vvEPA
             United States
             Environmental Protection
             Agency
             \
             Great Lakes National
            ' Program Office
             536 South Clark Street
             Chicago, Illinois 60605
EPA-905/3-84-003
Contaminants in Fish
From Great Lakes
Harbors  and Tributary
Mouths  1980-81

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                                           EPA 905/3-84-003
                                           April  1984
   Contaminants in Fish From Great Lakes
    Harbors and Tributary Mouths 1980-81
           David S. DeVault, III
      Surveillance and Research Staff
    Great Lakes National  Program Office
United States Environmental  Protection Agency
           536 South Clark Street
          Chicago, Illinois   60605

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                                 DISCLAIMER

This report has been reviewed by the Great Lakes National Program Office,
U.S. Environmental Protection Agency (USEPA), and approved for publication.
Approval does not signify that the contents necessarily reflect the views
and policies of the USEPA, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use.

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                                  FOREWORD

The Great Lakes National  Program Office (GLNPO) of the U.S. Environmental
Protection Agency was established in Region V, Chicago to focus attention
on the significant and complex natural  resource represented by the Great
Lakes.

GLNPO implements a multi-media environmental  management program drawing
on a wide range of expertise represented by universities, private firms,
State, Federal and Canadian governmental agencies and the International
Joint Commission.  The goal of the GLNPO program is to develop programs,
practices and technology necessary for a better understanding of the
Great Lakes system and to eliminate or reduce to the maximum extent
practicable the discharge of pollutants into the Great Lakes system.
The GLNPO also coordinates U.S. actions in fulfillment of the Agreement
between Canada and the United States of America on Great Lakes Water
Quality of 1978.
This study was carried out under a cooperative agreement between GLNPO,
and the States of Ohio, and Wisconsin.   The samples were collected by
state personnel and analyzed by USEPAs Central Regional Laboratory
data analysis and program coordination was provided by GLNPO.
                                    n

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                                  ABSTRACT

Composite fish samples collected from Great Lakes  Harbors  and  Tribu-
taries between 1980 and 1981 were analyzed by  gas  chromatography-
electron capture detector and gas chromatographic-mass  spectrometry
for a wide range of pesticides and priority pollutants.   Severe  PCB
contamination was observed in Sheboygan River  fish with  moderate to
severe PCB contamination in samples from the Milwaukee,  Kinnickinic,
Fox, and Ashtabula Rivers.  The Ashtabula River samples  also contained
several chlorinated aromatic and aliphatic hydrocarbons.   Polynuclear
aromatic hydrocarbons were detected in fish from the Black,  Kinnic-
kinnic and Menominnee Rivers, while a number of benzene  derivatives
were observed in samples from the Fox and Wolf Rivers.
                                     iii

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                                  CONTENTS

Foreword.	1 i
Abstract	  i 11
Tabl es	  v
Acknowl edgements	vi
Introducti on	  1
Methods	  2
Results	  8
Discussion	  17
References	  22
                                     IV

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                                   TABLES


Table 1  Sample Collection Data	  3

Table 2  Compounds Specifically Scanned by GC/Ms	  6

Table 3  Gas Chromatographic Results for Harbor and Tributary
         Mouth Fish	  9

Table 4  Results of GC/MS Scans of Harbor and Tributary
         Mouth Fish	  13

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                               Acknowledgements

I thank the many people in the Fisheries and Natural  Resources Departments
of the States of Wisconsin and Ohio for collecting the samples and pro-
viding valuable site information.   I also thank Dr. James Clark,  (USEPA,
Environmental Research Laboratory, Gulf Breeze, Florida), Mr.  David
Rockwell  (USEPA, Great Lakes National  Program Office) for reviewing
and commenting on the report.  I also wish to thank Mary Martin and
Gaynell Whatley for typing the manuscript.
                                    VI

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                            INTRODUCTION

The Great Lakes Fish Monitoring Program (GLFMP) is a cooperative program
between the U.S. Environmental Protection Agency, Great Lakes National
Program Office (GLNPO), U.S. Fish and Wildlife Service (USFWS), U.S. Food
and Drug Administration (USFDA) and the eight Great Lakes states.  It is
designed to provide a coordinated approach to monitoring contaminants in
Great Lakes fish.  The GLFMP consists of 3 elements to: (1) monitor temp-
oral and special trends in contaminants known to be a problem in Great
Lakes fish, (2) evaluate the potential exposure of the fish consuming
public to hazardous contaminants, (3) locate source areas of PCB and
other known contaminants in the Great Lakes and to detect emerging problems
and previously unknown contaminants before the entire lake ecosystem is
affected.

This report presents data from a limited number of analysis performed under
element 3 of this program.  Samples from Astabula River (Ohio), Black River
(Ohio), Sheboygan River (Wisconsin), Memonimee River (Wisconsin), Kinnickinic
River (Wisconsin), Fox River (Wisconsin), Wolf River (Wisconsin) and
Chequamegon Bay (Lake Superior, Wisconsin) were analyzed for PCB and
common pesticides by gas- liquid chromatography electron capture detection
(GC/EC) as well as scanned for over 100 priority pollutants using gas
chromatography - mass spectrometry (GC/MS).
                                   -1-

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                                METHODS

State personnel  collected indigenous fish from harbor and tributary mouth
sites in the Great Lakes basin using gillnets, trap nets, electro-shock
and other conventional methods.   Individual  fish were weighed,  measured
for length and wrapped in solvent rinsed aluminum foil  in the field.  Fish
were then frozen and shipped to the US Environmental  Protection Agency's
(USEPA) Central  Regional Laboratory (CRL) in Chicago for compositing and
analysis.

