EPA-R3-72-003
August 1972 Ecological Research Series
An Evaluation of DDT and
Dieldrin in Lake Michigan
Office of Research and Monitoring
U.S. Environmental Protection Agency
Washington, D.C. 20460
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and
Monitoring, Environmental Protection Agency, have
been grouped into five series. These five broad
categories were established to facilitate further
development and application of environmental
technology. Elimination of traditional grouping
was consciously planned to foster technology
transfer and a maximum interface in related
fields. The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
U. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ECOLOGICAL
RESEARCH series. This series describes research
on the effects of pollution on humans, plant and
animal species, and materials. Problems are
assessed for their long- and short-term
influences. Investigations include formation,
transport, and pathway studies to determine the
fate of pollutants and their effects. This work
provides the technical basis for setting standards
to minimize undesirable changes in living
organisms in the aquatic, terrestrial and
atmospheric environments.
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EPA-R3-72-003
August 1972
AW EVALUATION OF DDT AND DIELDRIN
IN LAKE MICHIGAN
By
The Lake Michigan Interstate Pesticides Committee
of the
Lake Michigan Enforcement Conference
Project Nos. 16050 EYV,EYS, EPV,ESP
Prepared for
OFFICE OF RESEARCH AND MONITORING
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20^60
Environmental Protest-ton A
Great lakes National Pro-ran Offic
Library
For sale by the Superintendent of Documents, U.S. Government Printing Office
Washington, D.C. 20402 - Price $1.25
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EPA P
This report has bean reviewed by the environmental
Protection Agency and approved fcr publication.
Approve! does not signify that the contents necessarily
reflect the viev;s ond policies of tho. rnvi ronnen tal
Pro-c.ecti.-n Agency, nor doas mention of trade naims or
corruneici
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ABSTRACT
The presence of pesticides and particularly the chlorinated hydrocarbon
insecticides in Lake Michigan water is responsible for biological
accumulations that affect a wide variety of legitimate uses. The data
collected from waters, wastewaters, invertebrate organisms and fish all
suggest that DDT plus analogs and dieldrin are observed consistently at
levels that warrant concern from both a public health and wildlife
preservation standpoint. The sources of these chlorinated hydrocarbon
insecticides include not only industrial and wastewater effluents but
also diffuse sources such as from agricultural activities and municipal
pest control programs.
The evaluation of the chlorinated hydrocarbon insecticides in both
wastewater and biological specimens is complicated by the presence of
products such as polychlorinated biphenyls and phthalates. These
products interfere with the analysis for the target insecticide and,
indeed, have biological implications of their own.
This report is submitted in fulfillment of four cooperative grants to
the Lake Michigan Enforcement Conference participating state under the
sponsorship of the Environmental Protection Agency and include grant
numbers 16050 EYV (Wisconsin), 16050 EYS (Indiana), 16050 EPV (Michigan)
and 16050 ESP (Illinois) for an investigation of "Evaluation of Pesticide
Sources and Levels Tributary to Lake Michigan".
iii
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CONTENTS
Section
I Conclusions
II Recommendations
III Introduction
IV Pesticide Monitoring - Lake Michigan Open Water
V Total Pesticide in Lake Michigan
VI Lake Michigan Tributary Waters
VII Biological Monitoring of Tributaries
VIII Fish Monitoring
IX Additional Investigation
X Impact of Chlorinated Hydrocarbon Contamination
on the Lake Michigan Ecosystem and Economy
XI Status of Legislation Affecting Pesticide Usage
in the Lake Michigan Basin
XII Acknovledgements
XIII References
Appendices (See list, pages vi thru x)
I - Chlorinated Hydrocarbon Insecticides
in Lake Michigan Waters
II - Chlorinated Hydrocarbon Insecticides
in Lake Michigan Tributary Waters
III - Chlorinated Hydrocarbon Insecticides
in Biological Monitors
IV - Chlorinated Hydrocarbon Insecticides
in Lake Michigan Fish
V - Chlorinated Hydrocarbon Insecticides
in Municipal Wastewater Effluents
VI - Industrial Wastewater Evaluation
of PCBs in Lake Michigan
VII - Chlorinated Hydrocarbon Insecticides
in Stream Sediments
VIII - Five State Pesticide Legislation
1
5
7
11
15
17
21
23
27
31
35
37
39
59
77
97
109
117
127
131
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FIGURES
Appendix I
Appendix II
Appendix III
No.
1
Page
2
1
Lake Michigan Basin Office Open Lake
Sample Stations
Lake Michigan Basin Major River Pesti-
cide Sampling Stations
Continuous Water Sampler
Indiana Biological Pesticide Monitoring
Stations - Indiana State Board of Health
61
71
vi
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TABLES
Appendix I
No,
1
Page
5
6
7
8
Chlorinated Pesticide Analytical Data
For Lake Michigan
Lake Michigan Interstate Pesticide Com-
mittee Analytical Quality Control Inves-
tigation - Data Comparison
Chlorinated Pesticide Analytical Data
For Lake Michigan
Pesticides in Lake Waters (ppt)
Water Treatment Plants (ppt)
Pesticides in Lake Michigan Municipal
Water Intakes, 1970
Pesticides in Lake Michigan Water Intakes
Lake Michigan Open Water Pesticides -
July, 1969
1*8
50
53
55
57
Appendix II
5
6
Tributary Monitoring Station for Insecti-
cides - Lake Michigan Drainage Basin
Pesticide Concentrations in Wisconsin
River Waters
Pesticides in River Water Samples -
Michigan Drainage, 1970
Pesticides in River Water Samples -
Indiana Drainage, 1970
Pesticides in River Water Samples -
111 inois Drainage, 1970
Lake Michigan River Water Pesticides -
July, 1969
60
62
66
72
73
vii
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TABLES CONTINUED:
Appendix III
No.
1
Pesticides in Biological Samples -
Wisconsin Drainage, 1968-69
Pesticides in Biological Samples -
Michigan Water Resources Commission
Pesticides in Biological Samples -
Indiana State Board of Health
82
91
95
Appendix IV
8
Bureau of Commercial Fisheries -
March, 1970
A Comparison Between DDT (DDT, DDE, DDD)
and Dieldrin Concentrations in Bloater
Chubs, Coho Salmon and Lake Trout Col-
lected in 1969 and 1970
Summary of DDT and Dieldrin Values of
120 Separate Analyses of Lake Michigan
Chubs (Coregonus Hoyi) , Fall 1969
Mean Pesticide Residues in Lake Michigan
Fish - 1968
Concentrations of Pesticides Found in
Fish Collected in Lake Michigan in
Illinois
PCB-Pesticide Residues in Lake Trout
From Lake Michigan - 1971
Relative PCB-Pesticide Residues in Lake
Trout Fry and Eggs From Lake Michigan -
1971
PCB-DDT Residues in Fish From the Great
Lakes Region - 1971
98
99
100
101
10*4.
105
106
107
Appendix V 1 Sewage Treatment Plants (ppt) 110
2 Concentrations of Pesticides (ppt) Found
in Sewage Treatment Plants Tributary to Lake
Michigan in Illinois H5
viii
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TABLES CONTINUED:
Appendix VI
No.
•^B—«•
1
PCB Form Letter
Page
118
Appendix VII
Pesticides in Stream Sediments - July,
1969 - Data From the Wisconsin Alumni
Research Foundation
129
Appendix VIII
1 Status of Legislation Accepting Pesticide
Usage in the Lake Michigan Basin-Indiana
2 Status of Legislation Accepting Pesticide
Usage in the Lake Michigan Basin-Illinois
3 Status of Legislation Accepting Pesticide
Usage in the Lake Michigan Basin-Michigan
h Status of Legislation Accepting Pesticide
Usage in the Lake Michigan Basin -
Minnesota
5 Status of Legislation Accepting Pesticide
Usage in the Lake Michigan Basin -
Wisconsin
132
136
137
138
ix
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PROCEDURES
Appendix I
No.
WBPWB
1
Page
Analytical Techniques Used in Lake Water
Analyses by the Lake Michigan Basin Offices
of the United StatesEnvironmental Pro-
tection Agency
Analytical Techniques Used in Lake and
River Water Analysis by the Wisconsin
Department of Resources - Laboratory of
Hygiene
Water Analysis Procedure - Wisconsin
Alumni Research Foundation
51
56
Appendix II
Michigan Water Resources Commission Field
and Analytical Procedures
68
Appendix III
Field Methods for Biological Sampling -
Wisconsin Department of Natural Resources
Analytical Methods for Biological Samples -
Wisconsin Department of Natural Resources
Biological Collection and Analytical Pro-
cedure - Michigan Water Resources Commission
78
79
93
Appendix VII
Pesticide Analysis of Sediment Samples -
Wisconsin Alumni Research Foundation
128
x
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SECTION I
CONCLUSIONS
1. The analysis of water samples from the open waters of Lake Michigan
strongly suggests a real and inherent variability that makes water samp-
ling for the purpose of developing general residue levels impractical. The
concentrations present challenge the limit of detectability of the analytical
methods employed. Several laboratories recorded substantial analytical
discrepancy when analyzing split samples, thereby further complicating
interpretation of results.
2. After cautious interpretation of the data, the committee generally
agreed that the most likely concentrations of DDT in open lake waters
were between one and ten parts per trillion. Those analyses that revealed
unusually high levels of pesticide were probably the result of artifacts
such as surface scums of floating oils, suspended debris or in-laboratory
contamination.
3. The data accumulated by municipal water intake sampling strongly
suggest concentrations of chlorinated hydrocarbon pesticides in the inshore
waters were higher than in open lake waters and much more variable. The
biological accumulation potential is, therefore, greater in inshore waters
since most of the important biological representatives spend an extended
period of time within these inshore water areas.
!*-. Tributary streams to Lake Michigan discharge chlorinated hydrocarbon
pesticides into the lake. Urban and fruit-growing areas are the more
significant contributors of pesticides to the lake than are diversified
agriculture areas.
5. Dieldrin levels in tributary streams and lake waters were generally
at the limit of detectability, one part per trillion or less.
6. Most sewage treatment plant discharges contained less than ten parts
per trillion DDT. For those plants with more than ten parts per trillion
total DDT, there were likely point sources. However, in the City of
Milwaukee, no point source was found. The Milwaukee system is so complex
that it is virtually impossible to eliminate all potential sources by
field investigation. Sewage treatment plants with dieldrin concentrations
above the detectable levels also had identifiable point sources.
7. Lake Michigan waters contain many substances that are extractable and
measureable by commonly used methods for pesticide analyses and are,
therefore, potential interferences in typical pesticide analytical proce-
dures. The polychlorinated biphenyls constitute a complex of such substances
that are present in Lake Michigan. Phthalate esters more recently have
been identified at detectable levels. These chemicals are present in
greater concentrations in biological and wastewater samples than in open
lake waters. The polychlorinated biphenyls are present in sufficient
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quantity, with sufficient evidence of biological impact, to warrant an
independent evaluation.
8. Biological sampling with sentinel organisms (clams) reflected
unusually high pesticide concentrations and sources. Subtle concen-
tration differences that might be brought about by a relatively small
discharge relative to the stream could not be detected by clam
analyses. Resident arthropods generally contained higher levels of DDT
and its analogs than sentinel clams. Resident fish appeared to be
the most reliable biological monitor.
9. The biological magnification of chlorinated hydrocarbon insecticides
in sport and commercially valuable species of fish suggests that fish
should be used to reflect concentration trends in the lake water. It
is believed that the residue levels established during the last two
years will be adequate to serve as a base line to establish the trend
in future years. It seems unlikely these trends can be conveniently
established by water sampling because of analytical and sampling
complications.
10. The levels of DDT in sport and commercially valuable species of fish
exceed the five parts per million action level established by the Food
and Drug Administration, essentially preventing sale of Lake Michigan
fish. Other chlorinated hydrocarbon pesticides do not exceed the establish-
ed residue tolerances, although dieldrin levels approach the action limit.
Exotic chemicals other than chlorinated hydrocarbons were not measured in
this study.
11. The four states in the Lake Michigan Drainage Basin have adopted
legislation authorizing various pesticide use control programs. Wisconsin,
through basic legislation and subsequent rules, has essentially prohibited
the use of chlorinated hydrocarbons that have been found in Lake Michigan.
Michigan and Indiana have adopted adequate use control legislation but
the rules have not yet been promulgated. Illinois has a legislative
restriction on DDT but not on other chlorinated hydrocarbons. Michigan,
Illinois, and Indiana have adopted legislation regulating commercial
pesticide applicators. Wisconsin legislation regulating commercial
applicators is still pending.
12. The effect of the pesticides in Lake Michigan on fish reproduction
potential is not resolved as yet - this concern in part generated the
establishment of a technical committee to review pesticide pollution
in the lake, Both Wisconsin and Michigan are able to hatch and rear
coho fry in adequate numbers to sustain the anadromous fish stocking
program using Lake Michigan brood fish. The effect on natural repro-
duction in lake trout is not known.
13. The pesticides in Lake Michigan through biological magnification
may have a potential effect on both domestic and wild animals that
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eat fish or other organisms from the lake. Hazards to wild bird popu-
lations and mink ranching operations are being investigated. Prelimi-
nary data suggest that exotic chemicals including chlorinated hydro-
carbon insecticides produce measurable changes on reproductive potentials.
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SECTION II
RECOMMENDATIONS
1. Fish sampling for pesticide residues should be established in
accordance with the Bureau of Sport Fisheries and Wildlife and Com-
mercial Fisheries' recommendations. This monitoring should be con-
ducted within the Federal structure or should be contracted to an
agency with the ability both to collect and process the collections
from the entire lake. Analyses and sampling must be performed in the
same way in order to compare data or correlation data must be estab-
lished if new collection or analytical techniques are used.
2. A water quality monitoring program should be initiated for inshore
waters in order to determine whether the pesticide burden of fish is
related to the pesticide concentration of inshore waters.
3. The conferees should insist on adequate legislation to record
pesticide usage of other than the chlorinated hydrocarbons.
k. As with pesticides, the discharge of polychlorinated biphenyls,
phthalates and other persistent chemicals should be abated to prevent
accumulations of these persistent compounds in Lake Michigan. Particular
attention should be devoted to possible replacements for chlorinated
hydrocarbons such as toxaphene, methoxychlor, chlordane and benzene
hexachloride.
5. The levels of metal contamination of Lake Michigan water and/or
fish should be clearly established at this time so that residue trends
can be assessed in the future.
6. Polychlorinated biphenyl concentrations should be ascertained for
water and fish. Control programs for polychlorinated biphenyls and
other exotic chemicals should be initiated.
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SECTION III
INTRODUCTION
In the late 19^-0's, when the organic insecticides first became avail-
able for general distribution, an extensive scientific effort was
extended toward evaluating the toxicity of these new products. Cottam
and Higgins, 19^6, evaluated the effects of DDT on fish and wildlife
principally from forest land and aquatic habitats. The authors concluded
that DDT should be used only where the need for specific control was
carefully evaluated. Metcalf, 19^8> summarized the mode of action of
organic insecticides and evaluated the toxicity data available to that
date. In the early 1950's, Rudd and Genelly reviewed the literature
concerned with the toxicity of pesticides to both wild and domestic
animals. Rudd and Genelly, 1956, summarized the toxicologies! data
available to that time. In general, the chlorinated hydrocarbons and
particularly DDT were recognized as only moderately toxic to mammals.
The California Pesticide Information and Safety Manual, 1968, gives the
acute oral toxicity of DDT to rats as approximately 120 mg/kg. The
dermal toxicity of DDT is approximately 2,500 mg/kg. Both dieldrin and
aldrin are somewhat more toxic to mammals than DDT. Both of these
compounds have an oral toxicity of approximately 50 mg/kg and an acute
dermal toxicity of perhaps 90 mg/kg. Endrin is the most toxic of the common
persistent chlorinated hydrocarbons with an oral toxicity to rats of
approximately 10 mg/kg, and a dermal toxicity of approximately 15 mg/kg.
It is apparent that the aquatic organisms are substantially more sensitive
than terrestrial organisms and in the early use of these products,
efforts were made to avoid exceeding acceptable levels in water. In
general, the acute toxicities of the chlorinated hydrocarbons were
recognized as legitimate risk factors when weighed against the benefits
accrued in both agriculture and public health.
By the mid 1950*s, conservationists were convinced that the organochlo-
rine insecticides were causing more damage than was generally recognized.
Evidence of reproductive failures associated with organochlorine pesti-
cides was noted in mid-1950 literature (Genelly and Rudd, 1956). The
mortality of grebes associated with DDD applications on Clear Lake,
California, demonstrated biological magnification. Many of the early
investigations of organochlorine implications in the environment were
seriously hampered by the inability to detect pesticides at levels that
havr •; '.nee been shown to produce significant, sublethal effects.
Prior to 1960, the standard analytical technique for DDT was the
Schechter-Haller method (Schechter et al., 19^5)• This technique was
adequate for residue analysis in higher organisms where accumulations
were in the part per million range but it was not adequate to measure
residue levels in water or lower organisms where accumulations were
not that high.
7
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By the early 1960's, there were many instances of wildlife mortality
due to organochlorine insecticide applications and especially DDT
applications. Rachel Carson (1962) highlighted actual and potential
environmental damages of pesticides in a popular and controversial
review which focused public attention on the problem. The Carson
review precipitated a report by the President's Science Advisory Com-
mittee (May, 19^3) that generally recognized concern for the environ-
ment. However, the report recommendations related mainly to developing
data substantiating or refuting allegations of detrimental effects.
The committee did recognize the persistence of some pesticides and
recommended that there be an orderly reduction of these materials.
In I960, Dale Coulson successfully applied the gas chromatograph
technique to residue analysis, but his colorimetric detector lacked
sensitivity desirable in residue analysis. Lovelock and Lipsky, I960,
first suggested the potential of the electron capture detector in
residue analysis. The electron capture detector was radically different
from conventional detectors and has extreme sensitivity but lacks
qualitative certainty.
During the 1960*s, literally hundreds of papers were published in
which the investigators utilized the gas chromatograph separation and
the electron capture detector for residue analysis. Hunt and Bischoff,
I960, clearly traced the effect of DDD applications on a resident
grebe population and Burdick _et al., (1964) found a correlation of
lake trout hatchery mortalities with DDT residues in the eggs. These
two studies clearly indicated that the acute toxicity was not the only
cause for concern for natural fish and wildlife populations, but that
residue accumulations had a far-reaching impact that could be attri-
buted to a wide variety of sublethal mechanisms.
The former Wisconsin Conservation Department in a survey report issued
in February, 1966, reported on pesticide residue analyses on 126 samples
from Wisconsin rivers and lakes (Wisconsin Conservation Department
Survey Report, February l4, 1966). Although most analyses were less
than one part per million of DDT and analogs, the report noted that
"every sample contained DDT and its analogs and about three-fourths
of them contained dieldrin". Hickey, 1966, working in cooperation with
the Wisconsin Conservation Department, developed residue data in herring
gulls associated with the Lake Michigan ecosystem and showed restively
higher levels attributed to food chain magnification. Hickey et al«f
(1966) found higher residues at virtual]y ail trophic levels LtTLake
Michigan than in organisms not associated with the lake.
The Bureau of Commercial Fisheries between 1965 and 1967 processed
approximately h^O fish samples from Lake Michigan and observed both
DDT, its analogs and dieldrin at levels substantially higher than
observations from Wisconsin lake fish (Carr and Reinert, 1968).
8
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In June, 1968, the Wisconsin Department of Natural Resources initiated
a survey of pesticides in invertebrate organisms as a method of evaluat-
ing point sources and regional contamination. This approach was later
revised, as a result of the Lake Michigan Enforcement Conference Pesti-
cide Committee (November, 1968) to include mussel monitoring as proposed
by Bedford et al., 1968.
In the early 1960's, several agencies initiated investigations on the
Great Lakes, particularly Lake Michigan, to evaluate the effect of
pesticides on various aspects of the lake ecology.
In January, 1968, the Federal Water Pollution Control Administration
called a Four-State Enforcement Conference on Pollution of Lake Michigan.
In March, 1968, the conferees concluded, "Pesticides are found in
Lake Michigan and its tributary streams resulting from the application
of these materials. The ever-increasing use of these materials threatens
water uses for recreation, fish and wildlife and water supplies."
The conferees took positive action toward a review and study of the
pesticide problem in Lake Michigan in the following recommendation:
"A technical committee on pesticides will be
established to be chaired by a member of the
Federal Water Pollution Control Administration
with representatives from each State. The
Committee shall evaluate the pesticide problem
and recommend to the conferees a program of
monitoring and control. The first report will
be submitted in six months to the conferees.
