBl years. In the discharge channel of Fisk Lake
is a small dam which serves to control the levels of the two lakes.
The Fisk Lake watershed lie s below Reeds Lake and is an o u tle t
for Reeds Lake drainage. It receives runoff from a total of 404 acres,
330 o f which lie w ith in the c ity o f East Grand Rapids. About 205 acres
of the total watershed are urban and residential areas. Three storm
sewers enter the storm canal near Wealthy Street on the south side o f
Fisk Lake. A minimum of 35% of the total watershed runoff enters Fisk
Lake through the storm canal. The canal also controls 69% of the total
urban and reside ntia l ru n o ff that enters Fisk Lake. Twenty-one percent,
roughly 85 acres of the Fisk Lake watershed, is marshland. Private
houses completely surround the lake with all urban and residential
areas in the Fisk Lake watershed served by storm sewers entering the
lake.
Hydrologie studies have been done on Fisk Lake by National Bio-
centric, Inc. (1978) showing that the storm canal contributed.42% of
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 28
w ■o 0) I O ) >o cca>
Q . ' O i
I f ) Q
DC
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fO c f - II
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 29 to ta l runoff during most storms. In terms o f volume o f water entering
the lake, 85.98 m illion gallons of stormwater enter the lake through
the storm canal annually. Thus, the storm canal then becomes an in
tegral part of the present study.
Design
Maps of the lake were obtained and the surface area was divided
in to areas near, and away from, the storm sewer. A prelim inary study
was done to evaluate selected physical, chemical, and biological para
meters including temperature, pH, carbon dioxide, chloride, to ta l
hardness, hydrogen sulfide, nitrates, nitrite s, phosphates, and sulfates
together with yeast/mold, total bacteria, and total coliform. Three
sampling stations were set up at the (I) storm sewer entrance; (II)
canal entrance to Fisk Lake; and (III) open water (Fig. 6, p. 30).
The main study was designed for evaluating heavy metal concentra
tions in water, substrate, benthic organisms, plants, and fish. Samp
ling and analyses were undertaken to determine:
(1) The extent to which the storm canal contributes lead, cad
mium, zinc, and copper to the lake environment;
(2) the concentrations of lead, cadmium, zinc, and copper in
stormwater, rainwater, lakewater, sediment, and tissues
from chironomids, snails, fish, and macrophytes; and
(3) any possible relationships between stormwater-contributed
metals and metal concentrations in the various trophic
levels of the Fisk Lake ecosystem.
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 30 FIGURE 6. ' SAMPLING STATIONS (A - K) IN FISK LAKE AND STORM CANAL (STATIONS I , I I , AND III'ARE USED IN THE PRELIMINARY STUDY)
K I (Across Lake) COpen Lake) (Across Lake)
Station III
FISK LAKE
S tation I I
ta tio n I
ABC
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 31 Methodology
Samples from the various stations were analyzed according to stan
dard techniques (EPA, 1979). All samples were analyzed using a Beckman,
model DB, Atomic Absorption Spectrophotometric unit (AA). Stock sol
utions were prepared according to methods described in the United States
Environmental Protection Agency (EPA) Methods fo r Chemical Analysis
of Water and Wastes (1979). From these stock solutions, standards
were prepared on the day of analysis at various concentration ranges,
fo r use in AA determinations o f samples. Standards fo r lead, zinc,
and copper were prepared from 1 ppm to 10 ppm whereas standards fo r
cadmium were prepared from 0.1 ppm to 1 ppm because o f it s lower
natural concentrations and a greater sensitivity for measurement with
the AA unit.
P a rticle Induced X-ray Emission (PIXE) is a process o f m u lti-
elemental analysis of samples using the tandem Van de Graaff acceler
ator in the Department o f Physics at Western Michigan U niversity.
The process has the d is tin c t advantage o f analyzing fo r as many as
13 elements, simultaneously. Although the process does not analyze
for all elements, it does provide information on three (copper, lead,
and zinc) of the four study elements. Only cadmium is not found in
the spectrum.
The process its e lf, involves a production of a high-energy proton
beam with the Van de Graaff accelerator. A PIXE spectrum is then
produced by the protons s trik in g a sample ta rg e t. When h ittin g the
target, protons in the beam interact with the electrons in the target
atoms to produce vacancies in the inner atomic shells. In the deexci-
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 32 tation process that follows. X-rays are emitted. These are detected
by a lithium drifted silicon (Si(Li)) detector that produces voltage
pulses proportional to the energy of the incident X-rays. Since atoms
of different elements have different electronic configurations and
binding energies, "characteristic" X-rays are produced for all detec
table elements. In short, the energies of the X-rays correspond with
the elements from which they were emitted. The X-rays emitted are thus
an indication of the elemental makeup of the target. The voltage
pulses from the detector are processed e le c tro n ic a lly to produce a
visual pulse amplitude (energy) spectrum (Fig. 7, p.33). Since the
detector plus impulse counter act as an energy analyzer and information
accumulator, the analysis is multielemental in nature. In terms of
the present study the PIXE process found and quantified as many as 13
elements, in some substrate samples.
For background inform ation, the spectrum produced in the PIXE
process is then compared w ith a spectrum produced by a sample o f pure
silicon dioxide. A computer program has been set up to subtract back
ground values and calculate proportionate spectral areas for numerous
elements. Since an area under the curve can be calculated and is pro
portional to the amount of element present in the sample, the computer
program prints out a "ppm" value for each element whose specific
X-rays are detected. This process is relatively new but has been
used fo r analysis by Folkman e ^ |fj_ ., (1973), Johansson and Johansson
(1977), C ahill (1975) and Andrus (1980). A more complete description
of the process can be found in Andrus (1980).
The samples fo r th is process must be homogeneous and dry in order
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 33
FIGURE 7. TYPICAL PIXE SPECTRUM FOR DRIED SAMPLE PELLET
>
s H* Z
u. o
o o cc ÜJ As Br Rb cc < o CO
4 6 8 10 12 14 16 ENERGY, keV
PIXE spectrum fo r the paper m ill waste water sample labeled NCASI 1.
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 34 to make a target pellet. The beam hits a 3/8-inch section on the
pellet. The area on the pellet then gives off the X-rays and produces
a PIXE spectrum. Thus, if the material is prepared properly, an av
erage composition can be estimated by the process. For this reason,
a ll samples were ground thoroughly in acid-washed mortar and pestle
before the pelletizing procedure. The pellet-making process involved
a hydraulic press and produced pe llets of approximately 1/2-inch dia
meter. These pellets were then mounted in the target beam path.
The mounting device is constructed in such a way th a t six p e lle ts can
be held simultaneously. After each PIXE run, the pellet "ladder"
must be reset to the adjacent pellet target. After six runs a new
target ladder must be mounted in the target area. A PIXE spectrum
is obtained for each target pellet and the results calculated in ppm
using the Western Michigan U niversity PDP-10 computer system. In
analyzing organic samples, an in itia l PIXE run was performed using
National Bureau of Standards orchard leaves for comparison (Table 2,
p. 35).
Stormwater and rainwater were collected in acid-washed 125 ml.
polyethylene b o ttle s. Three, 12-sample stormwater co lle ctio n s were
made, two during low flo w periods on A p ril 10 and May 17 of 1979, and
the third after a 0.5 inch rainfall on July 24, 1979. The samples
were preserved by acidification using 5 ml. n itric acid per lite r and
later analyzed using direct aspiration AA methods described in the
EPA (1979) manual. Rainwater was collected by using an uncapped
bottle placed in the study area. After collection, samples were
drawn through a 45 p filte r and analyzed using AA. Sampling areas
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 35
TABLE 2
A COMPARISON OF PIXE AND NBS ORCHARD LEAF VALUES (VALUES IN PPM)
PIXE NBS
K 16235.5 14700
Cd * 24133 20900
Mn 84.5 91
Fe 469.5 300
Cu 11.5 11
Zn 32.5 25
Pb 48 45
As 9 10
Br 10.5 10
Rb 14.5 12
Sr 41 37
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 36 included a series of sites within the storm canal (A-F), shallow
water near the canal outflow (G-H), water in the middle of the lake
( I ) , the shoal area at the opening to Reeds Lake (J ), and an area
near shore, fa r from the storm canal entrance (K) (Fig. 8, p.37).
Two separate substrate studies were undertaken. The firs t con
sisting of 11 sample analyses and the second; of 55 sample analyses.
Three d iffe re n t leaching methods were used as described by Agemian
and Chau (1977). The f i r s t group of 11 samples were 200-gram grab
samples collected from various areas in May, 1979 (Fig. 8, p.37).
A fter drying the substrate samples fo r 48 hours at 100°C, approx
imately 20 grams of each were homogenized using a m u llite mortar and
pestle. After homogenization, 1 gram of each was mixed with a 100
ml. IN hydroxylamine HCl - 25% acetic acid solution and then heated
at 85°C for three hours. The samples were then filtere d through 45 p
filte r paper and brought to volume in 100 ml volumetric flasks. These
samples were then analyzed by the d ire c t aspiration method of AA
analysis (EPA, 1980). Spiked samples were made to produce concentra
tions of 10 ppm fo r Pb, Zn, and Cu and 1 ppm fo r Cd. Spikes, stan
dards and blanks were run simultaneously as accuracy checks.
The second group of substrate samples was collected in June,
1980, from the same areas as with the previous except that 5 samples
were taken from each area (Fig. 8, p. 37). After drying, these samples
were subjected to two leaching methods and analyzed separately.
A 100 ml solution of 0.5 N HCl was used with a 5 gram sample of sub
strate. This mixture was shaken overnight (10 hours) at room temper
ature, filtered and subsequently, the leachate was analyzed by AA
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ■o FIGURE 8. Ic g WATER, SUBSTRATE. PLANT AND ANIMAL SAMPLING STATIONS Q. (A - K) IN FISK LAKE AND STORM CANAL ■o CD
(/>Ç2 3o' Drainage D is tric t 8 Outflow 5 From (S' Reeds Lake 3 CD
p.C
CD ■o Ic a O 3 ■o O
= sent to
oc ■o CD (/) o' 3
A-B-C 38
methods. The second Teaching method involved 1 gram of each ground
sample in 100 ml of 0.05 N EDTA, a chelating (metal-complexing)
agent. This solution was heated fo r 2 hours at 80°C. Once completed,
the material was filtered, cooled and brought to a 100 ml final vol
ume. The re su ltin g leachate was analyzed by AA methods.
All substrate samples were subjected to PIXE analysis. Samples
of about 10 grams were ground with a m u llite mortar and pestle.
Two grams of homogenized substrate powder was subjected to 5000 psi
in the pelletizing hydraulic press. The pellets were then analyzed
by the PIXE process.
Plant sampling involved the macrophyte Arrow Arum, Peltandra
v irq in ic a , an emergent aquatic found in dense growth clusters in a ll
areas of the lake except for the deeper portions. Samples of the
plants were collected at two different times during the study. In
October, 1979, 32 plant samples were collected fron the sample sta
tions (Fig. 8, p.37 ). These corresponded with most areas of substrate
co lle ctio n . The 32 samples were a ctu a lly 16 stem and 16 le a f samples,
collected and placed in sealable polyethylene bags. These were air-
dried in a temperature/humidity controlled room and la te r hand-ground
in an acid-washed mortar and pestle. The second plant collection was
made in June, 1980 and was more extensive, involving a total of 160
samples equally divided between stems and leaves. These were c o l
lected from areas proximate and nonproximate to the storm sewer en
trance to Fisk Lake (Fig. 8, p.37 ). This second set of samples was
oven-dried overnight at 100°C. The samples were then hand-ground
with a mortar and pestle and the resulting powders were stored in
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 39 5 dram glass sample bottles.
All plant samples were subjected to similar analyses. In pre
paration for AA analysis, one gram of plant tissue was digested using
n it r ic (HNOg), s u lfu ric (HgSO^) and perchloric (HClOg) acids accord
ing to a method modified from Adrian (1973). Four m illilite rs of
HNOg was added to each sample w ithin a 25 ml volum etric fla s k .
These solutions were allowed to digest overnight before adding 2 ml
of a seven-to-one mixture of HClO^/HgSO^. These digested mixtures
were then heated gently until they cleared. Spiked samples and acid
blanks were run along with the tissue digests to determine metal lev
els and recovery percentages. After digestion, the mixtures were
diluted to 10 ml or 25 ml with distille d water and analyzed by AA
procedures. The analyses were made w ith e ith e r 0.5 gram samples in
10 ml volumetries or 1-2 gram samples in 25 ml flasks. Proportional
amounts o f acid mixtures were used in each case.
