FINAL PROJECT REPORT
DISTRIBUTION OF CONTAMINANTS IN WATERS OF MONROE HARBOR
(RIVER RAISIN), MICHIGAN AND ADJACENT LAKE ERIE
by
V.E. Smith, J.E. Rathbun, S.G. Rood
Cranbrook Institute of Science
Bloomfield Hills, Michigan 48013
K.R. Rygwelskl
Computer Sciences Corporation
Grosse lie, Michigan 48138
W.L. Richardson and D.M. Do!an
U.S. Environmental Protection Agency
Grosse lie, Michigan 48138
CR810232
(April 1, 1983 - May 17, 1985)
Project Officer
M.D. Mull in
Environmental Research Laboratory-Duluth
Large Lakes Research Station
ERL-Duluth, Grosse He, Michigan 48138
U.S. ENVIRONMENTAL PROTECTION AGENCY
ENVIRONMENTAL RESEARCH LABORATORY-DULUTH
LARGE LAKES RESEARCH STATION
GROSSE ILE, MICHIGAN 48138
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ABSTRACT
Monroe Harbor, Michigan, at the confluence of the River Raisin and
western Lake Erie, has been identified by the International Joint Comission
as a Class A Area of Concern. Previous state and federal studies of the
site have documented water quality problems that included contamination of
water, sediments and fish with certain organic and metal toxins. The current
project was designed to address questions of contaminant distribution, fate
and biological effects In this aquatic system. This data report describes
the results of surveys of selected organochiorines and metals In waters of
Monroe Harbor and adjacent Lake Erie.
Contaminants emphasized in the study were polychiorinated biphenyls
(PCBs) and heavy metals (chromium 1 copper, zinc) which were known to he
prevalent In the system, and were potentially toxic at current levels.
Seasonal surveys of contaminant distribution In the water column were
designed to support exposure/effects studies and mass balance modeling. For
descriptive purposes, the concentration data were plotted as spatial profiles
(i.e., by station) for all surveys, and as temporal profiles (i.e., by
survey) for selected stations. Both total and particulate PCBs and total and
filtrate (i.e., dissolved) metals were measured In composite and/or grab
samples.
The distribution data for three representative sites sampled In all O
surveys indicate the following. Mean concentration values at Station 1
111
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represented the upstream boundary conditions of 8.6 + 3.0 ng/L for total
PCBs, 2.3 + 1.9 g/L for total chromIum, 4.1 + 2.1 i.ig/L for total copper, and
8.3 + 5.8 ug/L for total zinc. Downriver near the turning basin (Station 4),
concentrations generally Increased to 119 + 121 ng/L for total PCBs, 3.1 +
1.9 pg/L for total chromium, 4.7 + 2.3 ig/L for total copper, and 8.5 + 4.8
pg/L for total zinc. Further downriver at or near the river mouth on Lake
Erie (Stations 6 or 26), concentrations generally decreased to Intermediate
levels of 18 + 10 ng/L for total PCBs, 2.6 + 1.7 pg/I for total chromium, 4.3
+ 2.2 pg/I for total copper, and 10 + 5.8 pg/L for total zinc. Relative to
both the upriver and lake boundary conditions, PCB concentrations in the
turning basin were dramatically higher. Metals concentrations tended toward
slightly higher levels In the turning basin and the lake relative to the
upriver boundary levels. In general, the contaminant concentrations In water
were highest at the power plant discharge near Lake Erie (Station 29).
Concentrations of all four contaminants were more variable but not markedly
higher during high flow conditions in the spring.
Potential sources of contaminants that may elevate concentrations at
or below the turning basin Include the Monroe WWTP (mainly zinc and PCB),
automotive and paper plant discharges (PCB), and polluted turning basin
sediments (metals and PCB).
Where both surface and bottom waters were sampled below the turning
basin, PCB concentrations were higher near the surface, and metal levels were
more elevated near the bottom.
Some technical problems concerning PCB sample clean-up and routine
collection of filtrate and particulate fractions for PCB analysis were not
fully resolved in this study.
iv
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Add tlona1 water quality data, which may relate to toxicity effects or
contaminant availability, was not presented here, but will be included in
forthcoming reports on modeling results.
V
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TABLE OF CONTENTS
Page
FOREWORD...
ABSTRACT.. .. ... ..
FIGURES . . . . . . .
TABLES . . . . . . . . .
ABBREVIATIONS AND SYMBOLS
ACKNOWLED 4ENTS . . .
• S
• S
• S
• U
• S
Sample Strategy . . .
Collections . . . .
Extractions
Clean—Up .
Analysis and Quantitation
Quality Assurance . .
• I • • S S • I • • S S
• • . . S S • • • • • S
• . a • a • • • • • • •
• • S S • • S S S S S U
• S S S S S S • S • S •
• . • S S • S • S • S •
• I S I S S S S S S S S
• . . . . I S S S I I I
• S S S S I • • S I S •
• S S S S S I S • S • S
• S S • • S S ii
iii
vii
xii
xi v
xv
1
2
6
B
• S S S S 5 8
• S S • U U 8
• . . . • . 10
• U U S S S 12
• S S
• S S
• . U
5.0 REFERENCES CITED . • . . • . •
6.0 APPENDIX . • . • • . . . . .
S S • I S • • I • S S S S S S I
. S S
S S * • S S S S 4.6
• S • S a . U S S I I I S S I
• S • • S S • S S • I • • I I S S • • I
• . • • . • a a a • • a • a • • . • • a
• S • S • I S S S S S S S S U S S S S •
• S • • S a • . . • a I S • S I S I S •
• S S S S I • S S • S I S S S • S S S •
e 5$ S U S • S S S S S S S • S S S U
• S S S I • S S S I S S S I
• • • • . a a • a • . a I S S • S S S S
U S I S S S S S S S S • S S S • • S S
1.0 INTRODUCTION . . . •
1.1 Conclusions .
1.2 Recommendations
2.0 BACKGROUND . . . . •
2.1 Basin Descrptlon . .
2.2 Hydrology .
2.3 Industrial Influences
2.4 Contaminant Sources .
3.0 APPROACHES AND METHODS . •
3.1
3.2
3.3
3.4
3.5
3.6
S 5 5 S I S • S 5 5 I S S S • S S S
• S
• S
• S
• I
• S
• S
4.0 RESULTSAND DISCUSSION . .• .
• •....•. . . . . .