The States shall seek legislation to license
commercial applicators."
The technical committee completed the "Report on Insecticides in Lake
Michigan" in November, 1968. The report identified potential problems
resulting from pesticide use in the Lake Michigan Basin and made recom-
mendation for monitoring and control. The pesticide committee con-
cluded early that only insecticides appeared to warrant consideration
since there was no evidence suggesting significant amounts of other
pesticides in the Lake Michigan ecosystem. This conclusion was a
matter of priority and meant that there were immediate and pressing
problems that warranted consideration first.
Probably, there was more information available on Lake Michigan than
the other Great Lakes, but the only significant data available were
on DDT and dieldrin residues in fish. Concentration estimates of these
chemicals in the waters of Lake Michigan were essentially nonexistent
and those that were recorded were open to question because of analytical
and collection methods.
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An immediate reviev of the hazards of pesticides to the Lake Michigan
ecosystem was difficult since the quantity of pesticides in the water
had not been established. The committee, through the Bureau of Com-
mercial Fisheries, collected open water samples from both the southern
and northern basins. Split sample analyses by three independent labor-
atories gave reasonable reproducibility with the following levels of
insecticides reported:
DDT 2.0 nanograms/liter (parts per trillion)
DDD 1.0 nanograms/liter (parts per trillion)
DDE 0.5 nanograms/liter (parts per trillion)
Dieldrin 1.0 nanograms/liter (parts per trillion)
These levels of insecticides challenged the limits of detectability
of the most sensitive quantitative techniques available and left the
impression that the levels were essentially zero. However, one part
per trillion is 1.67 x 1012 molecules per liter and the samples from
open lake water, collected throughout the greater portion of the lake,
when viewed in this respect, were contaminated. Furthermore, it was
suspected that inshore areas had variable but higher concentrations.
The committee subsequently reviewed the potential hazards these
insecticides might produce in the Lake Michigan system.
The Lake Michigan Enforcement Conference Technical Committee on Pesti-
cides in its report dated November, 1968, outlined an investigational
program designed to elucidate information essential to evaluating the
impact of pesticides on Lake Michigan. In February, 1969, the Lake
Michigan Enforcement conferees accepted the pesticide committee report
which called for monitoring of chlorinated hydrocarbon pesticides in
Lake Michigan water, tributary streams, fish and other biological
specimens.
10
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SECTION IV
PESTICIDE MONITORING - LAKE MICHIGAN OPEN WATER
The pesticide committee recommended two sampling areas in the central
portion of the lake, one in the northern basin and one in the southern
basin, and three collections per year at these sites. It was further
recommended that the Chicago water intake at the Central District Fil-
tration Plant be sampled weekly for insecticides.
The original proposal planned for the City of Chicago was to provide
the analytical support to this program as part of its routine water
analysis.. Unfortunately, that support did not materialize and in
April, 1970, the Lake Michigan Basin Office of the Environmental Pro-
tection Agency began the analysis. Between April, 1970, and January,
1971> twenty-one samples were processed in accordance with the analy-
tical procedure outlined in Appendix I, Procedure 1. The data are
tabulated in Appendix I, Table 1.
The data revealed the common presence of ten chlorinated hydrocarbons.
Total DDT plus analogs recorded during the summer ranged between 2 and
66 parts per trillion, principally as DDT. These values appear high
when compared with the original lake data which suggested two parts
per trillion in open lake water collected in the summer of 1968.
The committee recognized this analytical discrepancy and subsequently
initiated through the Lake Michigan Basin Office of the Environmental
Protection Agency, a series of quality control samples so that the
analytical procedures and data reliability could be evaluated among
participating laboratories. These analytical comparisons are provided
in Appendix I, Table 2.
These data were reviewed by the committee on April 13, 1971> and the
following conclusions regarding the analytical reliability of pesti-
cide analysis on lake water were drawn:
1. The levels of chlorinated hydrocarbon pesticides present in Lake
Michigan water challenged the sensitivity of the techniques that
were employed and available at the initiation of the program.
2. The presence of interfering compounds probably accounts for the
interpretations suggesting the presence of all except DDT, DDE
and dieldrin. Phthalates and polychlorinated biphenyls are at
least two compounds known to be present in Lake Michigan waters
that produce false pesticide readings.
3. The level of DDT plus analogs in Lake Michigan water (southern
basin) is somewhere between one and ten parts per trillion. No
judgment was made on actual variability of these pesticides in
the water.
11
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k. Laboratory or sampling contamination may account for unusually
high recording since the analysis challenges the limits of detec-
tability and yet is sensitive to one part per trillion.
The Lake Michigan Basin Office of the United States Environmental
Protection Agency made 22 collections, all in the southern basin, on
11 dates during 19^9 and 1970. Appendix I, Table 3 is a summary
tabulation of those data with station locations identified in Appen-
dix I, Figure 1. The data suggest similar concentrations in surface
water and deep water for total DDT on six of ten occasions. On four
occasions the difference between surface and bottom collections was
apparent but the concentration of DDT appeared to be distributed verti-
cally throughout the water mass. These data further permit comparison
of the analyses from a single laboratory at the Chicago water intake
and other Lake Michigan waters (southern basin). A nonpaired com-
parison of the concentration of total DDT in samples from the Chicago
water intake (Appendix I, Table l) and from the southern basin of Lake
Michigan (Appendix I, Table 3) indicates a calculated student's "T"
value of 2.46, indicating a significant difference. From these data
one might conclude that even if the absolute levels recorded are in
error, there is a high probability that there is more total DDT at the
Chicago water intake than in open lake waters. Unfortunately, there
are sufficient seasonal differences in the data from the Chicago intake
to temper this conclusion.
The Wisconsin Department of Natural Resources also provided analyses
of open water of Lake Michigan as part of its general sampling program.
The data are tabulated in Appendix I, Table 4. The analytical pro-
cedures utilized by the Wisconsin Department of Natural Resources for
water analysis are described in Appendix I, Procedure 2.
Thirteen samples were collected from Green Bay, two of which contained
DDT plus analogs, at detectable levels. Typically the limit of detec-
tability would be two parts per trillion, but several of the Green
Bay samples had impaired the detectable concentration of twenty-five
open lake water samples collected from Lake Michigan between Sturgeon
Bay and Kenosha. One sample (#359) had 1,510 parts per trillion DDT
(the collection was made five miles off Sturgeon Bay so it was prob-
ably without shoreline influence and it is possible that an oil slick
from the vessel engine could have accounted for this residue level),
13 samples had less than two parts per trillion, four samples contained
five parts per trillion or less, and three had ten parts per trillion
or more. These residue levels are considerably less than those recorded
by the Lake Michigan Basin Office and are consistent with the determin-
ation of July, 1968.
Two one liter open water samples were collected with a brass kemmerer
water sampler at 100-foot intervals and composited into a single analy-
sis to be compared with the surface collection. At one station, 25
miles off Milwaukee, both the surface sample and the profile sample
12
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contained approximately three parts per trillion. A second compari-
son five miles off Kewaunee revealed no pesticides in the surface
water sample and 11 parts per trillion in the profile sample composite.
A second series of profile samples was collected off Two Rivers at
different depths in April, 1971 and analyzed individually. The four
profile samples taken between the surface and 325 feet have remarkably
reproducible levels of total DDT as shown below:
Depth (feet) Total DDT (parts per_trillion)
3 U
100 3
200 5
325 3
Profile analyses were completed after an additional sample collected
from Port Washington was processed to determine the extraction effi-
ciency. The raw water sample contained eight parts per trillion total
DDT and one part per trillion dieldrin. It was spiked and analyzed by
the procedure in Appendix I, Procedure 2 and the results are tabulated
below:
Total % %
DDT Efficiency Dieldrin Efficiency
Raw Water 8 — 1
With 10 ppt dieldrin 8.8 78%
With 20 ppt dieldrin 20.0 95$
With 20 ppt DDT 33.5 128$
With 1»Q ppt DDT 57.0 123$
Slightly more DDT was recovered than was added, suggesting the extrac-
tion efficiency is acceptable. The Wisconsin Department of Natural
Resources analyzed Lake Michigan waters from six municipal water in-
takes and there was <1 ng/1 DDT in 10 of the 22 samples processed.
Twelve samples with DDT>1 ng/1 had unusual variability, with one
sample from Milwaukee showing 221 ng/1. These data are presented in
Appendix I, Table 5« An explanation for the apparent variability
in these samples is that the water intakes are inshore and subject to
wave action and lake currents.
The Michigan Water Resources Commission analyzed 20 samples from Lake
Michigan municipal water intakes. Appendix I, Table 6 is a summary
of that data, collected from November, 1970 to April, 1971. The results
from inshore water are consistent with the Wisconsin data.
13
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The Illinois Environmental Protection Agency analyzed six water samples
from water intakes of Illinois communities. All were less than one
part per trillion total DDT and 0.1 part per trillion dieldrin, sub-
stantially lower than those levels reported by Wisconsin, Michigan,
and samples analyzed by the United States Environmental Protection
Agency. Indiana did not analyze lake water for chlorinated hydro-
carbon insecticides. WARF, Inc., sampled Lake Michigan in July, 19&9,
using private funds. This survey included water, sediment, fish and
plankton from tributary streams as well as the lake. Sixty-six sites
were sampled between July 8 and July 29, 19^9 • Open water collections
were made at 3^ of the 66 sample sites and processed in accordance with
the procedures outlined in Appendix I, Procedure 3« The data on open
water are tabulated in Appendix I, Table 8. Twenty-one of the 3^
samples revealed less than five parts per trillion total DDT, thirteen
samples exceeded five parts per trillion, and one sample exceeded
20 parts per trillion. These data are consistent with the Wisconsin
open water data.
Dieldrin concentrations obtained by the WARF survey revealed much less
variability than did total DDT, but residue levels were higher than
anticipated. This absence of variability in dieldrin concentrations
suggests that extraction efficiency is reasonably efficient or at
least consistent and that the variability observed is indeed real and
not merely analytical scatter. WARF found benzene hexachloride in
open lake waters. It appeared as a gas chromatograph peak in virtu-
ally every sample and was confirmed by thin layer chromatography tech-
niques. It seems most unlikely to be a result of pesticide applica-
tion since relatively little benzene haxachloride has been used and
furthermore, benzene hexachloride is more degradable than other chlor-
inated hydrocarbons. The WARF report (1970) calls particular attention
to the presence of unknown hexane-soluble, electron-capturing compounds
that may be part of peaks identified and quantified as pesticides by
gas chromatography. In spite of this potential source of over-estimates
of pesticides, the levels in water developed by WARF are relatively
low with a most probable number of total DDT at less than five parts
per trillion.
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SECTION V
TOTAL PESTICIDE IN LAKE MICHIGAN
In view of the analytical difficulties associated with water analysis,
it is not possible to offer confident poundage estimates of the pesti-
cides in the lake. It seems feasible, however, to offer the range
that the poundage might include. The volume of the lake is approxi-
mately 1,170 cubic miles or 108 x lO1^ pounds of water. Assuming
conservatively that the water has two parts per trillion of DDT plus
analogs (suggested by the Wisconsin and WARF data), then the total DDT
in Lake Michigan water is 21,600 pounds.
The Lake Michigan Basin Office data suggest approximately 20 parts
per trillion of DDT plus analogs as 216,000 pounds of DDT in the lake
water. Even the higher of these levels is reasonable if one consi-
ders the tonnage of DDT that was utilized in the Lake Michigan Drain-
age Basin. If the lower figure is accurate, the lake seems efficient
in purging itself of DDT, presumably through precipitation to the bot-
tom sediment where it may be biologically less active than when in the
water. A second explanation, if the lower figure is accurate, is that
pesticide contributions to the lake are really very small. It is more
likely that the truth is in a combination of relatively substantial
use in the basin over the years, relatively little contribution to the
lake itself and a comparatively inefficient precipitation and/or de-
gradation process.
15
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SECTION VI
LAKE MICHIGAN TRIBUTARY WATERS
Water and biological monitoring on tributary streams was intended for
two purposes:
1. To permit a material balance calculation of pesticide input and
loss.
2. To identify unusual pesticide sources.
The monitoring of river water was completed by the states. The ten
largest were selected for more intensive sampling because they had
the majority of flow into the lake. Two stations were selected on
the Milwaukee River to separate the urban and rural contribution.
The rivers selected are tabulated in Appendix II, Table 1 and are
geographically identified in Appendix II, Figure 1.
The Wisconsin Department of Natural Resources sampled four stations
on three rivers: the Menominee River (boundary water between Wiscon-
sin and Michigan), the Fox River, and two stations on the Milwaukee
River. In addition to these major stream sampling sites, the Wiscon-
sin Department of Natural Resources made pesticide analyses on other
Wisconsin tributary waters with lesser flow.
Composite samples were recommended to minimize the hazards of grab
sampling of stream waters but the method of composite collection was
left to the states. The Wisconsin Department of Natural Resources
used variable flow tube pumps for composite collections. Three-day
composites were collected in 20-liter, hexane-washed carboys and the
contents were sub-sampled for analysis. The results are tabulated
in Appendix II, Table 2.
1. Fox River - Brown County.
Five composite samples were collected from the Fox River, 0.1 mile
above the mouth. One sample contained 16 parts per trillion DDT.
The limit of detectability was two parts per trillion in only two
samples. Three samples had interferences that masked a low level
of DDT. In the sampling collected on May 7> 1970, there was a strong
suggestion of polychlorinated biphenyl interference. Of four
grab samples collected from the Fox River on August 27-29, 1969,
two had a strong indication that DDT and analogs were present.
The Fox River receives continual industrial and domestic waste-
water but the most likely pesticide concentration was less than
ten parts per trillion, suggesting that the sewage treatment plants
and the paper-making discharges have, at worst, a minor effect on
the DDT and dieldrin in the stream waters.
17
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2. Menominee River - Marinette County
Four collections were made on the Menominee River, 0.2 miles above
the mouth of the river. All were two to three day composites and
two parts per trillion detectability was achieved on three of the
four occasions. DDT and dieldrin were found. The collections were
all made below the Menominee-Marinette industrial and domestic
outfalls. The DDT levels are apparently less than two parts per
trillion and dieldrin levels are apparently less than 1 part per
trillion.
3. Milwaukee River - urban
Five urban collections were made at the Wells Street crossing in
downtown Milwaukee. These samples revealed unusual variability.
A sample in April had h6o parts per trillion DDT and 650 parts
per trillion dieldrin. Two other samples had 2 parts per trillion
DDT and three had 1 part per trillion dieldrin. This variabil-
ity suggests that if the tributary streams are responsible for
pesticides in the lake, water analysis cannot readily be used in cal-
culating a material balance. Intensive sampling of discrete water
strata or slug loadings would be essential to calculating a material
balance.
h. Milwaukee - rural
The Milwaukee River rural sample was taken above the City of
Grafton in Ozaukee County. Five composite collections (two days)
were made during the summer of 1970. Interfering substances were
not present and consequently the limit of detectability was at
or near two parts per trillion. Four of the five rural Milwaukee
River collections revealed less than two parts per trillion DDT.
One sample revealed l6 parts per trillion dieldrin. These data
suggest that, if the rural area is responsible for pesticide con-
tributions, slug loadings that are unpredictable and virtually
impossible to use in developing a material balance on the lake
are responsible.
The Wisconsin Department of Natural Resources provided additional compo-
site and grab sample analyses on other Wisconsin streams in an effort
to find those streams that were discharging unusual pesticide loads.
In essence, the Sturtevant tributary and the north branch of the Pike
River (Racine County) were the only collections that revealed high
levels of chlorinated hydrocarbon insecticides (Appendix II, Table 2).
Composite tributary sampling was requested of Michigan on the Grand,
Kalamazoo, Manistee, Muskegon and St. Joseph Rivers. Three composite
samples were collected on these rivers by the Michigan Water Resources
Commission and one other sample was taken on each of five non-specified
streams. The results of these analyses are tabulated in Appendix
II, Table 3> Collection and analytical procedures for composite
samples are described in Appendix II, Procedure 1. DDT and its
18
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metabolites and isomers were found in all samples at concentrations
from 41 to 184 parts per trillion. The highest concentrations were
found during the fall of 1970 in the lower peninsula streams, but
there appeared to be considerable polychlorinated biphenyl interfer-
ence in these samples. Relatively little difference in DDT concentra-
tions was found between streams or dates in the 1971 samples.
Low levels (<1 to 3 parts per trillion) of dieldrin were found in
21 of 29 stream samples.
The Indiana State Board of Health processed river water samples from
Burns Ditch, Trail Creek and the St. Joseph River. Collections of
water samples were made with a DU-1 Brail's ford automatic sampler.
The samples were set to fill a one gallon jug in 2^ hours and were
secured to the bank or a dock by a rope tie with enough of the coupling
tube in the water to assure that any fluctuations in the water level
would not interrupt the sampling. A total of 2k composite collections
was made between June and November of 1970. The results of these
analyses are tabulated in Appendix II, Table k. In general, lindane,
heptachlor, aldrin, DDE, dieldrin, endrin and DDD were not detected
at a ten parts per trillion limit of detectability. On 10 occasions,
DDT was observed at recordable levels between 11 and 47 parts per
trillion. These data are similar to those from Wisconsin streams.
The Indiana data for Trail Creek are particularly significant since
they attempted to quantify the pesticide usage in the basin at the
time of sampling. The land usage in the drainage basin was as follows:
Michigan City residential 5,203
Farmland 19, 9^ (56.0$)
Woodland and Swamp 9,972 (27.9$)
Orchards ^99 (
DDT usage was recorded only in the orchards amounting to 6 pounds,
suggesting that the DDT entering the lake from Indiana is from appli-
cations made in past years.
The Illinois Environmental Protection Agency reported on only two
grab samples from the Waukegan River and Pettibone Creek in November
of 1970. The samples had 6.2k and 1^.95 parts per trillion total
DDT (Appendix II, Table 5).
The Wisconsin Alumni Research Foundation survey of July, 1969, included
grab water samples from 62 tributary streams discharging to Lake Michi-
gan. Samples were processed in accordance with procedures outlined
in Appendix I, Procedure 3 and the data are tabulated in Appendix II,
Table 6. Polychlorinated biphenyl concentrations were not included
In this series and the limit of detectability for chlorinated hydrocar-
bons was ten parts per trillion.
19
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Of the 62 samples, 38 were less than ten parts per trillion. The
scatter in total DDT concentrations is similar to that observed in
Wisconsin data (Appendix II, Table 2). Stream water pesticide level
comparisons between Wisconsin data, Michigan data and WARF data con-
firm this scatter, as seen in the following table.
RIVER
Fox
Pike
Kewaunee
Manitowoc
East Twin
West Twin
Menominee
Peshtigo
Milwaukee
Oconto
Pensaukee
No. Br. Pike
Sheboygan
Galien
St. Joseph
Kalamazoo
Grand
Muskegon
Manistee
Boardman
Manistique
38,
10
10
2,
65,
29,
5,
Wisconsin
Analysis
Total DDT
183, 10, 10, 16
, 10, 10, 2, 2
2
1
, 10
1
1
10, 2, 2
2
85, 5, 15
2
2
60, 10, 30
2
WARF
Analysis
Total DDT
M «BM
49.1
10
10
10
27.6
53.8
10
10
10
49.1
260
Michigan
Analysis
Total DDT
V HI M
4, 19, 4
56.9 96, IT
10 113, 11, 5
10 84, 11, 2
11.4 119, 22,
10 152, 12,
24.4 184, 7, 11
10 159, 1, 65
10 11, 8, 2
12
1
The apparent scatter between Wisconsin data and WARF data with results
comparable in quantitation strongly suggests a real variability and
not merely inconsistent extraction and analysis. The Michigan data
reported in Appendix II, Table 2 has been corrected for an analyti-
cal error. The collections of May and July, 1971, are reasonably con-
sistent with WARF, Inc., and Wisconsin data.
It appears from 100 or more analyses on tributary stream waters that
it is virtually impossible to resolve the discharge levels of pesti-
cide either because of unreliable analytical procedures or because of
real variability that would require analytical support unwarranted from
a cost-benefit standpoint.
