EPA-660/3-74-002
JANUARY 1974
                                   Ecological Research
        Pesticides  in  the  Illinois  Waters
                  of  Lake  Michigan
                                      30
                                                  01
                                  Office of Research and Development
                                  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
   1.  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 660/3-74-002
                                                         January 1974
               PESTICIDES IN THE  ILLINOIS WATERS

                       OF LAKE MICHIGAN
                              by
                       Robert A.  Schacht
           Illinois Environmental  Protection Agency
                       2121 West  Taylor
                   Chicago, Illinois   60612
                     Project No.  16050 ESP
                  Program Element No.  1BA023
                      Roap/Task 03 ACQ 01
                        Project Officer
                        LeRoy E.  Scarce
              Region V, Illinois  District Office
                Environmental Protection Agency
                   Chicago, Illinois   60609
                         Prepared  for
              OFFICE OF RESEARCH AND  DEVELOPMENT
            U.S.  ENVIRONMENTAL PROTECTION AGENCY
                    WASHINGTON, D.C.  20460
For sale by the Superintendent or Documents, U.S. Government Printing Office, Washington, D.C. 20402- Price Sl.25

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                         EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental Protection Agen-
cy and approved for publication.  Approval does not signify that the con-
tents necessarily reflect the views and policies of the Environmental
Protection Agency, nor does mention of trade names or commercial pro-
ducts constitute endorsement or recommendation for use.
                                 11

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                              ABSTRACT
This study was initated to determine present levels of pesticides  in
Lake Michigan fish, sediments, and water.  Data was collected on  six
species of Lake Michigan fish (yellow perch, chubs, carp,  coho salmon,
alewife, and brown trout); open lake and tributary stream  and ravine
sediments; and open water, tributary stream, and sewage treatment plant
effluents.  Samples analyzed for pesticides were selected  from the fol-
lowing list:  Heptachlor, heptachlor epoxide, dieldrin, methoxychlor,
lindane, aldrin, endrin, DDT and its analogs.  Additional  analyses were
accomplished for polychlorinated biphenyls (PCB's), di-n-butyl phthalate:
(DBP), and di(Z-ethylhexyl) phthalate:  (OOP).

The data indicate that PCB's were found at levels as high  or higher than
DDT in Lake Michigan water, sediment, and fish.  PCB's have been  found
to complicate the routine analysis of DDT which may have caused earlier
DDT data in the literature to be reported at levels higher than actual.
Both DDT and the polychlorinated biphenyls were found at levels which
cause concern for aquatic life and warrants the controlled use of these
compounds.

This report was submitted in fulfillment of Grant No. 16050 ESP between
the Office of Research and Development of the U.S. Environmental  Pro-
tection Agency and the Illinois Environmental Protection Agency.   This
project was proposed and performed by the Illinois Environmental  Pro-
tection Agency, Chicago, Illinois.  The survey was made in the Illinois
waters of Lake Michigan.
                                  111

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                              CONTENTS
Section                                                           Page
    I       Conclusions                                             1
   II       Recommendations                                         3
  III       Introduction                                            5
   IV       Pesticide Monitoring Lake Michigan Fish                 7
    V       Pesticide Monitoring Lake Michigan Sediments           13
   VI       Pesticide Monitoring Lake Michigan Water               23
  VII       Results and Discussion                                 33
 VIII       Acknowledgements                                       37
   IX       References                                             39
    X       Appendi ces
               Appendix A.   Analytical Quality Control Data       43
               Appendix B.   Field Methods                         53

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                              FIGURES

No.                                                             Page
1.          Locations of sediment sampling stations.              14
2.          Locations of water sampling  stations.                 24
                                VI

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                               TABLES
No.                                                              Page

 1    Pesticides found in edible portions of four species  of
     Lake Michigan fish (1970)                                     9

 2   Pesticides, PCB's, and phthalates found in edible portions
     of five species of Lake Michigan fish (1971)                 10

 3   Pesticides, PCB's, and phthalates found in edible portions
     of two species of Lake Michigan fish (1972)                  12

 4   Pesticides found in sediments from Lake Michigan and trib-
     utary streams and ravines in Illinois (1970)                 16

 5   Pesticides, PCB's, and phthalates found in Lake Michigan
     sediments and in tributary stream and ravine sediments  in
     Illinois (1971)                                   '           18

 6   Pesticides in water samples from Lake Michigan and trib-
     utary sources in Illinois (1970)                             26

 7   Pesticides found in water samples from several Illinois
     streams and sewage plants tributary to Lake Michigan (1971)   28

 8   Pesticides found in water samples from Illinois streams
     and sewage treatment plants tributary to Lake Michigan  (1972) 30
                                 vxi

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                             SECTION I

                            CONCLUSIONS
1.  The polychlorinated biphenyls (PCB's) were found in Lake Michigan
fish and sediments at levels which cause concern for aquatic life.
Aroclor 1254 was consistently found in fish flesh ranging from 0.1  to
3.3 ppm.  Levels of Aroclor 1254 found in Lake Michigan sediments
ranged between 2.48 and 46.92 ppb while tributary stream sediments
ranged between 1.54 and 232.00 ppb.  While not consistently found,
Aroclor 1242 was detected in fish flesh at levels ranging from N.D.
to 2.2 ppm.  Aroclor 1242 found in Lake Michigan sediments ranged
from N.D. to 106.07 ppb while tributary stream sediment levels ranged
from N.D. to 553.00 ppb.  The controlled use of these compounds ap-
pears warranted.

2.  Levels of DDT, PCB's, and dieldrin in edible portions of six
species of Lake Michigan fish were generally below interim guidelines
for maximum concentration in fish flesh.  These guidelines are 5.0  ppm
for both DDT and PCB's and 0.3 ppm for dieldrin.  Other chlorinated
hydrocarbon insecticides were not consistently found in the edible
portions of fish flesh.  Fish analyzed included yellow perch, coho
salmon, chubs, brown trout, carp and alewife.

3.  Both offshore and tributary sediments showed highest levels for
PCB's and DDT followed by methoxychlor and dieldrin.  Tributary sedi-
ments showed levels higher than open lake sediments.  Highest con-
centrations for PCB's were found in industrial areas in Waukegan and
North Chicago.  Highest concentrations of DDT were found in residential
areas in Highland Park, while highest levels of both dieldrin and meth-
oxychlor were found in Lake Forest.  Concentrations of total DDT, meth-
oxychlor, and dieldrin in Lake Michigan sediments ranged from 1.02  to
29.13, 0.13 to 6.60, and 0.03 to 1.25 ppb for each parameter respec-
tively.  Concentrations of total DDT, methoxychlor and dieldrin in  the
tributary and ravine sediments ranged from 0.42 to 942.00, 0.19 to
175.00, and 0.01 to 30.80 ppb for each parameter respectively.

4.  PCB's and phthalates showed highest maximum concentrations in the
sediments.  Maximum levels of Aroclor 1242 and Aroclor 1254 were 553.00
ppb and 232.00 ppb respectively.  Maximum levels of di(2-ethylhexyl)
phthalate and di-n-butyl phthalate were 218.00 ppb and 120.00 ppb re-
spectively.  Methoxychlor was the only pesticide found at concentrations
greater than 100.00 ppb.  The maximum concentrations of this pesticide
found was 175.00 ppb.  Maximum concentrations for the majority of the
isomers of DDT were below 50.00 ppb.  Maximum levels for p,p'-DDD and
p,p'-DDT were 66.50 ppb and 72.80 ppb respectively.

5.  Sediment sampling has been shown to be useful in determining areas
of high pesticide, PCB, or phthalate concentration and can be useful
in indicating areas of future sampling.

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6.  In most cases sewage treatment plant effluents were shown to dis-
charge higher concentrations of the pesticides, PCB's and phthalates
than the tributary streams.  Offshore water showed consistently low
concentrations for all parameters.  In the tributary streams Aroclor
1242 ranged from N.D. to 1810.0 ppt while Aroclor 1254 ranged from
61.0 to 841.0 ppt.  Di-n-butyl phthalate was found in concentrations
ranging from a trace to 147.0 ppt in 1972 and was not detected in 1971.
Di(2-ethylhexyl) phthalate was not detected in the tributary streams.
In sewage treatment plant effluents Aroclor 1242 ranged from N.D. to
4020.0 ppt.  Levels of Aroclor 1254 ranged from 97.0 to 568.0 ppt.  Di-
n-butyl phthalate was detected at levels from 55.0 to 250.0 ppt.  Di-
(2-ethylhexyl) phthalate was found only in 1971 at levels from N.D. to
760.0 ppt.

7.  The North Shore Sanitary District plant at Waukegan showed highest
levels for total DDT, methoxychlor, phthalates, and PCB's.  The North
Shore Sanitary District plant at North Chicago showed highest levels
for heptachlor epoxide and dieldrin.  Maximum concentrations of DDT and
methoxychlor were 259.0 and 106.0 ppt respectively.  Maximum concentra-
tions of heptachlor epoxide and dieldrin were 17.2 and 64.3 ppt re-
spectively.

8.  In sewage treatment plant effluents methoxychlor was the only pes-
ticide found at concentrations greater than 100.00 ppt.  Maximum con-
centrations of the majority of the isomers of DDT were below 50.0 ppt.
This level was exceeded by o,p'-DDT and p,p'-DDT with maximum concen-
trations of 74.6 ppt and 132.6 ppt respectively.

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                             SECTION II

                           RECOMMENDATIONS
1.  Future research on Lake Michigan should be directed to determine
the effects of various pesticides and exotic chemicals on aquatic life.
Polychlorinated biphenyls (PCB's) and phthalates require further study.

2.  Data from this study indicates that possible sources of DDT, poly-
chlorinated biphenyls (PCB's), heptachlor epoxide, dieldrin, methoxy-
chlor, and phthalates should be included in future water sampling pro-
grams.  Industrial and municipal effluents should be monitored.

3.  Monitoring of fish samples should continue and be directed toward
determining trends.  Data on DDT, PCB's, dieldrin, and phthalate con-
centrations should be collected.  A continuous monitoring program
should be conducted on the entire lake by a single Agency of the Fed-
eral government.  Bordering Lake states should provide additional data
as budgetary restraints permit.

4.  Federal support of state monitoring programs, including sediment
sampling, should be directed toward determining inputs of pesticides,
heavy metals, and other exotic chemicals, results of which can be used
in enforcing regulations adopted as a result of monitoring programs.

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                            SECTION III

                            INTRODUCTION

The States of Illinois, Indiana, Michigan and Wisconsin were provided
grants to conduct a monitoring program on Lake Michigan to determine
levels of DDT and to develop an analytical capability for pesticide
analysis.  The pesticide monitoring program was coordinated by a
technical committee established under the Lake Michigan Enforcement
Conference.  An initial report with recommendations was submitted to
the conference in 1968 (The Lake Michigan Interstate Pesticide Com-
mittee of the Lake Michigan Enforcement Conference, 1968).

