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 ppb 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.


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
I1linois 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 O0f-

fice of Research and Development, and the help Provided by Mr. LeRoy
E. Scarce, the Grant Project Officer, was greatly appreciated.

37


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 ND 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 Waukegan in 1971. Lower levels
were obtained at this and the North Chicago plant in 1972.

31


APPENDIX A TABLE |

ANALYTICAL QUALITY CONTROL DATA

percent recovery for parameters tested

SAMPLE
IPARAMETER TESTED FISH SEDIMENTS WATER
PESTICIDES
Heptachlor
Epoxide 90-98% 95-98% 95-98%
Dieldrin 90-983 95-983 95-98%
Methoxychlor 90-98% "95-98% 95-98%
Lindane 90-983 95-98% 95-98%
Aldrin 90-98% 95-98% 95-98%
Endrin 90-98% 95-98% 95-98%
Heptachlor 90-98% 95-98% 95-98%
2,p' DDE 90-98% 95-98% 95-98%
op" ppp 90-98% 95-98% 95-98%
2,p' DDT 90-98% 95-98% 95-98%
ppp! DDE 90-98% 95-98% 95-98%
p.p' DDD 90-98% 95-98% 95-98%
psp! DDT 90-98% 95-98% 95-98%
POLYCHLORINATED
BIPHENYLS (PCB's)
Aroclor 1232 => => ==
Aroclor 1242 90-98% 90-98% 90-98%
Aroclor 1248 -- -- --
Aroclor 1254 90-98% 90-98% 90-98%
Aroclor 1260 -- -- --
PHTHALATES
di-n-buty!
phthalate 85-95% 90% 90%
(ppp)
di-(2-ethy/ hexy t)
phthalate | 85-95% 90% 90%
(pop)



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 al., 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 showed 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


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 I]linois 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


APPENDIX B
FIELD METHODS

53


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
jevel was found (30.80 ppb) approximately 50 yards upstream from Lake
Michigan in the Woodland Drive ravine in Lake Forest.

Methoxychlor

Concentrations of methoxychlor 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


SECTION IX
REFERENCES

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).

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).

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

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
QaTity Taboratory, DuLuth, Minnesota (1972).

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

Veith, Gilman D. and G. Fred Lee, "A Review of Chlorinated Bipheny1
39 Cay in Natural Waters", Water Research, Vol. 4, pp. 265-
269 (1970).

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).

Wisconsin Alumni Research Foundation. Progress Report No. 1, Lake
Michigan Pesticide Investigations WARF Institute, Inc. (1970).

39


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-buty1 phthalate:
(DBP), and di(2-ethylhexy1) 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 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.


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

Di-n-butyl phthalate: (DBP)

Di-n-buty] 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.

0, p'-DDE

0, 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.

0. p'-DDD

0, 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.

Bp. 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.

Pp, 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


Kellogg Creek
Bull Creek '
Dead River,
el
a2 ° 5 10

NSSD Waukegan STP
75

J, NSSD North Chicago STP

Scale tn miles

Ravine Park RavinegeNSSD Lake Bluff. STP LAKE HICHIGAN

Woodland Drive Ravine

Ferry Hall School Ravine:
Stone Gate Lane Ravine
Barat Ravine

018
Park Ave. Ravine sD Highland Park @ Park Ave. STP
Ravine Drive Ravine \.NssD Highland Park @ Ravine Or. STP

jLake County _ NSSD Highland Park @ Cary Ave. STP
Cook County

3)
EVANSTON

237
oho
oA3

A
Navy Pier

a)
CHICAGO
052

—f

055

062

FIGURE 1. LOCATIONS OF SEDIMENT SAMPLING STATIONS

14


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.

Di_(2-ethyThexy1) phthalate: (DOP)

DOP 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-buty] 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.

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

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

0, p'-DDT
Concentrations of 0, p'-DDT ranged from ND - 83.00 ppb. The maximum
level was found in the Woodland Drive ravine in Lake Forest.

BP, 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'-DOT
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


TABLE &

PESTICIDES FOUND IN SEDIMENTS FROM LAKE MICHIGAN AND TRISUTARY STREAMS AND RAVINES
mW juLinols (1970), Values are expressed in parts per billion (ppb) on a dry wolght
basis.

2, p' Isomers Ps p' Isomers
SAMPLE HEPTACHLOR TOTAL
LOCATION EPOXIDE DIELORIN DOE oop ooT DDE oop oor ooT

5 Telbutary Stresses and Ravines!

Waukegan River 9.60 4.09 oo 0.50 6.40 30.60 18.00 55.50
Pettibone Creek 9.30 21.40 1.02 27.50 67.30 258.00 340.00 728.82
Lake Bluff-Ravine 2.60 137 0.61 6.50 4.60 58.80 2:00 gh.5t
Lake Forest-Moodland Orive Ravina 57.00 30. 17.00 83.00 52.00 353.00 375.00 942.00
Lake Forest-Barat Creek 3.10 3.40 110 7.50 8.57 27.50 50.10 97.50

Hightand Park-Ravine Drive Ravine wet attr eth dtr air ai a ey aetna

0.38 0.29 0.75 ore 0,06 tat ww 3.75

0.98 0.64 0.65 0.02 VIS 423 1473 7.78

1.35 0.80 _ 0.50 3.00 12.60 13.00 29.13

t 0.58 0.28 eal 0.25 0.77 2.88 1,20 5.15

Highland Park (Park Avenue) 0.26 0.55, 3.60 4.00 0.48 0.02 +90 10.97

Wightand bark (Gary Rvonue)) ote Hed ye ee 4 iH is Hee
ghlan ry Avenue] . e ‘ . : :

1 50 yards upstream from Lake Michigan.
2 40-80 yards offshore of the Indicated sewage treatment plant.