20
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SECTION VII
BIOLOGICAL MONITORING OF TRIBUTARIES
The Enforcement Conference Pesticide Committee recommended a seasonal
biological monitoring program in most tributaries during the ice-free
season to identify sources of pesticides. Living mussels were selected
as the monitor organism because they siphon a large volume of water
and have the potential ability to concentrate the chlorinated hydro-
carbons in their flesh. Wisconsin and Indiana also sampled other
resident invertebrates. The data from Michigan, Wisconsin, and Indiana
are summarized in Appendix III, Tables 1 to 3«
Wisconsin Biological Monitoring
The Wisconsin program included biological monitoring on virtually all
tributary streams in the Lake Michigan Drainage Basin. Most mussels
were collected from Ox Creek in Douglas County. Their background level
of chlorinated hydrocarbons was variable and generally low but the
absolute level was not germane, because the organisms would be permitted
to reach a new level of pesticide equilibrium that would represent
the test environment. Collection and analytical procedures are out-
lined in Appendix III, Procedures 1 and 2.
In Wisconsin, more than 50$ of the mussels analyzed for DDT and analogs
were below ten parts per billion, a concentration considered as back-
ground. Forty-five percent had concentrations between 10 and 100
parts per billion and represented a significant contamination. Three
percent of the samples exceeded 100 parts per billion. Those counties
which revealed samples with significant levels of apparent DDT included:
Door, Kenosha, Ozaukee, Racine and Sheboygan. The potential pesticide
sources on streams where mussels had high residue levels have been
evaluated and enforcement actions have been completed or are continuing.
High residue levels in mussels of Door County may result from runoff
from numerous orchards. Kenosha, Milwaukee, Ozaukee, Racine and
Sheboygan counties are relatively populous and industrialized with
numerous potential point sources that are now prohibited from using
DDT and dieldrin.
Only 13 mussel samples (1*$) contained a detectable concentration of
dieldrin, six of which exceeded ten parts per billion. The higher
levels of dieldrin were all from mussels in southeastern streams that
are industrialized. Enforcement actions have been completed and sur-
veys in 1971 will establish the success of the enforcement program.
Michigan Biological Monitoring
The Michigan Water Resources Commission processed IT mussel samples
from Michigan streams. The data are tabulated in Appendix III, Table 2.
21
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Field and laboratory techniques are described in Appendix III,
Procedure 3.
Concentrations of total DDT found in mussels ranged from 27 to 83
parts per billion with a mean of 51 parts per billion. Mussels held
in north shore streams averaged 33.2 parts per billion with no indivi-
dual collection greater than 4o parts per billion total DDT. Mussels
in the lower peninsula tributaries usually had higher concentrations
of DDT. Two other areas with relatively high concentrations of DDT
in the mussels were the Grand Traverse Bay-Leland Peninsula region
and the Lake Michigan shoreline from the Manistee River to the Black
River in Van Buren County. Mussel collections from five streams in
these regions averaged 67.6 parts per billion and four streams aver-
aged 65.0 parts per billion. All other lower peninsula streams had
concentrations in mussels ranging between 27 to h-k parts per billion.
All dieldrin concentrations were less than ten parts per billion and
most were less than three.
Indiana Biological Monitoring
Ten mussel samples were analyzed from Indiana streams discharging into
Lake Michigan (Appendix HI, Figure 1). The data are tabulated in
Appendix III, Table 3« Seven mussel samples had less than ten parts
per billion DDT, and one had ^8 parts per billion DDT.when it was
removed from Burns Ditch in July, 1970. Dieldrin was less than ten
parts per billion.
The Indiana Board of Health collected resident invertebrates from
the same streams as the mussel collections and noted little correlation
between the two.
22
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SECTION VIII
FISH MONITORING
The Enforcement Conference Pesticide Committee recommended that four
species of fish be collected in April and October at four sampling
stations on Lake Michigan. Two samples of ten fish (five of each
sex) were to be examined in accordance with the following schedule:
Station
Green Bay
Species
Alewives
Yellow Perch
Number of
Samples
2
2
2
2
Composition of
the Samples
5 males, whole body
5 females, whole body
5 males, whole body
5 females, whole body
Waukegan,
Saugatuck,
Charlevoix
Alewives
Yellow Perch
Chubs
Coho Salmon
2
2
2
2
2
2
2
2
2
2
5 males, whole body
5 females, whole body
5 males, muscle only
5 females, muscle only
5 males, muscle only
5 males, whole body
5 females, muscle only
5 females, whole body
5 females, muscle only
5 males, muscle only
The collection and analyses were done by the Bureau of Commercial
Fisheries. Data gathered by the Bureau between 1965 and 1968 were
essentially the only data available to the committee when the 1968
report was prepared. Unfortunately, the Bureau of Commerical Fish-
eries was unable to complete the schedule but did continue the moni-
toring that had been initiated in the mid-1960's and developed residue
levels over the investigational period.
Appendix IV, Table 1 is a summary of data accumulated by the Bureau
of Commercial Fisheries between 1965 and 19&9. Thg commercially impor-
tant species including lake herring, lake trout and coho salmon all
exceed five parts per million total DDT, an action level established
by the United States Food and Drug Administration. Apparently, the
0.3 parts per million dieldrin tolerance is not exceeded in these
commercially important species.
During the summers of 1969 and 1970, the Bureau of Commercial Fisher-
ies processed chub, coho salmon, and lake trout samples for total
DDT and dieldrin. Appendix IV, Table 2 is a summary of analyses from
these collections (Relnert, 19TO). Twenty-three lake trout were
23
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collected from the South Haven-Saugatuck area of Lake Michigan in
May, June and July, 1970. DDT concentrations (DDT, DDD, DDE) in nine-
teen of these fish between 558 and 660 millimeters (22-26 inches)
ranged from 10.9 to 28.1 parts per million with an average of 18.8
parts per million. Dieldrin concentrations ranged from O.l4 to 0.45
parts per million with an average of 0.27 parts per million. Three
smaller lake trout of 320, 366, and 483 millimeters contained 3.9,
6.2 and 11.1 parts per million of DDT and O.l8, 0.15, and 0.20 parts
per million of dieldrin respectively. One large fish (736 millimeters)
contained 22.7 parts per million DDT and 0.2 parts per million dieldrin.
Thirty chubs were collected on September 23 off Saugatuck, Michigan.
Each was analyzed and had DDT concentrations between 4.7 to 19.7 parts
per million with an average of 10.2 parts per million. Dieldrin con-
centrations ranged from 0.12 to 0.28 parts per million with an average
of 0.19 parts per million.
Five coho salmon from the 1968 year class were collected off Waukegan,
Illinois, in early May and measured 434 millimeters to 510 millimeters
with an average of 477 millimeters total length. Weight ranged from
493 grams to 1,232 grams with an average of 967 grams. DDT concentra-
tions were from 2.1 to 3.2 with an average of 2,8 parts per million.
Dieldrin concentrations were from 0.05 to 0.09 parts per million and
averaged 0.07 parts per million.
Twelve coho salmon collected off Ludington, Michigan, in late August
were from 568 to 730 millimeters in length (average 658 millimeters)
and weighed from 2,785 grams to 5A78 grams with an average of 3,663
grams. DDT concentrations in these fish ranged from 9-0 to 16.7 parts
per million and averaged 14.1 parts per million. Dieldrin concentra-
tions were from 0.05 parts per million to 0.18 parts per million with
an average of 0.12 parts per million. A comparison of DDT and dieldrin
concentrations between fish collected in 1970 and 1969 indicates there
has been no detectable change in the concentrations of these insecti-
cides (Appendix IV, Table 2).
The Bureau of Commercial Fisheries evaluated the analytical reliability
of pesticide measurements in fish flesh. One hundred twenty analy-
ses were made from a single collection of chubs (Coregonus hoyi).
Total DDT ranged between 6.5 and 15.3 parts per million with a mean of
9.9 (Appendix IV, Table 3). The standard deviation was 1.84, indi-
cating a coefficient of variation of 18 percent, entirely acceptable
considering the analytical difficulties involved. This program sub-
stantiates the reliability of fish sampling at least as long as analy-
ses are confined to one laboratory. The data may not be entirely
accurate but precision is good and the data can be used to make loca-
tion comparisons and establish residue trends in the fish.
Although too few fish analyses from the mid-1960's are available to
predict long-term residue trends, the data from 1969 and 1970 are suf-
ficient to be used for this purpose. The data suggest no significant
24
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difference between 19&9 an<^- 19TO between the southern and northern
basin. It is obvious there are differences among species and larger
fish tend to accumulate higher levels of DDT. Significantly, the
larger fish with the high residue levels are those species of highest
commercial value and these generally exceed the action level estab-
lished by the Food and Drug Administration.
The State of Wisconsin Department of Natural Resources also analyzed
fish samples from Lake Michigan for chlorinated hydrocarbons. The
results of that survey are tabulated in Wisconsin Department of
Natural Resources Management Report #3^ and a summary of the data is
tabulated in Appendix IV, Table k of this report. A total of 563
samples was analyzed for total DDT and dieldrin. These data also in-
dicate that the larger trout and salmon generally exceeded the five
parts per million action level established by the Pood and Drug Admin-
istration but dieldrin levels did not exceed the 0.3 parts per million
action level for that insecticide.
The Illinois Environmental Protection Agency processed 11 fish samples
from Lake Michigan and found less DDT and dieldrin than Wisconsin and
the Bureau of Commercial Fisheries (Appendix IV, Table 5). There is
no obvious explanation for this difference.
The Bureau of Sport Fisheries and Wildlife, Fish-Pesticide Research
Laboratory has long recognized the analytical complication of poly-
chlorinated biphenyls in fish pesticide residue data. Fish samples
from Lake Michigan were processed both with and without polychlori-
nated biphenyl separation. Those tabulations are recorded in Appendix IV,
Table 6. The data show that some of what is recorded as total
DDT is most likely part of the polychlorinated biphenyl complex, but
the polychlorinated biphenyl complex is not additive with the DDT
complex.
The polychlorinated biphenyl data of the Bureau of Sport Fisheries
and Wildlife indicates that future analysis will require a separation
of polychlorinated biphenyls from the chlorinated hydrocarbon insec-
ticides. Most existing residue data in fish include the polychlori-
nated biphenyls with the insecticides. This analytical combination
makes it conceivable that a future reduction in the insecticide resi-
due level could go undetected if the polychlorinated biphenyl residues
continued to increase.
Appendix IV, Table 7 is a summary of relative polychlorinated biphenyl
pesticide residue levels in fish eggs and fry and Appendix IV, Table 8
is a summary of 79 analyses for total DDT-polychlorinated biphenyl
levels.
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SECTION IX
ADDITIONAL INVESTIGATION
The Michigan Water Resources Commission recognized the potential con-
tamination of Lake Michigan from a dieldrin application intended for
Japanese beetle control and in 1968 initiated an investigation to
evaluate the impact of this specific application on the environment,
including Lake Michigan. In the fall of 1968, the Michigan Department
of Agriculture approved the application of dieldrin and chlordane on
Jj-,225 acres of Chikaming Township, Berrien County. In October, the
application was made using 6,227 pounds of dieldrin and 10 pounds of
chlordane. Residue measurements of dieldrin and chlordane were made
on water, sediments and tissues from caged mussels, both before and
after treatment on four stream locations and two control streams
(Fetterolf, 1971).
Prior to treatment, mean concentrations of chlordane were less than
0.2 parts per billion in water, less than 50 parts per billion in
sediments and less than 3^ parts per billion in mussel tissues. The
mean dieldrin concentrations prior to treatment were less than 0.02
parts per billion in water, five parts per billion in sediments and
7.8 parts per billion in mussel tissues. Following treatment, the
chlordane concentrations in water, sediments and mussels reached indi-
vidual station highs of 3.4, 22,000 and 7,530 parts per billion, re-
spectively; and the dieldrin concentrations reached 2, 2,000 and 1,137
parts per billion, respectively.
Movement of chlordane from treated land to stream waters occurred
primarily in the first three months after application. Dieldrin con-
centrations in stream waters were lower initially but persisted through-
out the 21 months of measurements.
Chlordane concentrations in stream sediments remained low but measure-
able up to one year after treatment. In October, 1969, subsequent
applications of chlordane to portions of the previously treated water-
sheds reduced the value of continued monitoring. Dieldrin was still
present in the sediments 21 months after application and at concentra-
tions between 60 and 250 parts per billion.
Nine months after the insecticide applications, mussels at test stations
contained chlordane concentrations as much as 33 times higher and
dieldrin concentrations 112 times higher than at control stations.
These levels dropped sharply by the end of the first year of sampling.
An estimated 11.3 pounds of dieldrin were contributed to Lake Michigan
in stream water in the 21 months following treatment representing
O.l8 percent of the total 1968 applications.
Bedload, allochthonous and autochthonous organic materials appeared
to play a significant but unmeasured role in the transport of insecti-
cides in the streams. The biological significance of insecticides
27
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found in this manner in Lake Michigan are unknown. Resident fish
populations were reduced in numbers and altered in species compo-
sition for as long as 12 months following the insecticide applica-
tions.
The Wisconsin Department of Natural Resources, in conjunction with
the tributary stream monitoring program, included residue analysis of
resident invertebrates. The data are included in the tabulation pre-
sented in Appendix III, Table l (Lueschow et al., 1970). Nearly 50
percent of all invertebrate sample analyses for chlorinated hydrocar-
bons fell below ten parts per billion DDT (ng/kg), a level which was
considered to be background. As with mussel samples, those inverte-
brate samples where the concentration of DDT exceeded ten parts per
billion were considered significantly contaminated and follow-up
investigations at those sites have been initated to identify point
sources.
Over 80 percent of all samples had dieldrin concentrations less than
ten parts per billion. Many samples were less than two parts per bil-
lion. The sample distribution of highest chlorinated hydrocarbon
residues was found to be remarkably consistent with the fish residue
observations by KLeinert ^t al., 1968. Where point sources were iden-
tifiable, enforcement action is underway.
In 1969, the Wisconsin Department of Natural Resources promulgated
relatively stringent restrictions on all chlorinated hydrocarbons which
effectively prohibited their use for most routine purposes (MR 8
Administrative Code). Particularly DDT and dieldrin were restricted
and essentially none was used in Wisconsin subsequent to the 1969
season. Selected follow-up biological investigations on the Wisconsin
tributaries will be conducted in 1971 to evaluate the trend in the
invertebrate population.
The Indiana Board of Health also analyzed resident invertebrates, in
addition to the mussel samples (Appendix III, Table 3). The Indiana
experience suggested that the resident invertebrates revealed signi-
ficantly higher residue levels and were the organisms of choice to
evaluate low pesticide loads in the tributary streams.
The Indiana Board of Health conducted a more extensive investigation
on Trail Creek in an attempt to establish the important sources of
DDT and dieldrin. Water samples from all stations were highest in
August at a time when stream flows were lowest and runoff was least.
Industrial sources such as dry cleaning establishments were viewed
as unlikely contributors. This left groundwater as a potential source
and analyses of artesian water correlated closely with Trail Creek
waters.
The Wisconsin Department of Natural Resources also initiated monitoring
program of municipal waste sources. Samples were both grab and 24-
hour composites, collected and returned to the laboratory for extraction.
28
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One hundred twenty-five samples were processed and are tabulated in
Appendix V, Table 1. In general, the limit of detectability was ten
parts per trillion. The most extensive monitoring was done at the
Milwaukee Jones Island plant, Grafton, Racine and Oshkosh. Milwaukee
and Oshkosh were considered typical communities with no known industrial
wastes contributing chlorinated hydrocarbons. The weekly monitoring
was initiated at the request of the enforcement personnel to cover
the spring cleaning season when stores of recently restricted DDT
would or might be discharged into a drain system. Racine, Grafton
and Portage were selected for more extensive sampling because these
communities had known sources of dieldrin. High pesticide levels
recorded at Plymouth and Sheboygan are probably influenced by poly-
chlorinated biphenyls.
The Wisconsin Department of Natural Resources in the stream monitoring
program observed unusually high dieldrin levels below wool processing
plants. A relatively comprehensive evaluation of this type of dis-
charge was made at Grafton, Wisconsin, and reported in June, 19&9
(Lueschow). This particular discharge was responsible for a dieldrin
concentration in river water of 500 parts per trillion where background
levels were less than 20 parts per trillion. The dieldrin concentra-
tion in invertebrates was approximately four parts per million and
background was 0.015 parts per million. Enforcement action was com-
pleted before mussels were placed in this section of the stream.
Information obtained in this investigation was the basis for enforce-
ment action at other similar industrial sites located in the Lake
Michigan Drainage Basin.
The Wisconsin Department of Natural Resources and Michigan Water Re-
sources Commission noted in numerous situations the presence of peaks
on the gas chromatograph that were typical of polychlorinated biphenyl
contamination. A subcommittee of the Lake Michigan Enforcement Con-
ference Pesticide Committee recommended a survey of industries sus-
pected of discharging these products. A review of potential polychlor-
inated biphenyl users in the state suggested there were far more than
could conveniently be investigated. Therefore, Michigan and Wisconsin
elected to conduct a mail survey of those industries that had poten-
tial discharges of polychlorinated biphenyls. The questionnaire used
by Wisconsin is represented in Appendix VI and a similar one was used
in Michigan.
A total of 112 questionnaires was sent and 58 were returned (52$).
Fifty-two industries reported they were not now using polychlorinated
biphenyls and Vf suggested they never had been used. Three industries
were currently using polychlorinated biphenyls and five industries
reported using them within the last three years. The Michigan Water
Resources Commission initiated ^6 questionnaires and had 22 returned
29
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It was concluded that the majority of industries that were using poly-
chlorinated biphenyls, particularly as a component in a product, were
not aware of them. In general, those sources that did not know of
polychlorinated biphenyls in a raw material or product had relatively
little potential loss or at least little loss would be on a sustained
basis. Any losses would more likely be a result of accident, clean-
up or some inadvertent loss of a raw material with polychlorinated
biphenyls as a component.
Wisconsin has not initiated further industrial investigations nor
taken enforcement action against polychlorinated biphenyl discharges
at this time. WARP, Inc., in the July, 19^9* survey provided sediment
analyses on Lake Michigan tributary rivers. The analytical procedures
are outlined in Appendix VII, Procedure 1. The data are tabulated
in Appendix VII, Table 1. In general, the chlorinated hydrocarbons
in stream sediments were consistent with stream water trends except
the characteristic benzene hexachloride peak was not observed. It
did appear that the southern portions of the lake (urbanized) had
higher chlorinated hydrocarbons in the sediment than did the northern
basin. The different sediment type between the two areas could be
partly responsible.
The Illinois Environmental Protection Agency collected seven grab
samples at sewage treatment plants tributary to Lake Michigan in
Lake County, Illinois in 1970. Total DDT values ranged from 2.5 to 11.2
parts per trillion (Appendix V, Table 2). These values are low com-
pared to results found by Wisconsin.
The Illinois Environmental Protection Agency also analyzed thirteen
sediment samples for pesticides in 1970. Samples were collected at
tributary streams, ravines, and offshore from sewage treatment plants
tributary to Lake Michigan. Total DDT values were found in the part
per million range and were comparable to values found by WARF in stream
sediments (Appendix VII, Table l).
30
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SECTION X
IMPACT OP CHLORINATED HYDROCARBON CONTAMINATION
ON THE LAKE MICHIGAN ECOSYSTEM AND ECONOMY
Hazards to Human Health
In November, 19&8, when the enforcement conference report was pub-
lished, the United States Food and Drug Administration had a "no toler-
ance" level of insecticides in fish used for human consumption. The
Bureau of Commercial Fisheries had analyzed approximately 30 species
of fish collected from Lake Michigan and had observed insecticides
in all species (Carr, 1968). In general, the levels of insecticides
in Lake Michigan fish were two to five times greater than levels ob-
served in the same species of fish from other Great Lakes and substan-
tially higher than fish collected from smaller Wisconsin lakes (KLein-
ert, et al., 1968). The committee formally requested an interpreta-
tion of this conflict from the Food and Drug Administration and was
advised that the Food and Drug Administration had no petition for a
tolerance in fish and no plans for establishing tolerances on the
initiative of the Commissioner (Food and Drug Administration correspon-
dence, June k, 1968). The Food and Drug Administration correspondence
further stated that they were in no position to comment on the effect
of pesticide contaminants on human health. The Food and Drug Adminis-
tration did say, however, that 0.3 parts per million of aldrin, dieldrin,
endrin, heptachlor or heptachlor epoxide in the edible portions of the
fish warranted legal action. In general, the Lake Michigan fish analyzed
by the Bureau of Commercial Fisheries, Wisconsin Department of Natural
Resources, and the Illinois Environmental Protection Agency do not exceed
these concentrations.