On September 23, 1969 the Sanitary Water Board of the Illinois Depart-
ment of Public Health accepted an EPA Research and Development grant
(16050 ESP) of $40,000 or 66.4% of eligible grant period costs, which-
ever is less.  On July 1, 1970 the Illinois Environmental Protection
Agency replaced the Sanitary Water Board and assumed the responsibil-
ities of the grant.  Analytical capabilities for pesticides were being
developed by the State throughout the grant period.  Data reflected in
this report was analyzed by Anderson Physics Laboratories, Inc. of
Urbana, Illinois, with quality control being accomplished by the Illi-
nois Environmental Protection Agency covering the period beginning in
the fall of 1970 through July 1, 1972.  Data collected by the Illinois
Environmental Protection Agency in 1970 appears in the four-state re-
port, "An Evaluation of DDT and Dieldrin in Lake Michigan", (The Lake
Michigan Interstate Pesticide Committee, 1970).  This report is made
to include additional data collected and analyzed to fulfill require-
ments of Project 16050 ESP.

Information on present levels of DDT in Lake Michigan was sought in
water, sediment, and fish tissue.  As the project progressed, more
parameters were analyzed.  Polychlorinated biphenyls (PCB's), phthal-
ates, heptachlor, heptachlor epoxide, dieldrin, methoxychlor, lindane,
aldrin, and endrin levels were examined.  Later in the project, a re-
duced number of stations were sampled with emphasis being placed on
sewage treatment plant and tributary inputs.  The total number of spe-
cies of fish, analyzed was reduced to allow an increased number of sam-
ples of yellow perch and chubs.  Sediment samples were collected in the
open lake and in tributary streams and ravines to determine present
levels.

Data from this monitoring program provided information on present levels
of various pesticides in Lake Michigan and indicated that PCB's and
other environmental contaminants should receive further study.

While PCB's were not separated during routine analyses for the pesti-
cides in 1970, this procedure was accomplished during 1971 and 1972.
Both Vieth and Lee (1970) and WARF Institute, Inc. (1970) reported that
PCB's may introduce serious errors or extreme difficulty in interpre-

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ting results in pesticide analyses.  While PCB's were found in Lake
Michigan, their biological significance was not known.  Studies were
initiated by the National Water Quality Laboratory in Duluth, Minnesota
(Nebeker, e_t al_., 1972) to determine the toxicity of PCB's to fish and
aquatic life.  This study indicated that PCB's were cumulative and did
exhibit a chronic toxicity at very low levels.  Further monitoring will
be needed to determine sources of PCB's.

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                            SECTION IV

                       PESTICIDE MONITORING

                        LAKE MICHIGAN FISH
In 1969 concern over DDT contamination in Lake Michigan  increased when
it was found that hatchery mortality of coho salmon could have been
caused by DDT (Willford, et a]_., 1969).  Although PCB's  were not re-
ported, this compound could have been involved.

The Illinois Environmental Protection Agency initiated a program in
1970 to obtain pesticide residue levels in several species of Lake
Michigan fish.  In 1971 and 1972, analyses were expanded from testing
for total DDT, heptachlor epoxide, and dieldrin to include polychlori-
nated biphenyls (PCB's), phthalates, methoxychlor, lindane (BHC),
aldrin, endrin and heptachlor.

A total of 255 fish were analyzed over the three year period including
samples of yellow perch, chubs, carp, coho salmon, alewife and brown
trout.  Difficulties in obtaining all species in 1972 limited collections
to yellow perch and chubs.  Fish were collected from commercial fisher-
men and the Illinois Conservation Department in the Chicago and Waukegan
regions of Lake Michigan.  Fish were separated by species and sex and
composited into samples of five fish whenever possible according to  re-
commendations of the technical pesticides committee (Lake Michigan  In-
terstate Pesticide Committee, 1968).

In most species, levels of polychlorinated biphenyls (PCB's) were as
high or higher than DDT.  Levels of PCB and DDT were all below the in-
terim guidelines of 5.0 ppm and 0.3 ppm for dieldrin established by  the
Food and Drug Administration  (Tables 1, 2, and 3).  Aroclor 1254 was
identified in all samples analyzed, including yellow perch, chub,  carp,
coho, and alewife.  Aroclor 1242 was found in several samples of yellow
perch, chubs, carp, and coho salmon.

Chubs most often had the highest levels of PCB's and DDT while perch
had the lowest.  Alewives shpwed PCB levels comparable to chubs.  Male
yellow perch, chubs, and alewife had higher concentrations of PCB and
DDT than females.

In this study heptachlor, heptachlor epoxide, methoxychlor, lindane,
aldrin, endrin and phthalates were not found in concentrations which
would indicate a present problem in fish flesh.  Levels of DDT were
lower than those found by Reinert (1970) in several species of Lake
Michigan fish.  Reinert based his work on whole fish while data in
this study is based on the edible portions only.  From the public
health standpoint, the edible portions of fish flesh are considered
to indicate a better picture of pesticide contamination since some

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pesticides may be concentrated in various organs or fatty tissues which
would be lost in cleaning or cooking and therefore would not be ingested.
Earlier studies indicated total DDT concentrations without the separation
of PCB's.  Since PCB's were separated in this study, more meaningful  data
had been produced.

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                                                                              TABLE 1
                                           PESTICIDES FOUND  IN EDIBLE PORTIONS OF FOUR SPECIES OF LAKE MICHIGAN FISH  (1970).
                                           Values are expressed In.parts per million (ppm) on a weight basis.
(O


SPECIES
Yellow Perch
Yellow Perch
Ye 1 low Perch
Yellow Perch
•Coho Salmon
Coho Salmon
Coho Salmon
Coho Salmon
Chubs
Chubs

NUMBER AND
SEX ANALYZED
5 Female
5 Female
5 Hale
5 Male
4 Male
4 Male
3 Female
2 Female
5 Mixed
' 5 Mixed

-SIZE IN
INCHES
9.0 - 10.0
9-0 - 9.5
9.0 - 9.5
8.5 - 10.0
24.5 - 31.0
28.0 - 29.0
26.0 - 27.5
25.0 - 27.5
10.5 - 11.5
10.5 - 11.5
- -
SAMPLE
LOCATION
Chicago
Chicago
Chicago
Chicago
Waukegan
Waukegan
Waukegan
Chicago
Waukegan
Waukegan

DATE
COLLECTED
11/19/70
11/19/70
1 1/ 19/70
11/19/70
1 1/23/70
11/13/70
11/13-23/70
11/13/70
12/22/70
12/22/70
o. p1 Isomers
HEPTACHLOR
EPOXIDE DIELDRIN DDE DDT
0.
0.
0.
0.
<0.
<0.
<0.
<0.
0 .
0.
0.1 0. 0.1
0.
0.
0.
<0.
<0.
<0.
<0.
0.
0.
<0. 0.1
0. 0.1
0. 0.1
0. 0.2
0. 0.2
0. O.I
0. O.I
0.3 0.4
0.3 0.3
Pi p'

ODE
0.5
0.4
0.6
0.6
1.0
0.9
0.8
0.9
1.3
1.2
Isomers

DDT
0.3
0.3
0.6
0.5
0.6
0.4
0.3
0.5
1.1
1.0


ODD
0.2
0.1
0.2
0.2
0.3
0.2
0.2
0.2
0.4
0.3

TOTAL
DDT
1.2
0.9
1.6
1.5
2.2
1.8
1.5
1.8
3-5
3.1
     Brown Trout
                      3 Female
17-5 - 20.5   Chicago    11/13/70
                                                                                                  0.2
                                                                                                            0.3
1.3
0.8
         0.5
3.1

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                                       TABLE 2

PESTICIDES, FOB'S AND PHTHAUTES FOUND IN EDIBLE PORTIONS  OF  FIVE  SPECIES OF
LAKE MICHIGAN FISH (1971).  Values are expressed In parts  per million  (ppra)
on a wet weight basis.


SPECIES
Yellow Perch
Yellow Parch
Yellow Perch
Yellow Perch
Chub
Chub
Chub
Chub
Carp
Carp
Carp
Carp
Carp
Carp
Coho Salmon
Coho Salmon
Coho Salmon
Coho Salmon
Coho Salmon
Coho Salmon
Coho Sal iron
Alewl fe
Alewlfe
Alewlfe
Alewlfe
Alewlfe
Alewlfe
Alewlfe
Alewlfe
OOP •
DBP -
T "
ND -
NUMBER
AND SEX
ANALYZED
4 Halo
5 Hale
5 Female
5 Female
5 Female
5 Female
5 Hale
5 Hale
5 Hale
4 Hale
4 Female
5 Female
5 Female
5 Hale
5 Hale
4 Hale
5 Female
5 Female
5 Female
5 Hale
4 Hale
5 Hale
5 Hale
5 Female
5 Female
5 Female
5 Female
5 Male
5 Hale

SIZE IN
INCHES
7.0 - 10.5
8.0 - 11.0
8.0 - 12.0
8.0 - 10.0
3.0 - 10.0
10.0 - 10.5
9.5 - 12.0
10.0 - 12.0
17-5 - 27.5
17.0 - 23.5
18.0 - 25.0
22.5 - 25.5
23.5 - 30.0
18.0 - 23.0
18.5 - 21.5
18.0 - 20.0
18.5 - 21.0
18.5 - 22.0
19.5 - 22.5
20.0 - 23.5
18.5 - 21.5
6.0 - 7.0
6.0 - 7.0
6.0 - 7.0
6.0 - 7.0
6.0 - 7.0
6.0 - 7.0
6.0 - 7.0
6.0 - 7-0

SAMPLE
LOCATION
Chicago
Chicago
Chicago
Chicago
Waukegan
Waukegan
Waukegati
Waukegan
Chicago
Chicago
Chicago
North Chicago
North Chicago
Chicago
Chicago
Chicago
Chicago
Waukegan
Waukegan
North Chicago
North Chicago
Chicago
Ch 1 cago
Chicago
Chicago
North Chicago
North Chicago
North Chicago
North Chicago

DATE HEPTACHLOR
COLLECTED EPOXIDE DIELDRIN HETHOXYCHLOR
10/6/71 <0.1 <0.1 ND
10/6/71 <0.1 <0. ND
10/6/71 <0.1 <0. ND
10/6/71 <0.1 <0. ND
7/13/71 <0.
7/13/71 <0.
7/13/71 <0.
7/13/71 <0.
4/13 - "1/20/71 <0.
4/20/71 <0.
4/13 - 4/20/71 <0.
5/25/71 <0.
5/25/71 T
4/13 - 4/20/71 <0.
4/13 - 4/20/71 <0.
4/13 - 4/20/71 <0.
4/13 - 4/20/71 <0.
5/26/71 <0.
5/26/71 <0.
5/26/71 <0.
4/13 - 5/26/71 <0.
5/11/71 <0.
5/H/7I <0.
5/11/71 <0.
5/11/71 <0.
V28/71 <0.
4/28/7 t <0.
4/28/71 <0.
0. ND
0. ND
0.2 HD
0.2 ND
0.
<0.
0.
<0.