Table 1 gives the mean size, weight and collection date of the composite
samples.  After composite groupings were formed, each fish was chopped
into 2 to 3 inch cubes with a meat cleaver or butcher saw and ground twice
in a solvent washed Hobart meat grinder.  The ground fish was then thoroughly
mixed and stored in glass until analysis (EPA 1979a).  Some samples were
composited and ground by state personnel, using similar procedures,
prior to shipment to CRL.
 In CRL the samples were dried with anhydrous ^SCty and Soxhlet extracted
 with 1:1 acetone/hexane for 16 hours.  The extract was then concentrated
 to 10 ml in a Kuderna -Danish concentrator.  Two rnls of the concentrate was
 transferred to a pre-tared aluminum pan and the solvent evaporated for
 lipid determination.  Lipids were removed from the remaining extract by
 gel permeation chromatography using 100% ethyl acetate (EPA 1979a).  The
 elutriate from the gel permeation unit was divided into 2 aliquots, 1 for
 GC/MS analysis for priority pollutants and 1 for GC/EC analysis for PCBs
 and pesticides.
                                   -2-

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                                                       TABLE  1
                                              SAMPLE COLLECTION  DATA
CO
Sample
Number
1S82

1S88

1S90

1S95

1S97

1S02

1S01

OS99

2S09

2S10

2S04

1S99

1S98

1S11

1S09

1S14

2S14

Site
Location
Black River, Ohio

Ashtabula River, Ohio

lAshtabula River, Ohio

Ashtabula River, Ohio

Ashtabula River, Ohio

Sheboygan River, Wis.

Sheboygan River, Wis.

Sheboygan River, Wis.

Mi Iwaukee River, Wis.

Milwaukee River, Wis.

Menominee River, Wis.

Menominee River, Wis.

Kinnickinic River, Wis.

Wolf River, New London
Wis.
Wolf River, New London
Wis.
Fox River above
DePere, Wis.
Fox River, at Mouth

Collection
Date
10/21/81

10/28/81

10/28/81

10/28/81

10/28/81

9/30/80

9/30/80

9/30/80

7/15/81

7/1 5/81

8/15/81

8/15/81

7/15/81

9/15/80

9/15/80

10/10/80

11/15/81

Species
carp

northern pike

blue gill

brown bullhead

yellow bullhead

carp

carp

northern pike

red Horse Sucker

black Crappie

carp

bullhead

carp

carp

walleye

carp

carp

# Fish/
Sample
3

1

3

3

1

1

3

2

15

3

5

5

3

5

3

5

5

Mean Length
(Range) (MM)
464.0
(422-493)
520.0
(NA)
148.0
(144-154)
262.0
(232-286)
152.0
(NA)
640.1
(NA)
408.9
(NA)
708.7
(NA)
243.8
(NA)
182.9
(NA)
639.6
(604-704)
283.4
(254-300)
559.0
(508-599)
566.4
(NA)
442.0
(NA)
406.0
(NA)
427.0
(410-445)
Mean Weight
(Range) (G)
1391.7
(1025-1700)
1724.0
(NA)
53.0
(41-60)
267.7
(170-325)
130.0
(NA)
3950.0
(NA)
1430.0
(NA)
2750.0
(NA)
200.0
(NA)
200
(NA)
4170.0
(3600-5400)
350.0
(300-450)
12433.0
(12200-12800)
2100.0
(NA)
800.0
(NA)
900.0
(NA)
1090.0
(900-1250)
Lipid
10.0

6.7

4.4

6.5

1.9

8.0

8.7

10.1

2.2

3.7

33.2

2.2

22.8

9.6

6.2

3.1

8.3


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1S12

1S07

IS 06

1S16

1S15

Fox River, above
Depere, Wis.
Fox River, below
DePere, Wis.
Fox River, below
DePere, Wis.
Chequamegan Bay
Ashland, Wis.
Chequanegan Bay,
Ashland, Wis.
10/15/80

10/15/80

10/15/80

8/15/80

8/15/80

rock bass 5

carp 5

walleye 5

white sucker 5

Walleye 5

177.8
(NA)
452.0
(NA)
383.5
(NA)
463.0
(NA)
462.3
(NA)
160.0 3.2
(NA)
1400.0 10.9
(NA)
400.0 10.7
(NA)
960.0 4.3
(NA)
1000.0 8.3
(NA)

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The GC/MS portion of the extract was screened by a Varian 2700 gas chromato-
graph equipped with a flame photometric detector to determine the sample volume
adjustments required for 6C/MS analysis as well  as what, if any, additional
cleanup was required (EPA 1979a).  This was then analyzed by a Hewlett-Packard
5985 automated gas chromatograph/mass spectrometer using the following oper-
ating conditions (EPA 1979b):
     Column:  30m x 0.2mm SE-54 fused silica capillary
     Carrier Gas:  Helium at 25 cm/sec.
     Mass Range:  45-450 AMU
     Electron voltage:  70 EV
     Temperature Program:  TI = 50C for 1 min.
                           T  300 for 20 min.
                           rate: 100C to 300C  by 10C/min.
Priority pollutants were identified and quantified by the Hewlett-Packard
5985 Quantid program.  This program uses the response factor for the internal
standard (DIO-phenanthrene) and the external standard in the base/neutral or
acidic standard mixture.  Unknown peaks which were 10 percent above baseline
noise were identified by computer or manual search of the NBS and Wiley mass
spectral libraries.  Identification required a match of at least 5 major
ion peaks.  Compounds identified in this process are indicated as tentative
(T) in Table 4 as they were not compared with authentic standards.  Quanti-
tation of tentative compounds was estimated on the basis of a 1 point
internal standard calibration procedure (EPA 1979b).  Table 2 lists those
compounds for which authentic standards were used.
The second aliquot from the gel permeation unit  was separated into a mixed
and a pesticide fraction on a activated Florisil column by eluting first
with 6% diethyl  ether in hexane and, secondly, with 50% diethyl ether in
hexane.  The second fraction was refrigerated for later pesticide analysis.
The first fraction was further separated into a  PCS and a pesticide fraction
on silica gel  by eluting first with hexane (PCB  fraction) and secondly with
                                   -5-