Representative plant samples were also prepared for PIXE analysis
from each of the two plant samplings using methods similar to those
described for substrate.
Chironomid larvae, known to be p o llu tio n to le ra n t organisms
(Mason, 1968), were chosen as benthic detritus-feeding representatives.
These organisms are larval forms of common aquatic Diptera (flie s)
found in freshwater systems. They were assigned to the Family
Chironomidae by observation of jaw parts under the dissecting micro
scope. About 1200 larvae were collected from two areas of the lake
and storm canal using dip nets, sieving screens and forceps. The
chironomids were collected from areas corresponding with Stations
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 40 G, H, and K on Fisk Lake (Fig. 8, p. 37). The organisms were then
kept in refrigerated distilled water for 48 hours to eliminate intes
tinal substrate materials. They were then washed several times in
d istille d water and placed on acid-washed watch glasses and dried
overnight in a drying oven at 100®C. These were then divided into
0.25 gram samples and digested using a modified Adrian (1973) method
sim ila r to th a t used w ith the plant samples. The ra tio of acid, how
ever, was 1 ml of HClOg to 2 ml o f HNOg. S u lfu ric acid was not used
due to p re cip ita te problems with animal tissues. Generally the 2:1
ratio of nitric/perchloric acids was used with all animal tissues.
The resu ltin g digests were d ilu te d to a known volume and analyzed
using AA procedures.
Physa snails were used as a second benthic organism. These are
epifaunal grazers rather than infaunal sediment feeders like the
chironomid larvae. The snails were collected from the same two areas
as delineated for the chironomid larva. About 500 snails were col
lected from the two areas. Their tissues were dissected and samples
made from shells, soft bodies and total body. Approximately 150
snails from the storm sewer area were dissected and a sim ilar number
from the other area. These were all dried, digested and analyzed
following the same procedure used for the chironomid larva.
Prior to AA digestion, pellets were made of the snail tissue
and chironomid larva and were analyzed by the PIXE process. The
p e llets were saved and eventually used in AA analyses because o f a
limited amount of sample material with the benthic organisms.
Fish were collected from August, 1979 to November, 1979 using
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 41 a fyke net (hoop net). The net was set up in an area near the storm
canal lake entrance where the water was deep enough to cover the
whole apparatus. The net was checked every th ird day. The fis h
were collected and frozen in marked polyethylene bags. Eight species
of fish were collected. These included two sunfish species Lepomis
gibbosus and I. macrochirus, yellow perch Perea flavescens, white
sucker Catostomus commersoni, 1arge-mouth bass Micropterus salmoides,
black crappie Pomoxis nigromaculatus, brown bullhead Ictalurus neb-
ulosus and northern pike Esox lu c iu s . The fis h were weighed and
then dissected while partially frozen to facilitate easier tissue
separation. Tissues collected included g ill with rakers, bone, skin
without scales, liver, muscle and, in some instances, kidney and
gonads. The tissue was placed on acid-washed watch glasses and oven-
dried at 100°C overnight. This material was then hand-ground with
a mortar and pestle and placed in acid-washed and labeled 5-dram sam
ple bottles. The tissue was then digested using the Adrian (1973)
method as with the benthic organisms. Because of greater amounts
of muscle tissu e , more s p lit sampling and spike analyses were made.
In general, two gram samples of fish were digested in 25 ml volumetric
flasks where tissue samples were large enough. AA analyses were then
conducted as in previous tissue analyses. Selected fis h tissue pow
ders were also prepared and analyzed using the MXE process as de
scribed fo r previous samples.
The C o rva llis, Oregon Environmental Research Branch o f the
Environmental Protection Agency made sample exchanges to cross-check
the accuracy of analytical equipment. A total of 33 Fisk Lake plant.
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 42
animal, and substrate samples were sent to the Oregon laboratory
while Dr. Dan Krawczyk o f the EPA sent 13 samples w ith known metal
content to the Geology Department at Western Michigan U niversity.
The EPA samples consisted o f 10 dry and 3 liq u id v a rie tie s . The
dry samples were analyzed using Adrian's (1973) method w ith a 2:1
mixture of HNOg and HClOg. The water concentrates sent by the EPA
were made into analyzable samples by firs t adding 10 ml of the con
centrate and 1 ml of n itric acid and then diluting up to 100 ml final
volume with d is tille d water. Blanks and standards were made up using
similar acid concentrations. The concentrates were diluted by a
fa cto r of 10 instead o f the EPA-suggested 100 because o f low levels
of resolution with this particular model of atomic absorption unit.
I f metal levels were too high, fu rth e r d ilu tio n s were made.
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 43
CHAPTER I I I
Results and Discussion
Prelim inary Survey
A preliminary survey of selected chemical parameters was under
taken before the sampling for heavy metals. Samples were collected
at three sites: Station I, located at the storm sewer; Station II,
located where the storm sewer canal enters the lake, and; Station III,
located in open lakewater (Table 3, p. 44). Most parameters exhibit
higher values at Stations I and II than those obtained at Station III.
According to criteria established by the EPA (1976), stormwater en
tering Fisk Lake exceeds lim its for orthophosphate, chlorides, and
bacteria. Water introduced through the storm sewers and canal is
obviously polluted during certain stages of flow.
Heavy Metals in Water
The stormwater showed detectable levels of three of the four
metals under consideration (Table 4, p. 45). Lead, zinc, and copper
were a ll detected in water samples taken at points where the storm
water entered the canal from drainpipes, and in part of the storm canal
(Stations A-H). At low flow conditions, only zinc and copper were
detected. At high flow conditions, after a substantial rain, lead
was also found with zinc and copper. Cadmium was below levels of
detection in all water samples. The rainwater samples, collected
simultaneously with those from stormwater, failed to show detectable
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 44
IT) 0 £ 0 0 0 c 0 0 %"2® - 0 0 #- g 1 % in^ s i : C/1 8 s IP. 0» ^•- •f- m cn ro^in O p—cncvj 3 omo 0 r- in om ^ m CD 0 0 0 85K pevim cvj ^ +» O in CO O) CO CVJ m mom n 0 ^ >— CNJO «5“ CMO aoMo 0 0 0 IT) •> rZpr» 0 m evj 1-^ III C I— tn e 5 o 855 855 SR591 m ’i C cvj p— »— 85'' 0 0 0 moo 0 0 cvi 0 moiin 0 0 0 GO 10^ S8S885m mrZ 895N (V#- hZcscC 8R5 C 0 0 •I— rs. r.5^ n in <71 0 0 m N 0#"2SR5 CM 0 0 0 m V 0 CM 0 n CVI SR88SS§88 g H i 555 @85 in cn CM m 1010 3 s- gON in 0) 13 p—10 m CO in r— CM O) 0 R e o o mNm tOCSi*-- n 0 0 0 mi0 V 4-> eoin ro cvji— rCrCfC mo V g§R rsiino) 855 295 ocncM 01 OJ ncMCNj IP. CO in 0 ^ 0 Ll I 0 ) 0 0 0 CD CM cn in — j •«-> om o O ', o O 4-» I— 00 #- in o n «r CO CO m ^ r^mo in om mcNj 0 m<^o 1 # • • #1 1 1 • I - "O QO0IO • 00 0 ) 885 +J 8RB85“ "O 13 c » f- 1 3 0 g • 5 CM •— OJOO 0 COOcor*»o n i/j otf>e ^ 0 0 m"»o 1 1 1 • • »WcD • I— W rScsîio 13 u13 « •I— s 5 & 1 1 5 ** 0 s 5Z'15SS.J i ! l i S I t K X £ I f 8 55£gagggg Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ■DCD O Q. C g Q. ■D CD TABLE 4 WC/) METALS DETECTED IN THREE SETS OF STORMWATER AND RAINWATER SAMPLES ASSOCIATED WITH FISK LAKE 3o' 3 CD LOW FLOW (APRIL 10, 1979) STATION ■D8 METAL ABC D E FG H I J K RW (O'3" i Pb .3 .2 .3 .15 .2 .15 .16 .05 ND ND ND ND* 3 CD Zn .2 .1 .2 .1 .1 .1 .1 .1 ND .1 ND ND c"n 3. 3" Cu .021 .015 .015 .016 .016 .015 .012 .014 .010 .011 .008 ND CD ■DCD O CQ. LOW FLOW (MAY 17, 1979) Oa 3 ■D Zn .2 .3 .4 .1 .1 .1 .1 ND ND ND ------ND O Cu .2 .2 .3 • .1 .1 .1 .1 .1 .1 .1 ------ND CD Q. HIGH FLOW (JULY 24. 1979) ■D CD Pb 1.5 1.2 2.0 1.8 1.5 1.3 .7 .5 .1 .1 ND (/) Zn .8 .5 1.0 .4 .5 .2 .1 .1 .1 .1 ------ND Cu .8 .3 .4 .2 .1 .2 .1 .1 .1 .1 ------ND *ND - Not detectable tn■Pk **Results in ppm 46 levels of any of the metals. Open lake water contained only copper in detectable levels. Stormwater entering Fisk Lake had maximal lev els of 2.0 ppm, 1.0 ppm, and 0.6 ppm of lead, zinc, and copper, re spectively. Concentrations of metals in open water samples from Fisk Lake are similar to those found by Mathis and Cummings (1973) in Illin o is River water where mean concentrations of lead, cadmium, zinc, and cop per were found lower than 0.1 ppm, Whipple and Hunter (1977) found lead, zinc, and copper at detectable levels in samples of stormwater from 10 storm events in Lodi, New Jersey. As with Fisk Lake waters, the researchers reported metal concentrations to follow a lead >zinc > copper hierarchy. In a ll cases, high flow periods showed higher metal amounts than the low flow periods. Wilber and Hunter (1979) point out that particulates tend to settle near the point of entry into a freshwater body. Because heavy metals appear to be attached to sus pended particles (Sartor et ^ . , 1974), it is likely that the metals w ill be concentrated near the influent site. Water was found to contain detectable quantities of lead, zinc, and copper at Stations A through G (Fig. 6, p. 30 ) during high flow periods. None of the metals were detected in samples from Stations I and J. These find in gs concur with previous findings that the metals leave the water column quickly and become part of the substrate. In addition to the pattern of metal distributions, the concentrations of lead, zinc, and copper are in the same order of magnitude as reported in the literature (Sartor et a l., Enk and Mathis, 1977, and Wilber and Hunter, 1979). Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 47 Heavy Metals in Sediment Sediment samples were collected and analyzed from Stations A through J with an additional control sample, K (Fig. 8, p. 37 ). The original collection, consisting of 11 samples, was analyzed using PIXE and AA methods (Tables 5-7, pp. 48-50 ). Highest lead, zin c, and cadmium concentrations were found in the substrate at Station H, whereas the substrate copper values were highest at Station J (Figs. 9, 10, 11, 12, pp. 51-54). Lead levels were found to range from a high of 1203.9 ppm at Station H to a low of 60.0 ppm at Station I. Cadmium levels ranged from a high of 16 ppm at Station H to a low of 0.5 ppm at Station F. Zinc concentrations ranged from a high of 950 ppm at Station H to a low of 80 ppm at Station F. Copper values differed greatly throughout the lake and storm sewer areas from a high of 740 ppm at Station J to a low of 90 ppm at Station F. The second substrate sampling, totaling 55 samples, provided a broader data base. These samples were analyzed by PIXE and AA procedures (Tables 8-10, pp.55-57 ). Distributions of metals in the sediment fo r the second substrate sampling were s im ila r to those found in the f ir s t sampling (Figs. 13, 14, 15, and 16, pp. 58-61 ). Mean lead values ranged from 1178.0 ppm at Station H to 225.8 ppm at Station F. Mean cadmium concentrations ranged from 7.1 ppm at Station H to 0.84 ppm at Station F. Mean zinc levels ranged from 691.2 ppm at Station H to 119.6 ppm at Station F. Mean copper concentrations ranged from 642.0 ppm at Station J to 34.8 ppm at Station F. Concentrations of lead, zinc, and copper for most areas of Fisk Lake were found to be in higher orders of magnitude than reported by Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ■o o cû. g Q. ■OCD (£(/) 3O 3" CD Table 5 8 "Ov< ë ' Métal concentrations in samples of Fisk Lake substrate. Results were obtained using PIXE procedures, i 3 CD Station p. 3" Metal A B C D E F G H I J K CD CD Lead* 890.8 588.1 536.1 439.0 480.0 388.4 855.3 1203.9 600.1 411.2 307.2 ■D O Q. C Copper 203.0 254.1 161.1 240.2 141.7 88.3 265.3 343.3 387.1 510.1 325.0 aO 3 ■O Zinc 316.9 469.8 401.8 275.8 391.4 142.9 501.3. 858.2 351.2 408.9 204.1 O CD Q. *Results in ppm TD CD C/) C/) 4!» 00 ■DCD O Q. C g Q. ■O CD C/) o" 3 Table 6 O Métal concentrations in samples of Fisk Lake substrate. 8 Results were obtained using AA procedures - 2N EDTA leaching method. ■D (O'3" i 3 CD Station "n c 3. Metal A B C D E FGHI J K 3" CD Lead* 230 120 220 110 130 100 290 600 60 210 235 ■DCD O Q. Copper 280 140 200 140 120 90 220 220 200 740 180 C Oa 3 Zinc 420 200 400 160 180 60 220 820 240 220 150 ■D O Cadmi um 2.8 2.6 3.6 3.8 5.0 0.6 6.1 8.1 5.5 2.1 2 CD Q. ■D ♦values in ppm CD (/) ■DCD O Q. C g Q. ■D CD C/) OC/) o Table 7 CD Métal concentrations in samples of Fisk Lake substrate. ■D8 Results were obtained using AA procedures - Hydro>o'l ami ne - HCl - Acetic Acid leaching method (O'3" 3i CD Station 3. 3" Metal A BCD E F G HI J K CD ■DCD Lead* 940 200 740 500 400 720 840 1180 480 ■ 380 250 O Q. C Zinc 650 190 570 180 250 80 610 950 460 520 210 Oa 3 ■D Copper 200 150 300 110 100 90 350 160 310 360 340 O Cadmi um 1.1 2.1 2.2 1.9 2.3 0.5 3.1 5.1 3.2 2.1 1 CD Q. ■D ♦values in ppm CD I en(/) o" CJl o 51 w X to LU CL to to g " to CO to 5 $ u z c cc. QC 8 y S c_> UJ CL u IL 8 8 8 8 § 8 8 i 8 8 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 52 o z t—I «/) il to o u S il =3ce. ü_ O o_ i l o i o oo I o. s 00 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 53 w 1 % l u «9 igs CCLU g SSÎ K | 2 g k g : II (/) g i O S s g 8 o Q. O. rsi Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 54 tn ui _> ll Ito o CO CD=> CO «0 si I I i l s 2 B Ë l i . z w w « D . U J § E fe g i§ •-HfiC s I 888 Ë n. 5 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 55 W » « O N m m CO o; N o Q N g 00 WlÂ*^ W N m m ^ m M ::fSK%8 i éûi^i 5 m N O lA o I m mo%o»o»m 00 ^ m o i m o m ^ «o w p iÂooÔnn m in m c M p « c m I Q « m g ^ N ^ N oi«r 8 ^ 3 3 3 3 N #—m m *n O i o tn ^ m o m m c M ^ o in inmiA ^ m ♦ c a i o n W cm rZ 9 ^ »A m m »Q R «o nno 8 CM m ^ m m CM * 8 8 2 3 * N m o» m m oi«»-«o«> CM w m m m m o% o » « r o C q c  in c n o c M s z s a R 8 il Kmoa m mm v5ÿ@ in 3 8 3 3 3 8 II m «o c\»m m o$ CM o o m rvi *mm^m u> «C «RSSS S857i?iCM m în CM m = 8 : ^ 2 N m m m m «0 CM œ V m m m m CM CM m «I CM VÇgCMO% z i i i i i % m m o V o» R m m «o ^ en : v#"omo% OOto*^m I lA m m m V ^ m- CM lA c*» m- |m 5 3 § § 5 2K 3N R m m m m * I m mowmcM I «ncoomm mmomv o m O Ç Q lA I C O RR83% m g « n m m 8 Z 3 S 3 V « O N I V « O 8 « n o f t ^ m o C M N m O V I ^ ! #— N m g » 21 il 3 R R 8 3 3 S 3 Z 8 S VOO^mCM *^m «o m m i ^ «rrCpWaC I m %MK=813 cn^N^cA I #— «AmNmm I tn ES s S r CM m F“ m ^ I CM CDNNNIA I « tf> ^o% lO u> omcocMN «opm^cô i n o m u i o 8 5 = 5 = RRKgR in m o g m £ A Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 56 lA ^W $C ^ V OD 1 1 ~ 40 \ * * * • - • o * * ^ O in 3 5 R % R 8 « 8 1 " CM — in M" 1 CM iO 1 1 04 a 1 0 40 ^ CM P— CM m— CMCTIQCMr* Q CM 400CM o S œ S S 0 in m ^ — a % 3 S 3 3 i 1 40 1 40 W iO C M ^C O 1 ^ 1 CM CM CM CM CM CM o * O Q ^ r ^ CO < 3 1 0 CM m If S K g g g a CM M 3 m s a a z a i o ^ 0 0 in 40 1 o 1 O 40 40 z | CM cn 0 0 o cncMcncM cn cn o m * » C M O tn r«» o «n r— a R a a a V CM m CM m » £ 3 3 3 8 8 cn — CM CM cn i GO 1 ^ C O C M O - -* 1 1 o | Q « o ^ r » > o cn ™ fn ^ 8 S 3 S S 8 P S S 8 8 i? 1 " CM m cn CM CO 3 1 s CM4 0 0 4 0 CD 1 00 1 40 1 » u .| m 00 o m r» 00 *“ 0 * “ 0 O o 04 0 CD lO CO CM cn CM V 40 S 8 3 g S n* — CM CM cn a 40 in 40 04 ^ CM CM 1 1 ^ cn o o o — — o U} 0 0 0 ^ 04 00 — 04 40 04 a s R s s 8 !! CM CM CM cn % 40 00 CM o 00 o 1 1 ^ 40 00 a | O r - . - C M — rC m 40 in m 04 s a s g a jj4 40 cn 2 in R f— CM R CM CM 4 T O C n»C M 0 CM 1 1 *** w | 0 a Q in in 3 8 5 3 2 R S K g g g cn 3 cm£ 3 3 00 00 CO V CM cn in I 1 0 1 0 cdI rC 1 cn R 2 5 8 ^ 0 R a s a s cn CMCM^CMm- CM & P o CM — «r o <74 ca CM 1 < 1 « r ^ c n v B to CM CM CM CM 0% cn ig* 3 M ? a a s = 1 # tx Ik |K £ 3 - a 3 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ■OCD O Q. C g Q. ■O CD C/) C/) 3O 2, T a b le 10 m Individual and mean metal concentrations found In samples of o Fisk Lake substrate. Results were obtained using AA procedures - .IN EDTA leaching method o ^■D :______CÛ3" A i Ç 0 E F G H i JK i 3 4 2 0 35 0 360 110 231 160 5 80 925 590 4 2 0 205 CD 4 8 0 425 4 1 0 465 4 3 2 115 765 1 140 615 562 140 ___ "n c 3. 4 5 6 .0 3 9 5 .0 390.0 323.0 351.6 1 3 3 .0 6 9 1 .0 1054.0 605.0 505.2 166.0 3" CD 3 . 2 3 . 0 2 .0 2 .1 2 .1 2 . 0 5 .1 5 . 0 5 .4 2 .0 2 .6 ■DCD 2 . 6 2 . 8 2 .0 3 .1 2 .3 2 .1 5 . 0 8 .5 3 .2 2 .3 2 .2 O Cd ______CQ. a 2.84 2.88 2.0 2.7 2.22 2.06 5.04 7.1 4.08 2.18 2 .3 6 O 3 ■D 3 4 0 300 3 62 ISO 321 120 3 55 6 60 365 3 6 2 263 O 3 5 0 4 35 425 6 9 0 390 145 6 8 0 712 321 4 2 0 201 Zn ___ 3 4 6 .0 3 8 1 .0 3 9 9 .8 4 7 4 .0 3 6 2 .4 1 3 5 .0 5 5 0 .0 6 9 1 .2 3 3 8 .6 3 9 6 .8 2 2 5 .8 CD Q. 200 145 105 145 71 3 2 102 222 395 505 442 195 165 143 323 152 38 155 256 205 725 3 1 0 Cu ■D 197.0 157.0 127.8 251.8 119.6 3 5 .6 1 3 3 .3 242.4 281.0 637.0 362.8 CD (/) C/) ‘values In ppm c n 58 oo g 5 tn LU LOo o oo 00 oo = 1 ooz o $ 49 en 0 g 1 LU OC => LU c es s “ 8 iil LU •> 2 o o oo 00o o: 2 o 8 1 «0 Q. Q. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 59 CO LU o to LU OC to 00 to o oc LU O z o LU o to I t o. s Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 60 5 o a. ii o in ocLU cs $ 8 Ë 2 M ^ ^ 5 w li-l to o to HH SE O. 1 s g 8 8 o . o. M Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 61 o ex to to o z s 19 LU is îs OU o LU Z 3 C9 II § ^ B: W g 5 LU tO O to #—# SE O. O § s s 8 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 62 other researchers. Mathis and Cummings (1973) found much lower metal concentrations in the substrates of Peoria Lake and the Illin o is River when compared with those o f Fisk Lake. They reported tha t lead ranged from 140 ppm to 3 ppm with a mean of 28 ppm in industrial areas with control stream substrates ranging in lead concentrations from 27 ppm to 13 ppm with a mean o f 17 ppm. Cadmium ranged from 12.1 ppm to 0.2 ppm with a mean concentration of 2.0 from the industrial area whereas the control stream substrate had cadmium concentrations ranging from 0.5 ppm to 0.3 ppm with a mean of 0.4 ppm. Zinc showed the highest values, ranging from 339 ppn to 6 ppm with a mean value of 81 ppn in the industrial area with concentrations from control streams ranging from 41 ppm to 18 ppm w ith a mean value o f 30 ppm. When compared with levels found by Namninga and Wilhm (1977), the Fisk Lake sub strate levels are two orders of magnitude greater than the 2.0 ppm copper and 9.0 ppm zinc levels found by these researchers. Forstner and Wittman (1979) summarized data from several lacustrine sediment studies (Table 11, p. 63) and found that these values were consis tently lower than those found in Fisk Lake sediments. Substrate concentrations of lead, cadmium, and zinc were found to be highest at Station H (Figs. 13, 14, and 15, pp.58-60 ), located at the point where stormwater enters Fisk Lake. Copper was highest at Station J. As mentioned by Sartor et al^. (1974), Whipple and Hunter (1977) and Forstner and Wittman (1979), most o f the heavy metals in stormwater are associated with fine particulates. With such high levels of metals in the substrate at Station H, it is probable that most of the heavy metals in the stormwater are settling out at Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. "OCD O Q. C S Q. "O CD Table 11 C/) Métal concentrations in substrate from selected United States lakes 3o" (From Forstner and Wittman, 1979) O ■D8 Lake Constance Lake Michigan Wisconsin Lakes Lake Washington Lake Erie B* MV* B MV B MV B MV B MV CD Zinc** 124 380 120 317 15 92 60 230 7 42 3. 