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                                                                TAELE  2
                                                              (Continued)

                         PESTICIDES, FOB'S AMD PHTKALATES FOUND IN  EDIBLE  PORTIONS OF FIVE SPECIES OF
                         LAKE MICHIGAN FISH (1971).   Value! are expressed  In parti per million  (ppn)
                         on • wet weight b»U.

SPECIES
Yellow Perch
Yellow Perch
Yel low Perch
Yellow Perch
Chub
Chub
Chub
Chub
Carp
Cerp
Carp
Carp
Carp
Carp
Coho Salmon
Coho Saloon
Coho Salmon
Coho Saloon
Coho Salmon
Coho Salmon
Coho Salenn
Alewlfe
Alewlfe
Alewlfe
Alewlfe
Alewlfe
Alewlfe
Alewlfe
Alewlfe
NUMBER
AND SEX
ANALYZED
4 Hale
5 Hale
5 Female
5 Female
5 Female
5 Female-.
5 Hale
5 Hale
S Hale
4 Hale
4 Female
5 Female
5 Female
5 Hale
S Hale
4 Hale
S Female
5 Female
S Female
S Hale
4 Hale
5 Hale
5 Hale
$ Female
5 Female
S Female
5 Female
5 Hale
S Hale

SIZE IN
INCHES
7.0 - 10.5
8.0 - II .0
8.0 - 12.0
8.0 - 10.0
9.0 - 10.0
10.0 -.10.5
9.5 - 12.0
10.0 - 12.0
17.5 - 27.5
17.0 - 23.5
18.0 - 25.0
22.5 - 25.5
23.5 - 30.0
18.0 - 23.0
18.5 - 21.5
18.0 - 20.0
18.5 - 21.0
18.5 - 22.0
19.5 - 22.5
20.0 - 23.5
18.5 - 21.5
6.0 - 7.0
6.0 - 7.0
6.0 - 7.0
6.0 - 7-0
6.0 - 7.0
6.0 - 7.0
6.0 - 7.0
6.0 - 7-0

SAMPLE
LOCATION
Ch 1 cago
Chicago
Chicago
Chicago
Vaukegan
Vaukegan
Waukegan
Waukegan
Chicago
Chicago
Chicago
North Chicago
North Chicago
Chicago
Chicago
Ch 1 cago
Chicago
Vaukegan
Waukegan
Uaukegan
North Chicago
Chicago
Chicago
Chicago
Chicago
North Chicago
North Chicago
North Chicago
North Chicago

DATE
COLLECTED
10/6/71
10/6/71
10/6/71
10/6/71
7/13/71
7/13/71
7/IV71
7/13/71
4/13 - 4/20/71
4/20/71
4/13 - 4/20/71
5/25/71
5/25/71
4/13 - 4/20/71
4/13 - 4/20/71
4/13 - 4/20/71
4/13 - 4/20/71
5/26/71
5/26/71
5/26/71
4/13 - 5/26/71
5/11/71
5/11/71
5/11/71
V 11/71
V 28/71
V28/7I
V28/71
V28/7I
o. D' Isomeri P. p' Isoraers Aroclor
TOTAL
DDE DDD DDT DDE ODD DDT DDT 1242 1254
0. <0. O.I 0.5 0. 0.4 1.2 .1 .3
<0. <0. O.I 0.2 0. 0.2 0.6 .1 .2
<0. <0. <0.l O.I <0. O.I 0.3 " .1
<0. <0. <0.l O.I <0. <0.l 0.3 " .1
<0. <0. 0.3 1-8 0. 1.2 3-5 .2 2.5
<0. *
T   •  Trace

-------
                                                                  TABLE 3

                            PESTICIDES,  PCB'S AND PHTHALATES FOUND IN THE EDIBLE PORTIONS OF TWO SPECIES OF
                            LAKE  MICHIGAN  FISH  (1972).  Values are expressed  In parts per million  (ppm) on
                            a wet weight basis.
SPECIES
Chubs
Chubs
Chubs
Chubs
Chubs
Chubs
. Chubs
Chubs
Yellow Perch
Yellow Perch
Yel low Perch
Yellow Perch
Yellow Perch
Yellow Perch
NUMBER AND
SEX ANALYZE*
5 Hale
5 Female
5 Female
5 Female
5 Female
5 Female
5 Female
5 Female
5 Female
k Female
5 Hale
5 Female
5 Hale
5 Hale
SIZE IN
INCHES
8.5 - 10.0
8.5-10.0
9.0 - 9.5
8.5 - 9.»
8.0 - 8.5
8.5 - 10.0
8.5 - 10.0
8.0 - 8.5
8.0 - 9.5
8.5 - 9.0
8.0 - 9.5
8.5 - 9-5
9.0 - 9.5
8.0 - 9.0
SAMPLE
LOCATION
Waukegan
Waukegan
Waukegan
Waukegan
Waukegan
Waukegan
Waukegan
Waukegan
Waukegan
Waukegan
Waukegan
Waukegan
Waukegan
Waukegan
DATE HEPTACHLOR
COLLECTED EPOXIDE DIELDRIN
5/25/72 
-------
                             SECTION V

                        PESTICIDE MONITORING

                       LAKE MICHIGAN SEDIMENTS
In 1970 and 1971, fifty sediment samples were collected in tributary
streams and ravines in Lake County and at stations offshore from from
Lake and Cook Counties in Illinois (Tables 4 and 5).   Stream and ra-
vine sediment samples were collected approximately 50 yards upstream
from Lake Michigan.  Lake samples were collected 40 to 80 yards off-
shore from seven North Shore Sanitary District (NSSD) sewage treatment
plants and at stations approximately one to three miles offshore using
a Ponar dredge   (Figure 1).  As could be expected offshore stations
contained low levels of pesticides, PCB's, and phthalates.  Tributary
stream and ravine sediments reflected possible contamination from re-
sidential spraying programs.  Some of the exotic chemicals were found
in greater concentrations in industrial areas and off sewage treat-
ment plants in Lake County.  Analysis of sediments was found to be use-
ful in locating areas in which additional sampling could possibly de-
termine sources.

At the offshore stations, PCB's were usually found in highest concen-
trations followed by DDT, methoxychlor, dieldrin, and heptachlor ep-
oxide.  Concentrations averaged less than 7.0 ppb for total DDT, 1.24
ppb for methoxychlor, <0.5 ppfa for dieldrin, and <0.6 ppb for hepta-
chlor epoxide.  Aldrin, endrin, lindane, heptachlor, and di-n-butyl
phthalate were not detected in sediments of the open lake Di(2-ethyl-
hexyl) phthalate was rarely found in the open water sediments.

Tributary stream and ravine sediments reflected highest concentrations
of PCB's and total DDT followed by methoxychlor, heptachlor epoxide,
dieldrin, and heptachlor.  Lindane and the phthalates were not con-
sistently found in the tributary sediments.  Aldrin and endrin were not
detected.

Concentrations of total DDT, dieldrin, and lindane found in stream sed-
iments compared favorably with results found by the Wisconsin Alumni
Research Foundation (WARF Institute, Inc., 1970) in its survey of 73
sediments samples collected in streams tributary to Lake Michigan.
                                  13

-------
Wisconsin _
Illinois
Kellogg Creek
Bull Creek
Dead River,
Unnamed Channel^
Waukegan Rlver«f

1
.2 05
NSSD Waukegan STP Sc>)e ,„
. 5
|
I
10
miles
                        I. NSSD North Chicago STP

        Petti bone CreekJ  g

     Ravine Park Ravlne'HSSD Lak« Bluff STP                LAKE MICHIGAN

  Woodland Drive Ravine A .,,J» ,  ,   .      „,..
Ferry Hall School RavlnJ\'NSSD Lak" F°reSt STP
  Stone Gate Lane Ravine
            Barat Ravine


           Park Ave.  Ravine VMSSD^HIghland Park @ Park Ave. STP
         Ravine Drive Ravine A.NSSO Highland Park § Ravine Dr. STP
.  .   ,       Cary Ave. Ravine X,_   »21
L2!«_(:0!tn£V!	._—^\^~	NSSD Highland Park @ Cary Ave. STP
Cook County
                                                             .62
                  FIGURE  1.     LOCATIONS  OF SEDIMENT  SAMPLING STATIONS
                                           14

-------
                      OPEN WATER SEDIMENTS


Heptachlor epoxide
Heptachlor epoxide levels averaged below 0.6 ppb and ranged from
ND - 1.35 ppb at a point 40 - 80 yards offshore from the North Shore
Sanitary District sewage treatment plant in Lake Bluff.

Dieldrin
Concentrations of dieldrin averaged less than 0.5 ppb and ranged from
0.03 - 1.25 ppb.  The highest level was found at lake bed station number
43 offshore from Chicago.

Methoxychlor
Concentrations of methoxychlor averaged 1.24 ppb and ranged from 0.13 -
6.60 ppb.  The highest level was found at station number 37 offshore
from Chicago.

Pi (2-ethylhexyl) phthalate:  (POP)
Di (2-ethylhexyl) phthalate was rarely found in the open water sedi-
ments.  This chemical was found in three out of ,24 samples at values
ranging from ND - 7.18 ppb.

o,p'-DDE
Concentrations of o,p'-DDE ranged from <0.1 - 0.97 ppb.   The highest
level (0.97 ppb) was found 40 - 80 yards offshore from the North Shore
Sanitary District plant at Park Avenue in Highland Park.  Twenty samples
collected in 1971 averaged 0.07 ppb.

o,p'-DDD
Concentrations of o,p'-DDD ranged from 0.02 - 5.47 ppb.   The highest
level (5.47 ppb) was found at lake bed station number 46 offshore from
Chicago.  Twenty-four samples collected in 1971 ayeraged 1.01 ppb.

o,p'-DDT

Concentrations of o.p'-DDT ranged from 0.02 - 4.00 ppb.   The highest
level (4.00 ppb) was found 40 - 80 yards offshore from the North Shore
Sanitary District plant at Park Avenue in Highland Park.  Twenty-two
samples collected in 1971 averaged 0.24 ppb.

p.p'-DDE

Concentrations of p.p'-DDE ranged from 0.06 - 4.82 ppb.   The highest
level (4.82 ppb) was found at lake bed station number 43 offshore from
Chicago.  Twenty-four samples collected in 1971 averaged 1.21 ppb.
                                 15

-------
                                       TABLE *

PESTICIDES POUND IN SEDIMENTS FROM LAKE MICHIGAN AND TRIBUTARY STREAMS AND RAVINES
IN ILLINOIS (1970).  Values are expressed In parts per billion (ppb) on • dry weight
basis.

SAMPLE
LOCATION
Tributary Strewn and Ravines1
Waukegan River
Pettlbone Creek
Lake Bluff-Ravine
Lake Forest-Woodland Drive Ravine
Lake Forest-Barat Creek
Highland Park-Ravine Drive Ravine
Like Sedlmnts>
Waukegan
North Chicago
Lake Bluff
Lake Forest
Highland Park (Park Avenue)
Highland Park (Ravine Drive)
Highland Park (Cary Avenue)
1 SO yards upstream from
2 40-80 yards offshore of

HEPTACHLOR
EPOXIDE

9.80
9.30
2.60
57.00
3.10
lulojj

0.38
0.98
1.35
0.58
0.26
0.17
(o!S5J
Lake Michigan.
the Indicated


DIELDRIN

4.09
21.40
1.37
30.80
3.40
2.64
(10.41)

0.29
0.64
0.80
0.28
0.55
0.08
0.28
10.42)

sewage treatment
o.