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                                                       TABLE 2
                                             Compounds Scanned by GC/MS
 Bis (2-Chloroethyl) Ether
 1,3-Di chl orobenzene
 1,4-Di chlorobenzene
 1,2-Di chlorobenzene
 Nitrobenzene
 Hexachloroethane
 N-Ni trosodi propylami ne
 Isophorone
 Bis(2-Chloroethoxy) Methane
 1,2,4-Trichlorobenzene
 Naphthalene
 2-Chl oronaphthalene
 Dimethylphthalate
 Acenaphthylene
 Fluorene
 N-Ni trosodi pheny1 ami ne
 4-Bromophenylphenyl Ether
*Phenanthrene/Anthracene
 Di-N-Butyl phthal ate
 Fluoranthene
 Butyl Benzylphthalate
 Bis(2-Ethylhexyl)Phthalate
*Benzo(A)Pyrene
*Perylene
*Methoxychlor
 2-Chlorophenol
*2,4-Dimethylphenol
 2-Nitrophenol
 2,4-Dichlorophenol
 P-T-Butylphenol
 P-Chloro-M-Cresol
 2,4,6-Trichlorophenol
 4-Nitrophe
 4,6-Dinitro-Ortho Cresol
 Pentachlorophenol
 Hexachlorobutadi ene
 Acenaphthene
 2,4-Dinitrotoluene
 2,6-Dinitrotoluene
 Diethylphthalate
 1,2-DiphenyIhydrazine
 Hexachlorobenzene
 Di-N-Octylphthalate
 Dibromobipheny1
 Pyrene
 Chrysene/Benz(A)Anthracene
*Benzo(B)Fluoanthene
*Indeno(l,2,3-C,D)Pyrene
 Phenol
*Tetradifon
*Triflan(Trifluralin)
*2,4,D-Isopropyl Ester
 Alpha BHC (A-BHC)
*Beta-BHC  (B-BHC)
*Gama-BHC  (G-BHC)
 Heptachlor
*Aldrin
*Dieldrin
*DCPA (Dacthal)
*Isodrin
*Heptachlor Epoxide
*0xychlordane
*Gama Chlordane
*0,P DDE
*P,P DDE
*0,P, ODD
*Endrin
*Chlorobenzilate
*Endosulfan-II
*0,P-DDT P.P-DDD
*P,P DDT
 Benzo(G,HsI)Perylene
*Kepone(Chlordecone)
 *Computer match only.  Standards are not  run.   All  others matched and quantified with authentic standards.

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20% diethyl ether in benzene (pesticides).  All fractions were concentrated

to the appropriate volumes and analyzed on a Perkin-Elmer (PE-3920B) dual

column gas chromatograph with electron capture detectors using the following

operating conditions (EPA 1979b):

     Channel 1:

     Column:  3% SP-2100 Supelcoport
     Length, Diameter:   2.4m, 3.175mm (ID)
     Injection Column:   5 ul               Injection Temperature:  270C
     Column Temperature:  200C            Detector Temperature:  325C
     Carrier Gas:  95% Argon/Methane (5%)
     Flow Rate:  25 ml/min
     Standing Current:  1

     Channel 2:
     Column:  1.5% SP-2250/1.9% SP-2401 on Supelcoport
     Length, Diamter:  2.4m, 3.175mm (ID)
     Standing Current:  1
     Flow Rate:  25 ml/min


All compound analyzed by GC/EC (Table 3) were compared to Authenic Standards.

The data are reported as mg/kg wet weight and are not corrected for extraction

efficiency.
                                   -7-

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                                  RESULTS
GC/EC
GC/EC analysis identified 19 pesticides  and industrial  compounds  in  the
22 composite samples analyzed (Table 3).   These include compounds  currently
in use in the Great Lakes basin and those whose use has been  banned, such
as PC8 and DDT, or severely restricted such as  chlordane and  heptachlor.

RGB's were the most predominant contaminant found,  occurring  in  all  samples
at concentrations ranging from 0.175 mg/kg to 98.44 mg/kg.  The  highest  PCB
concentrations occurred in fish from the Sheboygan  River with concentrations
ranging from 38.60 mg/kg to 98.44 mg/kg.   Elevated  PCB concentrations also
occurred in samples from the Fox River (2.01 mg/kg  to 20.89 mg/kg),  the
Ashtabula River (1.72 mg/kg to 10.68 mg/kg), the Kinnickinnic River  (17.73
mg/kg) and the Milwaukee River (6.63 mg/kg to 15.54 mg/kg).  All  samples
exceeded the International Joint Commission's (IJC) objective of 0.1 mg/kg
total PCB for whole fish (IJC 1978).  The contribution of the individual
Aroclor mixtures to the total PCB varied from site  to site but was con-
si stant between samples at each site.  With the exception of  carp from
the  Kinnickinnic River, those samples with total PCB concentrations
ranging from 1.72 mg/kg to 98.44 mg/kg were dominated by Aroclor 1248.
Those samples with lower total PCB concentrations were dominated by  the
more highly chlorinated, more persistant (Mieure et al. 1975, Sloan  et al.
1983) Aroclors 1254 and 1260.

DDT  and metabolites occurred in all samples with total DDT ranging from
0.023 mg/kg in bullheads from the Ashtabula River to 1.93 mg/kg in Northern
pike from the  Sheboygan River.  Total DDT was below the IJC objective of