4.1
Spatial Profiles, PCBs • .
. • . . • • . • . . . • . . . .
4.2
Temporal Profiles, PCBs .
. . • . . . . • . . . . . . . .
4.3
Organics Quality Control •
. . . • • . . • . . • . .
4.4
Spatial Profiles, Metals .
. • . . . • • . • • . • • • • .
4.5
4.6
Temporal Profiles, Metals
Metals Quality Control • .
. . . . . • . • . . • . . .
. . • . . . • . . • . • • , • . a
14
14
17
22
23
24
26
31
32
35
36
38
40
41
vi
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FIGURES
Page
2.1 River Raisin drainage basin . . . . . . . . . . . . . . . . . . . 57
2.2 River RaisIn 11—year average daily flow (cfs) 12 km upstream
from Lake Erie • • • • . . • . . . . . . 58
2.3 Peak flows in the River Raisin at Monroe since 1938 . . . • . . . 59
2.4 Lake Erie level at gage 3087 . • . . . . . . . . . . . . . . . . 60
2.5 TheMonroeHarborstudya ....., .•••••• 61
2.6 River Raisin depth profiles (feet) . . . . . . . . . . . . . . . 62
2.7 Industries tn the Monroe Harbor study area . . . . . . . . . . . 65
2.8 The Monroe Power Plant cooling intake and discharge . . . . . . . 66
3.1 Stations sampled during Monroe Harbor Survey 1 (July
12—17, 1983) . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.2 Stations sampled during Monroe Harbor Survey 2 (September
13—18, 1983) . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.3 Stations sampled during Monroe Harbor Survey 3 (October 25 —
November 1, 1983), including the Waste Water Treatment Plume . . 69
3.4a Stations sampled during Monroe Harbor Survey 4 (April 2-5,
1984): River stations . . . . . . . . . . . . . . . . . . . . . 70
3.4b Stations sampled during Monroe Harbor Survey 4 (Apr11 2-5,
1984): Lake Erie stations . . . . . . . . . . . . . . . . . . . 71
3.5a Stations sampled during Monroe Harbor Survey 5 (May 9, 1984):
River stations . . . . . . . . . . . . . . . . . . . . . . . . . 72
3.5b Stations sampled during Monroe Harbor Survey 5 (May 9, 1984):
Lake Erie stations . . . . . . . . . . . . . . . . 73
vii
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FIGURES (CONT’D.,)
Page
3.6 Stations sampled during Monroe Harbor Survey 6 (May 30, 1984),
Survey 7 (June 12), Survey 8 (July 10), Survey 9 (July 25)
and Survey 10 (August 1) . . . . . . . . . . . . . . . . . . . . 74
4.1 Spatial profile of total PCB In composite (a) and grab (b)
whole water samples, Monroe Harbor Survey 1 . . . . . . . . . . . 75
4.2 Spatial profile of total PCB In composite filtrate water
samples, Monroe Harbor, Survey 1 . . . . . . . . . . . . . . . . 76
4.3 Spatial profile of total PCB In composite (a) and grab (b)
whole water samples, Monroe Harbor Survey 2 . . . • • • . . . . . 77
4.4 Spatial profile of total PCB in composite whole and filtrate
water samples, Monroe Harbor Survey 3 . . . . . . . . . . . . . . 78
4.5 Spatial profile of total PCB In grab whole water samples,
Monroe Harbor WWTP plume, Survey 3, daily concentration (a)
and station averages (b) . . . . . . . . . . . . . . . . . . . . 79
4.6 Spatial profiles of total PCB in grab filtrate water samples,
Monroe Harbor WWTP plume, Survey 3 . . . . . . . . . . . . . . . 80
4.7 Spatial profile of total PCB in whole water and particulate
grab samples, Monroe Harbor, Survey 4 . . . . . . . . . . . . . . 81
4.8 Temporal profile of total PCB in grab whole water and
particulate samples at Station 1, Monroe Harbor, Surveys 5—10 . . 82
4.9 Temporal profile of total PCB in grab whole water and
particulate samples at Station 4, Monroe Harbor, Surveys 5-10 . . 83
4.10 Temporal profile of total PCB In all grab and composite whole
water samples at Station 1, Monroe Harbor, Surveys 1—10 . . . . . 84
4.11 Temporal profile of total PCB in all grab and composite whole
water samples at Station 4, Monroe Harbor, Surveys 1—10 . . . . . 85
4.12 Spatial profile of total and dissolved chromium In grab and
composite water samples, Monroe Harbor, Survey 1 . . . . . . . . 86
4.13 Spatial profile of total and dissolved copper in grab and
composite water samples, Monroe Harbor, Survey 1 . . . . . . 87
4.14 Spatial profile of total and dissolved zinc in grab and
composite water samples, Monroe Harbor, Survey 1 . . . . • . . . 88
v ii,
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FIGURES (COP4T’D .)