DDE

...
1.02
0.61
17.00
1.10
(*!w

0.39

0.03
0.05
0.97
0.01
0.04
W.25)

plant.
p1 Isoners

DDD

...
35.00
...
62.00
2.73
53.00
(S9.55J

0.75
0.65
...
...
3.60
1.87
0.02
(1.38)


PI p1 Isoners

DDT

0.50
27.50
6.50
83.00
7.50
17^50
TWIST

»«•
0.02
0.50
0.25
4.00
...
0.50
TTToBT



DDE

6.40
67.30
4.60
52.00
8.57
27.20
T57TW

0.06
1.15
3.00
0,77
0.48
0.45
TOST



DDD

30.60
258.00
58.80
353.00
2V.50
120. 00
(141.3!)

l.4l
4.23
12.60
2. SB
0.02
0.01
TPtTT



DDT

18.00
340.00
24.00
375.00
50.10
81.60
7,niB.l2)

1.14
«.73
13.00
1.20
1.90
0.89
(jili)


TOTAL
DDT

55.50
728.82
94.51
942.00
97.50
300.21
(369.TO

3.75
7.78
29.13
5.15
10.97
3.23
6.40
TjPisT



-------
p.p'-DDD
Concentrations of p.p'-DDD ranged from 0.01  - 12.60 ppb.   The  highest
level (12.60 ppb) was found 40 - 80 yards offshore from the North
Shore Sanitary District Lake Bluff plant.  Twenty-four samples collec-
ted in 1971 averaged 3.04 ppb.

P,P'-DDT
Concentrations of p,p'-DDT ranged from 0.11  - 13.00 ppb.   The  highest
level (13.00 ppb) was found 40 - 80 yards offshore from the North
Shore Sanitary District sewage treatment plant at Lake Bluff.   Twenty-
four samples collected in 1971 averaged 1.21 ppb.

Aroclor 1242
Concentrations of Aroclor 1242 ranged from ND - 106.07 ppb. The
highest level was found 40 - 80 yards offshore from the North  Shore
Sanitary District sewage treatment plant at North Chicago.  Twenty-four
samples collected in 1971 averaged 23.66 ppb.

Aroclor 1254
Concentrations of Aroclor 1254 ranged from 2.48 - 46.92 ppb.  The  high-
est level (46.92 ppb) was found at lake bed station number 43  off  of
Chicago.  Twenty-four samples collected in 1971 averaged 14.66 ppb.
                       TRIBUTARY SEDIMENTS

Heptachlor Epoxide
Concentrations of heptachlor epoxide ranged from 0.02 - 57.00 ppb.   The
highest level (57.00 ppb) was found in the Woodland Drive ravine in
Lake Forest approximately 50 yards upstream from Lake Michigan.

Dieldrin
Concentrations of dieldrin ranged from 0.01 - 30.80 ppb.  The highest
level was found (30.80 ppb) approximately 50 yards upstream from Lake
Michigan in the Woodland Drive ravine in Lake Forest.

Methoxychlor
Concentrations of methbxychlor ranged from 0.19 - 175.00 ppb.  The
highest level (175.00 ppb) was found in Barat Ravine in Lake Forest
approximately 50 yards upstream from Lake Michigan.

Lindane
Concentrations of lindane were detected in 4 of 13 samples.  Levels
ranged from ND - 0.15 ppb.
                                17

-------
                                                                   TABLE 5

                             PESTICIDES,  PCB'S AND PHTHALATES FOUND IN LAKE MICHIGAN SEDIMENTS AND IN TRIBUTARY
                             STREAM AND RAVINE SEDIMENTS  IN  ILLINOIS  (1970.  ValiM* are expressed In parti per
                             billion (ppb) on •  dry weight bails.
SAMPLE
LOCATION

-------
TABLE 5
(CONTINUED)
PESTICIDES. PCt'S AND PHTHALATES FOUND IN OWE Ml CHI SAN
STREAM AND RAVINE SEDIMENTS IN ILLINOIS (1971). Values
billion (ppb) on a dry Might basis.

SAMPLE
LOCATION
<1 to 3 MILES OFFSHORE
NSSD Park Ave. STP (Highland Park)
NSSD Lake Forest STP (Lake Forest)
NSSD Lake Bluff STP (Lake Bluff)
NSSO North Chicago STP (North Chicago)
NSSD Uaukegan STP (Vaukegan)
Lake Bed Station 60
Lake Bed Station 55
Lake Bed Station 52
Lake Bed Station 49
Lake Bed Station 46
Lake Bed Station 43
Lake Bed Station 40
Lake Bed Station 37
Lake Bed Station 34
Lake Bed Station 31
Lake Bed Station 28
Lake Bed Station 24
Lake Bed Station 21
Lake Bed Station 18
Lake Bed Station 15
Lake Bed Station 12
Lake Bed Station 8
Lik« Bed Station 5
Lake Bed Station 2
-10 to 50 YARDS UPSTREAM FROM LAKE
Bull Creek (2 Ion)
Dead River (21 on)
Unnamed channel (Uaukagan)
Uaukegan River (Uaukagan)
Pettlbone Creek (North Chicago)
Stone Gate Lane Ravine (Lake Forest)
Barry Hall School Ravine (Lake Forest)
Cary Avenue Ravine (Highland Park)
Ravine Drive Ravine (Highland Park)
Park Ave. Ravine (Highland Park)
Bjrjc lUvlna (Lake Forest)
Ravine Perk Ravine (Lake Bluff)
Kellogg Creek (Zlon)
o

DDE

0.01
...
0.01

— '•-
0.10
0.06
0.04
0.04
0.25
0.26
0.09
0.14
0.02
0.02
0.04
0.04
0.02
0.01
0.02
0.03
0.04
...

-------
Heptachlor
Concentrations of heptachlor ranged from ND - 0.24 ppb.  The highest
level (0.24 ppb) was found in the Waukegan River approximately 50
yards upstream from Lake Michigan.

Pi (2-ethylhexyl) phthalate;  (POP)
OOP was detected in 5 of 13 samples collected in 1971.  Concentra-
tions ranged from ND - 218.00 ppb.  The highest concentration (218.00
ppb) was obtained from an unnamed channel in Waukegan.

Di-n-butyl phthalate;  (DBP)
DBP was detected in 2 of 13 samples collected in 1971.  Concentrations
ranged from ND - 120.00 ppb.  The highest concentration (120.00 ppb)
was obtained approximately 50 yards upstream from Lake Michigan in
the Park Avenue Ravine in Highland Park.

o, p'-DDE
Concentrations of o, p'-DDE ranged from ND - 17.00 ppb.  The maximum
level of 17.00 ppb was found in the Woodland Drive ravine in Lake
Forest.

o. p'-DDD
Concentrations of o, p'-DDD ranged from ND - 62.00 ppb.  The maximum
level was found in the Woodland Drive ravine in Lake Forest.

o. p'-DDT
Concentrations of o, p'-DDT ranged from ND - 83.00 ppb.  The maximum
level was found in the Woodland Drive ravine in Lake Forest.

p. p'-DDE
Concentrations of p, p'-DDE ranged from 0.17 - 67.30 ppb.  The highest
level was found in Pettibone Creek in North Chicago.

p, p'-DDD
Concentrations of p, p'-DDD ranged from 0.08 - 353.00 ppb.  The high-
est level was found in Woodland Drive ravine in Lake Forest.

p, p'-DDT
Concentrations of p, p'-DDT ranged from 0.11 - 375.00 ppb.  The high-
est level was found in Woodland Drive ravine in Lake Forest.

Aroclor 1242
Concentrations of Aroclor 1242 ranged from ND - 553.00 ppb.  The
maximum level (553.00 ppb) was found in an unnamed channel in
Waukegan.
                                 20

-------
Aroclor 1254
Concentrations of Aroclor 1254 ranged from 1.54 - 232.00  ppb.   The
maximum level (232.00 ppb) was found in Petti bone Creek in  North
Chicago.
                                 21

-------
                           SECTION VI

                      PESTICIDE MONITORING

                       LAKE MICHIGAN WATER


Forty-five samples were collected at open water stations, water
treatment plants (raw water), tributary streams, and sewage treatment
plant final effluents over the three year study.  In 1971 and 1972,
water sampling was expanded at the tributary streams and sewage treat-
ment plants to determine inputs after it has been established that
total DDT levels in Lake Michigan were in the range of one to ten
parts per trillion (Lake Michigan Interstate Pesticide Committee,
1972).  There are only two counties in Illinois which border Lake
Michigan.  These are Lake and Cook counties.  All sewage treatment
plant effluents and tributary stream sources enter Lake Michigan from
Lake County (Figure 2).

In 1971 and 1972, analyses were performed on total DDT and its analogs,
polychlorinated biphenyls (PCB's), phthalates, heptachlor, heptachlor
epoxide, dieldrin, methoxychlor, lindane, aldrin, and endrin.  In  1970,
water samples were analyzed for DDT, dieldrin, and heptachlor epoxide
only (Tables 6, 7, and 8).

In 1970, six crib samples from water treatment plants and 3 open water
samples showed concentrations of DDT, heptachlor epoxide and dieldrin
all below 1 ppt.

A total of 23 sewage treatment plant samples were collected in the
three year period.  North Shore Sanitary District plants at North
Chicago and Waukegan were sampled each year.  Sewage treatment plants
at Lake Bluff, Lake Forest, and three at Highland Park were sampled
in 1970 only.  Sewage treatment plant effluents generally showed
higher concentrations of both PCB's and DDT than did the tributary
streams.  Concentrations of PCB's greatly exceeded concentrations  of
other pesticides in 1971 sampling but showed reduced values in 1972.
Dieldrin showed a decrease from 1971 while DDT showed increased con-
centrations.  While di (2-ethyhexyl) phthalate was found in sewage
treatment effluents at concentrations up to 760 ppt in 1971, it was
not found in 1972.  In 1972, di-n-butyl phthalate was found in both
sewage treatment plant effluents and tributary streams.  Lindane,
aldrin, endrin and heptachlor were not detected in sewage treatment
plant effluents or the tributary streams.