In April, 1969 the Food and Drug Administration established a five parts
per million interim guideline for DDT plus analogs in fish and began
seizing interstate commercial shipments of Lake Michigan fish. The gover-
nors of five states bordering Lake Michigan and Lake Superior subsequently
appointed an interdisciplinary committee to review the consequences of
this action. In October, 1969, »s a result of action by the Five States
Interdisciplinary Committee on Pesticides, the Michigan Health Department
transmitted a petition to the Food and Drug Administration requesting a
residue tolerance for DDT and its analogs of 15 parts per million in the
edible portion of other fish. The petition reviewed the toxicological
support for the acceptability of these levels. In early 1970, the State
of Michigan held public hearings to establish the requested levels of DDT
plus analogs in fish shipped within the State of Michigan. The Food and
Drug Administration in July, 1970, rejected the Michigan petition for the
increased federal tolerance on DDT plus analogs because DDT is a potential
carcinogen (Food and Drug Administration correspondence, July 16, 1970).
31
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Impact of Insecticide Residues on Commercial Fishing
The Food and Drug Administration interim guideline of five parts per
million DDT plus analogs on fish shipped in interstate commerce will
have essentially no effect on the commercial fishing of Lake Erie or
Lake Ontario where concentrations are generally less than five parts
per million of DDT plus analogs. Lake Michigan fish, on the other hand,
where the principal commercial species are coho, chubs and whitefish,
have DDT concentrations which generally exceed the five parts per million
interim guideline. The Bureau of Commercial Fisheries, 1966, catch
value records indicate a commercial catch value on Lake Michigan of
$2,8l6,000 (Reinert, 1970). By applying the five parts per million DDT
interim guideline to this catch, approximately 80$ of the Lake Michigan
commercial catch is nonmarketable in interstate commerce. Approximately
eight percent of the commercial catch from Lake Superior would exceed
the five parts per million DDT maximum (lake trout) and be unacceptable
for interstate commerce.
Lake Superior chubs, whitefish and lake herring would not be affected
by the interim guideline since residue levels in these species are less
than five parts per million. Based on the 1966 catch estimates for the
entire Great Lakes, approximately k-2. percent of the commercial catch
would be unacceptable for interstate commerce.
The impact of pesticide residues on the commercial fishery is only one
in a series of difficulties encountered by the commercial fishing indus-
try on the Great Lakes. Commercial fishing for lake trout, chubs, her-
ring and walleyes has been reduced in recent years due to sea lamprey
predation, over-exploitation and alewife competition.
Impact of Insecticide Residues on Sport Fishing
The sport fishing for coho salmon and other anadromous fishes has been
burgeoning in the last three to four years, despite the publicity of
pesticide residues in these species. Since sport fishing has undergone
such a dramatic increase, it is virtually impossible to establish the
trend that might have been characteristic if the insecticide residues
had not been involved.
It seems unlikely that pesticide residues will influence sport fishing
when the objective is for sport or trophy only and fish are readily
available. Sport fishing for food, however, could be influenced by the
well-publicized seizures of "contaminated" fish. A Michigan survey of
salmon fisherman expenses (19&7) indicated a trip cost of $19.50 per angler
day. In view of this relatively high cost of sport fishing, it seems more
than likely that sport fishing is predicated on sport and trophy rather
than food. Recent publicity regarding filleting and cooking techniques and
the safety factor associated with the five parts per million residue level
may also have contributed to a general disregard of the contaminants among
sport fishermen.
32
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Although the sport fishermen appear to be disregarding the implica-
tions of insecticide residues in Great Lakes fish, it remains to be
seen if the general public, that acts through legislative processes
to support the sport fishery, will also ignore the residue implica-
tions. The state legislatures and the Great Lakes Fishery Commission
will be responding to the general public as well as to the sportsmen.
Hazards to Fish Production
The effects of organochlorine pesticides on fish production have been
studied by numerous investigators, including Allison et al., 1964;
Boyd, 1964; Burdick _et al., 1964; Cuerrier et al., 1957; Johnson, 1967;
Macek, 1968; and Johnson and Pecor, 1969. Allison (1964) found a high
mortality of cutthroat trout sac fry whose parents had been exposed
to 0.3 and 1.0 parts per million DDT in water for 30 minutes once
each month for about 15 months or to one mg/kg in the food once each
week for about 15 months. There was no mortality at lower concentra-
tions.
Boyd (1964) observed abortion of young in mosquitofish (Gambusia af-
finis) which survived exposure to concentrations of organochlorine
pesticides that killed other mosquitofish.
Several researchers have found that organochlorine pesticides accumu-
lated in the eggs of "normal" adult fish may be toxic to the fry during
the last stages of yolk absorption or when the fry begin to feed
(Burdick, 1964; Cuerrier, 196?; Johnson, 196?; and Macek, 1968).
Johnson and Pecor (1969) reported an unusual sac fry mortality which
occurred in Michigan trout hatcheries in 196?. The syndrome was par-
ticularly apparent on coho salmon fry that had progressed to the latter
stages of yolk sac absorption. Eggs taken from Lake Michigan brood
stock had a substantially greater sac fry mortality than eggs taken
from Lake Superior or far west brood stock. The investigators noted
that the concentration of DDT and analogs of Lake Michigan brood stock
eggs were three to five times higher than Lake Superior brood stock
eggs. They further suggested that higher concentrations of DDT were
found in affected fry than in normal fry from the same parent. The
concentration of DDT and analogs (wet weight) from Lake Michigan fish
ranged between 1.09 and 2.76 parts per million, with the higher concen-
tration associated with a higher mortality in the sac fry. Johnson
and Pecor (1969) further postulated a mechanism that could account
for the mortality. It was observed at the time of fry mortality that
the last fraction of yolk present in the gut contained 6 to 12 times
more DDT than the general body tissues and that absorption of this
most concentrated fraction could have killed the fry. Johnson has
continued to monitor the hatchery mortalities in 1968 and 1969. In
September, 1970, Johnson suggested the results were inconsistent and
he could not establish a distinct correlation between mortalities and
DDT concentrations. He further observed that the question is academic
33
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since the hatcheries are able to rear adequate numbers of fry despite
a loss during yolk sac absorption.
The recorded observations on lake trout and the observed effects on
coho salmon still suggest a real threat to the Lake Michigan lake
trout population. Even if the lamprey control programs are success-
ful, there still appears to be a strong possibility that the lake
trout population will be unable to recover due to fry mortality.
Hazards to Bird Reproduction
Hickey et al., (1966) working in the Green Bay area concluded that
there were DDT and analogs in all trophic levels of the Lake Michigan
ecosystems, and further suggested concentration factors for several
trophic stages. The most striking aspect of this work was not the
concentration factor or the fact that the organochlorlne pesticides
were ubiquitous but was the quantity of organochlorlne present in the
various trophic levels of the Lake Michigan ecosystem. Keith (1966)
suggested that DDT residues in Green Bay herring gulls were related
to lower egg hatchabllity, but had little effect on chick survival.
He concluded the data were not consistent with earlier works where
DDT fed in diet of quail and pheasant affected chick survival and not
hatchability. Hickey (1968) makes a strong case of the correlation
between the introduction of DDT and the simultaneous demise of raptorial
bird populations due to metabolic reproductive failure. Current re-
search in Wisconsin by Hickey and others suggests that the nesting
populations of the bald eagle in Lake Michigan and Lake Superior have
been adversely affected by chemical pollutants.
Reproductive Failure in Mink
The Mink Ranchers Association representatives have suggested that
mink that were fed Lake Michigan fish have failed to reproduce. The
implications have been that Lake Michigan fish have higher pesticide
levels and could be responsible for the reproductive failure.
Mr. H. F. Travis, United States Department of Agriculture, has recently
attempted to correlate the reproductive failure in mink with insecti-
cide levels and has suggested that reproductive failures can Indeed be
induced by feeding Lake Michigan coho salmon and by feeding other
foods spiked with DDT plus analogs and dieldrin at a concentration
comparable to the residue levels in Lake Michigan fish. This work is
yet unpublished, along with other investigations currently under way
to resolve this question.
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SECTION XI
STATUS OF LEGISLATION AFFECTING PESTICIDE USAGE
IN THE LAKE MICHIGAN BASIN
Recommendation Number 2 of the Lake Michigan Enforcement Conference
Pesticide Report of November, 1968, called for appropriate legislation
to regulate Insecticide usage. Appendix VIII Is a summary of the status
of legislation germane to insecticide use control In the five states
as compiled by the Governors' Five State Interdisciplinary Committee on
Pesticides. The basic residue problem on Lake Michigan has been with
chlorinated hydrocarbons and particularly DDT. Illinois, Michigan and
Wisconsin all have restrictions on the use of DDT. Wisconsin further
considers most of the chlorinated hydrocarbons as restricted materials
typically requiring special permit for application. At this time,
Michigan, Illinois, and Indiana have some legislation that regulates
commercial applicators while Wisconsin has not yet enacted this type
of legislation.
The State of Illinois has enacted rules jointly with the Department
of Agriculture and the State Board of Health that prohibit the use
of DDT except by permit and specifically prohibit the use of DDT for
Dutch elm disease control effective January 1, 1970. This regulation
should prevent DDT contamination of Lake Michigan since it restricts
sale and urban use as well as agricultural use. Other chlorinated
hydrocarbon insecticides are not regulated.
The State of Indiana regulates pesticides through the State chemist's
office. Senate Enrolled Act Number 559, 1971; authorizes the Indiana
State chemist to identify restricted pesticides and prepare rules and
regulations concerning these pesticides. The identification of the
restricted products and publication of rules have not yet been com-
pleted, but the legislative intent seems adequate to protect Lake
Michigan from chlorinated hydrocarbon insecticides.
Michigan was the first Lake Michigan state to enact legislation restrict-
ing the sale of DDT. This legislation did not pertain to use or trans-
port so recently the State Legislature has passed an amendment to its
economic poison law (effective January 1, 1972) that provides for a list
of restricted use pesticides as well as licensing of restricted use
pesticide dealers. The State agencies are currently in the process
of promulgating rules to Implement the intent of this Legislature.
35
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SECTION XII
ACOOWLEDGEMEWTS
This report to the Lake Michigan Enforcement Committee was prepared by
the Pesticide Committee in response to Recommendation Number 15 of the
conference held in January and March, 1968. The first report was
submitted In November, 1968, by the following committee representatives.
Dr. Donald Mount, Federal Water Pollution Control
Administration, Chairman
Mr. Benn J. Leland, Illinois Sanitary Water Board
Mr. Stephan Kin, Indiana Water and Waste Laboratory
Mr. John Favinger, Indiana Natural Resources Department
Mr. Carlos Fetterolf, Michigan Water Resources
Commission
Mr. Lloyd A. Lueschow, Wisconsin Department of Natural
Resources
Mr. John Carr, Bureau of Commercial Fisheries
Dr. Oliver Cope, Bureau of Sport Fisheries and Wildlife
In the three years of this study, the committee membership has reflected
the personnel changes inherent in a long-term study. The present
committee hereby presents to the Enforcment Conference the current
report of the committee. The report has been prepared by Lloyd A. Lueschow
of the Wisconsin Department of Natural Resources and reflects the Input
of all four state representatives, as well as the Federal agencies
participating in the pesticide committee. The present committee
members include:
Dr. Donald Mount, United States Environmental Protection
Agency, Chairman
Mr. Lloyd A. Lueschow, Wisconsin Department of Natural
Resources
Mr. Stephan Kin, Indiana Water and Waste Water Laboratory
Mr. John Favinger, Indiana Natural Resources Department
Dr. Jim Bedford, Michigan Water Resources Commission
Mr. John Carr, Bureau of Sport Fisheries and Wildlife
Dr. Dick Schoettger, Bureau of Sport Fisheries and
Wildlife
Mr. Robert Schacht, Illinois Environmental Protection Agency
37
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The committee received invaluable counsel and guidance from a substan-
tial number of representatives of other private and public agencies.
Particular mention should be made of the contribution provided by Dr. John
Birdsall, Wisconsin Alumni Research Poundatlonj John Neal, Ontario Water
Resources Commission and LeRoy Scarce. United States Environmental
Protection Agency.
The rapid and extensive accumulation of data by the state agencies
involved was made possible by the Environmental Protection Agency
Research Grants EYV, EYS, EPU, ESP 16050 to each of the participating
states. This report also serves as partial fulfillment of the grant
obligation to the Environmental Protection Agency by Wisconsin, Indiana,
and Michigan. Illinois has elected to provide a separate report at a
later date.
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SECTION XIII
REFERENCES
1. Cottam, Clarence and Elmer Higgins. I9k6. DDT: Its Effect
on Fish and Wildlife. United States Department of Interior,
Circular II.
2. Metcalf, Robert L. 1948. The Mode of Action of Organic Insec-
ticides. Chemical-Biological Coordination Center - National
Research Council, Washington, D.C.
3. Rudd, Robert L. and Richard E. Genelly. 1956. Pesticides:
Their Use and Toxicity in Relation to Wildlife. State of Cali-
fornia, Department of Fish and Game. Game Bulletin No. 7.
k. Pesticide Information and Safety Manual. 1968. University of
California, Division of Agriculture Sciences.
5. Genelly, Richard E. and Robert L. Rudd. 19!?6. Effects of DDT,
Toxaphene and Dieldrin on Pheasant Reproduction. Auk, 73(4).
6. Schechter, M. S., S. B. Soloway, R. A. Hayes, and H. L. Haller.
1945. Indiana Eng. Chem. Analy. Edition 17 (11).
7. Carson, Rachel. 1962. Silent Spring. Houghton Mifflin Company,
Boston.
8. President's Science Advisory Committee - Panel on the Use of
Pesticides. 1963. Report on the Use of Pesticides, Chemical
and Engineering News. Volume 4l, May 27, 1963.
9. Coulson, Dale M., Leonard A. Cavanagh, John E. Devries, and
Barbara Walther. 1960. J. Agriculture and Food Chemistry.
Volume 8, No. 5, pp. 399-402.
10. Lovelock, J. E. and S. R. Lipsky. I960. Electron Affinity Spec-
troscopy - A New Method for the Identification of Functional
Groups in Chemical Compounds Separated by Gas Chromatography.
Journal American Chemical Society. Volume 82, page 431.
11. Hunt, Eldridge G. and Arthur I. Bischoff. I960. Inimical Ef-
fects on Wildlife of Periodic DDD Applications to Clear Lake.
California Fish and Game. Volume 46, pp. 91-106.
12. Burdick, G. E., E. J. Harris, H. J. Dean, T. M. Walker, Jack
Skea and David Colby. 1964. The Accumulation of DDT in Lake
Trout and the Effect of Reproduction. Transactions of the Ameri-
can Fisheries Society. Volume 93> No. 2.
13. Wisconsin Conservation Department Survey Report, February 14,
1966. Pesticide Residues in Wisconsin Fish.
39
-------
lA. Hickey, Joseph J. 1966. On the Relationship of Herring-Gull
Reproduction to Pesticide Residues in Lake Michigan. Bureau of
Sport Fisheries and Wildlife, Fish and Wildlife Service, Department
of the Ontario Contract No. 1^-16-0008-724.
15. Hickey, Joseph J., J. A. Keith and Francis B. Coon. 1966. An
Exploration of Pesticides in a Lake Michigan Ecosystem. Journal
of Applied Ecology, Volume 3 (Supplement) Pesticides in the Envir-
onment and Their Effect on Wildlife.
16. Carr, John F. and Robert E. Reinert. 1968. DDT and Dieldrin
Levels in Great Lakes Fish. Eleventh Conference on Great Lakes
Research, Special Report No. 5.
IT. Bedford, J. W., E. W. Roelofs and M. J. Zabek. 1968. The Fresh-
water Mussel as a Biological Monitor of Pesticide Concentrations
in a Lotic Environment. Limno. and Oceanog., 13:118-126.
l8. Lake Michigan Enforcement Conference Proceedings. March, 1968.
19. Lake Michigan Enforcement Conference Pesticides Committee. Report
on Insecticides in Lake Michigan. November, 1968.
20. Reinert, Robert E. March, 1970. Pesticide Concentration in Great
Lakes Fish, Pesticide Monitoring Journal. Volume 3> No. 4.
21. Poff, Ronald J. and Paul E. Degurse. 1970. Survey of Pesticide
Residues in Great Lakes Fish. Wisconsin Department of Natural
Resources Management Report
22. Fetterolf, Carlos M. , Jr., John L. Hesse, James W. Bedford and
Bonnie M. Sanders. 1971 • Pesticide Monitoring of the Aquatic
Environment; Michigan Portion of Great Lakes Basin. Michigan
Department of Natural Resources. January 30 , 1971 .
23. Lueschow, Lloyd A., Donald R. Winter and Douglas J. Dube. December,
1970. Survey of Pesticides in Aquatic Macro-Invertebrate Benthic
Organisms in Wisconsin Waters Tributary to Lake Michigan. Wisconsin
Department of Natural Resources.
24. KLeinert, Stanton J., Paul E. Degurse and Thomas L. Wirth. 1968.
Occurrence and Significance of DDT and Dieldrin Residues in Wis-
consin Fish. Technical Bulletin No. *H, Wisconsin Department of
Natural Resources.
25. Indiana Pesticide Monitoring Program Interim Report. 1970*
Indiana State Board of Health, Division of Water Pollution Control.
26. Lueschow, Lloyd A. June, 1969. Report of Investigation of Indus-
trial Waste, Grafton, Wisconsin. Wisconsin Department of Natural
Resources.
ko
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27. Food and Drug Administration Letter Dated June 4, 1968, to
Dr. Donald Mount, Chairman, Pesticides Committee of the Lake
Michigan Enforcement Conference.
28. Food and Drug Administration Letter Dated July 16, 1970, to
Dr. Kenneth R. Wilcox, Michigan Department of Public Health.
29. Allison, D., B. J. Kallman, 0. B. Cope and C. C. VanValin. 1964.
Some Chronic Effects of DDT on Cutthroat Trout, United States
Bureau of Sport Fishery, Wildlife Resources Report No. 64, p. 30.
30. Boyd, C. E. 1964. Insecticides Cause Mosquitofish to Abort,
Progressive Fish Culturist 26(3): 138.
31. Burdick, G. E., E. J. Harris, H. J. Dean, T. M. Walker, J. Skea
and D. Colby. 1964. The Accumulation of DDT in Lake Trout and
the Effect on Reproduction. Transactions of the American Fisheries
Society, 93(2): 127-136".
32. Cuerrier, J. P., J. A. Keith and E. Stone. 1967. Problems with
DDT in Fish Culture Operations. Le Naturaliste Canadian, Volume 94:
315-320.
33. Johnson, H. E. 1967. Effects of Endrin on Reproduction in a
Freshwater Fish (Oryzias latipes), Ph. D. Thesis, University of
Washington, p. l49.
34. Macek, K. J. 1968. Reproduction in Brook Trout (Salvellnus
fontinalis) Fed Sublethal Concentrations of DDT. Journal of Fish-
eries Research Board of Canada, 25(9): 1787-1796.
35. Johnson, H. E. and C. Pecor. 1969. Coho Salmon Mortality and
DDT in Lake Michigan. Transactions of the Thirty-fourth North
American Wildlife and Natural Resources Conference, 159-166.
36. Johnson, H. E. Personal Correspondence Dated September 17, 1970.
37. Keith, J. A. June, 1966. Reproduction in a Population of Herring
Gulls (Larus argentatus) Contaminated by DDT. Journal of Applied
Ecology 3 (Supplement) 57-70.
38. Hickey, Joseph J. and Daniel W. Anderson. October, 1968. Chlori-
nated Hydrocarbons and Egg Shell Change in Raptorial and Fish-
Eating Birds, Science.
39« Wisconsin Alumni Research Foundation. January, 1970. Progress
Report No. 1. Lake Michigan Pesticide Investigations, WARF
Institute, Inc.
4l
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APPENDIX I
CHLORINATED HYDROCARBON INSECTICIDES
IN LAKE MICHIGAN WATERS
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APPENDIX I, PROCEDURE 1
ANALYTICAL TECHNIQUES USED IN LAKE WATER ANALYSES
BY THE LAKE MICHIGAN BASIN OFFICE
OF THE UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
ANALYTICAL CONDITIONS
All samples were analyzed according to the "FWPCA Method for Chlori-
nated Hydrocarbon Pesticides in Water and Wastewater-1966" with Lake
Michigan Basin Office modification (employing tall form 600 ml beakers
for concentration of samples under a filtered air stream, instead of
the Kuderna-Danish concentration system).