4.15 Spatial profile
composite water
4.16 Spatial profile
composite water
4.17 Spatial profile
composite water
4.18 SpatIal profile
composite water
4.19 Spatial profile
composite water
4.20 SpatIal profile
composite water
4.21 Spatial profile
composite water
4.22 Spatial profile
composite water
4.23 Spatial profile
composite water
4.24 Spatial profile
composite water
4.25 Spatial profile
composite water
4.26 Spatial profile
composite water
4.27 Spatial profile
composite water
4.28 Spatial profile
composite water
4.29 Spatial profile
composite water
of total
samples,
of total
samples,
of total
samples,
of total
samples,
of total
samples,
of total
samples,
of total
samples,
of total
samples,
of total
samples,
of total
samples,
of total
samples,
of total
samples,
of total
samples,
of total
samples,
of total
samples,
Page
and dissolved chromium In grab and
Monroe Harbor, Survey 2 . . . . . . . . 89
and dissolved copper in grab and
Monroe Harbor, Survey 2 . . . • . . . . 90
and dissolved zinc In grab and
Monroe Harbor, Survey 2 . 91
and dissolved chromium In grab and
Monroe Harbor, Survey 3 . . . . . . . . 92
and dissolved copper In grab and
Monroe Harbor, Survey 3 . . . . . . . . 93
and dissolved zinc in grab and
Monroe Harbor, Survey 3 . . . . . . . . 94
and dissolved chromium in grab and
Monroe Harbor, Survey 4 . . • . • . . . 95
and dissolved copper In grab and
Monroe Harbor, Survey 4 . . • . . . . . 96
and dissolved zinc in grab and
Monroe Harbor, Survey 4 . . • . • . . . 97
and dissolved chromium In grab and
Monroe Harbor, Survey 5 . . . . . . . . 98
and dissolved copper in grab and
Monroe Harbor, Survey 5 . . . . • . . . 99
and dissolved zinc in grab and
Monroe Harbor, Survey 5 . . . . . . . . 100
and dissolved chromium in grab and
Monroe Harbor, Survey 6 . . . • • . . . 101
and dissolved copper In grab and
Monroe Harbor, Survey 6 . . . . . . . . 102
and dissolved zinc in grab and
Monroe Harbor, Survey 6 . . . . . . . . 103
ix
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FIGURES (CONID.)
4.30 Spatial profile
Composite water
4.31 SpatIal profile
Composite water
4.32 Spatial profile
composite water
4.33 Spatial profile
composite water
4.34 Spatial profile
composite water
4.35 SpatIal profile
composite water
4.36 SpatIal profile
composite water
4.37 SpatIal profile
composite water
4.38 Spatial profile
composite water
4.39 Spatial profile
composite water
4.40 SpatIal profile
composite water
4.41 Spatial profile
composite water
of total
samples,
of total
samples,
of total
samples,
of total
samples,
of total
samples,
of total
samples,
of total
samples,
of total
samples,
of total
samples,
of total
samples,
of total
samples,
of total
samples,
Page
and dissolved chromium In grab and
Monroe Harbor, Survey 7 . . . . . . . . 104
and dissolved copper In grab and
Monroe Harbor, Survey 7 . . . . . . . . 105
and dissolved zinc In grab and
Monroe Harbor, Survey 7 . . . . . . . . 106
and dissolved chromium In grab and
Monroe Harbor, Survey 8 . . • • . . . . 107
and dissolved copper tn grab and
Monroe Harbor, Survey 8 . . . . . . . . 108
and dissolved zinc tn grab and
Monroe Harbor, Survey 8 . . . . . . . . 109
and dissolved chromium in grab and
Monroe Harbor, Survey 9 . . . • • . . . 110
and dissolved copper In grab and
Monroe Harbor, Survey 9 . . . . • . . . ill
and dissolved zinc in grab and
Monroe Harbor, Survey 9 . . . . . . . . 112
and dissolved chromium in grab and
Monroe Harbor, Survey 10 . . . . . . . . 113
and dissolved copper in grab and
Monroe Harbor, Survey 10 . . . . . . .
and dissolved zinc in grab and
Monroe Harbor, Survey 10 . . . . . .
4.42 Temporal profiles of total and dissolved chromium at Station
l,MonroeHarbor,surveysl_lo . . . . . . . . .
4.43 Temporal profiles of total and dissolved copper at Station 1,
Monroe Harbor, Surveys 1—10 . . . . . . . . . . . . . . . . .
4.44 Temporal profiles of total and dissolved zinc at Station 1,
Monroe Harbor, Surveysl —1O. . . . . . . .........
114
115
116
117
118
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FIGURES (CONT’D.)
Page
. S
119
120
121
4.45 Temporal profiles of total and dissolved chromium at Station
4, Monroe Harbor, Surveys 1—10 . . . . . . . . . . . . . .
4.46 Temporal profiles of total and dissolved copper at Station 4,
Monroe Harbor, Surveys 1—10 . . . . . . . . . . . . . . . .
4.47 Temporal profiles of total and dissolved zinc at Station 4,
Monroe Harbor, Surveys 1—10 . . . • . . . . . . . . . . . .
. .
APPENDIX
A.1 River Raisin flows at Monroe during Survey 1
. .
.
47
A.2 River Raisin flows at Monroe during Survey 2 . . . . • . . . .
.
48
A.3 River Raisin flows at Monroe during Survey 3 . . . . . . . . .
.
49
A..4 River Raisin flows at Monroe during Survey 4 . . • . • . . . .
.
50
A.5 River Raisin flows at Monroe during Survey 5 . . . . . . . . .
.
51
A.6 River Raisin flows at Monroe during Survey 6 . . . • • . . .
.
.
52
A.7 River Raisin flows at Monroe during Survey 7 . . • • • . . .
.
.
53
A.8 River Raisin flows at Monroe during Survey 8 . . • • • . . .
.