Over the three year period, thirteen tributary samples were collected
at two locations in Lake County, Illinois.  Samples were collected
at the Waukegan River in Waukegan and Pettibone Creek in North
Chicago.
                                23

-------
  Wisconsin
 "III fools"
                 Wlnthrop
                 Harbor
                                       mile station
        Waukegan River,
                           SSD Waukegan STP
                           aukegan WFP
                       /NSSD North Chicago STP
                       'North Chicago WFP
      Petti bone Creek .1

                      •I NSSD Lake Bluff STP


                              Lake Forest STP
          Highland Park
Lake County
Cook County
 MSSD  Highland  Park @  Park Ave.  STP
"\NSSD  Highland  Park  @  Ravine  Drive  STP
    4SSD Highland Park § Cary Ave. STP
                                                        Scale In  miles
                             LAKE  MICHIGAN
                            Evanston
                       •4 mile station
                                                                          10
                           Chicago Central WFP
                             •4 mile station
                                      Chicago  South WFP.
              FIGURE  2.     LOCATIONS OF WATER  SAMPLING  STATIONS
                                           24

-------
                             STREAMS
Heptachlor epoxide
Heptachlor epoxide levels averaged  <0.6,  2.1  and 2.9 ppt for 1970, 1971,
and 1972 respectively.   Annual  ranges  were <0.2 -  1.0, ND - 5.4,
and 1.2 - 4.5 ppt during the respective  period.

Dieldrin
Dieldrin levels averaged 1.2, 10.4, and  2.5 ppt for 1970, 1971, and
1972 respectively.  Annual  ranges were 0.9 -  1.4, 2.1 - 22.5, and
1.7 - 3.7 ppt during the respective period.   The highest concentration
of dieldrin (22.5 ppt)  was  obtained at the Waukegan River on 8/18/71.

Methoxychlor
Concentrations of methoxychlor averaged  15.5  ppt in 1971 and 48.0 ppt
in 1972.  The range in  concentrations  during  1971 was 2.9 - 30.7 ppt
and 22.6 - 89.1 ppt in  1972.  Highest  levels  were obtained from
Petti bone Creek in North Chicago.

Di-n-butyl phthalate:  (DBP)
Concentrations of di-n-butyl phthalate were  not detected in 1971.  In
1972, levels averaged 93.6 ppt and ranged from a trace to 147.0 ppt.
Similar concentrations  were found at both stream stations.

o. p'-DDE
This isomer was not detected in 1971 and 1972.

o, p'-DDD
o, p'-DDD averaged 1.0 ppt in 1971 and 0.2 ppt in 1972.  This isomer
was consistently found in low concentrations  at both stream stations.

o, p'-DDT
o, p'-DDT averaged <0.651.4 and 8.4 ppt in 1970,  1971  and 1972.  Levels
found during this period were <0.3 - 0.9, ND - 2.7,  2.3 - 12.5 ppt
respectively.

p. p'-DDE
This isomer averaged 1.1, 2.5, and 9.2 ppt in 1970, 1971, and 1972.
Ranges of concentrations were 0.6 - 1.6, 1.7 - 2.9, 3.9  - 20.3 ppt
during this period.  There was a continued increase in the concen-
tration of this isomer over the 3 year period.

p. p'-DDD
This isomer averaged 4.5, 3.6 and 3.3 ppt in 1970,  1971  and 1972 re-
spectively.  Ranges of concentrations were 1.8 -  7.2, 2.2 - 5.0, 1.7  -
6.7 ppt during this period.
                                 25

-------
                                      TABU  t

PESTICIDES IN WATER SAMPLES FROM LAKC HI CHI SAN AND TRIBUTARY SOURCES IN ILLINOIS
(1970).  Values »r» expressed In parts par trillion  (ppt).

SAMPLE LOCATION
Tributary Streams1
Waukegan River
Petti bone Creek
Sewage Treatment Plants
NSSD Waukegan
NSSD North Chicago
NSSD Lake Bluff
NSSD Lake Forest
NSSD Highland Park - Park Avenue
NSSD Highland Park - Ravine Drive
NSSD Highland Park - Cary Avenue
Open Water Samples
Wlnthrop Harbor
Evans ton
Chicago11

Water Plant Intake Samples?
Waukegan
North Chicago
Highland Park
Evans ton
Chicago Central
Chicago South

1 $0 yards upstream from
2 Final effluent to Lake
3 4 miles offshore
DATE
COLLECTED

1 1/2/70
1 1/2/70

10/23/70
10/23/70
11/2/70
11/2/70
11/2/70
11/2/70
1 1/2/70

10/20/70
10/20/70
10/20/70


10/23/70
10/23/70
10/23/70
10/23/70
10/23/70
10/23/70

Lake Michigan
Michigan

HEPTACHL01
EPOXIDE

1.0
<0.2

0.7
0.6
<0.2
<0.2
<0.2
<0.2
<0.2
(<0.3)

<0.2
<0.2
<0.2
(<0. 2}

<0.2
<0.2
<0.2
<0.2
<0.2
<0.2
(<°>2)



DIELDRIN

1 4
-cMr

2.4
2.5
1.5
2.2
1.6
2.3
0.6

<0.2
<0.2
<0.2
l<0.2)

<0.2
<0.2
<0.2
<0.2
<0.2
<0.2
*<0-2)



o, p1 tsoners
DDT

<0.3
0 >9
it 0.6]

0.8
i.e
3)



p. p* Isootrs
ODD

1.6
WIT

0.4
0*3
Oq
* y
01
a 1
OB
• O
1.5
ToTrT

<0 1
^ w. 3
<0.3
^ 0» 3


tO.3
<0 1
w. j
<0.t
^ W« J
^0*3


-------
P. P'-DDT
This isomer averaged 4.5, 11.0 and 29.6 ppt in 1970,  1971,  and  1972.
Ranges of concentrations were 2.8 - 6.2, 9.3 - 13.0,  and 22.2 - 38.4
ppt during the respective time periods.  There was a  continued  in-
crease in the concentration of this isomer over the 3 year  period.

Aroclor 1242
This polychlorinated biphenyl was sampled only in 1971 and  1972
and averaged 712.0 and 139.0 ppt during this period respectively.
Ranges of concentrations were 140.0 - 1810.0 ppt in 1971  and ND -
653.0 in 1972.  The highest level (1810.0 ppt) was found at the
Waukegan River.

Aroclor 1254   '

Aroclor 1254 was sampled in 1971 and 1972 and averaged 258.0 and 213.0
ppt during this period respectively.  Ranges of concentrations  were
192.0 to 388.0 ppt in 1971 and 61.0 - 841.0 ppt in 1972.  The highest
level (841.0 ppt) was found at Pettibone Creek.
                    SEWAGE TREATMENT PLANTS

Heptachlor epoxide
Average concentrations were  <0.3, 5.4, and 2.8 ppt for 1970,  1971
and 1972 respectively.  Annual ranges were 0.2 - 0.7, 0.3 -  17.2,
and 1.2 - 7.8 ppt during the respective time period.   Concentrations
of heptachlor epoxide were comparable between plants  except  for a
high level of 17.2 ppt obtained at the North Shore Sanitary  District
sewage treatment plant at North Chicago on 8/4/71.

Dieldrin
Average concentrations were 1.9, 36.0, and 16.2 ppt for 1970,  1971,
and 1972 respectively.  Annual ranges were 0.6 - 2.5, 13.7 - 64.3,
and 6.3 - 29.2 ppt during the respective time period.  Highest levels
were obtained from the North Shore Sanitary District  sewage  treatment
plant at North Chicago.

Methoxychlor
Concentrations of methoxychlor averaged 36.0 ppt in 1971  and ranged
between ND and 106.0 ppt.  In 1972, levels ranged from 20.7  -  59.8
ppt and averaged 34.6 ppt.  Highest levels were most  often found at
the North Shore Sanitary District sewage treatment plant at
Waukegan.  -

D1(2-ethy1hexy1) phthalate;  (POP)
Di(2-ethylhexyl phthalate) was detected in sewage treatment  plant
effluents only in 1971 sampling.  Highest levels were obtained at the-
                                27

-------
                                                                                      TABLE 7

                                               PESTICIDES FOUND IN WATER SAMPLES FROM SEVERAL ILLINOIS STREAMS AND SEWAGE PLANTS
                                               TRIBUTARY TO LAKE MICHIGAN (1971).  Values are (((pressed In parts p«r trillion (ppt).
00
SAMPLE
LOCATION
Vaukegan River
Waukegan River
Pettlbone Creek
Pettlbone Creek
NSSD Uaukegan STP
NSSD Uaykegan STP
NSSD North Chicago STP
NSSD North Chicago STP
NSSD North Chicago STP
DATE
COLLECTED
8/18/71
7/29/71
8/26/71
7/29/71
8/4/71
7/22/71
7/2J/71
8/4/71
8/25/71
Keptachlor
Epoxlde
5.4
ND
1.4
1.6
WW
4.1
4.1
0.3
17.2

Dleldrln
22.5
14.5
2.5
2.1
(10.4)
23.8
38.8
64.3'
31.8
T3OT
Hethoxychlor
5.9
2.9
22.4
30.7
TislT
26.5
21.8
17.7
44.2
ND
73OT
DOP
ND
ND
ND
ND
TH6T
650.0
90.0
160.0
ND
90.0
TitToT
o.
DDE
ND
ND
ND
ND
7.5
ND
ND
MO
ND
PT5T
p.' liomers
ODD
2.5
ND
0.7
0.8
TW
NO
5.0-
ND
ND
rnir
DDT
0.8
ND
2.1
2.7
Tjrtir
3.1
HD
ND
2.3
ND
P. p' Isonars
DOE
2.4
1.7
2.9
Tfrfr
4.9
5.8
1.2
4.8
2.9
TOT
ODD
5.0
4.0
3.0
2.2
3-6
6.2
1.0
ND
ifrfr
DDT
13.0
9.3
10.0
11.8
TTTTof
8.2
3.0
2.3
13.5
6.5
TOTAL
DDT
23.7
15.0
18.7
20.4
37-7
27-3
20.0
4.5
20.6
"OOF
Aroelor
1242
18)0.0
—
187.0
140.0
(712.0)
2105.0
4020.0
1070.0
268.0
H4.0
11433.0)
1254
388.0
...
194.0
192.0
TitOF
139.0
472.0
568.0
250.0
153.0
_|i|:|_
                        OOP   -    dl  (2-ethylhexyl) phthalate

                        ND   -    Not  Detected

-------
North Shore Sanitary District plant at Waukegan with  concentrations
reaching 760.0 ppt.