AQUEOUS SEPARATION PROCEDURE
The total volume of each sample (one gallon) was extracted twice with
2^0 ml of 15 percent ethyl ether in hexane. Then ito ml of sodium
sulphate-saturated water was added to each sample, then extracted with
2^0 ml of hexane. Extracts were then dried with anhydrous sodium
sulphate (prerinsed with hexane), combined and evaporated to approxi-
mately *K) ml. Extracts were then placed on a florisil column.
The column was pre-eluted with 75 ml of hexane. The pre-eluted extract
was discarded and just prior to exposure of the sodium sulphate layer
to air, the Uo ml of extract was placed on the column and eluted with
200 ml of six percent ethyl ether in hexane and then with 200 ml of
15 percent ethyl ether in hexane. The eluates are collected in 600
ml tall form beakers and evaporated at room temperature under a stream
of carbon filtered dried air to 10 ml or less. The concentrates were
then quantitatively transferred to a graduated 10 ml centrifuge tube/
ground glass stopper. The eluate fraction was further concentrated to
approximately 0.2 ml.
GAS LIQUID CHROMATOGRAPHY
Reasonably positive indentification of a pesticide residue was indi-
cated by analyzing samples on two different gas chromatographic columns,
To economize time of analyses, two gas chromatograph units were em-
ployed, set up as follows:
1. Tracor Instruments, Inc., Model MT-220 Instrument Conditions:
Column: (Semi-Polar); Glass - 6 feet by £ inch outside diameterj
Support-Chromosorb W (HP); 80/100 mesh; Liquid Phase - 5 percent
QP-1, 3 percent DC-200 LMBO Nos. Jlkl and 7678 (2/2V71). Carrier
Gas: Nitrogen, prepurified, Matheson; 55 ml per minute. Temper-
atures: Injection - 250° C; Column Oven - 200° C; EC Detector
(Ni63) - 360° C.
hk
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MicroTek, Inc., Model GS-200R Instrument Conditions:
Column: (Non-Polar); Aluminum - 6 feet by -jj- inch outside diameter;
Support - Gas Chrom Q (60-80 mesh); Liquid Phase - OV-1T; Carrier
Gas: Nitrogen, prepurified, Matheson, 80 ml per minute. Tempera-
tures: Injection - 250° C; Column Oven - 165° C; EC Detector
(Ni.63) - 350° c.
Approximately 1-3 *O- of sample was injected into the inlet block
or column of the gas chromatograph unit for analysis. Quantitation
was accomplished by employing peak-area with base line correction
procedure calculation. Two water samples were spiked with known quan-
tities of the various pesticides and for DDT and analogs and dieldrin.
The recovery efficiencies are tabulated.
Lake Michigan Water 12/14/70 (ng/l)
Analysis Amount Est Analysis $
Parameter 1 _ 2_ Added Total 1 _ 2 _ Av Recovery
p, p'-DDE 3.7 -- 5.4 9.1 7.3 7.1 7.2 79
o, p'-DDE 6.4 — 5.4 11.8 15.0 17.4 16.2 137
o, p'-DDD 2.8 — 5.4 8.2 5.2 5.8 5.5 67
p, p'-DDT 6.5 — 8.1 14.6 15.0 12.7 13.9 95
o, p'-DDT 3.0 — 8.1 11.1 8.5 5.9 7.2 65
total DDT 22.4 — 32.4 54.8 4l.o 48.7 ^3.8 90
Dieldrin 5.6 — 5.4 11.0 10.3 5.8 74
45
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WISCONSljN
ILLINOIS
MICHIGAN
INDIANA
APPENDIX I, FIGURE 1
LAKE MICHIGAN BASIN OFFICE OPEN LAKE SAMPLE STATIONS
-------
APPENDIX I, TABLE 4
PESTICIDES IN LAKE WATERS (ppt)
DATA FROM THE WISCONSIN DEPARTMENT OF NATURAL RESOURCES
Location
LAKE MICHIGAN - GREEN BAY
Entrance Light
Sturgeon Bay Area
In Sturgeon Bay
Washington Island Area
Washington i^lary. Area
Jill i son Bay Area
LAKE I j.CI!j.'JAl;
0.5 mi. off Sturgeon Bay
0.5 mi- off Sturgeon Bay
0.5 ml. off Sturgeon Bay
0.5 ml . off Sturgeon Bay
*5.0 mi. off Sturgeon Bay
5.0 mi. off Sturgeon Bay
5.0 mi. off Sturgeon Bay
5 rat . SE Kewaunee
5 mi. SE Kewaunee
*2 mi. off Two Creeks
7 mi. off Two Rivers
10 mi. off Two Rivers
0.5 mi. off Manitowoc
0.5 ml. off Manitowoc
0.6 mi. off Manitowoc
NE Sheboygan
0.5 mi. off Milwaukee
0.5 mi. off Milwaukee
25 mi. off Milwaukee
25 ml. off Milwaukee
0.5 ml. off Kenosha
0.5 mi. off Kenosha
0.5 mi. off Kenosha
5.0 mi. off Kenosha
5.0 mi. off Kenosha
Lab
No.
362
480
481
657
664
363
484
658
665
659
364
!!79
660
360
1*85
656
663
359
486
655
776
780
162
782
896
361
483
661
781
330
478
7T9
777
371
477
662
372
472
Limit of DDT
Date Detectability Complex
6/04/69
7/21/69
7/21/69
8/19/69
9/23/69
6/05/69
7/22/69
8/19/69
9/23/69
8/19/69
6/05/69
7/22/69
8/21/69
6/05/69
7/22/69
8/19/69
9/23/69
6/05/69
7/22/69
8/19/69
6/11/70
6/11/70
11/12/68
6/11/70
8/05/70
6/06/69
7/23/69
8/22/69
6/11/70
6/18/69
7/25/69
6/11/70
6/11/70
6/18/69
7/25/69
9/22/69
6/18/69
7/25/69
5
2
S
2
2
2
2
70
10
2
2
2
10
2
2
2
2
2
2
2
2
5
2
2
2
2
1
1
2
2
2
1
1
none
4.8
17.5
none
none
none
none
none
none
22
5-5
none
none
1,510
21.1
none
11
none
20.5
none
2
none
none
none
6
none
3
3
none
5.2
none
none
3
Dieldrin Remarks
none
2.5
none
none
none
none
none
none
none
none
none
none
none
none
none
3
none
none
none
none
none
none
none
none
none
none
none
none
none
none
Ragged base line
GC peak where Aldrin would
be identified
GC peak where Kept. Epoxide
would be identified
Insufficient instrument
injection
GC peak where Lindane would be
identified (See 663 for curve
comments)
Interference
GC peak where Aldrin vould be
identified
No Strip Chart.
Interference
Interference
Base lint? interference
Interference
Drifting base line. Peak of
Heptachlor
13.6 ppt DDT & 75 ppt DDE
Profile
Peak where Aldrin would be
identified
325 feet deep
Peak where Heptachlor Epoxide
would be identified
6 ppt as DDE: trace DDT (pp)
Peaks at Lindane & Heptachlor
Epoxide
Interference
Profile sample: 3 ppt as DDE
Profile sample:3 ppt as DDE
Peaks at Lindane & Heptachlor
Epoxide
Peak at Heptachlor Epoxide
50
-------
APPENDIX I, PROCEDURE 2
ANALYTICAL TECHNIQUES USED IN LAKE AND
RIVER WATER ANALYSIS BY THE WISCONSIN DEPARTMENT OF
RESOURCES - LABORATORY OF HYGIENE
Water samples were collected in hexane mixed glass bottles with caps
protected by aluminum foil. They were transported to the Madison
laboratory where extraction and analyses were conducted. The time
between collection and analysis varied between one day and two weeks.
The general procedures included hexane extraction, florisil column
clean up and gas chromatographic identification and quantitation.
Some samples were confirmed with thin layer chromatography and some
were confirmed by mass spectrophotometer analysis at the Athens labor-
atory of the United States Environmental Protection Agency.
Water samples of 2,000 ml were extracted three times in teflon stop-
cock separatory funnels, first with 100 ml of hexane twice with 50
ml hexane. If an emulsion appeared it was broken by hot and cold
water treatment, the addition of propanol or addition of sodium chlor-
ide. The three hexane extracts were combined and dried with sodium
sulphate, then concentrated to 10 ml with a dry air stream on a 38° C
water bath. The 3.0 ml hexane extract with pesticide residue was flor-
isiled at this point to separate fats, pigments and other contaminants.
The extraction procedure efficiently partitions fats and oils from
the sample into the hexane carrier solvent. The fats and oils con-
tain most of the insecticides present to the organisms due to their
solubility in the fats and oils and their insolubility in water.
Along with the lipid soluble pesticides, the extraction process also
extracts other organic compounds that could have a high electron af-
finity and thus cause erroneous electron capture detector responses.
To remove the interfering substances from the hexane extract, absorp-
tion chromatography is used. The absorption material is a commercial
diatomaceous earth purchased as florisil. The florisil is activated
by heating to 100° C for 24 hours, followed by deactivation to a spec-
ific level by adding one to three percent water. This enables efficient
separation of the insecticides on the florisil column. The column
holder is a pyrex glass tube with a 22 mm inside diameter and of
adequate length to contain 300 ml of hexane solvent. It has fritted
glass and teflon stopcock at the bottom to permit a regulated flow
through the system. One-half inch of sodium sulphate is added to the
column and ko grams of deactivated florisil which is covered with
another one-half inch of sodium sulphate.
The florisil column is prewashed with 50 ml of hexane. The concen-
trated hexane extract of the sample is then added to the column.
The sample container is washed with 200 ml of six percent ethyl ether
and 9^ percent hexane solvent mixture. This mixture is added to the
florisil column and eluted through the column at a rate riot to exceed
51
-------
five ml per minute. When the column is almost empty, 200 ml or 20
percent ethyl ether and 80 percent hexane is added to the florisil
column. Each one of the elutions (9^/6, 80/20) is collected and
analyzed separately.
The two elutions and properly deactivated florisil will remove most
interferences and separate some of the insecticides. The first elu-
tion (six percent ethyl ether) vill contain:
Lindane DDT
EEC Perthane
Kelthane Methoxychlor
Aldrin Toxaphene
Heptachlor Strobane
Heptachlor Epoxide Chlordane
DDE DDD (TDE)
The second elution (20 percent ethyl ether) will contain:
Dieldrin Endrin
Lindane (Trace) Kelthane (Trace)
The two elutions are concentrated with a dry air stream to 10 ml or
less, depending on the suspected insecticide concentration in the
sample. These concentrated samples are at this time ready for injec-
tion into the gas chromatograph.
The gas chromatograph used for the analyses was a Hewlett Packard,
dual channel (Model It02). Both channels were equipped with Ni^3
electron capture detectors. The instrument columns were two to six
feet V-tubes of pyrex glass. These columns were packed with three
percent OV-17 (Phenyl methylsilicone, 50 percent phenyl), ten percent
silicone DC-200 (12,500 cstk), and ten percent silicone DC QF-1 on a
solid support of gas chrom Q (60-80 mesh) either singly or in varying
concentrations of each.
The analysis of environmental samples is a problem because the extrac-
tion process removes substances from the sample which the florisil
cleanup misses and these substances are detected by electron capture
systems and cause interferences.
One of the most common interferences with the analysis of the DDT
complex is the polychlorinated biphenyl (PCB). Because of the struc-
tural similarity between PCB's and some pesticides, the electron cap-
ture detector will give the same response for both. The PCB's have
210 isomeric formations that are detectable and the DDT complex has
only six formations that could be detected with electron capture
detector.
-------
Municipality
APPENDIX I, TABLE 5
WATER TREATMENT PLANTS (ppt)
Lab Date Limit of DDT
Ho. Collected Detect. Complex Dieldrin
SHEBOYGAN COUNTY
Sheboygan
Remarks
BROWN COUNTY
Green Bay
Green Bay
Green Bay
Green Bay
Green Bay
KENOSHA COUNTY
Kenosha
Kenosha
Kenosha
MILWAUKEE COUNTY
Milwaukee:*
Milwaukee
Milwaukee
Milwaukee
Milwaukee
Milwaukee
Milwaukee5
Milwaukee
Milwaukee
Milwaukee
RACINE COUNTY
Racine
Racine
Racine
785
786
877
887
888
806
807
808
759
760
761
762
81+9
850
765
763
853
85^
802
803
8o4
6/11/70
6/11/70
7/22/70
8/14/70
8/lVTO
6/23/70
6/23/70
6/23/70
6/05/70
6/05/70
6/05/70
6/05/70
7/10/70
7/10/70
6/05/70
6/05/70
7/10/70
7/10/70
6/23/70
6/23/70
6/23/70
10
2
2
1
1
1
1
1
2
2
1
1
1
1
1
2
1
1
110
15
30
none
none
none
25
3
20
20
none
221
none
none
none
28
none
none
9
8
11
none
none
none
none
none
none
none
none
none
PCB's
none
PCB's
none^
none
PCB's
none
none
none
none
none
none
none
none
Raw
Settled
Final
Settled
Final
Raw
Settled
In plant
Raw
In plant,
PCB's
Final
Floe
Final
Final
Final
Raw
Filtered
Final
In plant
Finished
Raw
7/10/70
none
none
Final
Data from the Wisconsin Department of Natural Resources
2Peak at Heptachlor Epoxide
3Howard Street
Fading base line with numerous peaks
5Linnwood Water Treatment Plant
53
-------
APPENDIX I, TABLE 6
PESTICIDES IN LAKE MICHIGAN MUNICIPAL WATER INTAKES*, 1970
(Concentrations in ppt)
Location Date Sampled DDE TDE o,p-DDT p,p'DDT Total Dieldrin
DDT
Bridgeman
Benton Harbor
St. Joseph
South Haven
Holland
Wyoming
Grand Rapids
Grand Haven
St. Joseph
Benton Harbor
South Haven
Holland
Grand Rapids
Muskegon
Ludington
Traverse City
Escanaba
Gladstone
Menominee
Bridgeman
11/24/70
12/10/70
12/10/70
12/10/70
12/10/70
12/10/70
12/10/70
12/10/70
2/16/71
2/16/71
3/09/71
4/14/71
4/14/71
3/09/71
3/09/71
3/02/71
2/25/71
2/25/71
3/23/71
4/14/71
«!
<1
4
<1
-------
APPENDIX I, TABLE 7
PESTICIDES IN LAKE MICHIGAN WATER INTAKES*
(Concentrations in ppt)
Sample Site** pp'DDT pp'TDE opDDT pp'DDE Total DDT Dieldrin
Waukegan
Worth Chicago
Highland Park
Evanston
Chicago Central
Chicago South
* Data provided by the Illinois Environmental Protection Agency
** Date of collection not recorded
0.1*7
0.26
0.18
0.32
0.15
0.16
0.06
0.12
0.08
0.03
0.03
0.0^
0.32
0.10
0.13
0.17
0.02
0.07
0.07
0.03
o.ok
O.OU
0.09
0.01
0.92
0.51
0.^3
0.56
0.29
0.28
0.13
0.07
0.09
0.10
0.09
0.10
55
-------
APPENDIX I, PROCEDURE 3
WATER ANALYSIS PROCEDURE
WISCONSIN ALUMNI RESEARCH FOUNDATION
OFFSHORE WATER SAMPLES
The sample was mixed well before sub-sampling. Four 2,000 ml portions
were measured and placed in four clean nanograde solvent bottles. Two
hundred milliliters of hexane were added to each bottle. The bottles
were placed in a case and put on a shaker for five minutes. The bottles
were removed from the case and shaken by hand for three minutes. The
bottles were allowed to stand for four hours and the above method of
shaking was repeated. The samples were then transferred to 2,000 ml
separatory funnels and the layers allowed to separate. After separation,
the lower layer was drained back into the extractor bottles. The hexane
layers were combined and dried with sodium sulphate. The hexane was
transferred to a two liter flask. The hexane was concentrated to two to
three ml on a steam bath and then transferred to a florisil column and
eluted the same as the inshore water samples. The elutions were evapora-
ted and made to two ml and injected into a gas chromatograph.
-------
APPENDIX I, TABLE 8
LAKE MICHIGAN OPEN WATER PESTICIDES*
July 1969
(Results expressed in ng/l)
Sample Location
No.
3
4
5
6
7
9
11
Ik
15
16
21
26
30
31
32
33
34
35
36
37
38
39
4o
k2
43
48
49
50
52
53
54
60
62
65
(| mile off shore) Total DDT
Little Suamico River
Pensaukee River
Oconto River
Peshtigo River
Menominee River
Clark Lake Creek
Kangaroo Lake Creek
Ahnapee River
Kewaunee River
East Twin River
Pine Creek
Pigeon River
Kinnickinnic River
Menominee River
Oak Creek
Root Creek
Pike River
Barnes Creek
Calumet River at
Calumet City
Burns Ditch
Trail Creek
Gall en River
Drain at Sawyer
PawPaw River
Black River
Muskegon River at mouth
into Muskegon Lake
White River
Pentwater River
Manistee River
Betsie River
Platte River
Bear River, Petoskey
Manistique River
Escanaba River
-------
APPENDIX II
CHLORINATED HYDROCARBON INSECTICIDES
IN LAKE MICHIGAN TRIBUTARY WATERS
•59
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APPENDIX II, FIGURE 1
LAKE MICHIGAN BASIN MAJOR RIVER PESTICIDE SAMPLING STATIONS
61
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APPENDIX II, PROCEDURE 1
MICHIGAN WATER RESOURCES COMMISSION
PIEID AND ANALYTICAL PROCEDURES
To obtain representative water samples from the major tributaries,
the Pesticides Committee of the Lake Michigan Conference recommended
that a continuous flow apparatus be used over a three day period.
This technique should moderate possible fluctuations in pesticide
concentrations over time. Michigan designed a completely submersible
sampler consisting of a five gallon carboy, two pieces of heavy-walled
glass tubing fitted through a rubber stopper, a 30-gauge hypodermic
needle and a perforated metal case (see attached diagram).
When the sampler is submerged to operating depth (l8 inches below
the surface), a small amount of water enters the bottle through the
water-intake tube until water pressure outside the bottle equals air
pressure within the bottle. Air then gradually escapes through the
air-outlet needle at a rate fixed by the size of the needle opening.
As air escapes, water slowly fills the carboy at a proportional rate
over the sampling period until the water level reaches the bottom of
the air-outlet tube. Sampling is then complete. Time required to
fill a five gallon carboy when a 30-gauge needle is used is approxi-
mately 30 hours. This time period could be extended by using a smaller
diameter needle or orifice.
Some of the advantages of this sampler are: 1. It is entirely sub-
mersible, thus reducing chances of vandalism; 2. It is entirely
independent of a power source, thus allowing increased versatility
and reduced chances of failure; 3. It fills at a uniform rate through-
out the sampling period; and ^. It is simple in construction and
quite inexpensive.
Immediately after removal from the stream, the composite sample is
mixed well and a one gallon aliquot for insecticide analysis poured
into a clean glass bottle containing 100 milliliters of hexane. All
gallon bottles had either teflon or aluminum-lined caps to avoid con-
tamination. A 250 milliliter aliquot is removed for turbidity and
suspended solids determination. The remainder of the sample is dis-
carded.
In streams where time did not permit a composite sample to be taken
or where it was impossible to use the continuous sampler, grab samples
were obtained by submerging a one gallon glass bottle to a depth
approximately 18 inches below the surface and allowing it to fill.
Prior to sampling 100 milliliters of n-hexane was added to the bottle.
Extreme care was taken to avoid any loss of the hexane during sampling.
68
-------
Samples of raw water at municipal water intakes were obtained by filling
a clean one gallon glass bottle (containing 100 milliliters of n-hexane)
from the raw water tap within the treatment facilities.
Mussels used as biological monitors of pesticides were held captive
in tributaries in chrome-plated barbecue baskets. The mussels were
placed in the streams at least one month prior to the anticipated
sampling date to allow ample time for them to reach equilibrium with
pesticide concentrations in the water. Studies have demonstrated that
at normal temperatures, equilibrium occurs within one to three weeks.
A sample consisted of three mussels which were placed in Whirlpak bags
for transportation to the laboratory. The source of mussels for this
study was the shallow sandy shoal areas of Gun Lake, Barry County,
Michigan.
LABORATORY PREPARATION AND ANALYSIS
The water samples were extracted according to the FWQA method (U. S.