.
54
A,9 River Raisin flows at Monroe during Survey 9 . .
.
.
55
AlO River Raisin flows at Monroe during 10
xi
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TAB LES
Page
3.1 Survey Sampling Strategy . . . . . . . . . . . . . . . . . . . . 122
3.2 Station Descriptions . . . . . . . . . . . . . . . . . . . . . . 123
3.3 Detection Limits — Metals . • . . . . . . . . . . . . . . . . . . 124
3.4 Monroe Harbor Studies Sample Blanks — Metals . . . . . . . . . . 125
3.5 Intercomparison with USEPA Environmental Monitoring and
Support Laboratory, Cincinnati . . . . . . . . . . . . . . . . . 126
3.6 Percent Recoveries Calculated from Standard Additions on
Samples from the Monroe Harbor Study . . . . . . . . . . . . . . 127
3.7 Results of Field Duplicates, Monroe Harbor Study, 1983—1984 . . . 128
3.8 VariatIon of Duplicates from Lake Erie During Storm
Conditions (Survey IV) . . . . . . . . . . . . . . . . . . . . . 128
3.9 Monroe Harbor Between Run Sample Replicates . . . 129
3.10 Extraction Efficiency of Particulate Filters . . . . . . . . . 130
3.11 DuplicateSampleAna lysis ........ . ., . . 131
3.12 Replicate Analysis of PCB QC Standards . 132
3.13 Replicate Analysis of Aroclor Mixtures . . . . . . . . . . . . . 132
4.1 Total PCB in Composite and Grab Whole Water Samples, Monroe
Harbor, Survey 1 . . . . . . . . . . . . . . . . . . . . . . . 133
4.2 Total PCB in Composite Filtrate Water Samples, Monroe Harbor,
Survey 1 . . . . . . . . . . . . . . . . . . . . . . . 134
4.3 Total PCB in Composite and Grab Whole Water Samples, Monroe
Harbor, Survey 2 . . . . . . . . . . . . . . . 13S
xii
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TABLES (CONT’D.)
4.4 Total PCB in Composite Whole (A) and Filtrate (B), Monroe
Harbor, October 25, Survey 3 . . . • . . . . . . . . . . .
4.5 Total PCB tn Grab Whole Water Samples, Monroe Harbor, WWTP
Plume, Survey 3 • . . . . . . . . . . . . . . . . . . . . .
4.6 Total PCB tn Grab Filtrate Water Samples, Monroe Harbor, WWTP
Plume, Survey 3 . . . . . . . . . . . . . . . . . . . . . • , .
4.7 Total PCB In Grab Whole Water (A) and Particulate (B) Samples,
Monroe Harbor, Survey 4 . . . . . . . . . . . . . . . . . .
4.8 Total PCB In Grab Whole Water (A) and Particulate (B) Samples
at Station 1, Monroe Harbor, Surveys 5-10 . . . . . . . . .
4,9 Total PCB in Grab Whole Water (A) and Particulate (B) Samples
at Station 4, Monroe Harbor, Surveys 5—10 . . . . .
Page
1 36
1 37
1 38
139
140
140
141
142
143
1 L5
147
14
149
1 50
151
1 52
153
4.10 Spatial Profiles
4.11 Spatial Profiles
4.12 Spatial Profiles
4.13 Spatial Profiles
4.14 Spatial Profiles
4.15 Spatial Profiles
4.16 Spatial Profiles
4.17 Spatial Profiles
4.18 Spatial Profiles
4.19 Spatial Profiles
of
of
of
of
of
of
of
of
of
of
Dissolved
Dissolved
Dissolved
Dissolved
Dissolved
Dissolved
Dissol ved
Dissolved
Dissolved
Dissolved
and
and
and
and
and
and
and
and
and
Total
Total
Iota 1
Total
Total
Total
Total
Total
Total
Metals,
Metals,
Metals,
Metals,
Metals,
Metals,
Metals,
Metals,
Metals,
Surveyl . . S S
Survey 2 . . .
Survey 3 . . .
Survey 4 . .
Survey 5 . .
Survey 6 . •
Survey 7 . •
Survey 8 . .
Survey 9 . .
Survey 10 . .
4.20 Summary of Data from Selected
Monroe Harbor (1983—1984) .
and Total Metals,
Stations for 10 Surveys of
S S • • • • • S S • • S • • S • • S
)(iii
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ABBREVIATIONS AND SYMBOLS
AAS — Atomic Absorption Spectroscopy
CFS - Cubic Feet Per Second
DCM - Dichioromethane
ECD — Electron Capture Detector
EMSL — Environmental Monitoring and Support Laboratory
EPA — Environmental Protection Agency
i.d. — Inner Diameter
IJC — International Joint Con nission
l CD — Kuderna—Danish
LAS — Laboratory Automation System
LLRS - Large Lakes Research Station
IPE — Linear Polyethylene
MDWR — Michigan Department of Natural Resources
MGD - Million Gallons Per Day
NOS A - National Oceanographic and Atmospheric Administration
PCB - Pol yc hi o ri na ted Bi phenyl (s)
PSI — Pounds Per Square Inch
PVC — Polyvinyl Chloride
QC — Quality Control
USEPA — United States Environmental Protection Agency
USGS — United States Geological Survey
WWTP — Waste Water Treatment Plant
Cr — Chromium
Cu — Copper
HNO — Nitric kid
H 2 S 4 — Sul furic kid
N 2 — Nitrogen
Ni — Nickel
Zn — Zinc
xiv
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ACKN0WLED ’iENTS
This report Is one of several resulting from a two-year study of the
distibution, fate and biological effects of organochiorine and heavy metals
in waters and sediments of Monroe Harbor — River Raisin ecosystem adjoining
western Lake Erie. The following principal Investigators and associates
from several participating institutions were involved In planning this
program.