Of

TABLE 8

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

oy p' Isomers p, p' Isomers Aroclor

SAMPLE DATE Heptachlor TOTAL —
LOCATION COLLECTED Epoxide Delrin Hethoxychler oer SOE = DoD oT DOE 00 oT oor sean Va54
Waukegan River S272 31 27.2 107.0 xo No W7 Tl 2.8 58.1 62.0 va.
Waukegan River 5/23/72 34 22.6 92.0 ND ND 1245 10.2 7 59.4 120.0 136.1
‘daukegan River 5/25/72 hs 29.4 72.0 ND ND 9.8 SAO 39.8 57.0 61
Waukegan River 6/29/72 3.8 23.5 T wD 0.7 23 29 6.7 8 84.0 19
Pettibone Creek SP2n/72 1.6 65.5 122,0 ND No 12.5 W720 $7.6 10 111.0
Pettibone Creek pesir 12 GH 7.0 “o No 7a ays 39.8 ND 107.0
Pettibone Creek . \. . ) . 3 5.9 6. 653.0 1.0

ear WOT 93.6) Woy | To.2y air 9.27 3.3) | Ta9.8y ary we Ur

NSD Waukogan STP 5/16/72 2.2 5 45.7 120.0 ND wD 1.3 r6 0? yo.5 94.1 no 139.
NSSD Waukegan STP 5/19/72 2.9 1.6 36.5 100.0 wD wo 2h 79 3 68.2 101.8 ND 105.
ASSD Woukegan STP 5/23/72 78 8.3 5 87.0 ND NO 16.1 09 al 49.1 82.2 WD 7
NSSG Weukegan STP 5/22/72 37 12.5 37.4 65.0 ND No TH 42.6 9.2 132.6 259.0 wo 118.
NSSD Waukegan STP OA 14 6.7 59.8 250.0 wD No v9 ee 16.3 30.7 17.0 fie
SSD Nerth Chicago STP 5/22/72 16 29.2 20.7 55.0 ND "O 53.5 Wh 65 110.9 208.3 cy 104
WSSO North Chicago STP 5/23/72 3.2 26.0 22.8 97.0 ND 4D 43.0 20.4 6.0 87.7 15741 wD Yoo.
SSD North Chleago STP 5/16/72 23 25.5 28.3 58.0 0 ND ND 32.2 18.2 0 5.2 75 1330 nD 132.
SSD North Chicago STP 5/19/72 1.2 21.8 5 70.0 ND wD M7 8g 7967 13h. No Vr.
MSSD North Chicago STP 6/17/72 1.2 6. No A -

cep =~ di-n-buty! phthalate
T = Trace
WD = Not Detected


TABLE 2

(Continued)

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Yellow Perch
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Coho Salmon
Coho Salmon
Coho Salmon
Coho Salmon
Aewife
Alewife
Alew! fe
Alewife

SPECIES
Chub
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carp
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carp
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Carp

i

= Trace

7



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 froni
61.0 to 841.0 ppt. Di-n-buty] phthalate was found in concentrations
ranging from a trace to 147.0 ppt in 1972 and was not detected in 1971.
Di(2-ethylhexy1) 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-buty] phthalate was detected at levels from 55.0 to 250.0 ppt. Di-
(2-ethyihexy!) phthalate was found only in 1971 at levels from N.D. to
.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.


‘=DD

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 bipheny] 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.

Di(2-ethyThexy1) phthalate: (DOP)

Di(2-ethylhexy] phthalate) was detected in sewage treatment plant
effluents only in 1971 sampling. Highest levels were obtained at the-

27


#4 mile station \

Winthrop
Harbor

—_—s

Scale In miles

»fISSD Waukegan STP
Waukegan Wi
Waukegan River «|

eJNSSD North Chicago STP
North Chicago WEP
Pettibone Creek ,|

«[NSSD Lake Bluff STP
LAKE MICHIGAN

NSSD Lake Forest STP

ISSD Highland Park @ Park Ave. STP
“\NSSD Highland Park @ Ravine Drive STP
L Lake County __________ WNSSD Highland Park @ Cary Ave. STP
Cook County

Highland Park

Evanston WFP oh mile station

Chicago Central WFP o4 mile station

Chicago South WFP

FIGURE 2, LOCATIONS OF WATER SAMPLING STATIONS

24


FIGURES

Locations of sediment sampling stations.