3" CD Copper 30 34 44 75 22 268 16 50 18 59 ■DCD O Lead 19 52 40 145 14 124 20 400 — — — — — — CQ. a O « « « ■B S M 3 Cadmi urn 0.21 0.68 2.5 4.6 0.14 2.4 ■D O CD Q. B* - Background MV* - Max. Value ■D **values in ppm CD C/) C/) w 64 Station H. Heavy Metals in Plants Two separate plant collections were made, mature growth samples being picked in October, 1979, and young growth samples being picked in June, 1980. Stem and le a f samples of Peltandra v irg in ic a were dried, dissolved in a wet-ashing process (Adrian, 1973), and analyzed by AA. A s p lit from the same sample at each station was pa lletize d and analyzed by PIXE. Although the data fluctuate considerably, metal concentrations are usually higher in mature plants (Tables 12-13, pp. 65,66 ), than in younger (Tables 14-15, pp. 67,68 ). Lead ranged from 157.5 ppm, in mature plant stems from Station H, to <1 ppm. in young plant samples from several areas. Cadmium values ranged from 0.55 ppm, in young plant leaves from Station G, to <1 ppn in young and mature plant samples. Zinc concentrations ranged from 245 ppn to 11 ppm and these extremes were found in mature leaves from Station H. Copper concentrations ranged from 455 ppm in mature leaves from Station H to 3.5 ppm in young stems from the same station. L ittle research has been done concerning heavy metals and higher aquatic plants. No reports were found concerning heavy metal con centrations in the emergent plant, Peltandra virginica, sampled at Fisk Lake. Heydt (1977), however, reports values fo r lead, cadmium, zinc and copper in some submergent higher plants from contaminated and non-contaminated areas in the Leine River, Gottingen, Germany (Table 16, p.68 )• He found little difference in metal content whether the plants were from contaminated or non-contaminated areas Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. CD ■ D O Q. C g Q. Table 12 ■D CD Means and standard deviations of metal concentrations in stems I and leaves of mature Peltandra virginica samples from I storm sewer affected and non-storm sewer affected o areas of Fisk Lake. Results were obtained using PIXE procedures. ■D8 (O'3" Storm sewer area Non-storm sewer area 3i Stem 24.1 + 45.8 6.9 + 6.6 CD Lead "n c Leaf 15.7 + 19.9 2.1 + 2.9 3. 3" CD ■DCD Stem 47.0 + 36.7 22.3 + 9.1 O Zinc Q. C Leaf 57.5 63.3 18.7+ 9.1 Oa 3 ■D O Stem 52.1 + 58.5 48.7 + 18.6 Copper CD Q. Leaf 124.9 + 175.6 226.5 + 125.0 ■D ♦values in ppm CD (/) (/) cr> tn ■DCD 0 Q. C g Q. $ 3" "O CD 1 WC/) Table 13 3o" O 3 Means and standard deviations of metal concentrations in stems and CD leaves of mature Peltandra virginica samples from storm sewer 0 affected and non-storm sewer affected areas of Fisk Lake. Results were obtained using AA procedures; n itric - perchloric - sulfuric (O' 3" acid digestion method 1 3 CD - 3. 3" CD Storm sewer area Non-storm sewer area ■DCD O Stem 21.7 + 32.8 7.5 + 6.2 CQ. Lead * + + Oa Leaf 15.1 13.9 5.2 4.3 3 ■D O Stem .18 + .08 .1 .+ .005 CD Cadmium Q. Leaf .11 + .02 .13 + .05 ■D + + CD Stem 60.1 44.9 33.6 10.6 Zinc (/) (/) Leaf 70.6 + 70.3 24.8 + 13.2 Stem 62.0 + 53.4 60.6 + 19.9 Copper Leaf 125.4 + 157.9 254.0 + 140.3 cn (Tl ♦values in ppm CD ■ D O Q. C g Q. ■D Table 14 CD Means and standard deviations of metal concentrations in stems and leaves C/) o" of young Peltandra virginica samples from storm sewer affected and 3 non-storm sewer affected areas of Fisk Lake. Results were obtained using PIXE procedures. ■O8 Storm sewer area Non-storm sewer area CD Stem 26.3 + 7.0 25.1 + 9.7 Zinc * 3. 3" Leaf 37.2 + 11.2 33.9 + 12.9 CD ■DCD O + Q. Stem 7.9 + 1.7 8.7 1.7 C Copper a O Leaf 9.0 +2.0 8.96 +1.9 3 ■D O CD Q. ♦values in ppm ■D CD C/) C/) cn CD ■ D O Q. C g Q. Table 15 ■D Means and standard deviations of metal concentrations in stems and leaves CD of young £. virginica samples from storm sewer and non-storm sewer affected areas of Fisk Lake. Results were obtained using AA procedures - n itric - perchloric acid digestion method. C/) 3o" O o Storm Sewer Area Non-storm Sewer Area ■DO (Q Stem 8.7 + 3.7 3.8 + 3.4 Lead i + + 3 Leaf 3.6 2.5 2.2 2.2 CD ■ n 3 3 " CD Stem .15 + .08 .104 + .02 S Cadmium ■ D o Leaf .18 + .11 .11 + .02 Q. C 1 3 "O o Stem 44.3 + 13.1 26.5 + 8.7 3 " 1—HCT Zinc CD Leaf 47.1 + 11.0 38.5 + 12.7 Q. 1—H§ 3 " "O + + CD Stem 10.3 3.2 11.8 3.8 3 Copper C/) + + w Leaf 8.4 3.2 8.4 2.5 o 3 CT> 00 CD ■ D O Q. C Table 16 g Q. Heavy metal concentrations in different organs of higher water plants. (from Heydt, 1977) "O CD n.d. = not determined, all data are dry mass related. C/) C/) CD Species Roots Stems Leaves Total (without roots) ■D8 Cd Zn Pb Cu Cd Zn Pb Cu Cd Zn Pb Cu Cd Zn Pb Cu (O' Potamogeton 0.33 54.9 2.20 16.09 — n.d. n.d. 1.18 241.5 5.80 49.87 3"3. pectinatus CD ■DCD O Potamogeton n.d. — 1.60 222.7 6.43 21.34 3.59 500.2 8.58 99.97 2.24 380.3 7.53 45.46 CQ. crispus Oa ■D O Callitriche n.d. — 0.96 348.1 15.86 22.92 1.58 690.5 37.46 49.72 1.28 555.9 18.27 31.49 palustrus CD Q. ■D CD (/) (/) 0» VO 70 of the river. The results from Heydt's (1977) study are in the same order of magnitude as those found in mature plants o f Fisk Lake. (Tables 12-13, pp.65,66 ). However, analyses of young plants from Fisk Lake show lower mean metal values (Tables 14-15, pp.67,68 ). In general, plants from stations, far from the storm sewer, were found consistently to contain lower mean concentrations of lead, cad mium, and zinc and higher mean concentrations of copper than those near the storm sewer (Figs. 17-21, pp.71-75 ). In most plant samples, more lead was concentrated in the stem portion, whereas levels of cop per and zinc were higher in leaf tissue. Similar cadmium concentrations were detected in leaf and stem, although concentrations were near the lower lim its of detection. Heavy Metals in Chironomids Although 1,200 chironomid larvae were collected, only 8 samples of sufficient mass were available for analysis (Table 17, p.76 ). The samples were collected from storm sewer Stations G and H, and non storm sewer Station K, areas. Lead concentrations differed greatly between storm sewer and con trol area with mean values of 133.9 ppm and 29.2 ppm, respectively. Mean cadmium concentrations were 4.53 ppm and 3.0 ppm fo r storm sewer and non-storm sewer chironomid samples. Mean zinc values also differed widely between storm sewer and non-storm sewer areas with tissue con centrations of 296.0 ppm and 139.9 ppm respectively. Mean copper con centrations in chironomid tissue were 59.5 ppm and 255.0 ppm in those collected from storm sewer and non-storm sewer areas. It was the only Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 71 CO to LO to OO sio z: to S3 to S i CD to a = § g to c u_ “ —^g O O (/) t_)to CQ li to CX3 i l to Q_ to CO CM to CM to o o o o o o o o i to t\J CO to o . Q. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 72 si to OSE 6 3 il 00 O : 8 = 3 Z ^ C t/l u_-I ® in il Si P- o o oO o o o o § s s Ë. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 73 */> ii s 8 2 U J 0 £ I p ÎT 8 s o ÎS w CO ii m O § 8 § 8 8 Ë o . Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 74 «-3to to to - tD o t o o o O s t n ro CM o . hsic Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. CD ■ D O Q. C g Q. ■D FIGURE 21. CD COMPARISON OF MEAN COPPER CONCENTRATIONS IN C/) C/) PLANT TISSUES USING PIXE AND AA METHODS ■D8 13.0 12.0 3. 3 " CD 11.0 ■DCD O Q. C 10.0 a PIXE 3O Cu ppm "O o CD 8.0 Q. ■D CD C/) C/) G, G,HIH, I J J, K, K, "■J c n 7) ■DCD O Q. C g Q. Table 17 ■D CD Means and standard deviations of metal concentrations in chironomid larvae C/) from storm sewer affected and non-storm sewer affected areas o f Fisk Lake. (O Results were obtained using AA procedures - n itric - perchloric 3o" O acid digestion method. ■D8 Storm Sewer Area Non-Storm Sewer Area Lead* 133.9 + 19.9 29.2 + 9.9 3. 3 " CD ■DCD O Cadmium 4 .5 3 + 1.28 3.0 + .85 Q. C Oa 3 "O O Zinc 296.0 + 75.0 139.9 + 3 8 .0 CD Q. ■D CD Copper 152.8 + 83.8 193.0 + 4 5 .2 C/) C/) *values in ppm c n 77 metal showing higher concentrations in the control area than in the storm sewer area (Fig. 22, p .78 ). These values for lead, cadmium, zinc and copper are much higher than those found by Lei and and McNurney (1974, Namminga and Wilhm (1977) or Enk and Mathis (1977) in chironomid la rva. Namminga and Wilhm (1977) found levels of 1.91 ppm, 1.32 ppm, and 57.05 ppm fo r copper, lead, and zinc, respectively. Lead concentrations of up to 43 ppm in chironomids from urban areas were reported by Leiand and McNurney (1974). All three studies indicate that benthos concentra tions are equal or higher than associated substrate concentrations. Maximum zinc levels in Fisk Lake chironomids represent about 75% of associated substrate values whereas other metal concentrations in chir onomids are less than 50% of their associated substrate values. Heavy Metals in Snails Since the snail (Physa sp.) lives on the substrate rather than in the substrate, it may be considered a substrate-associated (epifaunal) benthic organism rather than a substrate-dependent (infaunal) organism like the chironomid larva (Leland and McNurney, 1974). Inclusion of Physa sp. provides data on mean metal concentrations on another benthic organism of a different trophic level (Table 18, p.79 ). Mean concentrations of lead range from 45.1 ppm in soft body tissues from snails in the storm sewer area to 9.8 ppm in shells from snails in the non-storm sewer area. Cadmium concentrations were highest in Physa soft bodies from the storm sewer area, with a mean value of 1.31 ppm Mean zinc values ranged from 184.9 ppm in the soft bodies from the storm sewer area to 38.9 ppm in Physa shells from the control area. Highest Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 78 FIGURE 22. MEAN ZINC, LEAD, CADMIUM, AND COPPER CONCENTRATIONS IN CHIRONOMID TISSUES FROM STORM SEWER AND NON-STORM SEWER AREAS 300 r 150 200 100 Zn ppm Pb ppm 100 - 50 STORM • NON STORM NON SEWER STORM SEWER STORM SEWER SEWER 5.0 r 4.0 200 3.0 150 Cd #pm Cu ppm 2.0 100 1.0 50 0 STORM NON STORM NON SEWER STORM SEWER STORM SEWER SEWER Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 73 ■DCD O Q. C g Q. "D CD (/) C/) 3 T a b le 1 8 o ^ Means and standard deviations of metal concentrations In shell* total body* and ^ soft body samples of Physa sp. from storn sewer affected and non-storm sewer affected areas of FIsk Lake. Results were obtained using AA procedures - o nitric • perchloric acid digestion method. ■D 1- O Storm Sewer Area Non-Storm Sewer Area S h e l l Total Body S o f t Body S h e l l Total Body Soft Body L e a d * 2 9 .1 i 2 . 7 3 7 .6 ♦ 6 . 6 4 5 .1 i 4 . 9 9 . 8 ♦ 4 . 9 15.7 ♦ 1.5 13.05 ♦ 2.0 3. 3 " CD ■DCD Cadm ium < .1 < .1 1.31 + .59 < .1 < .1 .2 9 ♦ .0 5 O Q. C g. 3o Z in c 4 1 .5 ♦ 9 . 