Clarkson University — J.V. DePinto
— T.C. Young
Cranbroc,k Institute of Science — Y.E. Smith
Manhattan College — D.M. DiToro
Michigan Dept. of Natural Resources - F.J. Horvath
Ohio State University — C.E. Herdendorf
- L.A. Fay
Univ. of California, Santa Barbara — W.J. Lick
Univ. of Minnesota, Minneapolis - D.C. McNaught
U.S. Environmental Protection Agcy., - N.A. Jaworski
ERL—Duluth — K.E.F. Hokanson
— W.L. Richardson
The Cranbrook components of this program and this report were
supported by the EPA Office of Research and Development, Large Lakes
Research Station, Grosse lie, Michigan, under Cooperative Agreement CR810232.
Although all of the coauthors contributed broadly to the document
through their critical reviews, the primary responsibility for writing each
section can be ascribed as follows:
Abstract V.E. Smith
Section 1.0 W. Richardson
Sections 1.1, 1.2 V.E. Smith
xv
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ACKNOWLEDQv ENTS (CONT’ D.)
Sections 2.0-2.4 K. Rygwelski
Section 3.1 D. Dolan
Sections 3.2, 3.3 3. Rathbun
Section 3.4 S. Rood
Sections 3.5, 3.6 S. Rood, K.
Sections 4.0-4.2 Y.E. Smith
Section 4.3 S. Rood
Sections 4.4, 4.5 V.E. Smith
SectIon 4.6 K. Rygwelski
The authors are indebted to the professional staff of
Rygwel ski
the LLRS, and
other participating organizations, for their efforts In the field and
laboratory.
A general list of contributors Is given below.
Cranbrook Institute of Science
V.E. Smith
3. Spurr
J. Rood (Townsend)
S. Hendricks (Mathews)
S. Rood
J. Rathbun
3. Fisher
G. Noguchi
M. Ginnebaugh
J. Thomas
L.
L.
V.
S.
K.
E.
Hoy
Poe
Sawicki
Kuroda
Mottin
McCue
Project coordination; field support
Analytical and field support
Analytical support
Field support
Analytical and field support
Analytical and field support
Analytical support
Analytical support
Analytical and field support
Analytical support
Analytical support
Analytical support
Analytical support
Analytical support
Analytical support
Field support
U.S. Environmental Protection Agency
M. Mullin
W. Richardson
D. Dolan
N. Gessner
J. Filkins
D. Brokaw
D, Fielder
N. Hoeft
T. Chrapko
Project officer; lab
Project coordinator;
Field support
Analytical and field
Analytical and field
Analytical and field
Analytical and field
Analytical and field
Manuscript preparation
support
field support
support
support
support
support
support
1
xv i
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ACKNOWLED 4EWrS (CONT’D.)
Computer Sciences Corporation
P. Brown Analytical and field support
K. McGunagle Analytical and field support
K. Rygwelskl Analytical and field support
D. Griesmer Field support
B. Guerra Field support
E. Hovious Analytical and field support
C. Pochini Analytical support
R. Rockershousen Field and graphical assistance
D. Kiemans Field support
F. Gawronski Field support
W. Priem Field support
D. Caudill Manuscript preparation
I. Holman Field support
Clarkson University
J. DePinto Field support
T. Young Field support
T. Kipp Analytical support
R. Autenrieth Analytical support
Michigan Deparbnent of Natural Resources
F. Horvath Field support
B. Sayles Analytical support
3. Dalton Field support
Kopke, Inc .
1. Kopke Facilities support
E. Kopke Facilities support
The majority of the work associated with this report involved the
analysis of environmental samples for organochiorines and heavy metals, all
of which were performed by personnel of the Cranbrook Institute of Science.
More specifically, metals analyses were performed by K. Rygwelski, 3. Spurr,
D. Fielder, and 3. Thomas. Organochiorine extractions were performed by 3.
Rathbun, D. Brokaw, and H. Hoeft; extract clean—up by G. Sawicki, J. Fisher
and L. Hoy; capillary gas chromatography by 3. Rood (Townsend), S. Rood, 3.
xvii
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ACKNOWLEDt 4ENTS (CONT’D.)
Fisher, and G. Noguchi; and post—analytical data processing by M. Ginnebaugh,
1. Poel, and S. Kuroda.
Computer Sciences Corporation, especially K. McGunagle, provided
invaluable assistance with the data processing, storage, retrieval and
presentations.
Post-analytical data processing, especially the COMSIAR program, was
greatly facilitated by the efforts of D. Dolan, N. Mullin and K. McGunagle.
The authors are grateful to the individuals who provided coments and
reviews, especially A. Lemke, P. Erickson and N. Thomas.
The authors are also indebted to D. Caudill and T. Chrapko for their
skillful and patient support in the preparation of this manuscript.
xviii
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1.0 INTRODUCTION
The mouth of the River Raisin on western Lake Erie has been designated
by the International Joint Cc iinission (IJC) as one of 42 •Class A Areas of
Concern In the Great Lakes systen. This portion of the River Raisin, which
is partially dredged for navigation, has been one of the most severely
polluted areas due to the local concentration of Industries, landfills and
discharge of the wastewater trea nent facilities. Even though significant
improvements In water quality have been made In the past decade, residual
concentrations of toxic substances have remained in the water, sediments and
biota.
Because of Its history of contamination problems, this site was
selected tn 1983 by the EPA Large Lakes Research Station for a prototype
study to develop field methodologies and protocols for assessing ecological
effects of toxic substances. The primary purpose of the study has been to
develop a predictive capability whereby effects of substances could be
estimated, given their source loadings, transport and fate characteristics.