D. I., 1969). The extracts were concentrated over stream to approxi-
mately five milliliters and further concentrated to one milliliter
in a tube heater (Kontes Model #K-72000).
Pyrex columns, 1.1 by 29 cm, fitted with a fritted glass disk, were
packed with one gram of florisil: Celite (5:1) with a layer of
anhydrous sodium sulphate above and below the packing. The florisil
was used as received from Floridin, Inc., and was calibrated before
use to ensure conformation to the elution procedure used. A 0.5 ml
portion of the extract was first eluted with 30 ml of r)-hexane and
the eluate collected and reconstituted to 0.5 ml. The sample was
then eluted with 20 ml of 15 percent ethyl ether in hexane and this
eluate also reconstituted to 0.5 ml. The first eluate (n-hexane)
would contain lindane, aldrin, heptachlor, heptachlor epoxide, DDE,
DDD, DDT and chlordane; if present, while the second (15 percent ethyl
ether) would contain dieldrin, endrin and methoxychlor.
An Aerograph 17^+0 gas chromatograph, equipped with two tritium foil
detectors, was used for the analyses. It was fritted with a five foot
by 1/8 inch aluminum column packed with S. io. 30 on Varaport 30
(100/120 mesh) and a five foot by 1/8 inch Pyrex column with four
percent S. E. 30 and six percent QF-1 on Chrom. W A/W DMCS (80/100
mesh), The chromatograph was operated at a column temperature of 200°
C and a 20 ml per minute nitrogen flow. The injection temperature
was 275° C and the detector temperature 220° C. Standards were in-
jected at the beginning of each run, after every five samples, and
at the end of the run. Quantitations were based on peak heights.
Two mussels from each sample of three were individually prepared for
analysis. Each mussel was removed from its shell, drained and weighed
to the nearest mg and then blended with 50 ml of hexane-acetone (2:1)
in a Sorvall Omni-Mixer for three minutes at 10,000 rpm. The solvent
mixture was decanted and the sample blended twice more with 50 ml
69
-------
aliquots of additional solvent. The extract was dried over anhydrous
sodium sulphate and a 10 ml aliquot removed for determination of per-
cent fat by evaporation of the solvent in a vacuum at 60° C or over.
The remaining extract was concentrated to 5 ml over a steam bath.
The extracts were cleaned up in a manner similar to the water samples.
In this case, 2 grams of florisil: Celite (5:1) were used as column
packing and a two ml aliquot of the extract placed on the column.
The samples were eluted with n-hexane (kO ml) and 15 percent ethyl
ether in _n-hexane (20 ml) and the eluates concentrated to 0.5 ml for
gas chromatographic analysis.
The identities of the pesticides were confirmed on two different gas
chromatographic columns, but further confirmation (e.g. thin-layer
chromatography) has not been completed.
70
-------
WATER
SURFACE
SEA WALL
OR DOCK
AIR OUTLET
NEEDLE
GLASS CARBOY
CASE OF
EXPANDED METAL
CONTINUOS
WATER
SAMPLER
WATER
INTAKE TUBE
60 POUND ANCHOR
APPENDIX II, FIGURE 2
71
-------
APPENDIX II, TABLE 4
PESTICIDES IN RIVER WATER SAMPLES**
Indiana Drainage, 1970
(Concentrations in ppt)
River
Location
Date
DDE Dieldrin DDD DDT
Burns Ditch
Burns Ditch
Burns Ditch
Burns Ditch
Burns Ditch
Burns Ditch
Trail Creek
Trail Creek
Trail Creek
Trail Creek
Trail Creek
Trail Creek
St. Joseph
St. Joseph
St. Joseph
St. Joseph
St. Joseph
St. Joseph
St. Joseph
St. Joseph
St. Joseph
St. Joseph
St. Joseph
St. Joseph
Portage
Portage
Portage
Portage
Portage
Portage
Michigan City
Michigan City
Michigan City
Michigan City
Michigan City
Michigan City
South Bend
South Bend
South Bend
South Bend
South Bend
South Bend
Bristol
Bristol
Bristol
Bristol
Bristol
Bristol
Indiana Harbor
Indiana Harbor
6/11/70
7/03/70
8/04/70
9/01/70
10/06/70
11/03/70
6/11/70
7/03/70
8/04/70
9/01/70
10/06/70
11/03/70
6/10/70
7/02/70
8/05/70
9/02/70
10/07/70
11/04/70
6/09/70
7/02/70
8/05/70
9/02/70
10/08/70
11/04/70
6/30/70
8/11/70
*
*
*
•x-
*
*
#
*
*
#
#
•x-
*
•x-
*
*
•x-
•x-
•x-
•x-
*
•x-
*
•x-
*
*
•x-
*
*
•X-
#
•x-
*
•*
•X-
•X-
#
•X-
*
•X-
•X-
•X-
#
*
•X-
•*
•X-
•X-
•X-
*
*
*
•*
•*
#
•X-
•X-
*
•X-
•X-
#
*
*•
*
*
#
#
#
*
*
#
^f
*
*
*
*
*
#
*
*
47
•X-
•X-
13
#
*
21
«•
*
15
15
•X-
28
*
*
*
22
*
16
•X-
*
11
*
23
* <10.0 ppt
** Data from Indiana State Board of Health
NOTE: Lindane, heptachlor, aldrin and endrin were not detected in
any sample.
72
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APPENDIX II, TABLE 6
LAKE MICHIGAN RIVER WATER PESTICIDES**
July 1969
(Results expressed in ng/l)
Sample No. Location
Total DDT Dieldrin BHC
Est. PCB
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
33
34
35
36
37
38
39
Big Suamico River
Little Suamico River
Pensaukee River
Oconto River
Peshtigo River
Menominee River
Mud Lake Creek
Clark Lake Creek
N Jacksonport Creek
Kangaroo Lake Creek
Moonlight Bay
Stony Creek
Ahnapee River
Kewaunee River
East Twin River
West Twin River
Manitovoc River
Silver Creek
Calvin Creek
Pine Creek
Point Creek
Fisher Creek
Centerville Creek
Seven Mile Creek
Pigeon River
Sheboygan River
Black River
Sauk Creek
Milwaukee
Menominee River
Root Creek
Pike River
Barnes Creek
Calumet River
at Calumet City
Burns Ditch
Trail Creek
Gal i en River
S 10
+ 10
•*• 10
-t-10
-s.10
-------
APPENDIX II, TABLE 6
continued
(Results expressed in ng/l)
Sample No. Location Total DDT
40
4i
42
43
44
45
46
47
48
49
50
51
52
53
54
56
57
59
60
61
62
63
64
65
66
Drain at Sawyer
St. Joseph River
Paw Paw River
Black River
Kalamazoo River
Black River
Pigeon River
Grand River
Muskegon River at
mouth into Muskegon L.
White River
Pentwater River
Pere Marquette River
Manistee River
Betsie River
Platte River
Leelanan Lake
Boardman River
Lake Charlevois Outlet
Bear River, Petoskey
Millecoquins Creek
Manistique River
Sturgeon River
Whitefish River
Escanaba River
Ford River
16.0
^.10
36.0*
82.2*
t 10
<10
c.10
11.4*
< 10
-tlO
x.10
•^•10
24.4*
< 10
*. 10
-clO
•*• 10
600*
<• 10
* 10
•^ 10
<£10
975*
4 10
<. 10
Dieldrin BHC
*10 40
-------
APPENDIX III
CHLORINATED HYDROCARBON INSECTICIDES
IN BIOLOGICAL MONITORS
11
-------
APPENDIX III, PROCEDURE 1
FIELD METHODS FOR BIOLOGICAL SAMPLING
WISCONSIN DEPARTMENT OF NATURAL RESOURCES
Both random sample sites and selected sample sites were established
for the invertebrates organism analyses. Random sites were designed
to establish regional background levels in the organisms and specific
sites were established to evaluate specific waste sources. Aquatic
invertebrate samples were collected by hand picking or with dip nets
and minnow seines. At least ten grams wet weight were desirable but
that quantity was often impossible to obtain. The samples were norm-
ally mixed species of immature insects, fresh water shrimp, crayfish,
leeches and others. Fish samples were taken at some sites. In
addition to the resident invertebrate organisms, clams (Lampsilis sp.
and Fusconia sp.) were tethered at selected sites near the mouth of
the rivers tributary to both Lake Michigan and Lake Superior. The
objective of utilizing clams was to provide a biological filter that
offered a consistent pesticide accumulation mechanism. Clams were
collected from Oxbow Creek in Douglas County, the Eau Claire River in
Douglas County and Namakegon River in Washburn County.
Background residue data on control clams were generally less than
two parts per billion for DDT plus analogs at the time of collection.
However, some of the controls ranged as high as 20 parts per billion
DDT plus analogs at the time of collection. The background levels
of DDT and its analogs must, therefore, be considered variable. Most
usually the background residue levels were not considered important
unless they were unusually high since it was anticipated that the or-
ganisms would reach a new residue level equilibrium in the new environ-
ment.
The clams were tethered in the stream by means of a nylon cord tied
to a drill hole at the edge of one mantle. Recovery from the stream
sites was generally good, as long as the tether lines were totally
hidden and casual observers had no opportunity to interfere. The
clams normally assumed the same attitude in the stream when tethered
as they had assumed when they were originally collected, suggesting
that tethering did not interfere with their normal habits.
Both invertebrate organism and clam collections were preserved in the
field in glass containers with formalin and returned to the labora-
tory for subsequent analysis.
78
-------
APPENDIX III, PROCEDURE 2
ANALYTICAL METHODS FOR BIOLOGICAL SAMPLES
WISCONSIN DEPARTMENT OF NATURAL RESOURCES
Water, clams, invertebrates and algae were processed in this study
by hexane extraction, acetonitrile partitioning, florisil column
cleanup, gas chromatrographic identification, and quantitation. Thin
layer chromatography was used for identification and confirmation on
some samples.
Water samples of 2,000 ml were extracted three times in teflon stop-
cock separatory funnels, first with 100 ml of hexane, twice with 50
ml hexane. If an emulsion appeared, it was broken by hot and cold
water treatment, the addition of propanol or addition of sodium chlor-
ide. The three hexane extracts were combined and dried with sodium
sulphate, then concentrated to 10 ml with a dry air stream on a 38° C
water bath. The 10 ml hexane extract with pesticide residue was
florisiled at this point to separate fats, pigments and other contam-
inants.
Two or three clams from a site were removed from their shells and
partially dried on filter paper to remove excess water. They were
ground with a hand grinder and mixed to give a representative sample.
Fifty grams of this sample were mixed with enough sodium sulphate
to dry the sample. The 100 ml hexane extracts were combined and dried
with sodium sulphate and concentrated with the dry air stream on a
water bath to 10 ml. This final clam extract was then cleaned by a
florisil column to remove traces of fats, pigments and other contami-
nants.
Invertebrates, other than clams, were drained on filter paper to remove
excess water. Using 50 grams (if available) or less, the sample was
ground with sodium sulphate in a mortar and pestle. After pulveriza-
tion the sample was transferred to 250 ml centrifuge bottles. These
bottles were then stoppered with either glass stoppers or aluminum
foil-covered rubber stoppers and hexane was added. One hundred milli-
liters of hexane were first added to each bottle and the mixture was
shaken for three minutes, followed by centrifuging at 1,500 rpms for
10 minutes. The supernatant was then decanted and the sample was again
extracted with 50 ml of hexane and centrifuged for 10 minutes. The
supernatants from both spinnings were combined and concentrated to
10 ml by a dry air stream and were then ready for florisil cleanup.
Algae samples were collected and as much algae as was available was
used for extraction. The samples were filtered through tared, hexane-
rinsed fiber glass filter pads with a buchner funnel. The samples
were then dried in a dessicator for 15 minutes. The algae as well
as filter paper were mascerated by mortar and pestle with enough sodium
sulphate to dry the sample. The sample was then placed in a 250 ml
79
-------
centrifuge bottle with 100 ml of hexane and shaken for throe r,:imr'-on.
The sample was then centrifuged for ten minutes at 1,500 rprns. The
hexane was decanted and the sample re-extracted twice with 50 ml of
hexane. The hexane supernatants were combined and concentrated to
10 ml by a dry air stream and were then ready for florisil cleanup.
The extraction procedure efficiently partitions fats and oils from
the sample into the hexane carrier solvent. The fats and oils contain
most of the insecticides present in the organisms due to their solu-
bility in the fats and oils and their insolubility in water. Along
with the lipid soluble pesticides, the extraction process also extracts
other organic compounds that could have a high electron affinity and
thus cause erroneous electron capture detector responses. To remove
the interfering substances from the hexane extract, absorption chro-
matography is used. The absorption material is a commercial diatoma-
ceous earth purchased as florisil. The florisil is activated by heating
to 100° C for 2k hours followed by deactivation to a specific level
by adding one to three percent water. This enables efficient separa-
tion of the insecticides on the florisil column. The column holder
is a pyrex glass tube with a 22 ml inside diameter and of adequate
length to contain 300 ml of hexane solvent. It has fritted glass and
teflon stopcock at the bottom to permit a regulated flow through the
system. One-half inch of sodium sulphate is added to the column and
kO grams of deactivated florisil which is covered-, with another one-
half inch of sodium sulphate.
The florisil column is prewashed with 50 ml of hexane. The concen-
trated hexane extract of the sample is then added to the column. The
sample container is washed with 200 ml of six percent ethyl ether and
9k percent hexane solvent mixture. This mixture is added to the flori-
sil column and eluted through the column at a rate not to exceed five
ml per minute. When the column is almost empty, 200 ml of 20 percent
ethyl ether and 80 percent hexane are added to the florisil column.
Each one of the elutions (9k/6, 80/20) is collected and analyzed
separately.
The two elutions and properly deactived florisil will remove most
interferences and separate some of the insecticides. The first elu-
tion (six percent ethyl ether) will contain:
Lindane DDT
BHC Perthane
Kelthane Methoxychlor
Aldrin Toxaphene
Heptachlor Strobane
Heptachlor Epoxide Chlordane
DDE DDD (TDE)
80
-------
The second elution (20 percent ethyl ether) will contain:
Dieldrin Endrin
Ltndane (Trace) Kelthane (Trace)
The two elutions are concentrated with a dry air stream to 10 ml or
less, depending on the suspected insecticide concentration in the
sample. These concentrated samples are at this time ready for injec-
tion into the gas chromatograph.
The gas chromatograph used for the analyses was a Hewlett Packard,
dual channel (Model ^02). Both channels were equipped with Nigo elec-
tron capture detectors. The instrument columns were two to six feet
V-tubes of pyrex glass. These columns were packed with three percent
OV-17 (Phenyl methylsilicone, 50 percent phenyl), ten percent silicone
DC-200 (12,500 cstk), and ten percent silicone DC QF-1 on a solid sup-
port of Gas Chrom Q (60-80 mesh) either singly or in varying concen-
trations of each.
The analysis of environmental samples is a problem because the extrac-
tion process removes substances from the sample which the florisil
cleanup misses and these substances are detected by electron capture
systems and cause interferences.
One of the most common interferences with the analysis of the DDT
complex is the polychlorinated biphenyl compounds (PCB's), because of
the structural similarity between PCB's and some pesticides, the elec-
tron capture detector will give the same response for both types of
compounds. The PCB's have 210 isomeric formations that are detectable
and the DDT complex has only six formations that could be detected with
an electron capture detector.
81
-------
APPENDIX III, TABLE 1
PESTICIDES IN BIOLOGICAL SAMPLES*
Wisconsin Drainage, 1968-69
(concentrations in ppb)
Source
Lab No.
Date
Collected
DDT
Complex
Dieldrin
BROWN COUNTY
Clams
East River
East River
East River
Fox River
Fox River
Suamico River
Suamico River
Suamico River
Invertebrates
Duck Creek
Trout Creek
Unnamed Creek
CALUMET COUNTY
Invertebrates
Killsnake Creek
Manitowoc River
Manitowoc River
Manitowoc River
Pine Creek
Story Brook
DOOR COUNTY
Clams
Clarke Lake Outlet
Clarke Lake Outlet
Heine Creek
Heine Creek
Heine Creek
Lily Bay Creek
Lily Bay Creek
Lily Bay Creek
322
493
548
13099
13100
323
494
549
5/04/69
T/16/69
8/19/69
7/31/68
7/31/68
5/07/69
7/15/69
2
2
126A1
127A1
147
228A
149
152
150
151
148
330
500
332
501
329
499
553
11/14/68
11/14/68
4/25/68
4/07/69
5/14/68
5/14/68
5/19/68
5/14/68
5/14/68
5/06/69
7/15/69
5/06/69
7/15/69
9/18/69
5/06/69
7/15/69
9/18/69
13.0
13.0
54.0
Trace
Trace
2900.0
2000.0
28.0
84.0
27.4
26.0
65.3
10.0
23.9
26.0
10.0
Trace
8.0
16.0
* Data from the Wisconsin Department of Natural Resources
82
-------
APPENDIX III, TABLE 1
PESTICIDES IN BIOLOGICAL SAMPLES
continued
(concentrations in ppb)
Source
DOOR COUNTY CONTINUED
Clams continued
Riebolts Creek
Riebolts Creek
Riebolts Creek
Stoney Brook
Stoney Brook
Unnamed Creek
Unnamed Creek
Unnamed Creek
Invertebrates
Clark Creek
Heine Creek
Hubbards Creek
Lily Bay Creek
Little Sturgeon Creek
Little Sturgeon Creek
Mink River
North Bay River
Shivering Sand Creek
Shivering Sand Creek
(Some fish also)
Sugar Creek
Unnamed Creek
FLORENCE COUNTY
Invertebrates
Lamon-Tangue Creek
Popple River
Popple River Trib
Popple River So Br
Riley Creek
Wakefield Creek
(Some fish also)
Woods Creek
Lab No.
333
502
555
33^
556
328
498
552
157
154
158
240A
241A
243A
153
159
238A
239A
242A
156
304
303
305
306
301
300
302
Date
Collected
5/06/69
7/15/69
9/18/69
5/07/69
9/19/69
5/06/69
7/15/69
8/19/69
5/16/68
5/16/68
5/16/68
4/09/69
4/09/69
4/09/69
5/16/68
5/16/68
V09/69
4/09/69
V09/69
5/16/68
4/10/69
VlO/69
U/10/69
4/11/69
4/10/69
4/10/69
4/10/69
DDT
Complex
^.5
10.0
6.9
50.0
190.0
25.0
2350.0
309.0
3^.0
89.0
708.0
63.0
1.45
3.2
3.2
1.16
Dieldrin
6.0
6.0
33.0
0.68
0.9
1.8
0.58
83
-------
APPENDIX III, TABLE 1
PESTICIDES IN BIOLOGICAL SAMPLES
continued
(concentrations in ppb)
Source
Lab No.
Date
Collected
DDT
Complex
Dieldrin
FOREST COUNTY
Invertebrates
Pine River
Wolf River
GREEN LAKE COUNTY
648
654
T/07/69
7/07/69
100.0
Invertebrates
Sucker Creek
Sucker Creek
KENOSHA COUNTY
Clams
Barnes Creek
Pike River
Invert ebrate s
Barnes Creek
Pike River
Pike River
Pike River
Pike River So Br
KEWAUNEE COUNTY
523
524
307
516
6/25/69
6/25/69
5/26/69
7/16/69
10.0
12.2
4290.0
330.0
1350.0
14567
253A1
14568
14569
69A
5/03/68
4/11/69
5/03/68
5/03/68
7/11/68
143.0
2557.0
1210.0
150.0
100.0
25.0
322.0
589.0
30.0
10.0
Clams
Ahnapee River
Ahnapee River
Kewaunee River
Kewaunee River
Unnamed Creek
Unnamed Creek
Unnamed Creek
Invertebrates
Buck Creek
Casco River
East Twin River
East Twin River
(Some fish also)
Kewaunee River
335
503
337
558
336
504
557
5/07/69
7/15/69
5/07/69
9/20/69
5/07/69
7/15/69
8/19/69
3.9
10.6
14.8
15.0
9.7
< 1.0
233A
236A1
234A
235A
237A
4/08/69
4/08/69
4/08/69
4/08/69
4/08/69
84
16.0
12.0
11.0
0.54
-------
APPENDIX III, TABLE 1
PESTICIDES IN BIOLOGICAL SAMPLES
continued
(concentrations in ppb)
Source
Lab No.