                                    -8-

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                   Table 3
Gas Chromatographic Results for Harbor and Tributary
                 Mouth Fish (mg/kg)
Sample #
Aroclor 1248
Aroclor 1254
Aroclor 1260
Total PCB
P.P-DDT
O.P-DDT
P.P-DDE
O.P-DDE
P.P-DDD
O.P-DDD
Total DDT
G-Chlordane
Oxychlordane
Heptachlor
Heptachlor Epoxide
B-BHC
G-BHC (Lindane)
Hexachl orobenzene
Aldrin
Dieldrin
Endrin
Methoxychlor
Endosulfan II
Dacthal
Trifluralin
Black
River
1S82
0.42
0.57
0.29
1.28
<0.002
0.02
0.06
0.11
0.06
0.005
0.256
0.03
<0.002
<0.002
<0.005
<0.002
0.005
0.03
<0.003
0.02
<0.002
<0.01
0.004
0.004
0.007
Ashtabula River
1S88
4.17
2.39
<0.05
6.58
<0.002
0.04
0.13
0.30
0.13
<0.005
0.603
<0.002
<0.002
0.30
<0.005
<0.002
0.12
2.19
<0.003
0.01
<0.002
<0.01
0.01
<0.002
<0.002
1S90
8.81
1.85
<0.05
10.68
<0.002
0.02
0.02
0.05
<0.005
<0.005
0.09
<0.002
<0.002
<0.002
<0.005
<0.002
0.07
3.47
<0.003
0.01
<0.002
<0.01
0.015
<0.002
<0.002
1S95
2.01
0.79
<0.05
2.98
<0.002
<0.020
<0.002
0.01
<0.005
<0.005
0.032
<0.002
<0.002
<0.002
<0.005
<0.002
<0.002
0.71
<0.003
0.06
<0.002
<0.01
0.01
<0.002
<0.002
1S97
0.88
0.62
0.22
1.72
<0.002
<0.020
<0.002
0.005
0.004
<0.005
0.023
<0.002
<0.002
<0.002
<0.005
<0.002
<0.002
0.31
<0.003
<0.002
<0.002
<0.01
0.005
<0.002
<0.002
Sheboygan River
1S02
21.30
15.79
1.51
38.60
<0.002
0.11
0.61
0.15
<0.005
<0.005
0.876
0.04
0.20
<0.002
0.19
<0.002
0.08
0.09
<0.003
<0.002
<0.002
<0.01
0.01
0.01
<0.002
1S01
51.37
42.37
4.70
98.44
0.04
0.16
0.31
0.31
0.34
0.32
1.48
<0.002
0.40
<0.002
0.40
0.06
0.08
0.08
<0.003
<0.002
<0.002
<0.01
0.04
0.003
<0.002
OS99
31.3
29.25
2.55
63.14
0.15
0.26
0.87
0.35
<0.005
0.30
1.93
<0.002
0.47
<0.002
0.48
0.06
0.08
0.13
<0.003
<0.002
<0.002
0.08
0.02
0.002
<0.002
Milwaukee River
2S09
3.27
2.16
1.20
6.63
0.01
0.01
0.08
0.03
<0.005
0.02
0.15
<0.002
0.05
<0.002
0.02
0.06
<0.002
<0.002
<0.003
0.005
<0.002
<0.01
0.02
0.01
<0.002
2S10
7.36
5.32
2.86
15.54
0.02
0.04
0.14
0.08
<0.005
0.03
0.31
<0.002
0.04
<0.002
0.02
0.08
<0.002
<0.002
<0.003
0.02
<0.002
<0.01
0.01
0.01
<0.002

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                       Table 3 cont'd
Gas Chromatographic Results for Harbor and Tributary
               Mouth Fish  (mg/kg)
Sample^
Aroclor 1248
Aroclor 1254
Aroclor 1260
Total PCB
P.P-DDT
O.P-DDT
P.P-DDE
O.P-DDE
P.P-DDD
O.P-DDD
Total DDT
G-Chlordane
Oxychlordane
Heptachlor
Heptachlor-
epoxide
B-BHC
G-BHC(Lindane)
Hexachloro-
benzene
Aldrin
Dieldrin
Endrin
Methoxychlor
Endosulfan II
Dacthal
Trifluralin
Me nominee River
2S04
2.75
0.42
<0.05
3.195
<0.002
0.16
1.10
0.26
<0.005
0.18
1.703
<0.002
0.03
<0.002
0.005

<0.002
<0.002
0.02

<0.003
0.02
<0.002
<0.01
0.02
0.12
<0.002
1S99
0.06
0.33
0.36
0.75
0.01
0.03
0.14
0.07
<0.005
0.01
0.262
<0.002
<0.002
<0.002
0.023

0.04
0.01
0.005

<0.003
0.01
0.01
<0.01
0.03
0.01
<0.002
Kinnickinnic
River
1S98
5.76
8.25
3.72
17.73
0.06
0.17
0.85
0.36
<0.005
0.14
1.582
<0.002
<0.002
<0.002
0.08

0.03
0.01
0.05

<0.003
0.15
0.01
<0.01
0.01
0.12
<0.002
Wolf River
1S11 1S09
<0.05
0.09
0.06
0.175
0.08
0.07
0.05
0.01
<0.005
<0.005
0.215
<0.002
<0.002
<0.002
0.003

<0.002
<0.002
0.004

<0.003
0.01
<0.002
<0.01
0.03
0.01
<0.002
<0.05
0.49
0.32
0.835
0.02
0.02
0.08
0.01
<0.00
<0.005
0.135
<0.002
0.004
<0.002
0.004

0.002
<0.002
0.004

<0.003
0.01
<0.002
<0.01
0.01
0.002
<0.002
Fox River
above DePere
1S14 2S14 1S12
4.81
4.10
0.62
9.53
<0.002
0.05
0.31
0.13
<0.005
<0.005
0.496
<0.002
0.15
<0.002
0.09

0.09
<0.002
0.02

<0.003
0.09
0.01
0.01
0.02
0.003
<0.002
4.72
2.15
0.35
7.22
<0.002
0.02
0.04
0.02
<0.005
0.03
0.113
<0.002
0.04
<0.002
0.01

0.04
<0.002
0.01

<0.003
0.02
<0.002
<0.01
0.02
0.01
<0.002
1.29
0.57
0.15
2.01
0.004
0.003
0.02
0.04
<0.005
0.01
0.079
<0.002
0.02
<0.002
0.01

0.01
<0.002
0.003

<0.003
<0.002
<0.002
<0.01
0.02
<0.002
<0.002
Fox River
below DePere
1S07 1S06
12.90
7.03
0.96
20.89
<0.002
0.02
0.17
0.07
<0.005
<0.005
0.266
<0.002
0.15
<0.002
0.20

0.90
<0.002
0.01

<0.003
0.02
0.005
<0.01
0.01
0.01
<0.002
5.58
2.57
0.46
8.61
0.02
0.05
0.22
0.32
<0.005
0.04
0.652
<0.002
0.13
<0.002
0.13

<0.002
<0.002
0.013

<0.003
0.03
<0.002
<0.01
0.04
0.005
<0.002
Chequamegon
Bay
1S16 1S15
<0.05
0.28
0.35
0.655
0.05
0.01
0.11
0.05
0.04
<0.005
0.262
<0.002
0.02
<0.002
0.05

<0.002
<0.002
0.004

<0.003
0.01
<0.002
<0.01
0.01
0.002
<0.002
<0.05
0.24
0.14
0.40
<0.002
0.06
0.05
0.05
<0.005
0.04
0.203
<0.002
0.01
<0.002
0.01

0.01
0.002
0.004

<0.003
<0.002
<0.002
0.12
0.03
<0.002
<0.002

-------
1.0 mg/kg in all  but 4 samples  from the  Sheboygan,  Menominee,  and  Kinnickinnic
Rivers.   The ratio of DDE to the  parent  compounds  varied  from  sample to
sample,  however,  DDE was  predominant in  all  but  sample  #1511  (Wolf River).