Locations of water sampling stations.

Page
14

24


Section

I

II
III
Iv

Vv

VI
VII
VIII
IX

CONTENTS

Conclusions
Recommendat ions
Introduction
Pesticide Monitoring Lake Michigan Fish
Pesticide Monitoring Lake Michigan Sediments
Pesticide Monitoring Lake Michigan Water
Results and Discussion
Acknowledgements
References
Appendices
Appendix A. Analytical Quality Control Data
Appendix B. Field Methods

43
53


ras

TABLE 3

PESTICIDES, PCB'S AND PHTHALATES FOUND IN THE EDIBLE PORTIONS OF TWO SPECIES OF

LAKE MICHIGAN FISH (1972).
a wet welght basis.

Values are expressed In parts per milion (ppm) on

: 2, p'_tsomers. { tsomers

NUMBER AND = SIZE IN SAMPLE DATE HEPTACHLOR TOTAL AROCLOR
SPECIES SEX ANALYZED INCHES LOCATION COLLECTED — EPOXIDE =—-«DIELORIN © DBP_««DDE DDD DOT DDE DDD DOT DT 1254
Chubs 5 tale 5/25/72 0.1 O.t <0.) 0.10.1 0.6 2.0 0.2 1.7 46 2.8
Chubs 5 Female 5/25/72 <0,1 0.1 <0.1 0.10.1 0.3 1.2 0.1 0.9 2.6 2.5
hubs 5 Female Waukegan 5/25/72 <0.1 OL Ot 0.2.<0.1 0.2 1.0 0.1 0.7 2,2 2.5
Chubs 5 Female Waukegan 5/25/72 <0.1 oO. <0.) 0.1 <0.1 0.2 1.0 0.1 0.6 2.0 2.8
Chubs 5 Female Waukegan 5/25/72 <0.1 0.1 0.) 0.2. <0.1 0.3 143 0.1 0.9 2.7 2.9
Chubs. 5 Female Waukegan 5/25/72 <0.1 0.2 0.1 0.1 <0.) 0.3 22 0.1 1.1 3.0 2.3
Chubs 5 Female Waukegan 5/25/72 <0.1 0.2 0.1 0.1 <0.1 0.3 1.2 0.2 12 3.0 3]
Chubs 5 Female Waukegan 5/25/72 <0.1 ot <0.) 0.10.1 0.2 1.1 0.0 1.0 2.5 3
Yellow Perch 5 Female Waukegan 6/28/72 <0.) 0.1 ND <0. <0.1 <0.1 0.1 <0.1 <0,1 0.2 0.3
Yellow Perch 4 Female Waukegan 6/28/72 <0.1 <0.1 ND <0.1-<0,1 <O.1 <0.1 <Q. OT O.T 0.3
Yellow Perch = § Hale Waukegan 6/28/72 <0.1 <0.1 ND <0.1 <O.1 <0. <0.1 <0. <0.1 0.1 0.3
Yellow Perch 5 Female Wauke; 6/28/72 <0.1 <0.1 ND <0.) ND <0. <0.1 <0,1 0,1 0.8 0.2
Yellow Perch = 5 Hale Waukegan 6/28/72 <0.1 <0.1 ND <0.1 ND <O.1 0.1 <O.1 0.1 0.2 0.3
Yellow Perch = 5 Hale Waukegan 6/28/72 <0.1 <0.1 ND <O.1 ND <O.1 0,1 0,1 <0.1 0.2 0.3

DaP
ND

di-n-buty! phthalate
Not Detected


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 fran 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-ethylhexy1)
phthalate and di-n-buty] 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.


TABLE 5

PESTICIOES, PCB'S AND PHTHALATES FOUND IN LAKE HICHIGAN SEOIMENTS AND IM TRIBUTARY
STREAM AND RAVINE SEDIMENTS IH ILLINOIS (1971). Values are expressed In parts per