Di-n-butyl phthalate:  (DBF)
Di-n-butyl phthalate was not detected in six samples  analyzed  in
1971.  In 1972, levels ranged between 55.0 - 250.0  ppt  and  averaged
110.0 ppt.  Highest concentrations were most often  found  at the
North Shore Sanitary District plant at Waukegan.

o. p'-DDE

o, p'-DDE was found in only 2 of 6 samples in 1971  and  none of 10
samples in 1972.  Both concentrations (3.3 and 7.5  ppt) were ob-
tained from the North Shore Sanitary District plant at  Waukegan.

o, p'-DDD

o, p'-DDD was detected in 2 of 6 samples in 1971 and  none out  of 10
samples in 1972.  Both concentrations (5.0 and 5.8  ppt) were obtained
from the North Shore Sanitary District plant at Waukegan.

o, p'-DDT
o, p'-DDT averaged 0.6, 1.5, and 29.3 ppt in 1970,  1971,  and 1972
respectively.  Concentrations ranged from  <0.3 - 1.8,  ND - 3.5,
and 1.6 - 74.6 ppt during the respective time period.   Levels  in-
creased markedly in 1972 at both the North Chicago  and  Waukegan
North Shore Sanitary District plants.

p. p'-DDE
p, p'-DDE averaged 1.9, 4.3, and 17.7 ppt in 1970,  1971,  and 1972
respectively.  Concentrations ranged from 0.3 - 5.1,  1.2  -  6.1,
7.6 - 42.6 ppt during the respective time period.  The  maximum level
of 42.6 ppt was obtained at the North Shore Sanitary  District  plant
in Waukegan.

p. p'-DDD
p, p'-DDD averaged 0.7, 3.7, and 4.9 ppt in 1970, 1971, and 1972
respectively.  Concentrations ranged from 0.3 - 1.5,  ND - 6.2,
1.5 - 9.2 ppt during the respective time period. Similar levels were
obtained at both the North Chicago and Waukegan plants  of the  North
Shore Sanitary District.

p, p'-DDT
Higher levels of this isomer were found than any of the other  isomers
of the DDT complex.  Concentrations averaged 2.4, 7.8 and 70.3 ppt
for 1970, 1971, and 1972 respectively.  Concentrations  ranged  from
1.1 - 4.9, 2.3 - 13.5, and 10.6 - 132.6 ppt during  the  respective
time period.  A marked increase was noted in 1972 at  both the  North
Chicago and Waukegan North Shore Sanitary District  plants.
                                29

-------
                                       TABLE 8

PESTICIDES FOUND IN WATER SAMPLES FROH ILLINOIS STREAMS AND SEWAGE PLANTS TRIBUTARY
TO LAKE MICHIGAN (1972).  Values are expressed In parts per trillion (ppt).

SAMPLE
LOCATION
Vaukcgan River
Waukegan River
Wiukegan River
Waukogan River
Petti bone Creek
Petti bone Creek
Pettibcne Creek
O4
0 KSJ& Vaukogan STP
HSiD Vaukegan STP
NSSD Uaukegan STP
N5SD Ueukeaan STP
NSSD Vaukegaa STP
NSSD Ncrth Chicago STP
NSSO North Chicago STP
NSSD North Chicago STP
NSSD North Chicago STP
NSSO North Chicago STP
D6P - dl-n-butyl
T • Trace

DATE
COLLECTED
5/24/72
5/23/72
5/25/-»2
6/29/72
5/24/72
5/25/72
6/29/72

5/16/72
5/19/72
5/23/72
5/22/72
6/17/72
5/22/72
5/2J/72
5/16/72
5/19/72
6/17/72
phtlialate


Heptachlor
Epoxlde
3.1
3.4
4.5
3.8
1.6
1.2
2.6
TO7

2.2
2.9
7.8
3.7
1.4
1.6
3.2
2.3
1.2
1.2
TOT


o. p' 1 sowers

DUIdrln
2.6
2.1
2.0
2.6
3-1
1.7
&

14.5
11.6
8.3
12.5
6.7
29.2
26.0
2$. 5
21.8
TTCTiT



Hethoxychlor
27.2
22.6
29.4
29.5
65.5
72.4
89.1
TWToT

45.7
36.5
40.8
37.4
59.8
20.7
22.8
28.3
27.5
26.6
T5TIT



PBP
107.0
92.0
77.0
T
122,0
147.0
110.0
755nr

120.0
100.0
87.0
65.0
250.0
55.0
97.0
58.0
70.0
206.0
UI6.6J'



DDE
ND
ND
ND
ND
ND
ND
ND
7557

ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
TSbT



ODD
ND
ND
ND
0.7
NO
ND
0.6
TOT

ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
THbT



DDT
•'.•7
12.5
9.8
2.3
12.5
7.2
(8.* 4)

14.3
21.4
16.1
74.6
1.9
53.5
43.0
32.2
3*. 7
1.6
W^T


p. p' 1 sorters

DDE
7-1
10.2
5.4
12.9
4.7
3.9
20.3
WIT

7.6
7.9
9.9
42.6
10.4
37.4
20.4
18.2
14.8
tTTTTT



ODD
2.8
1.7
1.9
6.7
2.0
2.4
5.9
TUT

1.7
4.3
7.1
9.2
2.1
6.5
6.0
5.2
4.9
T5T3T



DDT
36. 5
35.0
22.7
22.2
38.4
26.3
26.4
lzT?T

70.5
68.2
49.1
132.6
16.3
110.9
67.7
77.5
79.7
10.6
(76.3)


TOTAL
DDT
58.1
59.4
39.6
44.8
57.6
39.8
(51.0)

94.1
101.8
82.2
259.0
30.7
208.3
157.1
133.1
134.1
•21.4
< 122.0)


Aroclor

1242
62.0
120.0
57.0
84.0
II D
ND
653.0
TT557&T

ND
ND
ND
ND
17.0
ND
ND
ND
ND
21.0
(iTBJ



1254
114.0
136.0
61.0
119.0
111.0
107.0
841.0
(213.6)

139.0
105.0
57.0
118.0
III.O
104.0
100.0
132.0
161.0
178.0
TT2O7


ND • Not Detected

-------
Aroclor 1242
Concentrations averaged 1433.0 ppt in 1971  and 3.8 ppt in  1972.
Ranges in concentrations in 1971 were 268.0 - 4020.0  ppt compared
to NO to 21.0 ppt in 1972.  The maximum level of  4020.0 ppt was ob-
tained at the North Shore Sanitary District plant at  Waukegan.

Aroclor 1254
Concentrations averaged 299.8 ppt in 1971  and 124.0 ppt in 1972.
Concentrations ranged between 139.0 - 568.0 ppt in 1971 and 97.0  -
178.0 ppt in 1972.  Highest levels were obtained from the North
Shore Sanitary District plant in Kaukegan in 1971.  Lower levels
were obtained at this and the North Chicago plant in 1972.
                                 31

-------
                            SECTION VII

                       RESULTS AND DISCUSSION


The monitoring program established by the Illinois Environmental  Pro-
tection Agency was directed to determine levels of pesticides dis-
charged as well as levels presently found in Lake Michigan water, sed-
iment, and fish.

Monitoring results indicate that levels of DDT, polychlorinated bi-
phenyls (PCB's), and dieldrin in edible portions of six species of
Lake Michigan fish were generally below interim guidelines for maxi-
mum concentration in fish flesh which are 5.0 ppm for both DDT and
PCB's and 0.3 ppm for dieldrin.  Other chlorinated hydrocarbon in-
secticides were not consistently found in the edible portions of fish
flesh.  The species of fish with highest fat content also had highest
PCB or DDT concentrations.  Chubs most often had the highest levels
of PCB's and DDT while yellow perch had the lowest.  Alewives showed
PCB concentrations comparable to chubs.  Male yellow perch, chubs,
and alewife had higher concentrations of PCB and DDT in the edible
portions of their flesh than did the females of the species.

Highest concentrations of the pesticides, PCB's, and phthalates in
sediments were obtained in the tributary streams and ravines indi-
cating possible contamination by residential spraying and industrial
discharge.  Highest levels were obtained in industrial areas in North
Chicago and Waukegan.  Open water sediments were considerably lower
for all parameters.  In the sediments polychlorinated biphenyls were
generally found at concentrations higher than the pesticides.  Aro-
clor 1242 concentrations ranged from ND at the Ravine Drive Ravine in
Highland Park to 553.00 ppb in an unnamed channel in Waukegan.  Aroclor
1254 levels ranged from 1.54 ppb in the Park Avenue Ravine in Highland
Park to 232.00 ppb in Pettibone Creek in North Chicago.  Although not
consistently found in the sediments one of the phthalates did reach a
concentration in excess of 200 ppb.  Di(2-ethylhexyl) phthalate was
found in both industrial and residential areas but in only 5 of 13 sam-
ples with levels ranging from N.D. - 218.00 ppb.  The maximum level was
obtained in an industrial area in Waukegan in an unnamed channel.  Di-
n-butyl phthalate was found in ohly 2 of 13 samples both located in
Highland Park.  Concentrations obtained were 25.00 and 120.00 ppb.

Total DDT, methoxychlor, dieldrin, and heptachlor epoxide were found
in highest concentrations in tributary sediments located in residential
areas indicating the past history of localized spray programs.  DDT
concentrations ranged from 0.42 from Bull Creek in Zion to 942.00 ppb
in the Woodland River Ravine in Lake Forest.  Ranges in levels of meth-
oxychlor, dieldrin, and heptachlor epoxide were 0.19 - 175.00, 0.01 -
30.80, 0.02 - 57.00 ppb respectively over the three year period.   Areas
of highest concentration were found in residential areas in Lake Forest.
                                  33

-------
Lindane and heptachlor concentrations were all  less than 1  ppb.   Al-
drin and endrin were not detected.

Water samples collected at six water treatment  plant intakes and at
locations approximately 4 miles offshore of Winthrop Harbor, Evanston,
and Chicago all showed levels of less than 1.0  ppt heptachlor epoxide,
dieldrin, and total DDT.   Water samples collected at tributary stream
and sewage treatment plants showed somewhat higher levels.   Lindane,
aldrin, endrin, and heptachlor, were not detected in sewage treatment
plant effluents or tributary streams.

In the tributary streams PCB's were found in highest concentrations
followed by the phthalates, methoxychlor, DDT,  dieldrin, and hepta-
chlor epoxide.

Aroclor 1242 ranged from ND - 1810.0 ppt in 1971  and 1972.   The  high-
est concentration of Aroclor 1242 was obtained  from the Waukegan River
in Waukegan.  Aroclor 1254 ranged from 61.0 - 841.0 ppt in  1971  and
1972.  The highest concentration of Aroclor 1254  was obtained in Petti-
bone Creek in North Chicago.

Di(2-ethylhexyl) phthalate was not detected in  the tributary streams
during the three year study while di-n-butyl phthalate was  found in
concentrations ranging from a trace - 147.0 ppt in 1972. Similar lev-
els were found at both stream stations.  Di-n-butyl phthalate was not
identified in the 1971 sampling.

Levels of methoxychlor increased considerably at  both the Waukegan
River and Pettibone Creek in 1972.  Concentrations at these stream
stations averaged 15.5 ppt in 1971 and 48.0 ppt in 1972. Highest con-
centrations were found on Pettibone Creek during  the study  period.
Levels of total DDT ranged from 6.3 - 59.4 ppt  at both stations  during
the three year period.  Highest concentrations  were obtained in  1972
at both Pettibone Creek and the Waukegan River.  The cause  of the in-
creased 1972 levels is unexplained.

Over the study period levels of dieldrin found  in Pettibone Creek were
less than 4.0 ppt while the Waukegan River samples ranged from 1.4 -
22.5 ppt.  Heptachlor epoxide concentrations from tributary streams
ranged from below detectable levels to 5.4 ppt  over the three year
period.  Sewage treatment plant effluents showed  higher values for
most pesticides.  The North Shore Sanitary District plant at Waukegan
most often had the highest levels for total DDT,  methoxychlor, di-
(2-ethylhexyl) phthalate, di-n-butyl phthalate, Aroclor 1242, and Aro-
clor 1254.  Maximum concentrations obtained at  this location were
259.0 ppt for total DDT, 106.0 ppt for methoxychlor, 760.0  ppt for
di(2-ethylhexyl) phthalate, 250.0 ppt for di-n-butyl phthalate,  4020.0
ppt for Aroclor 1242 and 568.0 ppt for Aroclor  1254.