One interesting result was the  high proportion of  0,P-DDT and  0SP-DDE to
the corresponding P,P isomers.   The predominance of the OsP-isomer has also
been observed in  sediment samples from several Great Lakes location (GLNPO
1981).  Several hypothesis including differential  degradation  rates and
the possible environmental impact of O.P-DDT and O.P-DDE  contaminated
kelthane are under investigation.

Hexachlorobenzene was detected  at low (0.003 mg/kg to 0.13 my/kg)  con-
centrations at all sites  except the Ashtabula River where high (0.71 mg/kg
to 3.47 mg/kg) concentrations occurred.   Methoxychlor was detected in
samples from the Sheboygan River, Fox River, and Chequamegon  Bay at low
(0.01 mg/kg to 0.17 mg/kg) concentrations.   The  pesticides aldrin/dieldrin,
endosulfan, chlordane, heptachlor and BHC occurred at low levels in most
samples.
The herbicides dacthal was detected in 73 percent  of the  samples.   Concen-
trations of dacthal were low ranging from 0.002  mg/kg to  0.12 mg/kg.   The
herbicide trifluralin was detected in one sample from the Black River
0.007 mg/kg.
                                   -11-

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6C/MS Scans
In addition to providing confirmation of PCB,  DDT,  hexachlorobenzene and
some others of the above pesticides and industrial  compounds,  GC/HS
scans revealed the presence of several  additional  compounds of environ-
mental concern (Table 4).

Chlorinated aliphatic and aromatic hydrocarbons were detected  in samples
from the Ashtabula River.  These included dichlorobenza1dehyde, penta-
chlorobenzene, hexachlorobenzene, pentachlorobutadiene, hexachloroethane,
hexachlorobutene and hexachlorobutadiene.

Polynuclear aromatic hydrocarbons (PAHs) were  detected in samples from
several sites,  Chrysene or benz(a)anthracene  was  found in samples from
the Kinnickinnic and Black Rivers at 0.10 mg/kg and 10.5 mg/kg respectively,
Phenanthrene or anthracene was found in Menominee  and Black River samples.
Fluorene was also detected in Black River samples.

Benzene derivatives were found in a number of  the  Fox and Wolf River
samples while pentyl furan and pentachlorophenol were detected in the
Menominee River.
                                   -12-

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                                                               Table 4
                                    Results of GC/MS Scans of Harbor and Tributary Mouth Fish (mg/kg)
 Sample #
 Chlorinated Aromatics
 Di chlorobenzaldehyde
 Pentachlorobenzene
 Hexachlorobenzene
 Chlorinated Aliphatic
  Hydrocarbons
 Pentachlorobutadi ene
 Hexachloroethane
 Hexachlorobutene
 Hexachlorobutadi ene
 Polynuclear Aromatic
  Hydrocarbons
 Chrysene/Benz(a)anthracene
 Fluorene
 Phenanthrene/anthracene
 Phenols
 Pentachlorophenol
.Heterocycli c Compound
 Pentyl Furan
 Napthalenes
 Napthalene
Menomi nee
River
2S04


<0.3








<0.60
<0.10
0.10

4.52




1S99


<0.2








<0.50
<0.10
<0.04

<2.30




Kinnickinnic
River
1S98


<0.2








0.46
<0.10
<0.12

<0.40




Wolf
River
1S11


<0.06








<0.04
<0.02
<0.02

<0.12




1S09


<0.06








<0.04
<0.02
<0.02

<0.12




Fox River
above DePere
1S14


<0.04








<0.02
<0.02
<0.02

<0.12




2S14


<0.28








<0.64
<0.12
<0.08

<2.84




1S12
I

<0.04








^<0.02
<0.02
<0.02

<0.08




Fox River
below DePere
1S07


<0.04








<0.04
<0.02
<0.02

<0.08



1
1S06


<0.04









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                                                Table  4 cont'd

                         Results  of GC/MS  Scans  of  Harbor  and Tributary  Mouth  Fish (mg/kg)
Sample#
Monocyclic Aromatics
Butyl hexyl benzene
Dimethy/(phenylmethyl )
benzene
Dimeythyl/ (Methyl propyl )
Benzene Thiol
Propyl heptyl benzene
Phthalates
Bis(2-Ethylhexyl)phthalate
Di-N-Butylphthalate
Di ethyl phthal ate
Ketones and Aldehydes
Benzaldehyde
Menominee River
2S04




32.10
15.64
<0.20

L 1S99




<0.80
35.0
<0.02

Kinnickinnic
River
1S98




4.30
<0.04
<0.08

Wolf River
1S11


2.4 T

1.80
<0.02
<0.04

1S09


2.3 T

0.30
<0.02
<0.04

Fox River
above OePere
1S14 2S14

0.4 T
1.6 T

0.50
<0.02
<0.02





0.05
<0.16
<0.24
0.6 T
1S12 _j
Fox River
below DePere|Chequamegon
i Bay
1S07 1S06 1S15| 1S16
0.4 T|
L J_2.4 T
0.4 T

0.60
<0.02
4.0 T
0.1 T
1.5
<0.02
<0.02 <0.02

1.2 T


3.4 0.12K0.201
<0.10 <0.02|<0.10|
<0.30 <0.04 <0.20|
I I
1 1
T = Compounds identified by computer  library  search  or  manual  spectral  interpretation.   These  compounds  were
    quantified using the internal  standard  (quantifications  are  therefore  only  approximate)  and  were not
    compared to authentic standards.   As  manual  interpretation was  impacted  by  time  constraints  detection
    limits have not been estimated.