To date, ten separate research organizations have been Involved with the
project, which has required focused, coordinated efforts by all.
This report presents only that part of the project which dealt with
defining the gradients of toxic substances within the water column. All of
the data have been stored in a c nputer data base and are available th all
1
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Investigators for further assessment and correlation of chemistry with
effects.
Secondarily, these data will provide an update on the status of water
quality for regulatory agencies, and may provide Information which could
lead to mitigative actions. The data also will be used to calibrate a mass
balance model which may be useful In the regulatory process. Most
Importantly, the study has led to development of research methods for dealing
with toxic substances In other highly Impacted areas of the Great Lakes.
1.1 CONCLUSIONS
The following conclusions were reached as a result of this study of
contaminant distribution In Monroe Harbor and adjacent Lake Erie waters.
(a) A large data base was compiled on the spatial and temporal
distribution of chromium, copper, zinc, polychiorinated biphenyls
(PCBs) and other selected organochiorines in the water column of
this contaminated harbor system. Measurements were made on both
whole (unfiltered) water and filtrate or particulate fractions of
water throughout the lower River Raisin and its discharge into
Lake Erie. The data will per nit calculations of partition
coefficients for these contaminants.
(b) In addition to the total PCB results described in this report, the
study also provided quantitative results for individual PCB
congeners and homologs. This analysis was based on high-resolution
gas chromatography using the first complete set of synthetic PCB
standards. The results showed the feasibility of applying
congeners-specific PCB analysis to a large number of environmental
samples representing water and other media.
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(c) The resulting spatial profiles of PCBs and metals generally show
that concentrations seen at the upstream boundary of Monroe Harbor
increased somewhat near the turning basin, and gradually diminished
downstream toward the Detroit Edison power plant intake. At that
point, concentrations often declined abruptly due to the presence
of Lake Erie water drawn upriver by the plant.
Cd) The plant discharge southward near the mouth of Plum Creek produced
Its own water quality gradient or plume In Lake Erie. However,
this gradient was generally not well—defined by contaminant levels,
except by zinc in Survey 4 and by copper tn Survey 5.
Ce) Levels of PCBs and metals at the upstream boundary (Station 1) and
In the open lake (Station 11) were typically similar within an
order of magnitude. Seasonal changes in concentrations at both
sites were within a factor of 2 or 3.
(f) Periodic high concentrations of PCBs at Stations 8 and 4 near the
turning basin Indicated continuing sources of these contaminants.
A mass balance study in progress will address the sources and fate
of this material. It is not clear at present whether the highest
levels of PCBs observed tn Mason Run (Station 8) were important in
terms of PCB mass being loaded to the turning basin.
(g) Temporal profiles indicate that PCB and metal concentrations were
most variable under high flow conditions In the spring. However,
the mean values during high and low water conditions were not
markedly different at the upstream boundary (StatIon 1).
Concentrations of PCB and metals in Monroe Harbor underwent large
fluctuations at times, especially within the turning basin. This
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may have depended on flow conditions in the river, as ll as
changes In rates of point source loadings. Contaminated sediments
at this site (see Filkins etal., 1985) may have been a major
source of pollutants during resuspension events.
(h) Two principal sources of metal loadings were recognized from these
surveys. Zinc at concentrations 5 to 10—fold higher than In the
river was regularly discharged from the Monroe WWTP (Station 7).
In contrast, copper and chromium levels In this effluent were
generally lower than In the adjacent river. The second principal
source of all three metals was apparently the automotive plant
(Ford) effluent at StatIon 9. There, levels were generally an
order of magnitude higher than In upstream river water. However,
after dilution at the river outfall (Station 5), the concentrations
were reduced to near ambient levels. Whether or not other primary
sources of contaminants exist may be Indicated by the results of
mass balance modeling. For example, an extensive landfill area
along the south shore of Monroe Harbor Is known to contain toxic
wastes (MDMR, 1983) and may be another source of contamination via
ground water.
(1) Where surface and bottom water were sampled regularly at Station 4,
PCBs concentrations seemed to be consistently higher In surface
water. However, metal concentrations were slightly more elevated
in bottom water.
(i) Difficulties were encountere j in cleaning up dichloromethane
extracts of some Monroe Harbor water samples prior to PCB ara yss,
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As a result, PCB quantitation has not been completed for these
samples.
(k) Further analysis of the data will be necessary to compare the
results of concurrent grab and composite sampling over 24—hour
periods at each station. While daily grab sampling Is more
economical, composite samples are more likely to reflect pulsed
loadings or periodic resuspension of contaminants. For Survey 1
only, the composite values averaged 10% higher than comparable grab
values.
(1) Changes in ratios of dissolved (or particulate) fractions to total
PCBs and metals, as a function of suspended solids concentrations,
may be defined after further analysis of these results. However,
difficulties were encountered in making reliable measurements of
PCB levels In filtrate and particulate samples. The problems were
mainly due to contamination of filters or filter holders, and to
insufficient mass collected in smaller volume samples prepared
under time constraints In the field.
(m) Analysis of system blanks, filter blanks and Florisil® blanks
Indicated that method interferences were seldom more than 10% of
sample values.
In) Replicate analysis of Aroclor mixture 1262 showed a consistently
high value as compared to the true value. Further investigation
is necessary to deternrfne the cause of this bias.
(o) Concentrations of chromium, copper and zinc observed in Monroe
Harbor and adjacent Lake Erie were all well below the EPA Water
Quality Criteria (1976) values for drinking water. However, copper
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and zinc levels in the river were generally within an order of
magnitude of those which have produced inhibitory effects in
crustacea (Mount and Norberg, 1984).