8 152.7 +11.8 184.9 ♦ 21.6 42.3 ♦ 11.6 103.0 ♦ 9.9 38.9 ♦ 7.0 "O o Copper 126.4 ♦ 53.1 182.2 ♦ 16.0 266.5 ♦ 20.9 84.0 + 8.2 171.9 ♦ 60.8 496.8 ♦ 211.1 CD Q. "values In ppm ■D CD C/) C/) •vj VO 80 A lead concentration of 45.1 ppm found in soft bodies of Physa closely approximates the lead concentration o f 42 ppm found in urban Physa by Leland and McNurney (1974). Highest levels of all metals were found concentrated in the soft body tissues. This could be due to some ingested sediment or particles of sediment caught inside the shell. According to Flegal and Martin (1977), ingested material can magnify metal concentrations in any benthic organism collected for analysis. As indicated with the chironomid studies mentioned previously, benthic organism tissue tends to magnify metal concentrations as com pared with those in surrounding substrate levels. In this study, some evidence of magnification was observed. Levels of copper found in soft bodies in both storm sewer (266.5 ppm) and control (496.8 ppm) areas exceeded copper values found in substrate from these areas (237 ppm and 286 ppm respectively). Copper concentrations in the snail bodies reach 112 percent and 174 percent of concentrations found in associated substrates. Namminga and Wilhm (1977) found sim ilarly increased copper concentrations in Physa. Other metal concentrations in snails were found to be between 10 percent and 30 percent of values found in associated substrates. Lead, cadmium, and zinc show higher mean values in storm sewer related snails than those from other areas of the lake (Fig. 23, p.81 )• Copper concentrations follow an opposite trend. These results suggest possible lead, cadmium, and zinc contamination o f benthic organisms liv in g in storm sewer areas. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 81 FIGURE 23. MEAN ZINC. LEAD, CADMIUM, AND COPPER CONCENTRATIONS IN PHYSA sp. TISSUES FROM STORM SEWER AND NON-STORM SEWER AREAS □ S oft Body Shell □ Total Body 1.0 Zn opm Cd ppm 100 - STORM NON STORM NON SEWER STORM SEWER STORM SEWER SEWER 496 300 200 Cu ppm Pb ppm 100 STORM NON STORM NON SEWER STORM SEWER STORM SEWER SEWER Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 82 Heavy Metals in Fish Dissected, dried, and powdered one-gram samples o f fis h tissue were analyzed by AA methods (Tables 19-22, pp. 83-86). Because the fish were a ll sampled from the same area near the storm sewer entrance, no conclusion can be drawn about heavy metal concentrations and lake- storm sewer geography. A comparison was made, however, w ith results of studying tissue in other selected studies. Lead in Fish Tissue: Highest mean lead values were 1.84 ppm in black crappie g ill and 1.67 ppm in northern pike liver (Table 19, p.83). Lead values are consistently greatest in skin, liver and g ill tissue and negligible in muscle and bone tissue (Fig. 24, p.87 ). As reported by Bussey (1974), outboard motors could be respon sible for g ill lead levels that were as high as 3.8 ppm. Fisk Lake has little motorboat activity, possibly resulting in lower overall lead levels. Lead values in Fisk Lake fis h were comparable to the mean value of 0.718 ppm found in New York State fresh water fish samples (Pakkala et al^, 1972). Because lead was not detected in muscle tissue, there is no evidence to support consequential lead contamination in any fish species analyzed. There is no evidence to indicate that lead is moving through the food chain from highly contaminated areas, such as Station H. Cadmium in Fish Tissue : Fisk Lake fish show negligible cadmium concentrations in bone Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. CD ■ D O Q. C g Q. ■D CD WC/) 3o" 0 3 T a b l e 1 9 CD 8 Ffsh siapli size, N. mean «eight, VT, weight range, R, and ■D lead content * standard deviation (ppm) for selected Fisk Lake species. Results were obtained"using AA procedures - n itric - perchloric acid digestion method. CQ'3" 1 Pumpklnseed Blu'i G111 Yellow Black Brown White Sucker Largemouth N o r th e r n 3 (Leoowls (lepçnis Perch Crappie Bullhead (Catostowus B a s s P ik e CD olfabosusi macrochirûàl (Perea (Pomoxls (Ictalurus comnersonTT (Hleropterus (Esox flavescensi nlgromaculatusl nebulosus) saltiM ldssP luclusi M 10 1 0 7 7 4 1 6 9 CD "O S t . 102.94 112.44 61.76 130.9 512.28 1065.3 142.55 1162.3 O Q. R (03.0-126.4) (92.8-135.6) (23.7-138.2) (64.1-187.7) (414.2-652.5) ------(151.5-402.0) (369.1-2189.0) C a o 3 B one • c 1 1.05 * 0.16 <1 < 1 < 1 < 1 < 1 « 1 T3 O GUI 1.22 *0.36 1.25 * 0.54 < 1 1.84 * 0.65 1.2 *0.24 2.1 1.20 * 0.31 1 .0 7 * 0 . 3 0 Muscle < 1 4 1 < 1 < 1 < 1 * 1 ( 1 < 1 (D Q. S k in 1 .2 7 * 0 . 5 2 1.49 * 0.59 1.08 * 0.13 1.23 *0.32 1.28 *0.55 < 1 1.08 * 0.18 1.6 *0.65 L i v e r 1 .2 1 * 0 . 5 2 1 .1 6 * 0 . 5 1 1.24 * 0.73 1.19 * 0.49 1.33 * 0.53 < 1 1.12 + 0.20 1.67 * 0.67 K id n e y 1 .0 5 * 0 . 1 0 T3 (D G o n ad s 1 .0 3 * 0 . 0 7 W(/) W00 7} CD ■a o Q. c g Û. ■D CD Table 20 (/) F i s h sample s i z e , N , mean «Might, fit., «Might range, R , and cadmium content 3o ' i standard deviation (ppm) for selected Fisk Lake species. O Results were obtained using AA procedures - n itric - perchloric acid digestion method. Punpklflsttd B l u i 6111 Yellow Black Brown White Sucker Largaaouth Northern 8 (LepomI: (Lepomi: Perch Grapple Bullhead (Catoitowui B a i l P i k e 5 aQlbboiuil macrochi n il) (Perea (Poamxli (Ictalurui commeriomfT ( M ic ro p terui (Eiox (O' flaveiceni) nlgromaculatui) nebuloiutV lalnolid e l I l u c l u t l 3: O N 1 0 1 0 7 7 4 1 6 9 Wt. 102.94 ' 112.44 61.76 • 130.9 512.28 1065.3 142.55 1162.3 c R (83.0-126.4) (92.B-13S.6) (23.7-138.2) (64.1-187.7) (414.2-652.5) ______(51.5-402.0)(369.1-2189.0) B o n e < .1 .1 6 1 .0 6 < .1 < .1 < .1 < .1 .11 1 .02 .11 1 .04 ■oCD O GUI . 1 4 1 *06 .18 1 .08 .20 1 .09 .12 1 .05 . 3 1 . 0 5 .2 3 .2 2 1 .0 9 .1 5 1 . 0 8 cQ. a N u i c l e < .1 ( . 1 < .1 ( .1 < .1 < .1 <.1 < 1 o 3 S k in .1 2 1 .0 4 .1 4 1 .0 6 .1 1 1 .0 2 .1 2 1 .0 6 .11 1 .03 (.1 <1 .13 1 .06 ■o o L i v e r . 1 2 1 .0 4 < 1 .20 1 .10 .22 1 .10 .22 1 .14 < .1 .1 6 1 .0 7 .1 2 1 .0 5 K id n e y .20 1 .12 .13 1 .05 CD a . G o n ad s .1 (/> 3o' 85 m Ot o CM CM c eo rC R fZ ts * S ♦1 + 1 ♦ 1 *1 ♦1 ♦1 •«'I Ot m 5 o! S « CM 12 8 i 5q •*•1 +1 ♦ 1 ♦1 +1 zew1 «M eo m- 1 s R ÎS 8 5 rs»C9t m to CM CO o %o 8 m 8 • yM U T9 r*» CM O to m CO cn to * • u 8 ♦ 1 + 1 + 1 ♦ 1 ♦ 1 •*•1 CO «7» ft* g*r€>«M e JS % S» N m CO to CM to C9t £SC9IU U' to & s ♦ 1 + 1 ♦ I + 1 ♦1 to •— We- ot to tn 8 ffn m 8 ü i CO to CM m O rî in j î ï . g + 1 ♦ 1 +1 ♦ 1 4^1 1 o CO m o r*. cn s % o o fli 8 ♦ 1 ♦1 ♦ 1 +1 + 1 O CM 11 R m i c5 to o m V 8 % 5 8 8 ♦ 1 ♦ 1 + 1 ♦1 +1 |3 é to •— •— s m i m c S Î 1 o 1 3 Zc Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. CD ■D O Q. C g Q. ■D CD WC/) 3o' O T a b l t 2 2 8 T3 F4ih wmple size, N, mean weight, B t., weight range, R, and copper content »< * standard daviatlon (ppm) for selected Fisk Lake species. ci' Results were oFtafned using AA procedures - n itric - perchloric acid digestion method. o " Pumpkin* wd Blue Gill fellow Black Brown White Sucker largenouth Northern (lepowis Perch Crappic Bullhead fCatostowus B a s s P ik e i s aerochirusl (Perea iPomoxis (Ictalurus coenersonTT (Micropterus (Esox 3 fiavetcensl nioromaculFtus) nebuiotusl salmoidetl iuciusl 3 " CD CD ■D N 1 0 1 0 7 7 4 1 6 9 O Q. Bt. C 102.94 112.44 61.76 130.9 512.28 1065.3 142.55 1162.3 a R O (83.0-126.4) (92.8-135.6) (23.7-138.2) (64.1-187.7) (414.2-652.5) ------(51.5-402.0)(369.1-2189.0) 3 ■D O B o n e 1 . 0 8 1 .2 5 1.12 1 .37 1.30 1 .27 1 .3 1 1 .6 1 2 . 5 0 1 1 . 1 5 .1 1.33 1 .53 1 . 2 8 1 .4 8 G i l l 9 . 7 0 1 5 . 4 6.80 1 6.70 4.00 1 2.00 7.24 1 5.27 13.30 1 5.60 7 .1 5 . 1 0 1 5 .2 0 7 .6 0 1 3 . 9 0 CD Q. M u s c le 1.81 1 .74 1.61 1 .87 2.88 1 1.25 3.43 1 1 .7 0 2 . 4 5 1 1 . 1 4 3 . 2 2 .2 7 1 .6 5 2 . 3 6 1 1 .9 5 S k in 3.41 1 1.83 3.16 1 1.51 5.82 1 2.38 3.16 1 1.84 2.75 1 1.37 3 .2 5 .4 5 1 3 .6 1 4 .8 0 1 2 .3 3 L i v e r 26.63 1 10.02 14.45 1 6.14 20.34 1 .22 21.73 1 14.4 21.95 1 9.24 9 .4 45.14 1 72,72 51.43 1 15.06 ■D CD K id n e y 9.14 1 2.66 7 .4 5 1 3 .6 0 G o n a d s 9 .4 7 C/) C/) CD ■D O Q. C g Q. FIGURE 24. ■D CD MEAN LEAD CONCENTRATIONS IN TISSIES OF C/) C/) SELECTED FISK LAKE FISH SPECIES 2.0 1. Perea flavescens 2. Micropterus salmoldes 8 ■D 3. Pomoxis nTqiromaculatus 4. Lepomis macrochirus 5. . Lepomis gibbosus 6. Esox lucius CD 7. Ictalurus nebulosus 3 . 3 " CD ■DCD O Q. C Pb mg/g i.o a O3 "O o CD Q. "O CD C/) C/) ‘“i s S16I7I BONE GILL MUSCLE SKIN LIVER KIDNEY GONAD 'vi00 88 and muscle, but show a mean value of 0.3 ppm in brown bullhead g ills (Table 20, p.84 ). Detectable levels of cadmium were also found in skin and liver tissue (Fig. 25, p.89 ). Mount and Stephan (1967) found substantial amounts o f cadmium in internal organs but little in bone of fish exposed experimentally to cadmium sulfate. Heavy metal concentrations in g ill and liver reflected water concentrations. But, they failed to find a significant amount o f cadmium in bone or flesh . Bussey (1976) found s im ila r re sults in fish tissues from Lake Powell with highest mean cadmium values of 0.243 ppm in g ills of black crappie and 0.78 ppm in liver of walleye. In general, cadmium in Fisk Lake fish tissue cannot be consid ered consequential. Because cadmium was jelow the lim its of detection in muscle tissue, it is unlikely that cadmium toxicity would be a problem with the eight species o f fis h analyzed. Zinc in Fish Tissue: Zinc concentrations varied from a mean level of 29.8 ppm in brown bullhead muscle to 354.1 ppm in northern pike g ills (Table 21, p. 85 ). In general, skin and g ill tissues had highest zinc concentra tions in all species of fish examined and the content was lowest in muscle (Fig. 26). Results obtained by Bussey (1976) indicate a zinc concentration hierarchy from highest to lowest of g ills > skin > liver ) bone > muscle. The results of this study are similar with zinc levels in skin > gills > liver > bone> muscle although highest individual Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. CD ■D O Q. C g Q. ■D FIGURE 25. CD MEAN CADMIUM CONCENTRATION IS TISSUES OF C/) C/) SELECTED FISK LAKE FISH SPECIES 1.0 ■D8 1. Perea flavescens 2. Micropterus salmoldes 3. Pomoxis nTqromaculatus 4. Lepomis macrochiru? 5. Lepomis gibbosus 6. Esox lucius 3 . 3 " 7. Ictalurus nebulosus CD ■DCD O Q. c Cd ppm .5 a 3O "O O CD Q. ■D CD C/) C/) □ □ElOBGDHDQQUQCDDaBOQEDUUUUBanQFIDBQBHBUUFlUPinii Ü — B* BONE GILL MUSCLE SKIN LIVER KIDNEY GONAD VO00 CD ■D O Q. C g Q. ■D 500 FIGURE 26. CD MEAN ZINC CONCENTRATIONS IN TISSUES OF C/) C/) SELECTED FISK LAKE FISH SPECIES 1. Perea flavescens 400 2. Micropterus salmoides ■D8 3. Pomoxis moromaculatus 4. Lepomi s macrochirus 5. Lepomis gibbosus 6. Esox lucius 7. Icta lu rus nebulosus 300 3 . 