bIN lon (ppb) on a dry welght basis,

SAPLE HEPTACHLOR
LOCATION EPOXIOE DIELDRIN —_HETHOXYCHLOR LINOANE =——-HEPTACHLOR or psp
<1 to 3 MILES OFFSHORE
WSSD Park Aves STP (Highland Park) 0,02 0.14 0.31 WD No aay No
NSSD Lake Forest STP (Lake Forest 0.01 on 0.55 WD ND "D ND
SSO Lake Bluff STP (Lake Bluff) 0.01 9.06 0.91 NO ND "DO xo
W5SO North Chleago STP (Worth Chicago) 0,02 0.13 0,80 WO NO ND NO
NSSO Waukegan STP (Waukegan) ND 0,03 0.30 NO NO 718 ND
take Bed Station 60 0.06 0.29 9.70 ND Li wo nO
Lake Bed Station 55 0.07 0.48 wu ND ND wo wo
Lake Bed Station 52 0.02 0.19 0.87 no wD 40 cry
Lake Bed Station 49 O15 0.67 ah ND No i "o
Lake Bed Station M6 on 0.52 173 nD no no nD
Lake Ged Station 43 0.08 1.35 2.18 wD cr) ND ND
Lake Bed Station 40 9.17 ¥.22 15 wD No ND wD
Lake Bed Station 37 0.12 0.86 6.60 ND NO ND 4D
Lake Bed Station 34 0.01 0, 0.71 No no 1 No
Lake Bed Station 31 0.01 0. 0.71 ND ND 4D 4D
he Bed Station 28 9.01 0. 0.92 wo wD wo "D
Station 24 0,01 0. 4.68 wo ND wD ND
Bed Station 21 No 0. 0.68 ND No wo 40
Bed Station 18 nD 0. 0.67 ‘fo 4D ND wD
id Station 15 0.01 9. 0.60 nD ND 4D ND
Statlon 12 0.02 0.07 0.52 wD ND no wo
Bed Station 8 0.02 0.11 0.59 ND wo ry
fad Station 5 0,02 0.23 o8 Wo wo wo
acetion u.02 x Lo 8D
Sa Cs 7 : w
1O_co YARDS UPSTREAM FROH LAKE
Bull Creek (Zton} 0.08 0.50 wD 0.06 WO ND
Dead River (Zion; 0.17 OMe wD 0.05 ND wo
Unnamed channel (Waukegan) bok 9.40 WD ND 218.00 ND
Waukegan River (Waukegen) 0.44 2.98 4D 0.24 WD nD
Pattibone Greek (North chicago) 0.57 2.hh ND 0.01 51.30 uo
Stone Gate Lane Ravine (Lake Forest 0.43 1.80 wD 0.05 82.30 40
Berry Hall School Ravine (Lake Forest) 0.95 41.00 0.01 0.08 id ND
Cary Avenue Ravine (Highland Park) 1.60 13.10 01 0.07 ND no
Ravine Orive Ravine (Highland Park) 2.54 9.10 ND 0.09 28.50 25.00
Park Ave. Ravine (Hightand Park) 9.50 6.90 0.03 0.12 57.00 ¥20.00
Barat Ravine (Lake Forest) 104 175.00 ND 0.08 NO 0
Ravine Park tains {take eluff) ed fas os 0.03 xo ”
Kellogg Creek (Zlon! . i
O99 Sree wy Troy WOT W.0ey WH. F c

0p = dl (2-ethythexy!) pheha!
DBP = di-n-buty! phthalate
ND = Hot Detected



EPA-660/3-74-002
JANUARY 1974

Ecological Research Series



APPENDIX A TABLE 3
ANALYTICAL QUALITY CONTROL DATA

Sample Fortification (in PPM)

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

48



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 I1linois 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 I1li-
nois Environmental Protection Agency covering the period beginning in
the fall of 1970 through July 1, 1972. Data collected by the I1linois
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-


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.


APPENDIX A

ANALYTICAL QUALITY
CONTROL DATA

43


TABLE 6

PESTICIDES IM WATER SAMPLES FROM LAKE HICHIGAN AND TRIBUTARY SOURCES IW ILLINOIS
(1970). Values ere expressed In parts per triltion (ppt).

DATE HEPTACHLOR 22 pt lsomere Psp! Isomers
SAMPLE LOCATION COLLECTED EPOXIDE DIELDRIN oor DE po por Tot
Telbutary Streans!
Waukegan River W/a/79 Ae 1.6 1.8 2.8 6.3
ett reel . 0.6 22 6:2 ya
Sewage Treatment Plants*
NSSD Waukegan 10/23/70 0.7 2.4 a
NSSD North Chicago 10/23/70 0.6 2.5 hy a3 33 “e
NSSD Lake Gluff 11/2/70 <0.2 15 0.3 0.9 12 25
HSSO Lake Forest 11/2/70 <0,2 22 1.5 0.8 V2 35
NSSD Highland Park - Park Avenue 11/2/70 <0.2 1.6 0.9 0.8 wa 3.2
NSSO Highland Park ~ Revine Drive 11/2/70 <0.2 2.3 3.8 1.5 49 9.1
NSSD Highland Park - Cary Avenue 11/2/70 <0.2 0.6 0. * a 2.6
Tor 3 : thr wr ir
en Water Samples?
Winthrop Harbor 10/20/70 <0.2 <0.3 <0,
Evstan 10/20/70 20:2 <0:3 203 <0 Me a3
Chic 10/20/70 <0.2 <0. <0. <0. <1.0 0.
0.2 cs 5 A se os
Water Plant Intake Sanples>
Waukegan 10/23/70 <0.2 <0.2 0.3 <0. 0 0.
North Chleago 10/23/70 <0.2 20.2 <0.3 33 63 phy oe
Highland Park 10/23/70 <0.2 <0.2 <0.3 <0.3 <0.3 <1 o.4
Evanston 10/23/70 <0.2 <0.2 <0.3 <0.3 <0.3 <1.0 0.5
Ghicago Central tovzu70 x0 x02 <0.3 «0.3 <0.3 <10 0.3
cago Sout! <0. <0. <0.3 <0. . 1.0 0.
co com wor eee eer
1 50 yards upstream from Lake Aichi gan
2 Final effluent to Lake Hichigan
3 4 alles offshore
4 4 miles offshore from Chicago Centra) water plant
5 Crib water samples ranging from 1/3 to 2 1/4 alles offshore.


fish samples were run as above except 10 grams of fish flesh was used
and all the oi] 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 F] 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-ethylhexy1) phthalate and di-n-buty1
phthalate with some fish oil. This fraction was reduced to 0.5 ml.
The phthalates were separated from the fish oi] 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% H20 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 F] was run only on
the 3M column but F2 and Fq were run on both. The shorter column
facilitated the analysis of methoxychlor and di(2-ethylhexy]) phthal-
ate.