(p) The quality control measures as applied in the organics work proved
to be more useful for documenting the quality of results than for
managing the quality of field and laboratory processes in progress.
Most of the final PCB data was not available until after all of the
field surveys were completed. Metals QC results were generally
available within a month after sampling.
(q) While this study was focused on selected toxic metals and
organochlorines which were certainly among the major contaminants
of the Monroe Harbor system, the possibility remains that other
unstudied contaminants were present at concentrations sufficient to
cause biological effects. Another study (Mathews etal., 1985) has
examined relationships between the selected contaminant levels and
various bioassay results. The present report also does not include
the results of more conventional analyses for an nonia, chlorine,
chioramines, nitrates and other water quality factors which might
contribute to toxicity.
1.2 RECOMMENDATIONS
Based on the results and conclusions of the Monroe Harbor study, the
following reconm endations are made.
(a) Further, intensive studies of this type should address the possible
role of in—place contaminants In causing ecosystem effects within
other Great Lakes areas of concern. Experience gained at Monroe
Harbor will be useful in designing such studies.
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(b) There Is need to develop more efficient techniques for organic
extraction of large-volume water samples to support Intensive
surveys of this type. Complementary methods are needed also for
sampling and processing solute (or filtrate) and particulate
fractions of water samples.
Cc) The unique distributional data produced here for PCB congeners
should be used to study the environmental behavior, chemical fate
and biological effects of individual PCBs, especially the more
toxic congeners.
(d) Elevated PCB levels observed in the Monroe Harbor turning basin
indicate a need for evaluation of sediments and groundwater as
possible major sources of contaminants in this system. The source
of relatively high zinc levels In the Monroe Wastewater Treatment
Plant discharge should be Investigated as well.
(e) In other such analytical studies which support biological effects
work, more preliminary work should be planned to identify all
classes of toxins present at levels which might produce effects in
test organisms. Preliminary work also should be focused on
suitable methods for sampling and analysis based on chemical matrix
problems, if any. Finally, the sampling program design should be
founded on more detailed reconnaissance of general water quality
indicators.
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2.0 BACKGROUND
2.1 BASIN DESCRIPTION
The River Raisin drains an area of 1,070 square miles (2,771 km 2 ) and
discharges Into Lake Erie at Monroe, Michigan. A portion of Michigan’s
southeastern lower peninsula and the northeastern portion of Fulton County,
Ohio lie within the boundaries of the basin. The drainage basin narrows down
to a 2.5 mile (4 km—wide) strip for the last 15 miles (24 km) of the river
(Figure 2.1). The area consists mainly of clay till reworked by glacial lake
water and veneered by lacustrine sands, silts, and clays. Two—thirds of
Monroe County are covered by a layer of this glacial drift that is less than
50 feet (15 m) in thickness. The underlying bedrock Is mostly carbonate in
composition (Mozola, 1970).
2.2 HYDROLOGY
Monroe County is essentially flat terrain. There is a gentle slope
southeastward from a maximum elevation of 730 feet (223 m) In the northwest
corner to 572 feet (174 in) at Lake Erie. This gradual decline of only 158
feet (48 m) in nearly 26 miles (42 km) explains the low velocities of streams
located In the county (Mozola, 1970).
Runoff in the drainage basin Is significant due to the clay till. The
runoff during rain events creates rapid stream fluctuations and very turbid
waters. Relative to other areas in Michigan, erosion in the River Raisin
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basin is considered to be high. The U.S. Department of Agriculture estimated
that 8.3 to 10.8 tonnes of topsoil per hectare per year are lost (Michigan
DNR, 1979). A 1967 paper by the U.S. Department of the Interior reported
that the average annual precipitation for the drainage basin area Is 31.52
inches (80.1 cm). Of this amount, approximately one—third runs off through
the river system.
Much of the area adjacent to the River Raisin is prone to flooding. A
large portion of the eastern fringe of the city of Monroe was marshland.
Over the last thirty years, approximately 80% of the marshlands have been
filled in for industrial and recreational uses. The river banks and
surrounding areas at the mouth of the River Raisin are man—made (Monroe
County Drain Commission, 1984).
The U.S. Geological Survey (USGS) maintains a stream flow gauge
(Station #04176500) in the River Raisin near Monroe. It is located In
Monroe County, on the left bank of the river (1.3 km downstream fr ii the
bridge on the Ida Maybe Road), at latitude 41°57’38 and longitude 83031152u.
The drainage area above this point in the river Is 1 ,042 square miles (2,699
km 2 ). The average discharge for a record period (1937-1981) was 709 cubic
ft/sec (19.9 m 3 /sec). The maximum and minimum discharge for the record
period was 14,500 cubic ft/sec (407.3 m 3 /sec) and 2 cubic ft/sec (0.06
n1 3 /sec) , respectively (USGS, 1982). River flows for an 11—year period are
displayed in Figure 2.2. Peak flow frequencies for this record period since
1938 are presented in Figure 2.3.
The City of Monroe maintaIns a stream flow gauge In the River Raisin at
Dam #1 (second low head dam relative to the river mouth). This gauge Is
located in the City of Monroe approximately 152 in downstream fran Maple
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Avenue (Petty, 1984). Daily readings are recorded by the Monroe Waste
Treatment Plant (WWTP).
The lake level Is monitored hourly by three National Oceanographic and
Atmospheric Administration (NOM) gauges located near the study area. Water
stage readings for Gage 3087 in the turning basin are presented in Figure 2.4
(January 1. 1975 to March 31, 1983). The other two gauges are located on
Lake
Erie at Toledo, Ohio (Station 3085) and the Fermi Power Plant, Stony Point,
Michigan (Station 3090).