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                                                             Table  4  cont'd

                                    Results  of  GC/MS  Scans of Harbor  and  Tributary Mouth Fish  (mg/kg)

Sample #
Chlorinated Aromatics
Dichlorobenzaldehyde
Pentachl orobenzene
Hexachlorobenzene
Chlorinated Aliphatic
Hydrocarbons
Pentachl orobutadi ene
Hexachloroethane
Hexachlorobutene
Hexachl orobutadi ne
Polynuclear Aromatic
Hydrocarbons
Chrysene/Benz(a)anthracene
Fluorene
Phenanthrene/ Anthracene
Phenols
Pentachl orophenol
Heterocyclic Compound
Pentyl Furan
Napthalenes
Napthalene
Black
River
1S82









10.5
0.05
0.17

<0.20




Ashtabula
River
1S88

3.8 T
5.14

4.8 T
0.1 T
6.3 T
2.8 T

<0.04
<0.02

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                                                TABLE 4  cont'd

                           Results  of  GC/MS Scans of Harbor  and  Tributary  Mouth  Fish  (mg/kg)

Sample #
Monocyclic Aromatics
Butyl hexyl benzene
Dimethy/penylmethyl benzene
Meythyl/ (Methyl propyl )
Benzene Thiol
Propyl heptyl benzene
 Phthalates
Bi s (2-Ethyl hexyl )phthal ate
Di-N-Butylphthalate
Di ethyl phthal ate
Ketones and Aldehydes
Benzaldehyde
Black River
1S82




0.25
1.08
<0.04


Ashtabula River
1S88




0.76
<0.02
<0.04
5.0 T

L1S90




<0.04
2.2
<0.08


L 1S95




<0.04
6.9
<0.08


1S97




0.24
4.36
<0.08


Sheboygan River
IS 02




<0.04
<0.02
<0.04


1S01




0.36
<0.02
<0.04


OS99




2.00
<0.02
0.12

!
Milwaukee River!
2S09




<1.0
19.80
<0.30

2S10 |

1
1
1
<1.0
28.60 |
<0.30
1
I
T = Compounds identified by computer library  search  or  manual  spectral  interpretation.   These compounds  were quantified
    using the internal  standard (quantifications  are therefore only  approximate)  and were  not compared to  authentic
    standards.   As manual  interpretation  was  impacted by time  constraints  detection  limits have  not  been estimated.

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                                 Discussion

These data illustrate the environmental persistance and continued existence
of sources to the Great Lakes of industrial contaminants and pesticides
whose use has been banned or restricted.  These include PCB, chlordane,
heptachlor and DDT.  The presence of herbicides presently in use in the
basin is also demonstrated.  Dacthal was above detection limits in samples
from most sites.  Dacthal has been reported in fish samples from the Pike
and Root Rivers (Wisconsin) (St. Amant et al. 1983), coho salmon from
Lakes Michigan, Huron and Erie (DeVault and Weishaar 1983, Clark et al.
1984) and in water from the Imperial Valley (California) (Picker et al.
1979).

Several  sites exhibited specific contaminant problems with severe fish
contamination identified in the Sheboygan, Black and Ashtabula Rivers.
Somewhat less severe problems occurred in the Milwaukee, Kinnickinnic,
and Fox Rivers.

The Sheboygan River samples contained extremely high PCB concentrations
reflecting the continued existence of PCB contamination in the lower
reaches  of that River.   Composite fish samples analyzed in 1978 ranged
from 10.0 mg/kg to 750 mg/kg total  PCB.  At that time both fish and sediment
indicated severe contamination in the Sheboygan River from below the
Sheboygan Falls Dam to Lake Michigan.  Studies conducted in 1979 indicated
that PCB had migrated into the underlying soil  stratums (DOA 1980).  Fish
analyzed in 1980 and 1981 by the Wisconsin Department of Natural  Resources
(WDNR) ranged from 34.0 mg/kg to 79.0 mg/kg total  PCB (St.  Amant et al.  1983),
                                   -17-

-------
in general  agreement with the present  study.   While  PCB concentrations  in
Sheboygan River fish appear to have  declined  since 1978 the fishery
remains severely impacted with WDNR  continuing to advise against
consumption.

Elevated PCB concentrations were also  found  in samples from the Kinnickinnic
and Milwaukee Rivers.  St. Amant et  al.  (1983) reported PCB concentrations
ranging from 5.0 mg/kg to 49.0 mg/kg and from 2.70 mg/kg to 34.0  mg/kg
in fish from the Kinnickinnic and Milwaukee  Rivers respectively,  in
general agreement with this study.  These authors also reported the
presence of a number of polynuclear  aromatic  hydrocarbons  (PAHs)  in-
cluding napthalenes, biphenyls, anthracene/phenanthrene, fluoranthrene
and pyrene in Milwaukee and Kinnickinnic River samples.  These were not
identified in our samples possibly due to our higher detection limits.
Their PAH detection limits ranged from .05 mg/kg to  0.10 mg/kg while
ours ranged from 0.10 mg/kg to 0.60  mg/kg.  The  present study quantified
chrysene/benz(a)anthracene, a carcinogenic PAH (USPHS 1983,  IJC  1983)
that had not been previously identified.
The composite sample from the Black  River contained  relatively low levels
of PCB and common pesticides.  However, 3 and 4  ring Polynuclear  Aromatic
Hydrocarbons (PAHs) which are known  or suspected carcinogens  were de-
tected (EPA 1980, IJC 1983).  Vieth  et al. (1981)  also reported  several
PAHs in a composite of 5 channel catfish and 1 fresh water drum.   These
included, among others, methyl naphthalene, phenanthrene,  fluoranthene,
pyrene, fluorene and acenaphthalene.  One of the most intensive  PAH
                                   -18-