The North Shore Sanitary District Plant at North  Chicago had highest
                                34

-------
levels for heptachlor epoxide and dieldrin.  Maximum concentrations
for these parameters were 17.2 ppt for heptachlor epoxide and 64.3  ppt
for dieldrin.

This study indicates that the polychlorinated biphenyls are present in
Lake Michigan in concentrations equal to or in excess of DDT.  It is
known that PCB's exhibit a.chronic toxicity to aquatic life at very low
levels (Nebeker et. al., 1972).  The fact that PCB's were not analyti-
cally separated TFonTUDT in earlier studies indicates that DDT concen-
trations were reported at levels higher than actual.  This study indi-
cates that both DDT and the PCB's were found at levels which warrant
concern for both aquatic life and wildlife.  The other pesticides and
the phthalates were found at lower levels which do not indicate the de-
gree of concern that do DDT and the PCB's.
                                35

-------
                            SECTION VIII

                          ACKNOWLEDGEMENTS
This project was initiated by the Sanitary Water Board of the Illinois
Department of Public Health and transferred to the Illinois Environ-
mental Protection Agency in July of 1970 when the Sanitary Water Board
was abolished.

Laboratory analyses were accomplished by Anderson Physics Laboratories,
Inc. of Urbana, Illinois with quality control being accomplished by the
Illinois Environmental Protection Agency special test unit laboratory.

Cooperation in obtaining fish samples were offered by the Illinois Con-
servation Department, Hope Fisheries of Waukegan, and Rocky's Fisheries
of Chicago and was greatly appreciated.  Assistance offered by the
North Shore Sanitary District in obtaining composite effluent samples
is also appreciated.

Completion of the grant including sample collection and report prepa-
ration was accomplished by Lake Michigan/DesPlaines Biological Sub-Unit
personnel in the Division of Water Pollution Control of the Illinois
Environmental Protection Agency.

Support of the project by the U.S. Environmental Protection Agency Of-
fice of Research and Development, and the help provided by Mr. LeRoy
E. Scarce, the Grant Project Officer, was greatly appreciated.
                                 37

-------
                             SECTION IX

                             REFERENCES
1.  Armour, J.A., and J.A.  Burke, "A Method for Separating  Polychlo-
    rinated Biphenyls from DDT and its Analogs", Journal  of the AOAC
    53, 761-768 (1970).

2.  Lake Michigan Interstate Pesticide Committee, Report  on Insecti-
    cides in Lake Michigan, Federal Water Pollution Control Admin-
    istration, Department of the Interior, Region V (1968).

3.  Lake Michigan Interstate Pesticide Committee, An Evaluation of  DDT
    and Dieldrin in Lake Michigan, U.S. Environmental  Protection~A~gency,
    Office of Research and Monitoring (EPA-R3-72-003)  (1972).

4.  Nebeker, Alan V., Frank A. Puglisi, and David L. DeFoe, Toxicity  of
    Polychlorinated Biphenyls (PCB's) to fish and other Aquatic Life,
    Final Report, U.S. Environmental Protection Agency, National  Water
    Quality Laboratory, DuLuth, Minnesota (1972).

5.  Reinert, Robert E., "Pesticide concentrations in Great Lakes  Fish",
    Pesticide Monitoring Journal. Vol. 3, No. 4, p. 233-240 (1970).

6.  Veith, Gilman D. and G. Fred Lee, "A Review of Chlorinated Biphenyl
    Contamination in Natural Waters", Water Research,  Vol.  4,  pp. 265-
    269 (1970).

7.  Willford, Wayne A., Joe B. Sills, and Everett W. Whealdon, "Chlori-
    nated Hydrocarbons in the Young of Lake Michigan Coho Salmon",  The
    Progressive Fish-Culturist, Vol. 31, No. 4, p. 220 (1969).

8.  Wisconsin Alumni Research Foundation.  Progress Report No. 1, Lake
    Michigan Pesticide Investigations WARF Institute,  Inc.  TT97I5T.
                                  39

-------
                             SECTION X

                             APPENDICES


                                                             Page No.

Appendix A    ANALYTICAL QUALITY CONTROL DATA

              Procedure for Laboratory Analysis                 45
              Table 1:  Percent Recovery                       46
              Table 2:  Limits of Detectability                 47
              Table 3:  Sample Fortification                    48

Appendix B    FIELD METHODS

              Figure 1:  Composite Water Sampler                54
              Field Sampling Procedures                         55
                                 41

-------
    APPENDIX A





ANALYTICAL QUALITY



   CONTROL DATA
        43

-------
                             APPENDIX A

                   ANALYTICAL QUALITY CONTROL DATA

                  PROCEDURE FOR LABORATORY ANALYSIS
ANALYTICAL CONDITIONS
All samples were analyzed according to the "FWPCA Method for Chlori-
nated Hydrocarbon Pesticides in Water and Wastewater" with the U.S.
Environmental Protection Agency Lake Michigan Basin Office modifi-
cation employing 1000 ml Erlenmeyer flasks fitted (24/40 ground
glass connections) with Snyder distillation columns in place of the
Kuderna-Danish concentration system for removal of solvents.

SEPARATION PROCEDURE - WATER
2000 ml of each gallon water sample was extracted three times with 250
ml of 15% ethyl ether in hexane.  Extracts were then dried over anhy-
drous sodium sulphate, combined in a 1000 ml Erlenmeyer flask, a Snyder
column attached, and all but 2 ml of the solvent removed by distilla-
tion (the Na£S04 was decontaminated by heating overnight at 450°C).
Nanograde methylene chloride has proven to be a superior solvent for
extracting polar and non-polar pesticides from water and various sub-
strates and may be substituted for the above mixture of ether and hex-
ane.

The 2 ml concentrated extracts were transferred to the standardized
florisil column as described in the following section.

Analysis of a fortified water sample indicated a high level of re-
covery (90 to 97%) for most materials tested except di(2-ethylhexyl)
phthalate where there was approximately 85% of the chemical found in
the third florisil fraction.

SEPARATION PROCEDURE - FISH
50 grams of the edible portion of fish was blended with 100 ml of re-
distilled alcohol in 100 ml of water and 100 ml of 50% diethyl ether
in hexane (all solvents were nanograde).  This mixture was filtered
in a Buechner funnel with a suction flask using #1 Whatman paper and
washed with hexane.

The solvent was removed in an Erlenmeyer flask with attached Snyder
column on a steam bath.  100 ml of H20 was added to the concentrate
and then extracted with 100 ml hexane in a separatory funnel.  The
hexane layer was dried over sodium sulfate and then reduced to about
8 ml.  This solution was placed in a centrifuge tube on a warm water
bath and purified air was blown over it to remove all the hexane.  The
remaining oil was weighed to determine its percentage in the fish flesh.
Next 100 mg of the fish oil was placed on the  florisil column  (later,
                                 45

-------
           APPENDIX A  TABLE 1




    ANALYTICAL QUALITY CONTROL  DATA



percent recovery for parameters tested
PARAMETER TESTED
PESTICIDES
Heptachlor
Epoxlde
Dieldrln
Methoxychlor
Llndane
Aldrlri
Endrtn
Heptachlor
o,p' DDE
oj)1 ODD
o,p' DDT
P.P1 DDE
p,p' DDD
P,p' DDT
POLYCHLORINATED
BIPHENYLS (PCB's)
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 125'i
Aroclor 1260
PHTHALATES
dl-n-butyl
ph thai ate
(DBP)
dl(2-ethylhexyl)
ph thai ate
(OOP)
SAHPLE
FISH
90-98?
90-98?
90-98%
90-98%
90-98%
90-98%
90-98%
90-98%
90-98%
90-98%
90-98%
90-98%
90-98%

90-98%
_ _
90-98%
_ _
85-95%
85-95%
SEDIMENTS
95-98%
95-98%
'95-98%
95-98%
95-98%
95-98%
95-98%
95-98%
95-98%
95-98%
95-98%
95-93%
95-98%

90-98%
_ _
90-98%
_.
90%
90%
WATER
95-98%
95-98%
95-98%
95-98%
95-98%
95-98%
95-98%
95-98%
95-98%
95-98%
95-98%
95-98%
95-98%

90-98%
_ —
90-98%

90%
90%
                      46

-------
            APPtNDIX A  TABLE 2




       ANALYTICAL  QUALITY  CONTROL DATA



limits  of detectablllty  for parameters tested

PARAMETER TESTED
PESTICIDES
Heptachlor
Epoxlde
Dleldrln
Methoxychlor
Llndane
Aldrln
Endrtn
Heptachlor
o.p' DDE
o.p' DDD
o.p1 DDT
P.P1 DDE
p,p' DDD
p,p' DDT
POLYCHLORINATED
BIPHENYLS (PCB's)
Aroclor 1232
Aroclor 1242
Afoclor 12*18
Aroclor 1254
Aroclor 1260
PHTHALATES
dl-n-butyl
"wr
dl-<2-ethyi-
hexyl)
ph the late
(OOP)

FISH
<25 PPT
<25 PPT
100 PPT
25 PPT
25 PPT
25 PPT
25 PPT
25 PPT
25 PPT
25 PPT
25 PPT
25 PPT
100 PPT

k PPB
__
2.5 PPB
__
2 PPB
10 PPB
SAMPLE
SEDIMENTS
<2.5 PPT
2.5 PPT
10 PPT
2.5 PPT
2.5 PPT
2.5 PPT
2.5 PPT
2.5 PPT
2.5 PPT
2.5 PPT
2.5 PPT
2.5 PPT
10 PPT

400 PPT
_—
250 PPT
^ —
200 PPT
1 PPB

WATER
<.2 PPT
.2 PPT
1 PPT
.25 PPT
.25 PPT
.25 PPT
.25 PPT
.25 PPT
.25 PPT
.25 PPT
.25 PPT
.25 PPT
1 PPT

1*0 PPT
__
25 PPT
__
20 PPT
100 PPT
                         47

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      APPENDIX A TABLE 3
ANALYTICAL QUALITY CONTROL DATA
 Sample Fortification (in PPM)

Chlorinated
hydrocarbon
pesticides
PCB's
Phthalates
5 replicates
Total number
of Tests
Fish
.01
.005
.002
.001
.0005
.10
.05
.02
.01
.005
1.00
0.20
0.05
0.01
0.002
25
Sediment
.001
.0005
.0002
.00005
.00002
.01
.005
.002
.001
.0005
.10
.02
.005
.001
.0002
25
Water
.0001
.00005
.00002
.000005
.000002
.001
.0005
.0002
.0001
.00005
.01
.002
.0005
.0001
.00002
25
               48

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fish samples were run as above except 10 grams of fish flesh was used
and all the oil obtained was placed on the florisil column, except
for chubs where 2 grams were used).  The florisil separation proce-
dure is listed in this appendix.  Three fractions were obtained from
this procedure.  This first fraction FI was subjected to a silicic
acid separation (procedure in this appendix), to separate the PCB's
completely from the pesticides.  The third fraction F3 from the flori-
sil procedure which was eluted with 200 ml of a 50-50 mixture of di-
ethyl ether-hexane contained di(2-ethylhexyl) phthalate and di-n-butyl
phthalate with some fish oil.  This fraction was reduced to 0.5 ml.
The phthalates were separated from the fish oil using Gelman's Instant
Thin Layer Chromatograms.  The entire oily residue was placed near the
bottom of the sheet and the sheet was developed with acetonitrile.
After the acetoniltrile rose 1" above the oil residue the sheet was
removed and dried.  It was then placed in 90% methanol - 10% HaO mix-
ture and this was permitted to rise 3" above the acetonitrile front.
This effectively removed the phthalate esters from the fish oil.  The
TLC sheet was cut at the acetonitrile and methanol fronts and the
phthalate esters were extracted in 10 ml hexane containing 10 drops of
H20.  This was then reduced to 1 ml prior to injection into the gas
chromatograph (fraction 4).