Date
Collected
DDT
Complex
Dieldrin
LANGIADE COUNTY
Invert ebrat e s
Hunting River
Hunting River
Nine Mile Creek
Pickerel Creek
Swamp Creek
Wolf River
Wolf River
MANITOWOC COUNTY
626
6kk
636
628
629
633
T/OT/69
7/H/69
7/10/69
7/09/69
7/09/69
7/10/69
7/10/69
0.05
cl.O
53.0
* 1.0
33.0
< o.l
Clams
Calvin Creek
Calvin Creek
Calvin Creek
Centerville Creek
Centerville Creek
East Twin River
East Twin River
Fisher Creek
Fisher Creek
Fisher Creek
Manitowoc River
Manitowoc River
Manitowoc River
Pine Creek
Pine Creek
Point Creek
Silver Creek
Silver Creek
West Twin River
West Twin River
Invertebrates
Branch River
Branch River Trib
East Twin River
Francis Creek
316
507
562
320
565
31^
559
319
508
561;
506
13101
13102
317
563
318
315
561
505
560
5/27/69
7/16/69
9/20/69
5/27/69
9/20/69
5/27/69
9/20/69
5/27/69
7/16/69
9/20/69
7/16/69
8/01/69
8/01/68
5/27/69
9/20/69
5/27/69
5/27/69
9/20/69
7/16/69
9/20/69
19.0
5.0
32.0
< 1.0
39.0
8.8
35.0
5.0
<1.0
28.0
^2.0
<2.0
5.8
*1.0
19.5
10.0
38.0
<1.0
21.0
230A
231A
119A1
121A1
V07/69
V07/69
11/12/68
11/12/68
Trace
13.0
13.0
85
-------
APPENDIX III, TABLE 1
PESTICIDES IN BIOLOGICAL SAMPLES
continued
(concentrations in ppb)
Source
Lab No.
Date
Collected
DDT
Complex
Dieldrin
MANITOWOC COUNTY CONTINUED
Invertebrates continued
Molash Creek
Mud Creek
West Twin River
MARINETTE COUNTY
Clams
Peshtigo River
Invertebrates
Beaver Creek
Harvey Creek
Holme Creek
Little Peshtigo River
Menominee River
Pike River Branch
MARQUETTE COUNTY
Invertebrates
Chapman Creek
Pox River
Klavitter Creek
(Some fish also)
Lunch Creek
Mecan River
Mecan River
(Some fish also)
Westfield Creek
(Some fish also)
White River
(Some fish also)
MENOMINEE COUNTY
Invertebrates
Pecore Creek
Wolf River W Br
Wolf River
232A
229A
120A1
327
84
287
285
282
283
288
85A
92A
86A
89A
88A
91A
87A
90A
529A1
527
528A1
4/08/69
4/07/69
11/12/68
5/07/69
9/05/68
4/09/69
4/09/69
4/08/69
4/09/69
4/09/69
11/05/68
11/05/68
11/05/68
11/05/68
11/05/68
11/05/68
11/05/68
11/05/68
7/08/69
7/08/69
7/08/69
86
13-0
2.5
10.0
3.0
141.0
62.0 20.5
Insufficient Sample
<10.0
84.0 29.0
410.0
<2.0
4.0
23.0
23.0 6.0
5.0 14.0
^10.0
410.0
-------
APPENDIX III, TABLE 1
PESTICIDES IN BIOLOGICAL SAMPLES
continued
(concentrations in ppb)
Source
Lab No.
Date
Collected
DDT
Complex
Dieldrin
MILWAUKEE COUNTY
Clams
Kinnickinnic River
Menominee River
Menominee River
Oak Creek
Oak Creek
Invertebrates
Kinnickinnic River
Kinnickinnic River
Lincoln Creek
Lincoln Creek
Lincoln Creek
Little Menominee Ri
Menominee River
Menominee River
Menominee River
Milwaukee River
Milwaukee River
Milwaukee River
Oak Creek
Oak Creek
Root River
Root River
OCONTO COUNTY
511*
309
513
310
515
7/15/69
5/26/69
7/15/69
5/26/69
7/16/69
10.0
196.5
76.0
69.0
11.2
11*571
11*572
1*7
1*8
1*6
a.^571*
ll*573
80
8lA
11*565
82A
79A
76A
ll*570
77A
78A
6/03/68
7/02/68
10/22/68
10/22/68
!0/2i*/68
5/29/68
7/03/68
6/05/68
6/05/68
i*/29/68
6/07/68
6/11/68
5/28/68
6/03/68
5/28/68
5/28/68
172.0
780.0
23!*. 0
1*03.0
7^0.0
365.0
2226.0
1*30.0
170.0
595.0
1*100.0
287.0
13.0
1*51.0
379.0
280.0
1*0.0
29.0
26.0
163.0
ioi*.o
1596.0
19.0
i*.o
27.0
19.0
Clams
Little Suamico River 321* 5/07/69 l6.0
Little Suamico River 1*95 7/15/69
Little Suamico River 550 9/18/69 <20.0
Oconto River 326 5/07/69 16.0
Oconto River 1*97 7/15/69 < 1.0
Pensaukee River 325 5/07/69 12.6
Pensaukee River 1*96 7/15/69 23.0
Pensaukee River 551 9/18/69 <10.0
87
-------
APPENDIX III, TABLE 1
PESTICIDES IN BIOLOGICAL SAMPLES
continued
(concentrations in ppb)
Source
Lab No.
Date
Collected
DDT
Complex
Dieldrin
OCONTO COUNTY
Invertebrates
Daly Creek 299 4/11/69
Kelly Brook 297 4/11/69
Little River 295 4/11/69
Little Suamico River 525A1 7/08/69
McCaslin Brook 290 4/07/69
Oconto R, 1st S Br 292 4/07/69
Oconto R, N Br 294 4/07/69
Pensaukee River, N Br 526A1 7/08/69
Peshtigo River 293 4/07/69
OUTAGAME COUNTY
Invert ebrat e s
Bear Creek
Duck Creek
OZAUKEE COUNTY
12 3A
124A1
11/14/68
11/14/68
2.5
3.6
-cl.O
433-0
^-50.0
10.0
759.0
Clams
Milwaukee River
Milwaukee River
Milwaukee River
Milwaukee River
Milwaukee River
Milwaukee River
Milwaukee River
13661
50
51
275
276
277
278
6/27/68
8/30/68
8/30/68
4/23/69
4/23/69
4/23/69
4/23/69
36
65
68
15
16.5
10.3
20.7
Invertebrates
Cedar Creek 14565 4/29/68 6o6o.O
Cedar Creek 62A 5/24/68 78.0
Cedar Creek 14562 5/24/68 104.0
Little Menominee River 64A 5/29/6-8 20.0
Milwaukee River 14564 4/29/68 5360.0
Milwaukee River 6lA 5/24/68 145.0
Milwaukee River 63A 5/27/68 124.0
Milwaukee River 14563 5/29/68 152.0
23.1
51
60
3.5
4.6
9.4
1150.0
18.0
10.0
2430.0
40.0
37.0
794.0
-------
APPENDIX III, TABLE 1
PESTICIDES IN BIOLOGICAL SAMPLES
continued
(concentrations in ppb)
Source
Lab No.
Date
Collected
DDT
Complex
Dieldrin
OZAUKEE COUNTY CONTINUED
Invertebrates continued
Milwaukee River
Milwaukee River
Milwaukee River
Milwaukee River
Milwaukee River
Sauk Creek
Sauk Creek
Sauk Creek
Sucker Creek
Sucker Creek
RACINE COUNTY
Clams
Pike R, No. Br
Root River
Root River
Invertebrates
Pike River, No. Br
Pike River , No. Br
Pike River, No. Br
Root River, E Br
Root River, W Br
Root River
Root River
Root River
SHAWANO COUNTY
Invertebrates
Comet Creek
Embarrass River
Pensaukee River
T1A
72A
T3A
74A
75A
14561
59A
60A
58A
57A
^9
308
53
1^575
14578
252A
14576
1^577
1^579
14580
14581
624
623
618
6/11/68
6/11/68
6/07/68
6/11/68
6/07/68
5/13/68
5/24/68
5/27/68
5/24/68
5/27/68
8/29/69
5/26/69
8/29/68
5/06/68
5/06/68
4/11/69
5/06/68
5/06/68
5/10/68
5/10/68
5/10/68
7/09/69
7/09/69
7/08/69
60.0
1986.0
90.0
105.0
1096.0
19400.0
47.0
18.0
102.0
42.0
40.0
25.3
33.0
289.0
6.0
9^3.0
144.0
99.0
71.0
211.0
14.0
12.0
<10.0
29.0
2500.0
39^.0
427.0
605.0
16.0
27.0
26.0
15.0
1660.0
1.7
28.0
262.0
15.0
46.0
37.0
21.0
33.0
89
-------
APPENDIX III, TABLE 1
PESTICIDES IN BIOLOGICAL, SAMPLES
continued
(concentrations in ppb)
Source
Lab No.
Date
Collected
DDT
Complex
Dieldrin
SHEBOYGAN COUNTY
Clams
Black Creek
Black Creek
Black Creek
Pigeon River
Pigeon River
Seven Mile Creek
Seven Mile Creek
Sheboygan River
Sheboygan River
Sheboygan River
Sheboygan River
Sheboygan River
Invertebrates
Mullet River
Onion River
Sheboygan River
Sheboygan River
Sheboygan River
WASHINGTON COUNTY
Invertebrat es
Cedar Cr, No. Br
Menominee River
Milwaukee River Br
Milwaukee River
Milvaukee River,
No. Br
Milvaukee River,
No. Br
WAUPAGA COUNTY
Invertebrates
Crystal River
Little Wolf River
Maple Creek
Waupaca River
313
512
568
510
566
311
509
1309T
13098
511
312
56T
5/27/69
7/16/69
9/20/69
7/15/69
9/20/69
5/27/69
7/15/69
8/01/68
8/01/68
5/06/69
5/27/69
9/20/69
13.1
<2.0
24.0
24.0
4.2
7.0
<2.0
<2.0
99.9
1080.0
2lj.l4.Al
94A2
96A
98A
246A1
VlO/69
11/19/68
11/19/68
11/19/68
4/10/69
3300.0
1*390.0
12111
65A
12112
12113
12114
12115
116A1
117A1
122A1
118
5/08/68
5/24/68
5/08/68
5/08/68
5/08/68
5/08/68
11/13/68
.11/13/68
11/14/68
11/13/68
10.0
51.0
10.0
136.0
10.0
33.0
14.0
8.0
7.2
1.3
1.0
6.0
16.0
90
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APPENDIX III, PROCEDURE 3
BIOLOGICAL COLLECTION AND ANALYTICAL PROCEDURE
MICHIGAN WATER RESOURCES COMMISSION
Biological intake of chlordane and dieldrin WHS assessed by holding
freshvater mussels in chrome-plated wire barbecue baskets at the six
monitoring stations during open water periods. Mussels have been found
to be good monitors of insecticides in lotic situations (Bedford,
et al., 1968). These animals filter large volumes of water and con-
centrate insecticides in their tissues to levels many times greater
than that in the water. Insecticide concentrations in the mussels
reach equilibrium with their environment in about two weeks. Thus
levels measured in these animals reflect the insecticide concentra-
tions which existed in the environmental waters for about two weeks
prior to sampling. Exposed mussels were retrieved prior to the in-
secticide applications of October 19-23, 1968, and at intervals there-
after. In most cases, three mussels were collected from each station
on each collection date. The mussels were analyzed for pesticide
content at the Michigan State University Pesticide Analytical Labora-
tory under the direction of Dr. Matthew Zabik.
Each mussel was removed from its shell, drained and weighed to the
nearest mg and was then blended with 50 ml of acetonitrile in a Sorvall
Omni-Mixer for three minutes at 10,000 rpms. The solvent mixture
was decanted and the sample blended twice more with 50 ml aliquots
of additional solvent. Fifty milliliters of n-hexane was added to
the combined extract and the insecticides were partitioned into the
hexane by removing the acetonitrile with ten percent sodium chloride
solution. The hexane extract was concentrated to a volume of less
than ten ml for introduction into a cleanup column.
Pyrex columns, 2 by 50 cm, fitted with a fritted-glass disk, were
packed with 10 g of a 5:1 mixture of florisil to celite. The florisil,
which was received activated at 649C, was deactivated with approximately
five percent water. The mixture was calibrated before use to ensure
conformation to the elution procedure used. Each sample was eluted
with 300 ml of n-hexane and then procedures generally follow those
recommended by Shell Development Company (196^) with several modifi-
cations.
A Beckman Gas Chromatograph k equipped with a discharge electron cap-
ture detector was used for the analyses. It was fitted with a six
foot (1.83 m) by 1/15 inch (1.59 mm) pyrex column packed with 11 per-
cent OJP-1 and three percent DC 200 on Gas Chrom Q and was operated at
a column temperature of 200° c and 30 ml per minute helium flow.
Standards were injected at the beginning of each run, after every ten
samples and at the end of the run. The identities of the pesticides
found were confirmed using columns packed with 2.5 percent QF-1 on
acid-base washed Chromsorb W and 2.5 percent S.E. 30 on Gas Chrom RP.
Quantitations were based on peak height and the concentrations were
based on the wet weight of the mussel.
93
-------
Lake Michigan
7. Otter Creek
8. Trail Creek
South Shore
Branch
Michigan City
6. Karwick Branch
APPENDIX III, FIGURE 1
INDIANA BIOLOGICAL PESTICIDE MONITORING STATIONS
INDIANA STATE BOARD OF HEALTH
-------
APPENDIX III, TABLE 3
PESTICIDES IN BIOLOGICAL SAMPLES
INDIANA STATE BOARD OF HEALTH
Indiana Drainage, 1970
(concentrations in ppb)
River and Location
Date
Total
Media DDE DDD DDT DDT Dieldrin
Burns Ditch, Portage
Burns Ditch, Portage
Burns Ditch, Portage
Burns Ditch, Portage
Burns Dttch, Portage
Trail Creek, Michigan City
Trail Creek, Michigan City
Trail Creek, Michigan City
Trail Creek, Michigan City
Trail Creek, Michigan City
St. Joseph, South Bend
St. Joseph, South Bend
St. Joseph, South Bend
St. Joseph, Bristol
St. Joseph, Bristol
St. Joseph, Bristol
St. Joseph, Bristol
St. Joseph, Bristol
Trail Cr Trib 1**
Trail Cr Trib 2
Trail Cr Trib 3
Trail Cr Trib k
Trail Cr Trib 6
Trail Cr Trib 7
Trail Cr Trib 8
* Less than 10 ppb
** Refer to Aunendix III. :
5'AV70
6/11/70
7/03/70
6/11/70
7/03/70
5/13/70
6/11/70
7/03/70
6/11/70
7/03/70
5/13/70
6/10/70
6/10/70
5/13/70
6/09/70
6/09/70
7/02/70
6/09/70
8/25/70
8/25/70
8/25/70
8/25/70
8/26/70
8/26/70
8/26/70
Fisure 1
Clams
Clams
Clams
Invert
Invert
Clams
Clams
Clams
Invert
Invert
Clams
Clams
Invert
Clams
Clams
Invert
Invert
Algae
Invert
Invert
Invert
Invert
Invert
Invert
Invert
for loca
*
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25
*
#
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100
*
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2k
168
258
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68
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10
26
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48
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12
16
150
130
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27
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37
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59
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•X-
95
-------
APPENDIX IV
CHLORINATED HYDROCARBON INSECTICIDES
IN LAKE MICHIGAN FISH
97
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APPENDIX IV, TABLE 2
A COMPARISON BETWEEN DDT (DDT, DDE, ODD) AND DIELDRIN CONCENTRATIONS
IN BLOATER CHUBS, COHO SALMON AND LAKE TROUT COLLECTED IN 1969 and 1970*
Species
Chubs
Coho
(Spring)
Coho
(Fall)
Lake trout
(22"-26")
1969
No.
fish DDT
120 Min.
Max.
Ave.
4 Min.
Max.
Ave.
12 Min.
Max.
Ave.
12. Min.
Max.
Ave.
6
15
9
1
5
3
9
17
12
8
24
17
.46
.29
.93
.83
.38
.50
.24
.07
.73
.98
.75
.98
Dieldrin
0
0
0
0
0
0
0
0
0
0
0
0
.12
.49
.27
.04
.15
.08
.14
.29
.22
.12
.39
.26
1970
No.
fish DDT
30 Min.
Max.
Ave .
5 Min.
Max.
Ave.
Min.
Max.
Ave.
19 Min.
Max.
Ave .
4
19
10
2
3
2
9
16
14
10
28
18
Dieldrin
.72
.65
.19
.05
.02
.82
.03
.66
.09
.94
.06
.80
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
12
27
19
05
09
07
05
18
12
14
45
27
Bureau of Commercial Fisheries data.
99
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APPENDIX V
CHLORINATED HYDROCARBON INSECTICIDES
IN MUNICIPAL WASTEWATER EFFLUENTS
109
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APPENDIX VI
INDUSTRIAL WASTEWATER EVALUATION
OF PCBs IN LAKE MICHIGAN
117
-------
APPENDIX VI
DEPARTMENT OF NATURAL RESOURCES
Box 450
Madison, Wisconsin 53701
(PCB Form Letter)
Dear Sir:
The nature of your business leads us to suspect you may have losses
of polychlorinated biphenyls (PCB's) to the environment. As you prob-
ably know, current research in many parts of the world indicates that
PCB's may be important in the environment as a toxicant causing signi-
ficant physiological imbalances, especially in reproductive processes.
Like DDT, PCB's contain chlorine, hydrogen, and carbon (chlorinated
hydrocarbons), are virtually insoluble in water but soluble in fat,
are extremely persistent, accumulate through food chains in fish and
birds, and are found worldwide.
PCB's have a wide variety of uses because of their unique properties
such as low volatility, adhesion, and resistance to fire, chemicals,
oxidation, and hydrolysis. They are included in many products and
formulations such as electrical insulation, fire-resistant heat trans-
fer and hydraulic fluids, lubricants for use at high temperatures and
pressures, sealants and expansion media, synthetic rubber, floor tile,
printer's ink, coatings for paper and fabrics, paints, varnishes,
waxes, asphalt, adhesives, resins, elastomers, and pigments.
Brand names of products containing polychlorinated biphenyls are:
American Made; Foreign Made:
Arochlor 1100 series Clophen
1200 series Fenchlor
lj-000 series Kannechlor
Chlorextol Pyralene
Dykanol Sovol
Interteen
Noflamol
Pyranol
Pydraul
Therminal FR series
118
-------
While you may not be using any of the above products directly, you
may be using products containing them as additives.
PCB's have been found in Lake Michigan water, sediments, fish and
birds. The Federal-Interstate Conferees on Pollution of Lake Michigan
and its Tributary Basin recognized the importance of each State inven-
toring the use of and possible losses of PCB's in the Lake Michigan
Basin and have asked us to initiate the following questionnaire survey.
Your responses by mail will save the necessity of having a staff mem-
ber call on you for an onsite investigation. It is not our intent to
ban the use of these materials, but we must become knowledgeable of
possible sources to the environment.
Please answer the attached questions. Thank you for your anticipated
cooperation in this matter.
Very truly yours,
Division of Environmental Protection
Thomas G. Frangos
Admini strator
Attach.
119
-------
Name of Business
Address
Name of Person Filling Out Questionnaire
Telephone
QUESTIONNAIRE
1. Are you currently using any of the afore-mentioned brand named products
in your products or operations?
2. Have you used any of these products in the last three years? (if no,
refer to question No. 7)
3. How do you use these compounds?
Product Pounds Per Year Use of Product
Estimate your disposal/or losses of these products to the environment
in pounds per year.
A. Atmosphere
B. Soils
C. Sewers and Drains
D. Dumps
E. Incinerators
F. Industrial Waste Haulers
G. Other Disposal Procedures
5. Comment on disposal techniques or loss characteristics.
120
-------
-2-
6. What action are you taking to reduce your losses to the environment?
T. The following products do or may contain PCB's. Do you manufacture (M)
formulate (F), incorporate (l), or use (u) any of these products in
your operations?