-------
analysis of Black River samples  was  conducted  by  Baumann  et  al.  (1983).
They quantified 18 PAHs in brown bullheads  and 24 PAHs  in sediments.   They
also found that PAH concentrations were correlated with a high  incidence
of tumors in fish.  While there  are  distinct differences  between  the  3
studies in both the compounds identified and concentrations  reported,  these
are to be expected as a result of the more  intensive analytical methodologies
employed in the Vieth et al. (1981)  and Baumann et al.  (1982) studies, as
well differences in habits of the species analyzed.
The high concentrations of known and potential carcinogens in fish and
sediments from the Black River has resulted in the Ohio Department of
Health (ODOH) advising the public against swimming, wadding  or  con-
suming fish from the lower 8.0 km of the river.
High concentrations of PCB and hexachlorobenzene and the presence of
several other chlorinated hydrocarbons characterized the Ashtabula River
samples.  Studies by Veith et al. (1979), Veith et al.  (1981) and Kuehl
et al. (1981) have compiled a lengthy list  of  contaminants in  fish from
the Ashtabula River.  Compounds which have been identified include chlori-
nated benzenes  (tri, tetra, penta, hexa), chlorinated styrenes  (hexa,
hepta, octa), chlorinated butadienes (tetra,  penta, hexa),
tetrachlorobutadiene, pentachlorobutadiene, tetrachloropropene,
pentachloropropane, pentachloronorbornene,  pentachloroanisole,  as well as
PCB.  This study confirms the presence of several of the above  compounds
and has added dichlorobenzadehyde, hexachloroethane, hexachlorbutene and
pentylfuran to  this list.  While quantiative comparisons are not possible
due to the differing species composition and
                                   -19-

-------
compositing schemes used in the different studies,  this data is in general
agreement with the earlier data.  The contaminant problem in the Ashtabula
River has resulted in the Ohio Department of Health (ODOH) and the Ohio
Environmental Protection Agency (OEPA) advising against consumption of
fish from the lower 3.2 km of the river.
Elevated PCB concentrations and the presence of several benzene derivatives
characterized the Fox River samples.  Veith et al.  (1981) reported 10.0
mg/kg total PCB for a composite sample of carp, sucker and channel catfish
taken below the DePere Dam in 1978, within our range of 8.61 mg/kg to
20.89 mg/kg in the same area.  St. Amant et al . (1983) reported mean PCB
concentration of 16.0 mg/kg and 6.0 mg/kg in 1980 and 1981 respectively for
fish in the lower (below DePere) Fox River.  They also detected PCB
substitutes such as isopropyl biphenyl, di-isopropyl  biphenyl  and santasols
          which were not detected in this study.
Sediment analysis conducted by USEPA in 1981 support the fish data as well
as add additional parameters of concern.  Sediment PCB concentrtions in the
Fox River ranged from 25.9 mg/kg below DePere to 1.2 mg/kg at the mouth.
Several benzene derivatives including monochlorobenzene, dichlorobenzene,
trichlorobenzene, methyl benzene and dimethyl benzene were also detected in
the sediments as were PAHs including phenanthrene/anthracene, fluoranthene,
fluorene, pyrene, acenaphthene and chrysene/benz(a)anthracene (GLNPO 1981).
That the PAHs found in the Fox River sediments were not detected in fish
is not surprising.  Fish are capable of oxidizing PAH via the mixed function
oxidase system.  Therefore the accumulation of PAHs above instrument de-
tection limit requires continued high level exposure, as is illustrated
by the study by Baumann et al. (1983) discussed earlier.  They quantified
                                   -20-

-------
fluoranthene at 22 mg/kg in Black River sediments.  However brown bullheads,
a bottom dwelling species ranged from 0.558 mg/kg to 1.938 mg/kg.  In the Fox
River sediments all PAH concentrations were below 2.1 mg/kg (GLNPO 1981).
This illustrates the need to utilize mechanisms other than fish tissue
to monitor the potential exposure to PAH of both animal and human populations.

Chequamegon Bay (Lake Superior) differed from the other sites in the
relative absence of typical organic contaminants found by both GC/EC
and GC/MS.  This data supports the low levels of PCB and pesticides
reported by Sheffy and St.  Amant (1980).
The data produced by this element of the GLFMP is in general  agreement
with that of other studies  and proves the feasibility of using GC/MS
scans and limited GC/EC analysis to screen areas for additional work.
The data does not allow quantitative intersite comparison nor rigorus
trend analysis.  These goals will be addressed with second level programs
using species of consistant size, age and lipid content at all  sites.
                                   -21-

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                                 REFERENCES
Baumann, P.C., Smith, W.D., and M. Ribick. 1982. Hepatic tumor rates and
polynuclear aromatic hydrocarbon levels in two populations of brown bull-
head (Ictalurus nebulosus).  In polynuclear aromatic hydrocarbons:  Sixth
intrnational symposium on physical and biological chemistry,  eds. M.W.,
Cooke, A.J. Dennis and G.L. Fisher.  Battelle Press, Columbus, Ohio.

Clark, J.R., DeVault, D., Bowden, R.J. and J.A. Weishaar. 1984. Con-
taminant Analysis of Fillets from Great Lakes Coho Salmon, 1980. J. Great
Lakes Res. 10(1): 38-47.

DeVault, D.S. and J.A. Weishaar. 1983. Contaminant Analysis of 1981 Fall Run
Coho Salmon (Oncorhynchus Kisutch).  U.S. Environmental Protection Agency.
Great Lakes National Program Office, Chicago, Illinois EPA 905/3-83-001

DOA. 1980.  Sheboygan Harbor, Wisconsin. PCB Investigations and Results.
Department of the Army, Chicago District, Corps of Engineers. Chicago,
Illinois

EPA. 1979a. Standard operating procedure:  Analysis of non-volatile
extractable organic compounds: sample extraction and screening by
gas chromatography. Method 625. U.S. Environmental Protection Agency.
Federal  Register 44:223.

EPA.1979b.  Standard operating procedure:  GC/MS/DS analysis of nonvolatile
organic compounds.  Method 625. U.S. Environmental Protection Agency. Federal
Register 44:223.