SEPARATION PROCEDURE ~ SEDIMENT

100 grams of sediment was mixed with 100 ml ethyi alcohol + 100 mi
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 mi anhy-
drous diethyl ether, and finally with 100 ml dry nanograde hexane.

49


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
Pettibone 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
0, 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.

0, p'-DDT

0, p'-DDT averaged <0.6,1.4 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.

Ps 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.


TABLES

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

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

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

Pesticides found in sediments from Lake Michigan and trib-
utary streams and ravines in I1linois (1970)

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

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

Pesticides found in water samples from several I1}inois
streams and sewage plants tributary to Lake Michigan (1971)

Pesticides found in water samples from Illinois streams

10

12

16

18

26

28

and sewage treatment plants tributary to Lake Michigan (1972) 30


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.

Di_(2-ethylhexy1) phthalate: (DOP)

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 0,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 0,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 averaged 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


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-ethylhexy]) phthalate was not detected in the tributary streams
during the three year study while di-n-buty] 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-buty] 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-ethylhexy1) phthalate, di-n-buty] 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-ethylhexy1) phthalate, 250.0 ppt for di-n-buty] 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 from DDT 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


SELECTED WATER
RESOURCES ABSTRACTS

INPUT TRANSACTION FORM
4. Title
PESTICIDES IN THE ILLINOIS WATERS OF LAKE MICHIGAN

Author(s) W
Schacht, Robert A. 19, Project No.
16050 ESP

1. Contract/Grant No

9. Organization
Illinois Environmental Protection Agency
Chicago, Illinois 60609 16050 ESP

«a

15. Supplement
U.S. Environmental Protection Agency
Research Report No. EPA 660/3-74-002, January 1974

16. Abstract

This study was initiated 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
following list: heptachlor, heptachlor epoxide, dieldrin, methoxychlor, lindane,
aldrin, endrin, DDT and its analogs. Additional analyses were accomplished for poly-
chlorinated biphenyls (PCB's), di-n-butyl phthalate (DBP), and di (2-ethylhexyl)
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.

17a. Descriptors
*Pesticides, *Polychlorinated Biphenyls, (Lake Michigan, *Fish, *Sediments, *Water,
Insecticides, Organic Pesticides, Chlorinated Hydrocarbon Pesticides, Aldrin, DDD, DDE,
DDT, Dieldrin, Endrin, Heptachlor, Aroclors, Effluents, Tributaries, Lake Sediments,
Salmon, Carp, Yellow Perch, Brown Trout, Pollutants, Pollutant Identification, Water

Pollution, Water Quality.
17b. Téentifiers CEES

Heptachlor Epoxide, Lindane, Methoxychlor, Phthalates, Chicago(I1l.), Waukegon(I1l.),
Alewife, Coho Salmon.

7c. COWRR Field & Group Q5B, OSA

418. Availability Send To:

WATER RESOURCES SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON, D. C. 20240

Abstractor Robert A, Schacht Institution IEPA, Chicago, Illinois

WRSIC 102 (REV JUNE 1971)


Aroclor 1254

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

21


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.

ii


APPENDIX A TABLE Z

ANALYTICAL QUALITY CONTROL DATA

limits of detectability for parameters tested

a SAMPLE
PARAMETER TESTED FISH SEDIMENTS WATER
PESTICIDES
Heptachlor
Epoxide <25 PPT <2.5 PPT <.2 PPT
Dleldrin <25 PPT 2.5 PPT 2 PPT.
Methoxychlor | 100 PPT 10_PPT 1 PPT
Lindane 25 PPT 2.5 PPT 25 PPT
Aldrin >| 25 pet 2.5 PPT 25 PPT
Endrin 25 PPT 2.5 PPT 25 PPT
Heptachlor 25 PPT 2.5 PPT 25 PPT.
2,p’ DDE 25 PPT 2.5 PPT +25 PPT
2,p' DoD 25 PPT 2.5 PPT 25 PPT.
o.p' DET 25 PPT 2.5 PPT +25 PPT
p,p' DDE 25 PPT 2.5 PPT 225 PPT
p.p' DoD 25 PPT 2.5 PPT 225 PPT
pp! DoT. loo PPT 1o_ PPT 1_ per
POLYCHLORINATED
BIPHENYLS (PCB's)
Aroclor 1232 - = =-
Aroclor 1242 4 PPB 400_PPT 4Q_PPT.
Afoclor 1248 == == =
Aroclor 1254 2.5 PPB 250 PPT 25 PPT
Aroclor 1260 = = =
PHTHALATES
di-n-buty! 2 PPB 200 PPT 20 PPT
ati aes
d~(2-ethyI-
phtnareee” 10 PPB 1 PPB 100 PPT
(vor)