121
-------
-3-
PROBABLE SOURCES
Product
Adhesives, Glues and
Pastes
Air Conditioning Sys-
tems, Units and Acces-
sory
Capacitors and Con-
densors
Compressors
Cutting Machines
and Tools
Die Casting
Electrical Wire and
Cable
Food and Kindred
Products
Furniture and Fix-
tures
Ink
Lighting Fixtures &
Equipment
Molded Rubber Products
(Synthetic)
"0" Rings
Oils (Cutting-
Hydraulic and Indus-
trial)
Paints and Allied
Products
PCB Component
Additive
Disposal/or
MFI Loss to Environ-
and/or U Trade Name ment-// Per Year
Capacitors, Con-
densors & Trans-
formers
Fluids
Fluids
Oils
Oils
Coatings
Heat Transfer
Fluid
Coatings
Additives
Balasts
Additives
Additives
Additives
Additives
122
-------
•4-
Product
Plastic Molding
Compounds
Printing Chemicals
Resins
Rubber Lined Products
Rubber Packing
Rubber Specialities
Rubber-Synthetic
Rust Inhibitors and
Removers
Sealants and Sealers
Seals
Shoe Finishes and
Polishes
Sponge Rubber
Transformers
Vinyl
Waxes and Polishes
PCS Component
Additives
Additives
Additives
Synthetics
Adhesives
Additives
Disposal/or
MFI Loss to Environ-
and/or U Trade Name ment-# Per Year
Adhesives
Adhesives
Additives
Oils
Additives
Additives
POSSIBLE SOURCES
Agricultural Chemicals
and Fertilizers
Asbestos and Fire
Resistant Curtains
Batting
Candles
Canvas Products and
Specialities
Dedusters
Fireproofing
Fireproofing
Extenders
Fireproofing
123
-------
-5-
Product
Castings
Cloth and Burlap
Cosmetics and Toilet
Preparations
Cushions
Detergents and Soaps
Draperies and Curtains
Drawing Compounds
Foundry Machinery -
Equipment and Supplies
Gaskets
Gummed Tape
Heating Equipment and
Parts
Hydraulic Cylinders
Hydraulic Drives
Hydraulic Presses
Industrial Curtains
Labels and Seals
Laminated Wood Pro-
ducts
Lubricators, Lubrica-
tion Systems and Com-
ponents
Motors (Hydraulic)
Paints (Strippers
and Primers)
PCS Component
Oils
Fireproofing
Dedusters
Fireproofing
Dedusters
Fireproofing
Hydraulic Fluid
Additives & Adhesives
Adhesive
Fluids
Fluids
Fluids
Fluid
Fireproofing
Adhesives
Adhesives
Additives
Fluids
Additives
Disposal/or
MFI Loss to Environ-
and/or U Trade Name ment-^ Per Year
Particle Board
Adhesives
-------
-6-
Product
Pesticides (insecti-
cides)
Petroleum Products
Plasticizers
Plastisols
Plastic Coated
Clothing
Plastic Coated Gloves
Plywood
Pressure Sensitive
Tape
Printed Circuit Boards
Reinforced Tape
Rubber Cement
Rubber Coating (Syn)
Rubber-Metal Bonding
Rugs and Carpets
Solvents
Stains
Textile Specialities
Upholstery
Vacuum Pumps and
Platers
Varnishes
PCB Component
Carriers
Additives
Additives
Additives
Vinyls & Plastics
Vinyls 80 Plastics
Glues
Adhesive
Coatings
Adhesive
Additives
Additives
Adhesives
Fireproofing
Additives
Additives
Fireproofing
Fireproofing
Capacitors,
Transformers
Additives
Disposal/or
MET Loss to Environ-
and/or U Trade Name ment-# Per Year
125
-------
-7-
Disposal/or
MPI Loss to Environ-
Product PCS Component and/or U Trade Name ment-# Per Year
Veneer Adhesives
Waxed Paper Coatings
Wood Fiber and Adhesives
Products
126
-------
APPENDIX VII
CHLORINATED HYDROCARBON INSECTICIDES
IN STREAM SEDIMENTS
.12?
-------
APPENDIX VII, PROCEDURE 1
PESTICIDE ANALYSIS OF SEDIMENT SAMPLES
WISCONSIN ALUMNI RESEARCH FOUNDATION
The samples vere mixed and two 25 gram samples were weighed into two
150 ml beakers. One beaker was placed in an air oven at 100° C and
dried for two to three days and the moisture was determined. The
other sample was transferred to a Waring blender jar (one quart) and
blended for two minutes with 200 ml of acetonitrile. The acetonitrile
was filtered through a plug of glass wool into a one liter separatory
funnel containing about 500 ml of tap water. The sample was then
blended for about one-half minute with an additional 50 ml of acetoni-
trile and then filtered into the separatory funnel. Two hundred milli-
liters of petroleum ether was added to the separatory funnel and shaken
for two minutes. The layers were allowed to separate and the bottom
layer was drawn off. The petroleum ether extract was washed two more
times with about 600 ml of tap water, discarding the water both times.
Ten grams of sodium sulphate was added to the petroleum ether extract
and the sample was filtered into a 300 ml erlenmeyer flask (rinse
separatory funnel with about TO ml of petroleum ether). The sample
was then taken down to about five ml on a steam bath. The sample
was then run through a florisil column using 20 grams of florisil
and 150 ml of five percent ether in petroleum ether and 250 ml of
15 percent ether in petroleum ether. The column elutions were made
up to 25 ml with hexane. Ten microliters or less of the cleaned-up
extract was injected into a gas chromatograph.
128
-------
APPENDIX VII, TABLE 1
PESTICIDES IN STREAM SEDIMENTS*
July, 1969
Data in mg/1
Sample No. Location Total DDT Dieldrin Est PCS
1
2
3
4
5
6
7
8
9
10
11
13
14
15
16
17
18
19
20
21
22
23
25
26
27
28
29
30
31
33
34
35
36
37
38
39
40
41
42
43
44
46
East River
Big Suamico River
Little Suamico River
Pensaukee River
Oconto River
Peshtigo River
Menominee River
Mud Lake Creek
Clark Lake Greek
N Jacksonsport Creek
Kangaroo Lake Creek
Stony Creek
Ahnapee River
Kewaunee River
East Twin River
West Twin River
Manitowoc River
Silver Creek
Calvin Creek
Pine Creek
Point Creek
Fisher Creek
Seven Mile Creek
Pigeon River
Sheboygan River
Black River
Sauk Creek
Milwaukee
Menominee River
Root Creek
Pike River
Barnes Creek
Calumet River at
Calumet City
Burns Ditch
Trail Creek
Galien River
Drain at Sawyer
St. Joseph River
Paw Paw River
Black River
Kalamazoo River
Pigeon River
1.07
.001
.006
.023
.002
.002
.001
.001
.011
.003
.015
.019
.102
.033
.079
.035
.037
.016
.082
.008
.026
.042
.067
.053
.173
.011
.067
.082
.114
.069
.137
.010
.063
.017
.143
.024
.009
.029
.035
.044
.053
.03
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.O4o
.040
.004
.002
.004
.001
.002
.002
.001
.001
.005
.001
.001
0.50
0.01
0.02
0.05
0.01
0.01
0.01
0.01
.028
0.01
0.01
0.03
1.10
.035
.21
.052
.12
.01
.01
.033
.015
.021
.036
7.2
.052
.065
3.2
4.4
.075
.20
.013
1.25
.021
.060
.037
.032
.08
.11
.043
.018
* Data from the Wisconsin Alumni Research Foundation
129
-------
APPENDIX VII, TABLE 1
continued
Data in mg/1
Sample No. Location Total DDT
*r
48
49
50
51
52
53
51*
56
57
59
60
61
62
63
64
65
66
Grand River
Muskegon River at
mouth into Muskegon Lake
White River
Pentwater River
Pere Marquette River
Manistee River
Betsie River
Platte River
Leelanan Lake
Boardman River
Lake Charlevoix
Bear River, Petoskey
Millecoquins Creek
Manistique River
Sturgeon River
Whitefish River
Escanaba River
Ford River
.061
.006
.008
.001
.007
.001
.012
.011
.005
.008
.008
.006
.002
.114
.003
.007
.069
.007
Dieldrin
.002
.001
.003
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
.001
Est PCB
.17
.01
.02
.01
.01
.01
.01
.01
.01
.01
.01
.01
.01
.80
.01
.04
1.46
.03
130
-------
APPENDIX VIII
FIVE STATE PESTICIDE LEGISLATION
131
-------
APPENDIX VIII, TABLE 1
STATUS OF LEGISLATION ACCEPTING PESTICIDE USAGE
IN THE LAKE MICHIGAN BASIN
Compiled by the Governor's Interdisciplinary Committee on Pesticides
INDIANA
Agency Responsible for Registration, Labelling - State Chemist
Body Responsible for Regulations, Rules - State Chemist and
Pesticide Review Board
Composed of: One Representative State Board of Health
One Representative Department of Natural Resources
One Representative Purdue University Agricultural
Experiment Station
One Representative Indiana Cooperative Extension
Service - Voting Members
State Toxicologist
State Veterinarian
A Terrestrial Ecologist
An Aquatic Ecologist
One Public Representative
One Pesticide Industry Representative
Two Public Representatives from Conservation Organiza-
tion - Members
Restricted Pesticides Use by Permit Only - Yes
Commercial Applicators Licensed or Approved
Aerial - Yes - Approval for private applicators only for
restricted pesticides
Aquatic - Yes - Approval for private applicators only for
restricted pesticides
Brush Control & Soil Sterilent - Yes - Approval for private
applicators only for restricted pesticides
Mosquitoes - Yes - Approval for private applicators only for
restricted pesticides
Space Fumigation - Yes - Approval for private applicators only
for restricted pesticides
Structural Pest - Yes - Approval for private applicators only
for restricted pesticides
Vertebrate Control - Yes - Approval for private applicators
only for restricted pesticides
Pests of Animals - No
Field Crops - Yes - Approval for private applicators only for
restricted pesticides
Fruit Crops - Yes - Approval for private applicators only for
restricted pesticides
132
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APPENDIX VIII, TABLE 1
STATUS OF LEGISLATION ACCEPTING PESTICIDE USAGE
IN THE LAKE MICHIGAN BASIN
continued
i
INDIANA CONTINUED
Lawn, Garden & Ornamental - Yes - Approval for private applica-
tors only for restricted pesticides
Forest & Shade Tree - Yes - Approval for private applicators
only for restricted pesticides
Agency Regulating Commercial Applicators - State Chemist
Regulation of Local Government Units Applying Pesticides - No
Licensing of Dealers Handling Restricted Materials -
Notice of Intent to Use Pesticides-Required -
Disposal
Agency Having Authority for Regulation - Pesticide Review Board
Disposal Sites Approved by State -
Adequate Incineration - No
Guidelines Developed - No
Basic Memorandum of Agreement Signed with USDA re Toxic Pesticides - Yes
Supplemental Memorandum of Agreement Signed with USDA re Ethyl
Parathion - Yes
Agency Testing for Pesticide Residues in Food - Public Health
133
-------
APPENDIX VIII, TABLE 2
STATUS OF LEGISLATION ACCEPTING PESTICIDE USAGE
IN THE LAKE MICHIGAN BASIN
Compiled by the Governor's Interdisciplinary Committee on Pesticides
ILLINOIS
Agency Responsible for Registration, Labelling - Agriculture
Body Responsible for Regulations, Rules - Agriculture & Public Health
Interagency Committee must advise and recommend.
Interagency Committee Composed of: Director, Dept of Agriculture
Director, Dept of Conservation
Director, Dept of Public Health
Director, Dept of Public Works and Buildings
Director, Environmental Protection Agency
Chief, Illinois Natural History Survey
Dean, College of Agriculture
Restricted Pesticides Use by Permit Only - Yes - DDT Only
Commercial Applicators Licensed or Approved
Aerial - Yes
Aquatic - Yes
Brush Control & Soil Sterilent - Yes
Mosquitoes - No
Space Fumigation - No
Structural Pest - No
Vertebrate Control - No
Pests of Animals - ETo
Field Crops - Yes
Fruit Crops - Yes
Lawn, Garden & Ornamental - Yes
Forest & Shade Tree - Yes
Agency Regulating Commercial Applicators - Agriculture
Regulation of Local Government Units Applying Pesticides - No
Licensing of Dealers Handling Restricted Materials -
Notice of Intent to Use Pesticides-Required -
Disposal
Agency Having Authority for Regulation - Agriculture and Public
Health
Disposal Sites Approved by State - Yes
Adequate Incineration - No
Guidelines Developed - Yes
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APPENDIX VIII, TABLE 2
STATUS OF LEGISL/TION ACCEPTING PESTICIDE USAGE
IN THE LAKE MICHIGAN BASIN
continued
ILLINOIS CONTINUED
Basic Memorandum of Agreement Signed with USDA re Toxic Pesticides
Yes
Supplemental Memorandum of Agreement Signed with USDA re Ethyl
Parathion - Yes
Agency Testing for Pesticide Residues in Food - Agriculture and
Public Health
135
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APPENDIX VIII, TABLE 3
STATUS OF LEGISLATION ACCEPTING PESTICIDE USAGE
IN THE LAKE MICHIGAN BASIN
Compiled by the Governor's Interdisciplinary Committee on Pesticides
MICHIGAN
Agency Responsible for Registration, Labelling - Agriculture
Body Responsible for Regulations, Rules - Agriculture
Restricted Pesticides Use by Permit Only - Yes - DDT Only
Commercial Applicators Licensed or Approved
Aerial - Yes
Aquatic - Yes
Brush Control & Soil Sterilent - Yes
Mosquitoes - Yes
Space Fumigation - Yes
Structural Pest - Yes
Vertebrate Control - Yes
Pests of Animals - Yes
Field Crops - Yes
Fruit Crops - Yes
Lawn, Garden and Ornamental - Yes
Forest and Shade Tree - Yes
Agency Regulating Commercial Applicators - Agriculture
Regulation of Local Government Units Applying Pesticides - No
Licensing of Dealers Handling Restricted Materials - Yes -
Statutory Authority for Licensing of dealers; currently
being implemented.
Notice of Intent to Use Pesticides-Required -
Disposal
Agency Having Authority for Regulation -
Disposal Sites Approved by State -
Adequate Incineration - Limited private facilities available
Guidelines Developed - Yes
Basic Memorandum of Agreement Signed with USDA re Toxic Pesticides -
Supplemental Memorandum of Agreement Signed with USDA re Ethyl
Parathion -
Agency Testing for Pesticide Residues in Food - Agriculture
136
-------
APPENDIX VIII, TABLE 1*
STATUS OF LEGISLATION ACCEPTING PESTICIDE USAGE
IN THE LAKE MICHIGAN BASIN
Compiled by the Governor's Interdisciplinary Committee on Pesticides
MINNESOTA
Agency Responsible for Registration, Labelling - Agriculture
Body Responsible for Regulation, Rules - Agriculture and Department
of Natural Resources Admin Order
Restricted Pesticides Use by Permit Only - Yes
Commercial Applicators Licensed or Approved
Aerial - Yes
Aquatic - Yes
Brush Control & Soil Sterilent - Yes
Mosquitoes - Yes
Space Fumigation - Yes
Structural Pest - Yes
Vertebrate Control - Yes
Pests of Animals - Yes
Field Crops - Yes
Fruit Crops - Yes
Lawn, Garden & Ornamental - Yes
Forest and Shade Tree - Yes
Agency Regulating Commercial Applicators - Agriculture
Regulation of Local Government Units Applying Pesticides - Yes
Licensing of Dealers Handling Restricted Materials - 1/1/72
Notice of Intent to Use Pesticides-Required -
Disposal
Agency Having Authority for Regulation - Agriculture and Pollution
Control Agency
Disposal Sites Approved by State -
Adequate Incineration - No
Guidelines Developed - Yes
Basic Memorandum of Agreement Signed with USDA re Toxic Pesticides - Yes
Supplemental Memorandum of Agreement Signed with USDA re Ethyl
Parathion - Yes
Agency Testing for Pesticide Residues in Food - Agriculture
137
-------
APPENDIX VIII, TABLE 5
STATUS OF LEGISLATION ACCEPTING PESTICIDE USAGE
IN THE LAKE MICHIGAN BASIN
Compiled by the Governor's Interdisciplinary Committee on Pesticides
WISCONSIN
Agency Responsible for Registration, Labelling - Agriculture
Body Responsible for Regulations, Rules - Agriculture, Department
of Natural Resources and Public Health -
Pesticide Review Board Concurs on Regulations to be Adopted.
Pesticide Review Board Composed of: Heads of three agencies listed.
Technical Council is advisory to Pesticide Review Board.
Technical Council composed of: One Representative From Agriculture,
Natural Resources and Public Health
Three Representatives from the University of
Wisconsin (one each from College of
Agriculture and Life Sciences, Water
Resources Center, and School of Natural
Resources)
Three Citizen Members (one representing each the
Pesticide Industry, the Agricultural
Industry, and Conservation interests)
Restricted Pesticides Use by Permit Only - Yes
Commercial Applicators Licensed or Approved
Aerial - No
Aquatic - No - Commercial Applicators are not licensed but
are required by law to do all work under the
immediate supervision of a representative of
the Department of Natural Resources
Brush Control & Soil Sterilent - No
Mosquitoes - No
Space Fumigation - No
Structural Pest - No
Vertebrate Control - No
Pests of Animals - No
Field Crops - No
Fruit Crops - No
Lawn, Garden & Ornamental - No
Forest and Shade Tree - No
138
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WISCONSIN CONTINUED
Agency Regulating Commercial Applicators - By Administrative Code
the Department of Agriculture requires commer-
cial applicators of pesticides to register
annually with the Department and submit infor-
mation of the amounts and kinds of pesticides
used or sold.
Regulation of Local Government Units Applying Pesticides - No
Licensing of Dealers Handling Restricted Materials - Dealers are
not licensed by the Administrative Code are
required to register with the Department of
Agriculture to be eligible to sell restricted-
use pesticides and they must report amounts
and kinds of such pesticides sold during the
preceding calendar year.
Notice of Intent to Use Pesticides-Required - Yes
Disposal
Agency Having Authority for Regulation - Department of
Natural Resources
Disposal Sites Approved by State -
Adequate Incineration - Wo
Guidelines Developed - Yes
Basic Memorandum of Agreement Signed with USDA re Toxic Pesti-
cides - Yes
Supplemental Memorandum of Agreement Signed with USDA re Ethyl
Parathion - Yes
Agency Testing for Pesticide Residues in Food - Agriculture
139
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1
Accession Number
w
5
2
Organization
Wisconsin
Subject Field & Group
SELECTED WATER RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
Department of Natural Resources
Illinois Environmental Protection Agency
Michigan Water Resources Commission and Indiana Nat. Res. Department
Title
An Evaluation of DDT and Dieldrin in Lake Michigan
10
Authors)
Lloyd A. Lueschow
16
Project Designation Environmental Protection Agency
Grant 16050 EYV, ESP, EPV, and EYS.
2] Note
22
Citation
Environmental Protection Agency report
number EPA-R3-72-003, August 1972.
23
Descriptors (Starred First)
Pesticides*, DDT*, Badrin*, PCB*, Lake Michigan*, Organochlorines in Fish*,
Water Monitoring, Water Pollution, Insecticide Residues.
25
Identifiers (Starred First)
Pesticide-Monitoring, Tributaries of Lake Michigan in Wisconsin, Illinois,
Indiana, Michigan
27
Abstract
The presence of pesticides and particularly the chlorinated hydrocarbon
insecticides in Lake Michigan water is responsible for biological accumulations that
affect a wide variety of legitimate uses. The data collected from waters, wastewaters,
invertebrate organisms and fish all suggest that DDT plus analogs and dieldrin are
observed consistently at levels that warrant concern from both a public health and
wildlife preservation standpoint. The sources of these chlorinated hydrocarbon insec-
ticides include not only industrial and wastewater effluents but also diffuse sources
such as from agricultural activities and municipal pest control programs.
The evaluation of the chlorinated hydrocarbon insecticides in both wastewater and
biological specimens is complicated by the presence of products such as polychlori-
nated biphenyls and phthalates. These products interfere with the analysis for the
target insecticide and indeed, have biological implications of their own.
This report is submitted in fulfillment of four cooperative grants to the Lake Michigan
Enforcement Conference participating states under the sponsorship of the Environmental
Protection Agency and include grant numbers 16050 EYV, 16050 EYS, 16050 EPV, and
16050 ESP.
Abstractor
LToyd A. Lueschov
'Wisconsin Dept. of Natural Resources, Madison, Wise.
WR.102 (REV JULY 1969)
WRS! C
SEND, WITH COPY OF DOCUMENT, TO: WATER RESOURCES SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON* D. C. 20240
£U S GOVERNMENT PRINTING OFFICE 1972
* GPO: 197U-389-930
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