EPA. 1980. Ambient Water Quality Criteria for polynuclear aromatic hydro-
carbons. U.S. Environmental Protection Agency, Office of Water Regulations
and Standards. Washington, D.C. EPA 440/5-80-069.

GLNP0.1981. Contaminants in sediments from Great Lakes Harbors and Tri-
butary Mouths. U.S. Environmental Protection Agency. Great Lakes National
Program Office, Chicago, Illinois.  In preparation.

International Joint Commission. 1978. Status Report on the Persistent
Toxic Pollutants in the Lake Ontario Basin. Great Lakes Water Quality
Board, Windsor, Ontario, Canada.

International Joint Commission. 1983. Annual Report of the Aquatic Eco-
system Objectives Committee.  Great Lakes Science Advisory Board. Windsor,
Ontario, Canada.

Kuehl, D.W., Johnson, K.L., Butterworth, B.C., Leonard, E.N. and G.D. Veith,
1981. Quantification of Octachlorostyrene and Related Compounds in Great
Lakes fish by gas chroinatography-mass spectremetry. J. Great Lakes res. 7:330.


                                   -22-

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Mieure, J.P., Hicks, 0., Kaley, R.6., and V.W.  Saeper.  1975.  Characterization
of polychlorinated biphenyls in: Conference Proceedings, national  conference
on polychlorinated biprenyls. F. Ayer ed. U.S.  Environmental  Protection Agency,
Office of Toxic Substances. EPA 560/6-75-004.

Picker, J.E., Yates, J.J., and W.E. Pereira. 1979. Isolation  and characteri-
zation of the herbicide dimethyl tetrachloroterephthalate by  gass chromato-
graphy - mass spectrometer - computer techniques. Bull. Environ. Contam.
Toxicol. 21: 612-617.

Sheffy, T.B. and J.R. St. Amant. 1980.  Toxic substances survey of Lake Michigan,
Superior and tributary streams; first annual report.  Wisconsin Department of
Natural Resources.

Sloan, R.J., Simpson, K.W., Schroeder, R.A. and C.R. Barnes.  1983. Temporal
trends toward stability of Hudson River PCB contamination. Bull. Environ.
Contam. Toxicol. 31: 377-385.

St. Amant, J.R., Pariso, M.E., and T.B., Sheffy. 1983.  Final  report on the
Toxic Substances Survey of Lakes Michigan, Superior, and Tributary Streams.
Wisconsin Department of Natural Resources. 31p.

USPHS. 1983 Third annual report on Carcinogens. U.S. Department of Health  and
Human Services. Public Health Service NTP 82-330.  229p.

Veith, 6.D., Kuehl, D.W., Leonard, E.N., Puglisi, A., A.E. Lemke. 1979. Fish
and Wildlife and Estuaries,Polychlorinated biphenyls and other organics
chemical residues in fish from major watershed of the United  States, 1976.
Pesticides Monitoring Journal. 13(1): 1-11.

Veith, 6.D., Kuehl, D.W., Leonard, E.N., Welch, K., and G. Pratt. 1981.  Fish
Wildlife and Estuaries, polychlorinated biphenyls and other organic chemical
residues in fish from majpr United States watersheds near the Great Lakes,
1978. Pesticides Monitoring Journal. 15(1): 1-6.
                                       -23-

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                                  TECHNICAL REPORT DATA
                          (Please read Instructions on the reverse before completing)
 REPORT NO.
 EPA-905/3-84-003
                                                          !. RECIPIENT'S ACCESSI Ol NO.
 TITLE AND SUBTITLE
 Contaminants in Fish From Great Lakes Harbors
 and  Tributary Mouths 1980-81
             . REPORT DATE
             April 1984
            6. PERFORMING ORGANIZATION CODE

             5GL                	
 AUTHOR(S)
 David S.  DeVault, III
                                                          B. PERFORMING ORGANIZATION REPORT NC
 PERFORMING ORGANIZATION NAME AND ADDRESS
 U.  S.  Environmental Protection Agency
 Great  Lakes National Program  Office
 536 South Clark Street, Room  958
 Chicago,  Illinois 60605
                                                          10. PROGRAM ELEMENT NO.
            11. CONTRACT/GRANT NO.
2. SPONSORING AGENCY NAME AND ADDRESS
TJ.  S.  Environmental Protection Agency
Great  Lakes National Program Office
536 South Clark Street, Room 958
Chicago,  Il'linois 60605
            13. TYPE OF REPORT AND PERIOD COVERED
               Monitoring.. 1Q80-BT	_
            14. SPONSORING AGENCY CODE

              Great Lakes National  Program
              Office, U.S.  EPA,  Region V
5. SUPPLEMENTARY NOTES
David  S.  DeVault, III
Project Officer
6. ABSTRACT

Composite fish samples collected from Great Lakes Harbors and Tributaries
between 1980 and 1981 were analyzed by gas chromatography-electron capture
detector and gas chromatographic-mass spectrometry  for  a wide range of
pesticides and priority pollutants.  Severe PCB contamination was
observed in Sheboygan River  fish with moderate to severe PCB contamination
in sampled from the Milwaukee,  Kinnickinic, Fox, and Ashtabula Rivers.
The Ashtabula River samples  also contained several  chlorinated aromatic
and aliphatic hydrocarbons.  Polynuclear aromatic hydrocarbons were detected
in fish from the Black, Kinnickinnic and Menominnee Rivers,  while a number of
benzene derivatives were observed in samples form the Fox and Wolf Rivers.
                               KEY WORDS AND DOCUMENT ANALYSIS
                 DESCRIPTORS
                                              .lDENTIFIERS/OPEN ENDED TERMS
                                                                        c.  COS AT I Field/Group
Gas  chromatography
Chromatographic-mass spectrometry
Fish
Herbicides
Pesticides
Contaminant s
18. DISTRIBUTION STATEMENT
Document is available to the  public through
the National Technical Information Service
 (NTIS).  Springfield. VA 22161
                                              19. SECURITY CLASS (ThisReport)
                                                                          1. NO. OF PAGES
20. SECURITY CLASS (Thispage)
                           22. PRICE
EPA Form 2220-1 (9-73)

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