47


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 m1 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 al] but 2 ml of the solvent removed by distilla-
tion (the NagSO4 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-ethyThexy1)
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% diethy1 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 oi] was placed on the florisil column (later,

45


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. ,


TABLE 2

PESTICIDES, PCB'S AND PHTHALATES FOUND IN EDIBLE PORTIONS OF FIVE SPECIES OF
LAKE MICHIGAN FISH (197]). Values are expressed Jf parts per ml }ion (ppm)
on a wet welght basis.

ot

NUHBER
AND SEX SIZE IN ‘SAHPLE DATE HEPTACHLOR

SPECIES ANALYZED INCHES LOCATION COLLECTED EPOXIDE DIELDRIN — METHOXYCHLOR =—-LINDANE = DOP oeP
Yellow Perch Halle 7.0 - 10.5 Chicago 10/6/71 <0.) «0.1 ND nO 0.3 «0.1
Yellow Perch = 5 Hale 8.0 - 11.0 thleago 10/6/71 <0.1 «0.1 4D ND 0.3 <0.
Yellow Perch 5 Female 8.0 - 12.0 Chicago 10/6/71 <0.1 <0.1 wo <0.) 0.2 <0.1
Yellow Parch 5 Female 8.0 - 10.0 Chicago 40/6/71 <0.1 <0.1 ND ND 0.4 <0.)
chub 5 Female 9.0°- 10.0 Waukegan ARYA <0.1 0.1 ND 13 a
chub 5 Female 10.0 - 10.5 Waukegan 3/71 “0.1 0.1 NO ni a
Chub 5 Hale 9.5 - 12.0 Waukegan myn “0.1 0.2 ND 1.2 0.1
Chub 5 Male 10.0 - 12.0 Waukegan TASTY <O.1 0.2 ND V3 oO.
Carp. 5 Male 17.5 = 27.5 Chicago aly = 420/71 “0.1 0.1 0.1 ND ND Ot
Carp 4 Male 17.0 = 23.5 Chicago 4p2o/71 <0.1 0.1 <0.1 No T <0.)
Carp 4 Female = 18.0 = 25.0 Chicago WIZ = 4/20/71 O11 on 0.1 wD nD “0.1
Carp S Female 22.5 - 25.5 North Chicago 5/25/71 «0.1 <0.1 No ND wo No
Carp 5 Female 23.5 - 30.0 North Chicago 5/25/71 T 0.1 No ND wD nD
Carp 5 Hale 18.0 - 23.0 Chicago 4/13 + wr2os71 0.1 Ot No No No ND
Coho Salmon 5 Hale 18.5 > 21.5 Chicago WAN3 ~ 4/20/71 0.1 0.1 wo no no 0.1
Coho Salmon 4 vale 18.0 - 20.0 Chicago A/\3 - 4/20/71 Ol <Ot 0.1 ND No ot
Goho Salmon 5 Female 18.5 - 21.0 Chicago 4/13 ~ 4720/71 <0.1 0.5 Wo NO no <0o.1
Coho Salmon 5 Female 18.5 - 22.0 Waukegan 5/26/71 <0.1 Or ND NO ND nD
Coho Salmon SFemle 19.5 - 22.5 Waukegan 5/26/71 0.1 0.1 ND no No ND
Coho Salmon 5 Male 20.0 ~ 23.5 North Chicago 5/26/71 <0.) Ont ND wo No uD
Coho Salmon 4 Male 18.5 ~ 21.5 North Chicago WN3 - 5/26/70 <0.1 O.1 No nD No «0.1
Alewife 5 hale 6.0- 7.0 Chicago SAVIN <0.1 0.1 ND wD ND
Aleuife 5 Hale 6.0 - 7.0 Chicago <0.t 0.1 ND wD wo
Alewife 5 Female 6.0- 7.0 Chicago <0.1 ot ND iT) no
Alewl fe 5 Female 6.0- 7.0 Chicago sawn <0.1 0. ND ct) ND
Alewlfe 5 Female 6.0- 7.0 North Chicago 4/28/71 <0.1 0.1 ND wo wo
Alewife 5 Fenale 6.0- 7.0 Worth Chicago 4/28/71 <0.1 0.1 ND no WD
Alewife 5 Hale 6.0 7.0 North Chicago 4728/71 <0.1 0.1 ND No no
Alewlfe 5 Male 6.0- 7.0 North Chicago 4726/7 <0.1 0.1 ND ND ‘HO

DOP = di (2-ethythexy!) phthalate
DBP. =~ di-n-buty! phthalate

T = Trace

uD = Hot Detected


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 OL

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 of Documents, U.S. Government Printing Office, Washington, D.C. 20402 - Price $1.25


SECTION VII
RESULTS AND DISCUSSION

The monitoring program established by the I]linois 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


TABLE 5

(CONTINUED)
PESTICIDES, PCB'S AND PHTHALATES FOUND IN LAKE MICHIGAN SEDIMENTS AND IM TRIBUTARY
STREAM AND

RAVINE SEDIMENTS IN ILLINOIS (1971). Values are expressed In parts por
bII Ton (ppb) on @ dry welght basis.