3 " CD ■DCD Zn ppm O Q. C a 200 3O "O o CD Q. 100 ■D CD C/) C/) ?» H2l3|4|5|6|7 12 3 4 5 6 7 1 2 3 4 5 1 7 nBBaBBQgmnBBDBBQ m BONE GILL MUSCLE SKIN LIVER KIDNEY GONAD va o 91 zinc concentrations were found in northern pike g ills. Mean zinc concentrations in muscle tissue ranged from 28.8 ppm to 36.5 ppm. Since the average person has a daily requirement of 10 to 15 mg, of zinc per day (EPA, 1976), these levels would not pre sent any danger in terms o f zinc to x ic ity . High zinc levels in spe c if ic organs or tissues may re s u lt from d ire c t exposure to the metals (gills or skin), metabolic storage (liver and bone) or meta b o lic functioning (muscle) (Underwood, 1956). Copper in Fish Tissue: Mean copper levels varied from 1.12 ppm in pumpkinseed ( Lepomis qibbosis) bone to 51.43 ppm in northern pike (Esox lucius) liver (Table 22, p.86). Liver tissue had the highest concentration of copper (Fig. 27, p.92), in all 8 species of fish analyzed. This finding is con s is te n t with th a t o f Underwood (1956) who states th s ; the liv e r appears to be the main organ o f the body fo r copper storage. In a study, conducted by Bussey (1976) to establish base level metal concentrations, copper levels were found to vary from 0.24 ppm in walleye bone to 170.8 ppm in trout liver. The results fa il to show any evidence that high copper levels found in the substrate at various areas within Fisk Lake have moved through the food chain into the fish (Table 20j.p.84). In fact, levels of copper found in Fisk Lake fish are similar to, or below, those found in species from uncontaminated Lake Powell (Bussey, 1976). Highest means for copper concentrations were found in the livers of the top predator fish, (Fig. 17, p. 71) largemouth bass (Micropterus salmoides) and northern pike (Esox lucius). In addition, the g ills Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 92 FIGURE 27. MEAN COPPER CONCENTRATIONS IN TISSUES OF SELECTED FISK LAKE FISH SPECIES Cu ppm 50 r 40 — OBGDOOn nQBDQno BONE GILL MUSCLE SKIN LIVER KIDNEY GONAD .1. Perea flavescens 2. Micropterus salmoides 3. ^omoxi s nTqromaculatus 4. Lepomis macrochini? 5. Lepomis gibbosus 6. Esox lucius 7. Ictalurus nebulosus Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 93 of the brown bullhead (Ictalurus nebulosus) contained high mean copper concentrations. Because of its bottom feeding habit, the brown bull head is exposed to copper-enriched sediments th a t may influence cop per levels in its gills. Copper concentrations in the muscle tissue of the fish range from 1.61 ppm in the bluegill (Lepomis macrochirus) to 3.43 ppm in the black crappie (Pomoxis nigromaculatus). Copper is a nutrient necessary for human metabolism and concentrations are low. Therefore these levels of copper do not appear to present a problem of toxicity to those who use the fish in the lake as a food source. Heavy Metals Throughout the Food Chain Forstner and V/ittman (1979) claim th a t to evaluate whether heavy metals are contaminating an area, a study must involve analyses of as many trophic levels as possible. A number of recent studies have reported the distributions of metals thro' jh food chain levels (Mathis and Cummings, 1973; Leiand and McNurney, 1974; Prosi ^ 1977; Enk and Mathis, 1977, and; Namminga and Wilhm, 1977). Classically it has been assumed that pollutants, such as metals, increase in concentration along the food chain and reach highest accumulations (bioaccumulation principle) in the tissues of the top predator in the ecosystem. However these recent studies found th a t the order o f metal concentrations was: water < fis h < aquatic macrophytes < benthic organisms < sediments The results of this study agree with this ordering. A hierarchy of metal fo r the Fisk Lake ecosystem could be represented by: Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 94 ra in w a te r < storm water < omnivorous fis h < carnivorous fis h < aquatic macrophytes < sn a ils, chironomids < sediment Although apparently contradictory to the concept of bioaccumula tion, the influence of bioavailability and numerous chemical and physical factors have not been critica lly evaluated. Hov/ever, one important chemical parameter, pH, was examined in recent lite ra tu re . Wilber and Hunter (1979) and others claim th a t important chemical parameters such as pH can influence the availability of the heavy metals. Consequently, the pH parameter was measured. A total of 55 in situ pH readings were made in the substrate and water (Fig. 28, p.95). Huang (1977) stated th a t in low pH aqueous so lu tio n , lead and cadmium are more soluble that at higher pH values. These metals become bound in the substrate. Since the mean value for substrate pH was 7.0, the metals could be more strongly bound than in lower pH environments. The high metal levels in the substrate may not be bioavailable. PIXE vs. AA Methods o f Analysis A combination of analyses, AA and PIXE procedure, were used on selected samples of substrate plants, chironomids, snails, and fish. In all analyses, only lead, zinc and copper were compared since the PIXE process was not se n sitive to cadmium. Individual substrate sample concentrations of lead, zinc and copper were plotted using values from two different AA leaching methods and the PIXE process (Figs. 9, 11, and 12, pp.51-54 ). Mean substrate concentrations of lead, zinc and copper using AA and PIXE methods were also plotted (Figs. 13, 15, and 16, pp. 58-61 ). PIXE values for lead Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. CD ■ D O Q. C g Q. FIGURE 28. ■D CD SUBSTRATE pH VALUES FROM FISK LAKE AND STORM CANAL (WATER VALUES INCLUDED) WC/) 7.2 3o" O 7.0 3 CD DRAINAGE ■D8 DISTRICT (O' OUTFLOW .FROM REEDS 7.0 \ 7.0 LAKE 7.0 7.0 7 0 7.0 7.0 3 . 5.9 6.9 3 " 7 0 CD 6.9 6.9 ■DCD Fisk Lake 7.0 7.0 O 7.0 Q. C Oa 3 ■D O 6.6 6.7 6.7 CD Q. 7.2 6.7 7.2 Water Temp. 22 C 6.7 Water pH 7.6-8.0 ■D CD (/) |6.8 7.6 , C J I 96 were generally higher than those obtained by AA leaching methods. This would be expected since the PIXE process is sensitive to all forms o f the lead atom whereas the AA methods only leach adsorbed lead from the substrate. Copper and zinc substrate concentrations obtained using PIXE and AA display greater differences but follow sim ilar high-low trends when graphed simultaneously (Figs. 9, 11, 12, 13, 15 and 16, pp.51-61 ). Individual mature plant sample concentrations of lead, zinc and copper were plotted using values obtained from PIXE and AA methods (Figs. 17-19, pp.71-73 ). Mean zinc, and copper concentrations were plotted using the results fron young growth samples (Figs. 20, 21, pp. 74-75). PIXE and AA methods produce s im ila r lead, zinc, and copper values when used to analyze the same plant samples. Lead, zinc, and copper concentrations from 10 snail and chironomid samples were plotted using values from PIXE and AA (Fig. 29, p.97 ). PIXE analyses produced higher lead and copper values but lower zinc values as compared with those produced using AA methods. Only copper and zinc were detected by PIXE analyses of 30 indi vidual fis h samples. Concentrations o f these metal values were plotted using PIXE and AA data (Figs.30-31, pp. 9 3 ,9 9 ). The PIXE analyses o f fish tissue closely approximate those obtained by AA. PIXE and AA analyses were also conducted on ten unknown samples from the EPA (Tables 23-24, pp.100,101). The PIXE values most closely approximate zinc concentrations obtained by AA while being higher than AA lead values and lower than AA copper values (Fig. 32, p.i02)* Particle induced X-ray emission (PIXE) is a relatively new process. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 97 a CO «Ct—I to o LU o to m z o CM to z o $ o ^ 5 O. «/> II o CM s s SSSSSS8*=’ I gg CD CO ië o s M s § W O W to t—t Sc s 8 8 S S o 8 ® o S 8 o e CL a CL o. NI Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 98 . ii ° 8 " s s = ill SP < - r - to 8 § 8 â o. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 99 00 CO CO oc5^ CO «F co“ 00 r>. _ j — Z • u • r s . • (OCO _ j ' VO to , VO z ' VO to VO CO ' vr> I , I f ) to ' If) z • V f) to ' If) ' ^ CO ■ ^ to to CO •CO ' CO ” ro to z ■ CO to ' CO o o o o o s o o o o o VO Vf) CO CM INI Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ^ Table 23 1 Q. Metal concentrations in 10 EPA standard samples. g Results were obtained using PIXE procedures. Q. ( ) indicate EPA given values. ■D CD C/) C/) 4 5 6 7 8 9 10 11 12 13 Pb 6.2 10.2 3 3 10.0 572.3 7.2 545.5 5.2 569.4 ■D8 (21.0) (11.0) (0.3) (0.3) (11.0) (520.0) (21.0) (520.0) (21.0) (520.0) Zn 79.2 55.8 121.8 121.2 51.6 1097.9 89.4 1112.6 80.7 1241.2 (124.0) ( 1) (130.0) (130.0) ( 1) (1300.0) (124.0) (1300.0) (124.0) (1300.0) CD Cu 5.0 3.1 176.0 173.4 4.8 897.8 5.1 816.0 5.0 880.9 (7.0) (5.0) (193.0) (193.0) (5.0) (1100.0) (7.0) (1100.0) (7.0) (1100.0) 3 . 3 " CD ■DCD O Q. C a 3O "O o CD Q. ■D CD C/) C/) o o CD ■ D O Q. C g Q. Table 24 ■D CD Métal concentrations in 10 EPA standard samples. C/) C/) Results were obtained using AA procedures - n itric - perchloric digestion methods. ( ) indicates EPA value. "O8 (O' 4 5 6 7 8 9 10 11 12 13 Pb 6.2 15.5 2 .2 11.2 435.0 6.5 425.0 6.2 445.0 (21.0) (11.0) (.3) (.3) (11.0) (520.0) (21.0) (520.0) (21.0) (520.0) 3" CD Zn 98.0 77.5 170.0 170.0 92.5 1060.0 121.0 1160.0 965.0 1120.0 ■DCD (124.0) ( 1) (130.0) (130.0) ( 1) (1300.0) (124.0) (1300.0) (124.0) (1300.0) O Q. C Cu 8.0 6.5 203.0 222.5 6.6 998.0 4.5 1015.0 5.2 1030.0 a 3O (7.0) (3.0) (193.0) (193.0) (3.0) (1100.0) (3.0) (1100.0) (3.0) (1100.0) "O o Cd 1 1 4.5 1 1 16.2 1 17.2 1 16.0 ( 1) ( 1) ( 1) ( 1) ( 1) (21.0) ( 1) (21.0) ( 1) (21.0) CD Q. "D CD C/Î(/) l€2 CO < CL t— <£>O mCM K a: 3 O M X 11 i ►“! u . o o to cc 2 E a. CL CL CL M Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 103 Several types of samples were analyzed including substrate, plant tis sue and animal tissue. AA analytical results from each type of sample were found to be sim ilar to those obtained by PIXE procedures. Quality Control Cross analyses of Fisk Lake substrate, plant and fish tissues were conducted by this laboratory and the EPA using PIXE, AA and Inductively Coupled Plasma Atomic Emission Spectroscopy (ICPAES) (Tables 25, 26 and 27, pp.l04-10$). All values for metal concentra tions obtained by each method were generally in the same order of magnitude. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 104 inCMCMcnço r».m m m C M ^ ^ %Ow^t>4tntsè csir*»m CM888S8 ^ m CO M» iH < ■ o i l » s .8 r>*. e n u > c o ^ o r«* oo r>» o CM r— a% m oo v m W % WO 2 w z O (M m - O m SS838 m ^ CM CM vo Ui V r - KO m (M en r» m V CM î | s «A O «A O lA o a r<% sm « M ^ î - g e o CM ^ ^ ^ M* u i CM cn ^ f o g o o o 8 8 8 8 8 . r» o &m f—m» s « O r > c 0 t n ^ tn m « o m c n s Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 105 m m _ j UJ e f e ± o 0 0 1 1 1 1 1 X 1 1 1 1 1 1 1—1 00 00 00 f— 1— 1 1 1 1 1 «/) CL 1 1 1 1 1 'f t n lu (U *_ E 3 o - o LO LO c o s - 0 ) « £ I f ) CM f— CM r — r — <4- u e t • o in O m cvj f— fO i . r— r — r— r — U Q. • r - C eC e t o i e t O O O O O i . T J . CL tO ej- tO CM rO C T J LU > (O o JC m • + J S- U J 0 ) • o X E 0 ) 00 LU LU 3 : Z CO LU LU 3 : z c 1—1 fO Q . C d E y- E E 4- E 4 - E E 4 - + J E 0) n> oi O) (O 0) Q (U 0) m •» I— c «O 4J 0) -LJ -L* 0) 4J 0) -P -P d) 0 } '- '- W ~ t o 00 _J to to -J to _l to to _l Q. c w ) 2 " Q . q j Q - lO 4 - u i c r e v j o — " 1 - c X i •o 0 ) w i t o C L t_ î 1— 0 ) U J u JH > e c - r - 1/5 (O n ) o - L . (U 1— 0) O O 3 T 3 c n o ® c c &_ > (O •r— d # '—^ t o C L to CM (T> 00 c 3 NI o Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 106 e»«A m«si i «Si «o u> «r m «Si • • • •••••••••••• ^ CQ ^ «o ^ «mio ^ p -« r u> ^ «n I o t c*% m V f» . RR2K332: : : : : I : II : III : I H f s CM P - CM « A 9 C D «O CO r<» CO O p * c»> « i n Y- « o CM m^CM CM CM #— «Cl ooooeooooooooooooooooo i l Ï5 ' «Si «A • c K I m fs i X j f - m* p— m» p— m# m» «-CM M> «• CO & "#-p-CMP-CM#—p—P— r-CMP-TTrrr*^' 11 21 SSSS288S28288SS88828S8 II ^ t»« sllllll RSlllilli.15 y Si. m^mcococococoRcy RNcM%m%%c%%S&m»n5 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 107 CHAPTER IV Conclusions arid Recommendations The purpose o f th is study was to determine the concentrations of lead, cadmium, zinc, and copper in various trophic levels of an urban lake ecosystem and the extent that urban ru n o ff contributes to these metal concentrations. Fisk Lake, a small urban lake with adjoining storm sewer served as a study site. It was divided into 11 stations (A-K) and samples of v/ater, substrate, plants, chironomids, snails, and fish species were collected from stations near, and away from, a large storm sewer entering the lake. Samples of each trophic level v/ere prepared and analyzed by using PIXE and AA methods, ftetal concentrations were determined fo r v/ater, substrate, plants, chironomids, snails, and fish species. As a result of this study, the following conclusions and recom mendations emerged: Conclusions 1. The classic "bioaccumulation" of toxic heavy metals is not readily evident in the data obtained for metal concentrations in various trophic levels of the Fisk Lake ecosystem. The pH values of 7.0 or higher in the sediment appear to be immobilizing the metals in the substrate (Huang, 1979). Atmospheric changes, such as "acid rain" could lead to lower pH values in stormwater entering the lake thereby making some of the metals more available to the Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 108 organi sms. 2. Metals were detected in stormwater going into Fisk Lake and the eventual resting place of most of these metals is probably the substrate at Station H, adjacent to the storm canal. 3. A highly .ntaminated substrate is not necessarily an indication o f to ta l ecosystem p o llu tio n . There is contamination o f the sub strate, plants, and some benthic organisms, but the benthos is the highest trophic level found with any elevated metal levels. 4. The benthic organisms do not seem to be passing the metals along the food chain in a form that is available for absorption by other organisms. 5. Values fo r metal concentrations obtained using the PIXE process were similar to those values obtained when using the traditional AA procedures. The PIXE process has advantages that include simultaneous analyses of as many as 14 metals, ease of sample preparation, and no need for acid-digest procedures. 6. In so far as lead, cadmium, zinc, and copper contamination, edible portions o f the fis h appear to be safe fo r human consumption. Recommendati ons 1. Older aquatic macrophytes (Peltandra v irq in ic a ) seem to have higher metal accumulations than younger plants of the same species. A close examination of this species might reveal other insights into the possible extraction of heavy metals by aquatic plants. 2. It may be possible, using more sensitive analytical tools, to gain insight as to how the metals move within a particular trophic level. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 109 3. An identification of the oxidative states of the heavy metals in the substrate would allow for a more complete explanation of potenti al bioavai1abi1i ty . 4. Since the benthos exhibit relatively high metal concentrations as compared to other organisms analyzed, extensive study of this group might indicate the actual relationship between the organisms and the heavy metal concentrations associated with them. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. no BIBLIOGRAPHY Ackermann, W. C. 1971. Minor Elements In I llin o is Surface Waters. Illin o is State Water Survey Technical L e tte r, No. 14. Adrian, W. J. 1973. A comparison of wet pressure digestion methods with other commonly used wet and dry-ashing methods. Analyst 98: 213-216. Agemian, H, and A. S. Y. Chan. 1977. A study o f d iffe re n t an a lytica l extraction methods for non-detrital heavy metals in aquatic sedi ments. Arch. Environ. Contamin. T oxicol. 6: 69-82. Akerlinch, G. 1950. The quality of stormwater flow. Nordish Hygien- ish Tidskrift. (Sweden) from Bradford, W. L., J. W. P. C. F. W )T ~ 6 1 3-622. ------ A lley, W. M. and S. R. E llis . 1978. Trace Elements From R ainfall And Snowmelt At Several L o ca litie s In The Denver, Colorado, Metropolitan Area. Univ. o f Kentucky, Lexington, Kentucky. American Public Works Association. 1969. Water P ollution Aspects Of Urban Runoff. Federal Water Pollution Control Administration, Water Pollution Control Series. WP 20-15. Andrus, J. A. 1980. Development Of A System For Water Q uality Analysis Using P article Induced X-Ray Emission. Unpubl. M.S. Thesis, Western Michigan U niversity, Kalamazoo, Michigan. Anderson, A. 1978. Atmospheric heavy metal deposition in the Copenhagen area. Environ. Poll. 17. AVCO Economic Systems Corporation. 1970. Stormwater P ollution From Urban Land Activity. Federal Water Quality Administration. Publ. No. 11034 FKL. Bender, J. A. 1975. Trace metal levels in beach dipterans and amphipods. B u ll. Environ. Contam. Toxicol. 14: 187-192. B it t e ll, J. E. and R. J. M ille r. 1974. Lead, cadmium, and calcium selectivity on a montmorilIonite, illite , and kaolinite. Environ. Qual. 3: 250-253. Bloom, H. and G. J. Ayling. 1977. Heavy metals in the Derwent Estuary. Environ. Geol. 2: 3-22. Bohn, A. 1975. Arsenic in marine organisms from West Greenland. Mar. Pollut. Bull. 6: 89-98. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. m Bowen, H. J. M. 1966. Trace Elements In Biochemistry. Academic Press, London. Bradford, G. R., et al. 1968. Trace and major element content of 170 high Sierra lakes in California. Limnol. Oceanogr. 13:526-529. Brown, A. L. 1971. Ecology Of Fresh Water. Howard U niversity Press. Cambridge, Mass. Bryan, E. H. 1970. Q uality Of Stormwater Drainage From Urban Land Areas In North Carolina. Water Resources Inst., U. North Carolina, Report No. 37. Bryan, G. W. 1971. The effects of heavy metals (other than mercury) on marine and estmarine organisms. Proc. R. Soc. Lond. B177: 389-410. “ Bryan, G. W. 1973. The occurrence and “seasonal variatio n o f trace metals in scallops Pecten maximum (L.) and Chlamys opercularis (L .). Mar. B io l. Assoc. U^. K. 53: 145-166. Bussey, Robert E ., David E. Kidd, and Loren D. Porter. 1976. The Concentrations Of Ten Heavy Metals In Source Selected Lake Powel1 Game Fishes. U. S. Department o f Commerce. National Technical Information Service. NSF, Washington, D. C. NSF/RA 761133 PB 273 026. Cahill, R. A., J. K. Kuhn, and G. B. Dreher. 1977. Distribution of major, minor and trace elements in sediments of northern Lake Michigan. Abstr. 20th Conf. Great Lakes Res. In t. Assoc. Great Lakes Res. Cahill, T. A. 1975. Ion-excited x-ray analysis of environmental samples. In J. F. Ziegler (Ed.), New Uses Of Ion Accelerators. New York: Plenum Press. Cheremisinoff, P. N., and Y. H. Habib. 1972. Cadmium, chromium, lead, and mercury: A plenary account for water pollution. Water Sewage Works 119: 46-53. Copeland, R. A., and J. C. Ayers. 1972. Trace element d is trib u tio n in water, sediment, phytoplankton, zooplankton, and benthos o f Lake Michigan. Environ, Res. Group Inc. Ann Arbor, Michigan. Corrin, M. L ., and D. F. S. Natusch. 1977. Physical and chemical characteristics of environmental lead. (From Lead In The Environ ment. ) Report prepared fo r NSF/RANN Div. NSF/RA 770214. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 112 Cumbie, P. M. 1975. Mercury levels in Georgia o tte r, mink, and fresh water fis h . B u ll. Environ. Contam. T oxicol. 14: 193-196. Charmadhikari, V. V. 1970. Quality Of Runoff From Diversified Urban Watersheds. M.A. Thesis, U. of Arizona, Dept, o f C iv il Eng. and Eng. Mech. Enk, M. D., and B. J. Mathis. 1977. D istrib u tio n o f cadmium and lead in a stream ecosystem. Hydrobioloqia 52: 153-158. Fagerstrom, T., N. Kurte, and B. Ansell. 1975. Statistical parameters as criteria in model evaluation: Kinetics of mercury accumulation in pike Esox Lucia. Oikos 26, 109-116. Farmer, J. G. 1978. Lead concentration p ro file s in lead-210 dated Lake Ontario sediment cores. S ci. Total Environ. 10: 117-127. Flegal, R. R., and J. H. Martin. 1977. "Contamination of biological samples by ingested sediment. Mar. Pollut. Bull. 3:90-92. Folkmann, F ., C. Gaarde, T. Huus, and K. Kemp. 1973. Proton induced x-ray emission as a tool for trace elemental analysis. Nuclear Instruments And Methods 116. Forstner, U. 1979. Cadmium in polluted sediments. Biogeochemistry Of Cadmium. Nriagu, H. 0. (ed.). New York:. Wiley. Forstner, U. 1976. Lake sediments as indicators o f heavy-metal p o llu tio n . Naturwissenschaften 63: 465-470. Forstner, U. 1977. Metal concentration in recent lacustrine sediments. Arch. Hydrobiol. 80: 172-191. Forstner, U., and G. T. W. Wittman. 