1 to 5 ml of the fractions were injected into the electron capture
GLC unit.  In these analyses two columns varying in length were used.
Both were packed with 3% QF-1 and  1% OV-17 on Supelcoport.  One was
3M X 1/8" and the other was 20" X  1/8".  Fraction FI was run only on
the 3M column but FZ and F^ were run on both.  The shorter column
facilitated the analysis of methoxychlor and di(2-ethylhexyl) phthal-
ate.

SEPARATION PROCEDURE - SEDIMENT
100 grams of sediment was mixed with 100 ml ethyl alcohol + 100 ml
H20 in a 1000 ml Erlenmeyer flask.  This mixture was extracted in the
Erlenmeyer flask with 100 ml of a  50-50 mixture of diethyl ether-hexane.

The ether-hexane layer was separated and dried with anhydrous sodium
sulfate.  It was then concentrated to less than 5 ml and subjected to
a florisil separation procedure.
                           <
The first fraction from this was further separated by means of a sili-
ca gel column.  This separated the PCB's from the remaining pesticides.
These procedures are listed in detail in a later portion of this ap-
pendix.  The various fractions were concentrated to volumes which were
appropriate for GLC analysis.

PREPARATION AND USE OF THE FLORISIL COLUMN
30 grams of florisil containing 3% water was prepared for chromato-
graphic separations by pre-elution with 50 ml acetone, 50 ml anhy-
drous diethyl ether, and finally with 100 ml dry nanograde hexane.
                                 49

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The pesticide extract in 2 ml hexane was carefully transferred to the
florisil column with 3-4 one ml portions of hexane.  The elution pat-
tern was as follows:

     Fl - 90 to 100 ml hexane eluted PCB's, o,p' and p,p' DDE,
     heptachlor, some (50%) alpha BHC, o.p' and p,p' DDT (20%).

     F£ - 250 ml 10% ether in hexane eluted the remaining chlo-
     rinated hydrocarbon insecticides including methoxychlor
     ethyl ene.

     FS - 200 ml 50% ether in hexane eluted di(2-ethylhexyl)
     ph thai ate.
                                                           "     "
The second and third fraction (Fe & FS) were collected ,4fi 500 ml Erlen-
meyer flasks, Snyder Columns attached, and volumes reduced on a steam
bath to ca. 5 ml.  The extracts were then transferredato a volumetric
flask at a concentration suitable for 6.L.C. determinations.

SILICA GEL SEPARATION OF PCB'S FROM DOT'S,,,...  n
The first florisil fraction (Fl) ..was reduced in volume to ca. 2 ml and
the PCB's,'separated from DDE and DDT on a silicic acid-celite or silica
gel column.  Silica Gel 60 (Mereck) 70-325 mesh heated for 3 to 4 days
at 22^C was found to be very : ef f ecti ve in separating these compounds.
The FI concentrate was transferred with three 1 ml portions of hexane
to a column containing 30 grams of Silica Gel 60 (The florisil and sil-
ica gel were pretested to verify the elution pattern).

210 ml dry hexane eluted by gravity in 60 to 90 minutes contained the
PCB's.  The following elution with 150 ml 10% ether in hexane removed
the DDE's and DDT's.  Both fractions were concentrated by distilla-
tion through a Snyder column.

The concentrates were adjusted to a suitable volume for G.L.C. analy-
sis.

INSTRUMENTATION
A Varian Aerograph 204 with 2 columns equipped with 63 Ni detector was
operated under the following conditions:

     1.  Port temperature of 225°C.

     2.  Column temperature of 200 to 210°C.

     3.  Detector temperature of 255°C.

     4.  High resolution column 1/8" X 8 meters packed with 100/200
         mesh Supelcoport containing 2.0% QF1 and 1.25% OV-17.
                                  50

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     5.  Short one meter column containing 4.0$ QF1  and 2.0% OV-17 on
         Supelcoport used for methoxychlor and di(Z-ethylhexyl)  phthal-
         ate.  Other columns used for fish analysis  are listed in the
         separation procedure for fish.

     6.  Two other columns of greater and less polarity than those men-
         tioned are useful for some confirmation tests.

A portion of the extracts analyzed by Anderson Physics Laboratories were
provided to the Environmental Protection Agency for varification on re-
sults.

Values obtained in analysis were not corrected in relation to percent
recovery.
                                  51

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 APPENDIX B



FIELD METHODS
    53

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                                                           Rubber Tubing
                                                                D
                Rubber Tubing
                           Sample —\
                      Glass Carboy  —^
Glass Tubing
   APPENDIX 8  FIGURE  1.   COMPOSITE WATER SAMPLER
                                     54

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                             APPENDIX B

                            FIELD METHODS

                      FIELD SAMPLING PROCEDURES
WATER SAMPLES
One gallon samples were collected in glass bottles with aluminum foil
placed between the glass and the cover.  Initially all samples col-
lected were grab samples.  During 1971 a composite sampler utilizing
two 5 gallon carboys was employed at the tributary streams.   A period
of 24 hours was covered during compositing.  The sample collected in
the 5 gallon carboy was mixed and a one gallon portion was saved for
analysis.  The carboy was then rinsed with nanograde hexane before
the sampler was again used.  Figure one of this appendix illustrates
the composite sampler.  To obtain a sample the upper carboy is filled
with water which is allowed to drain out slowly through the tubing in-
dicated by the letter D.  As the water drains from this carboy, the
vacuum created siphons a sample into the lower carboy.  The rate of
flow may be regulated by a pinch clamp on tubing D.  Samples were
collected through glass tubing to avoid contamination with any plas-
ticizer which could have been present in rubber tubing.  Care had to
be used so that the distance C on the figure was greater than A plus
B.  In 1972 composite samples from the North Chicago and Waukegan sew-
age treatment plant were provided by the North Shore Sanitary District.

FISH SAMPLES
Fish samples were collected either directly from a commercial fisher-
man or collected during netting operations by the Illinois Conserva-
tion Department.  For fish over one pound a fillet was taken, while
smaller fish were taken whole.  The sample then was labeled by species,
sex, length and weight and location, placed in aluminum foil, and put
on ice prior to delivery to the laboratory.  These samples were then
frozen until analyzed.

SEDIMENT SAMPLES
Sediment samples from streams and ravines were collected directly in 6
ounce glass bottles with aluminum foil placed between the glass and the
cover.  Samples of Lake Michigan sediment were collected with a Ponar
dredge.  No preservatives were added to sediment samples.  These sam-
ples were not refrigerated or frozen prior to analysis.

In general the lapse time between collection and analysis of all types
of samples ranged from several weeks to more than one month.
                                 55

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  SELECTED WATER
  RESOURCES ABSTRACTS
  INPUT TRANSACTION FORM
                                                                 j.  Accession No
                                                                 w
                                                                 II.  Contract/Gram ffo
                                                                   16050 ESP
                                                                 **..
  4.  Title

   PESTICIDES IN THE ILLINOIS  WATERS OF LAKE MICHIGAN
                                                                 5.  Reyort Dft
                                                                 6.   v,^,
                                                                 8.  Performicr- Organ''.aticn
  7. Aulhor(s)
   Schacht, Robert A.
   Illinois Environmental  Protection Agency
   Chicago, Illinois   60609
  15.  Supplementary Note:,
   U.S. Environmental  Protection Agency
   Research Report  No.  EPA 660/3-74-002, January 19T1*
                              determine present levels of pesticides in Lake Michigan
                               Data was collected on six species of Lake Michigan fish
                              coho salmon, alewife, and brown trout); open lake and
                              sediments; and open water, tributary stream, and sewage
                              Samples analyzed for pesticides were selected from the
                               heptachlor epoxide, dieldrin, methoxychlor, lindane,
                              analogs.  Additional analyses were accomplished for poly-
                              ),  di-n-butyl phthalate (DBP), and di (2-ethylhexyl)
 16. Abstract
This study was  initiated to
fish, sediments,  and water.
(yellow perch,  chubs, carp,
tributary stream  and ravine
treatment plant effluents.
following list:   heptachlor,
aldrin, endrin, DDT and its
chlorinated biphenyls (PCB's
phthalate (DOP).

The data indicate that PCB's  were found at levels as high or higher than DDT  in Lake
Michigan water, sediment,  and fish.  PCB's have been found to complicate the  routine
analysis of DDT which may have caused earlier DDT data in the literature to be reported
at levels higher  than actual.  Both DDT and the polychlorinated biphenyls were found  at
levels which  cause concern for aquatic life and warrants the controlled use of these
compounds.

This report is  submitted in fulfillment of grant number 16050 ESP under the sponsorship
of the U.S. Environmental Protection Agency.
  J7a. Descriptors
 *Pesticides, *Polychlorinated Biphenyls, (Lake Michigan, *Fish, *Sediments, *Water,
 Insecticides, Organic  Pesticides, Chlorinated Hydrocarbon Pesticides, Aldrin, ODD, DDE,
 DDT, Dieldrin, Endrin, Heptachlor, Aroclors, Effluents, Tributaries, Lake Sediments,
 Salmon, Carp, Yellow Perch,  Brown Trout, Pollutants, Pollutant Identification, Water
 Pollution. Water Quality.
  17b. Identifiers
 Heptachlor Epoxide,  Lindane, Methoxychlor, Phthalates, Chicago(111.), Waukegon(Ill.)»
 Alewife, Coho Salmon.
  17c. COWRR Field & Croup   Q5B,  05A

  IS.  Availability
  Abstractor Robert A. Schacht
                                                      Send To:

                                                      WATER RESOURCES SCIENTIFIC INFORMATION CENTER
                                                      U.S. DEPARTMENT OF THE INTERIOR
                                                      WASHINGTON. O. C. 2O24O
                                                IEPA. Chicago. Illinois
WRSIC IO2 (REV JUNE 19711

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