——eiisomers ap! Nsomers — Arcelor
sweL”E TOTAL
LOCATION ove opp por DDE oop oor oor yah 1254
<1 _to 3 MILES OFFSHORE

WSSD Park Ave. STP (Highland Park) 0.68 ayy 0.67 2.8) 0.62 493 VW 12,42
NSSD Lake Forest STP (Lake Forest) 0.22 0.12 0.43, 1.10 0.38 2.25 10.5) 7.02
WSSD Lake Bluff STP (Lake Bluff) 0.30 O13 o. 1.55 0.60 2.99 4436 VAS:
NSSD North Chicago STP (North Chicago) 0.31 0,06 ray 1.43, 0.31 2.55 106.07 26.54
NSSD Waukegan STP (Waukegan) 0.08 oe 0.94 0.23 0.12 1.37 17.32 1.97
Lake Bed Station 60 0.10 3.32 0.22 2.37 9.18 0.93 © 16.08 4M 8.63
Lake Bed Station 55 0.06 1.75 0.38 1.21 5.42 1.93 10.75 3.58 35
Lake Bed Station 52 0.04 1.58 0.36 wit 2.96 0.97 7.02 8.48 3.33
Lake Bed Station 49 0.04 0.93 0.16 140 6.18 1.30 10.01 13.65 1242
Lake Bed Station 46 0.25 5.47 Vh2 452 8.88 466 25.20 49.33 38.65
Lake Bed Station 43 0.26 3.64 0.75 4.82 3.74 7:25 26.46 83.35 46.92
Lake Bed Station 40 0.09 0.99 0.60 ay Ai2h N76 9.85 17.23 9.38
Lake Bed Station 37 Oth 0.93 0.13 2.88 3.28 2.82 10.18 30.82 33.50
Lake Ged Station 34 0.02 0.63 0.08 0.52 RAS 0.53 3.99 v.28 2.48

Lake Bed Station 31 0.02 0.52 0.06 0.48 1.74 0.73 3.55 ND 3:
Lake Bed Station 28 0.04 1.05 0.10 4,32 3.38 0.87 6.76 18.55 17.25
Lake Bed Station 24 0.04 0.61 0.09 0.88 2.02 1.39 5.03 2.48 5.83
u Station 21 0.51 oO. 0.46 1.72 0.34 3.16 6.60 6.64
Station 18 0.15 one 0.29 0.80 ont 1.36 10.53 $5.56
tal Station 15 0.10 0.07 0.39 0.76 0.29 163 a3 5.26
Lake Bed Station © 12 0.16 0.05 0.32 0.62 0.16 13h 19.28 17.45
Lake Bed Station 0.12 0,07 0.49 0.98 0.20 1.90 24.76 16.30
Lske Bed Station 5. 0.07 0.07 Oth hig oly 2.33 va 34.52

Leke Bed Station 2 a. o. 22 . 21 5 .
v “ot ay Thay 3.00) -U1.21) t 5) CT A)

ZNO to 50 YARDS UPSTREAM FROM LAKE

Bull Creek (Zlon) 0.02 0.04 NO O17 0.08
Dead River (Zion) 0.02 4D 0.07 0.19 oth
Unnamed channel (Waukegan) 0.24 2.75 0.50 0,66 5.56
Waukegan River (Waukegen) 0.85 1.68 0.39 VAT 4.80
Pettibone Creek (North Chicago) 0.06 41.00 21.00 7.60 41.00
‘Stone Gate Lane Ravine (Lake Forest), WD 9.50 2.95 6.70 49.00
Berry Hall School Ravine (Lake Forest) 0.73 1.63 9.00 5.82 20.70
Gary Avenve Ravine (Hightand Park) 0.10 20,50 6.95 7.46 66.50
having Ortve Raving (iighlend Perk) 1.60 8.00 ASH 6.72 4.20
(High rk) 0.29 16.00 27.00 22.90 62.20

NO 0.35 0.53 0.89 1.70

0.91 8.13 1.98 3k 18.90

0.22 ‘

WO = Hot Detected


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

4. 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 formaticn,
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.


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:

F] - 90 to 100 ml hexane eluted PCB's, 0,p' and Pap’ DDE,
heptachlor, some (50%) alpha BHC, o.p' and p,p' DDT (20%).

Fo - 250 ml 10% ether in hexane eluted the remaining chlo-

rinated hydrocarbon insecticides including methoxychior

ethylene. va

F3 - 200 ml 50% ether in hexane eluted di (2-ethyThexy1)

phthalate.

woot '

The second and third fraction (Fo & F3) were collected .¢a:'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 G.L.C. determinations.