1979. Metal P ollution In The Aquatic Environment. Springer-Veriag Berlin, Germany. Friberg, L., M. Piscator, G. F. Nordberg, and T. Kjellstrom. 1974. Cadmium In The Environment, CRC, Cleveland, Ohio. Fujiki, M. 1972. The transitional condition of Mirimata Bay and the neighboring sea polluted by factory waste water containing mercury. Proc. 6th In t. Conf. Water P o llu t., Res. Paper No. 12, Tokyo, Japan. Geldreich, E. E. 1968. The bacteriological aspects of stormwater p o llu tio n . J. W. P. Ç. F. 40: 1861-1867. Biddings, J. C. 1973. Chemistry, Man, And Environmental Change: An Integrated Approach. Canfield Press, Harper Row, New York, N.Y. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 113 Gresy, J. P., and J. G. Wiener. 1977. Frequency d is trib u tio n s of trace metal concentrations in five freshwater fishes. Trans. Amer. Fish. Soc. 106(1). Hagino, N., and K. Yoshioka. 1961. A study o f the cause o f it a i- ita i disease. J^. Jpn. Orthop. Assoc. 35. Hall, S. K. 1972. Pollution and poisoning. Environ. Sci. And Technol. 6: 31-35. Helsel, D. R., J. I. Kim, C. W. Randall, and R. C. Hoehn. 1979. Land-use influences on metals in storm drainage. J. W. P. C. F. 51(4): 709-717. Heydt, G. 1977. Schwermetallgchalte Von Wasser, Wasserflanqen, Chironomidae Und Mullusca Per Elseng. D ip l. A lb e it Univ., Heidelberg. Howell, R. B. 1978. Water P ollution Aspects Of P articles That Collect On Highway Surfaces. C a lif. Dept, o f Transportation, Sacramento, California. Huang, C. P. 1979. Interfacial reactions and the fate of heavy metals in soil-water systems. W. £. C. £. 49(5): 745-755. Johansson, S. A. E ., and T. B. Johansson. 1976. A nalytical application of partical induced x-ray emission. Nuclear Instruments And Methods 137. Knauer, G. A ., and J. H. Martin. 1973. Seasonal variations of cadmium, copper, manganese, lead, and zinc in water and phytoplankton in Monterey Bay, C a lifo rn ia . Limnol. Oceancg. 18: 597-604. Koli, A. K., et. al. 1978. True metals in source fish species of South Carolina. Bull. Environ. Contam. Toxicol. 20. Kopp, J. F ., and R. C. Kroner. 1967. Trace Metals In Waters Of The United States: A Five Year Summary Of Trace Metals In Rivers And Lakes Of The United States (Oct. 1, 1962 - Sept. 30, 1967)1 U. S. Dept, o f In te rio r, Federal Water P ollution S urveillance, C incinnati, Ohio. Leland, H. V., and J. M. McNurney. 1974. Lead transport in a riv e r ecosystem. Proc. I n t . Conf. Transp. P e rsist. Chem. Aquatic Ecosyst. , Ottawa, I I I : 17-23. Lewin, J ., B. E. Davies, and P. J. Wolfenden. 1977. Interaction between channel changes and historic mining sediments. River Channel Change. Gregory, K. J. (ed.). New York: Wiley and Sons. Pp. 353-367. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 114 Lucas, H. F. Jr., D. H. Edgington, and P. J. Col by. Concentrations of trace elements in Great Lake fishes. Fish. Res. Board Canada 27: 677-684. Malmquist, P. A. 1975. Heavy metals in urban storm water. Abstr. In t. Conf. Heavy Met. Environ. , Toronto, C-45/48. Mason, W. I . 1968. An Introduction To The Id e n tific a tio n Of Chironomid Larvae. U. S. Dept, of Interior, Cincinnati, Ohio. Mathis. B. J., and T. F. Cummings. 1973. Selected metals in sediments, water and biota in the Illin o is River. jJ. W. £. £. £. 45: 1573-1583. McCaull, J. 1971. Building a shorter life . Environment 13(7): 14-31 and 38-41. Me Elroy, A. D., S. Y. Chiu, J. W. Nebgen, A. A le ti, and E. Vandergrift. 1975. Water p o llu tio n from non-point sources. Water Res. 9: 675-681. Mennear, John H. (e d ito r). 1979. Cadmium T o x ic ity . Marcel Dekker, In c ., New York, N.Y. Mount, D. I . , and C. E. Stephen. 1967. A method fo r detecting cadmium poisoning in fis h . £. W ild l. Manage. 31: 168-172. Muller, G., and F. Prosi. 1977. Cadmium in fischen des mittleren und unteren neckars. Veranderungen seit 1973. Natwrwissenschaften 64. Muller, G., and F. Prosi. 1978. Verteilung von zink, kupfer, und cadmium in verschieden organen von plotzen (Rutilus rutilu s) (L.) aus neckar and elzeng. T. Naturforsch. 33c: 7-14. Murphy, B. R., et. a l. 1978. Cadmium and zinc in muscle o f b lu e g ill (Lepomis macrochirus) and largemouth bass (Micropterus salmoides) from an industrial contaminated lake. Environ. Poll. 17: 285. Nakamura, M., S. Nakano, and M. Tachikawa. 1974. Sediment deposits in Lake Biwa. Shiga Daigaku Kyoiku Gakubu Kiyo 24: 89-96. National Academy o f Science - National Research Council. Food and N u tritio n Board. 1974. Recommended Dietary Allowance, 8th ed. National Academy of Sciences, Washington, D.C. National Academy of Science - National Research Council. Food and N u tritio n Board. 1975. Toxicants Occurring N aturally In Foods, 2nd ed.. National Academy of Sciences, Washington, D.C. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 115 National Biocentric, Inc. 1978. Quarterly Report No. , Reeds Lake - Fish Lake Restoration. ERA #5804708-01-0, Washington, D.C. Pakkala, Irene S., M. N. White, D. J. Lisk, G. E. Burdick, and E. J. Harris. 1972. Residues of fish, w ildlife, and estuaries. A survey of lead content of fish from 49 New York State waters. Pestic. Mount. 5: 348-355. Palmer, C. L. 1950. The po llu tio n a l e ffe cts o f stormwater overflow from combined sewers. Sewage And In d u stria l Wastes 22: 154-165. P h illip s , D. J. H. 1976. The common missed M ytilus edulis as an indication of pollution by zinc, cadmium, lead and copper. II. Relationship of metals in the mussel to those discharged by indus try . Mar. B io l. 38: 71-80. Pitt, Robert, and R. Field. 1977. Water-quality effects from urban runoff. Water Works Assoc. 6f,(8): 432-436. Potter, L., D. Kidd, and D. Standford. 1975. Mercury levels in Lake Powell: Bioamplification of mercury in a man-made desert reservoir. Environ. Sci. Technol. 9: 41-46. Prosi, F. 1977. Schwermetallbelastunq In Per Sedimenten Per Elseng Und Ihre Auswirkung Auf Limnische Organismen. Unpublished Ph.D., Univ. Heidelberg, Germany. Rabe, F. W., and S. B. Bauer. Heavy metals in lakes o f the Coeur d'Alene River Valley, Idaho. Northwest Science (USA) 51(3): 183- 197. Randall, C. W., R. C. Hoehn, and T. J. Grizzard. 1979. Characterization Of Urban Runoff In Northern Virginia. Water Res. Center, Virginia Polytech. Inst, and State Univ. Randall, C. W. 1978. The impact of atmospheric contaminants on storm water q u a lity in an urban area. Prog. Water Tech. 10. Rehwoldt, R. E., et. a l. 1978. Historical and current heavy metal residue in Hudson River fish. Bull. Environ. Contam. Toxicol. 19. Roskam, R. T. 1972. Kopervergifting in zee. Koper In Het Nederlandsr M ilie u . TNO Nieuws, 416-418. Ruch, R. R., E. J. Kennedy, and N. F. Shimp. 1970. D istribu tion o f arsenic in unconsolidated sediments from Lake Michigan. Environ. Geol. Notes 37:1-16. Sandstead, H. H. 1974. Cadmium, zinc, and lead. Geochemistry And The Environment. Vol. %: The Relation Of Selected Trace Elements To Health And Disease, pp. 43-56. National Academy of Sciences, Washington, D.C. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 116 Sartos, J. D., 6. B. Boyd, and F. J. Agandy. 1974. Water p o llu tio n aspects of street surface contaminants. 2- k- £• Ç.» £• 45: 458-466. Satake, M., T. Asano, K. Yamamoto, T. Yonekubo, and Y. Nagaosa. 1975. D istrib u tio n o f heavy metals in Lake Biwa. Fukui Daigaku Kogakubu Kenkyu 23: 109-114. Schroeder, H. A. 1968. Airborne metals. Environment 10: 83-88. Schroeder, H. A ., A. P. Nason, and J. J. Balossa. 1967. Trace metals in rat tissues as influenced by calcium in water. J^. Nutr. 93: pp. 331-332. Shigorin, G. G. 1956. The problem o f c ity surface. Vodosnabzkenii I Tekaika from Bradford, W. L ., 1977. W. £. £. £. 49(4): 613-622. Shroeder, Henry A. 1974. The Poisons Around Us. Indiana University Press, Bloomington, Indiana. Spring, R. J. 1978. Dustfall Analysis For The Pavement Storm Runoff Study ( 1-405 Los Angeles), C a lif. Dept, o f Transportation, Sacramento, California. Stenner, R. D., and G. Nickless. 1975. Heavy metals in organisms o f the A tla n tic Coast o f south-west Spain and Portugal. Mar. P o llu t. Bull. 6: 89-92. Stenstrom, T ., and M. Vahter. 1974. Cadmium and lead in Swedish com mercial fertilizers. Ambro. 3: 91-92. Tatekawa, M., M. Nakamura, and S. Nakano. 1975. The p o llu tio n o f Lake Biwa in the light of the distribution of heavy metals. Proc. Intern. Congr. On The Human Environ. Kyoto, Japan. Pp. 402-407. Thomas, R. L ., J. M. Jaquet, A. L. W. Kemp, and C. F. M. Lewis. 1976. S u rfic ia l sediments o f Lake Erie. J^. Fish Res. Board Can. 33: 385-403. Underwood, E. H. 1971. Trace Elements In Human And Animal N u tritio n . 3rd. ed. Academic Press, New York, N.Y. Underwood, E. H. 1956. Trace Elements In Human And Animal N u tritio n . 3rd. ed. Academic Press, New York, N.Y. U. S. Environmental Protection Agency. 1979. Methods For Chemical Analysis Of Water And Wastes. C incinnati, Ohio. EPA-600/4-79-020. U. S. Environmental Protection Agency. 1976. Quality Criteria For Water. C incinnati, Ohio. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 117 Uthe, J. H., and E. G. Blight. 1971. Preliminary survey of heavy metal contamination in Canadian freshwater fis h . Fish Res. Board Canada 28; 786-788. Walters, L. J ., T. J. Wolery, and R. D. Myser. 1974. Occurrence of As, Cd, Co, Cr, Cu, Fe, Hg, N i, Sb, and Zn in Lake Erie sediments. Proc. 17th Conf. , Great Lakes Res. , pp. 219-234. Weible, S. R. 1964. Urban land runoff as a factor in stream pollution. J. W. P. Ç. F. 36: 914-922. Wheeler, G. L ., G. Provenzano, and R. Resek. 1977.Environmental Contamination By Lead And Other Heavy Metals. Vol. V^. Synthesis And Modeling. NSF Report - RANN Program GI-31605 and ERT 74-24726. Whipple, W. 1976. Characterization o f urban run off. New Jersey. Water Resources Research In s t. Publ. Rutgers Univ. Whipple, W., and J. V. Hunter. 1977. Non-point sources and planning for water pollution control. W. £. Ç. £. 49(1): 15-23. Wilber, W. G., and J. V. Hunter. 1979. Distribution of metals in stree t sweepings, stormwater solids and urban aquatic sediments. J. W. P. Ç. F. 51(12): 2810-2822. Wilber, W. G., and J. V. Hunter. 1975. Heavy metals in urban runoff. Proc. Southeastern Regional Conf. On Non-point Sources And Water P o llu t. Williams, C. H., and D. J. David. 1973. Aust. J. Soil. Sci. 3: 91-92. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.