SILICA GEL SEPARATION OF PCB'S FROM DDT'S.....

The first florisil fraction (F1) was neduced 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.effective in separating these compounds.
The Fj 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:

Port temperature of 225°C.
Column temperature of 200 to 210°C.
Detector temperature of 255°C.

F Vw DN

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

50


82

PESTICIDES FOUND IN ATER SAMPLES FROM SEVERAL
TRIBUTARY TO LAKE HICHIGAN (1971).

‘TABLE 7

Values are expressed In parts per trl

MOIS STREAMS AND SEWAGE PLANTS
ton (ppt).

2, p! tsomers Pp! Isomers Jor
‘SAMPLE OATE Reptachlor TOTAL Arcelor
LOCATION COLLECTED Epoxiide Dieldrin —Hethoxychior © DOP_—= DE. DD ODT.) DDE DoT y2kz 1254
Waukegan River e/iB/71 5.4 5.9 no No 13.0 23.7 388.0
Waukegan River Wrst rT) 29 wD no 3315.0 pa
Petibone treek srs ib 22.4 wo ND yo.9 18, H 198.0
Pettibone Cre u r 30.7 wo No n 20. 192.0
Ry 15.5) Wy | Woy a 5) wir
NSSD Waukegan STP syn 32 106.0 760.0 3.3 307 139.0
NSSD Waukegan STP a7) 7 26.5 650.0 7.5 27.3 492.0
SSD Waukegan STP WU A 218 90.0 HO 20.0 8.0
‘NSSD North Chicago STP 1/23/71 0.3 WF 160.0 NO 45 256,
NSED North Chlease st? Hae 17.2 ug ‘ND ND 20.6 23.0
NSSO Worth Chicago STF ASIN % NO 0 ND Ma 217.
th . Beer waiter dar ws: wee
oP = dll (2-athythexy?) phthalate
ND = Not Detected


Appendix A

Appendix B

SECTION X
APPENDICES

ANALYTICAL QUALITY CONTROL DATA

Procedure for Laboratory Analysis
Table 1: Per Cent Recovery
Table 2: Limits of Detectability
Table 3: Sample Fortification

FIELD METHODS

Figure 1: Composite Water Sampler
Field Sampling Procedures

41

Page No.

45

47
48

54
55


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).

Tn 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-ethyhexy1) 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-buty] 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


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, et 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.


5. Short one meter column containing 4.0% QF1 and 2.0% OV-17 on
Supelcoport used for methoxychlor and di(2-ethylhexy1) 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.

$1


Rubber Tubing

Rubber Tubing

TM

Water —\
Glass Carboy

Glass wcrle \ Screw Clamp

APPENDIX B FIGURE 1. COMPOSITE WATER SAMPLER

54


PESTICIDES FOUND IN EDIBLE PORTIONS OF FOUR SPECIES OF LAKE MICHIGAN FISH (1970).

‘TABLE 1

Values are expressed In.parts per milllon (ppm) on a welght basis.

~ 2 p' Isomers tsomers.

NUMBER AND = -SIZE IN SAMPLE OATE HEPTACHLOR TOTAL
SPECIES SEX ANALYZED INCHES: LOCATION COLLECTED EPOX1DE DIELDRIN = DDE boT ODE DOT DDD ooT
Yellow Perch 5 Female 9.0 - 10.0 Chicago 1419/70 0.1 0.1 0.1 0.1 0.5 0.3 0.2 2
Yellow Perch 5 Female 2. 9.5 Chicago 1719/70 oO. Ol <0.1 O.1 O4 0.3 Ol 0.9
Yellow Perch 5 Male 9.0- 9.5 Chicago 11719770 0.1 0.1 O.! o.1 0.6 0.6 0.2 16
Yellow Perch 5 Hale 8.5 - 10.0 Chicago 11/19/70 0.1 Ot 0.1 0.1 0.6 0.5 0.2 1s
“Coho Salmon 4 Male 24,5 - 31.0 Waukegan 11/23/70 <O.1 <0.1 0.1 0.2 1.0 0.6 0.3 2.2
Coho Salmon 4 Male 28.0 - 29.0 Waukegan 11/13/70 <0.1 <0.) 0.1 0.2 0.9 O.4 0.2 1.8
Coho Salmon 3 Female 26.0 ~ 27.5 Waukegan 11/13-23/70 <0.1 <0.1 O.t 0.1 0.8 0.3 0.2 5S
Coho Salmon 2 Female 25.0 - 27.5 Chicago 11/13/70 <0.) <0.1 Or 0. 0.9 0.5 0.2 1.8
Chuds 5 Mixed 10.5 - 11.5 Waukegan = 12/22/70 0.1 0.1 0.3 ou 1.3 Vt 0.4 3.5
Chubs "5 Mixed 10.5 - 11.5 Waukegan 2/22/70 0.1 0.1 0.3 0.3 1.2 1.0 0.3 3.1
Brown Trout 3 Female 17.5 - 20.5 Chicago 11/13/70 <0.1 <0.1 0.2 0.3 1.3 0.8 0.5 3.1