The port of Monroe Is served by a dredged channel 15,800 feet (4.8 km)
long, 300 feet (91.2 m) wide and 21 feet (6.4 m) deep from Lake Erie to the
mouth of the River Raisin. Fran the river mouth to the turning basin, there
Is a dredged channel 8,200 feet (2.5 Kin) long and 200 feet (60.8 m) wide
(Michigan DNR, 1979). See Figures 2.5 and 2.6 for depth contour maps.
2.3 INDUSTRIAL DEVELOPMENT
Most of the River Raisin is in agricultural production. Over 70% of
Lewanee and Monroe Counties are farmed.
Urban development of the basin is centered around three cities: Monroe,
Adrian and Tecumseh, Monroe, at the River Raisin mouth is the most populuous
and industrialized city in the basin. A 1980 census listed Monroe as having
a population of 23,531. Much of the industry is associated with automobile
manufacturing in nearby Detroit. Additional industries In the area are
primary metals, fabrication of metal products, machinery and transportation
equipment, manufacture of paper products, chemicals, furniture, food
processing and dairy related industries (Michigan DNR, 1979).
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Several paper product companies are located on the River Raisin within
the study area. Consolidated Packaging Corporation, South and North Plant
closed on February 1978 and July 1975, respectIvely (Figure 2.7). Their
products were corrugated and solid fiber containers. Time Container Company,
a paper products industry, is located upstream of the study site near the
Chesapeake and Ohio Railroad. Union Camp Corporation on the north shore of
the River Raisin produces corrugated paper board and containers. The
effluents from the primary treatment facilities of both Time Container and
Union Camp are sent to the Monroe WTP for secondary treatment (Michigan
Department of Public Health and the Michigan Water Resources Coniniss lon,
1969).
The Detroit Edison Plant is located near the mouth of the River Raisin
on the south side of the river. This fossil—fueled, steam-electric power
plant has an exceptionally large, once—through cooling system. Up to 85
m 3 /sec of water are pumped for cooling purposes. A map of the plant In
Figure 2.8 shows the Intake and discharge channels (Cole, 1978).
During spring runoff, the River Raisin makes up more than 95% of the
cooling water. However, during low flow in the summer, the river makes up
less than 5%, the balance of water is from Lake Erie. Water enters the
cooling system through a 100 meter-long Intake canal that is located about
650 meters upstream from the river mouth. After water passes through the
condenser, it Is released into a 350—meter long, concrete conduit where water
velocities are approximately 1 rn/sec at full operation. The water is then
discharged through a rock—walled canal averaging 175—meters wide. Plum Creek
joins the discharge canal, but contributes less than 1% of the volumetric
flow to Lake Erie. The average annual river discharge is equivalent to 20%
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of the total cooling water demand - the rest Is drawn from Lake Erie (Cole,
1978).
The Monroe Metropolitan Water Pollution Control Facility Is located on
the south bank of the River Raisin. The plant receives raw wastewater from
the City of Monroe, Frenchtown Township and Monroe Township. Under normal
operating conditions, all wastewater flows are conveyed to the treatment
plant. Under severe runoff Conditions, high flows In the collection system
exceed the plant capacity. During this time, untreated wastewater Is pumped
directly into the River Raisin from the Flood Pumping Station. The present
treatment facility can adequately provide secondary treatment for flows up to
30 MGD (113,550 in 3 ). Sludge disposal Is through a contract arrangement
with disposal In the State of Ohio (Monroe County Drain Con n1ssion, 1984).
2.4 CONTAMINANT SOURCES
Both toxic contaminant reserves in sediments and current toxic chemical
loadings to the River Raisin from existing Industrial, municipal and landfill
activities were considered as potential sources of toxins in the Monroe
Harbor study.
Copper, chromium, and zinc were analyzed in the study because of the
relatively high concentrations of these metals found in sediments In the
River Raisin and because of the toxic nature of these metals to cladocerans
and other freshwater invertebrates. Relatively high levels of toxic heavy
metals In the navigation channel have been reported in the literature. The
USEPA Great Lakes Surveillance Branch (1975) recommended that the
contaminated dredged sediments from the navigation channel should not be
disposed in the open lake. Nnong other contaminants, their analysis reveaed
high levels of copper (1450 mg/kg), zinc (970 mg/kg), and chromium (530
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mg/kg). Based on atomic absorption spectroscopy (AAS) by Cranbrook Institute
of Science and neutron activation analysis by the University of Michigan’s
Phoenix Memorial Laboratory (Jones, 1983), concentrations of these metals
were relatively high when compared to mean sediment-levels In southern Lake
Huron. Concentrations of some other metal also were found to be relatively
high in these studies, but their toxicity at these levels to freshwater blota
was negligible or unknown. In addition, several metals were excluded from
the Monroe Harbor study because of economic and instrumental limitations at
the EPA Large Lakes Research Station.
In addition to reserves of metals In the sediment, there Is an existing
potential for heavy metal discharge from primary metal production, plating,
and metal machining industries in the Monroe Harbor area.
Polychlorinated biphenyls (PCBs) were Included In the study of Monroe
Harbor because high levels of PCBs In fish were found In the area. In 1971,
the Michigan Department of Natural Resources collected fish in the River
Raisin and found up to 6.45 mg/kg of Aroclor 1254 -In northern pike (wet
weight) and up to 3.08 mg/kg of Aroclor 1254 tn carp (wet weight). The
results of a 1979 survey Included a single carp with 77.2 mg/kg of total PCB
(MDNR, personal con nunicatton).
PCBs have been linked to Industrial activity that use the persistant
compounds In lubricants and coolants for electrical equipment. PCBs have
also been found to be a by-product in paper recycling plants. These
Industrial uses and processes exist (or existed) in the River Raisin study
area; therefore, ft Is possible that the sediment and fish contamination
observed originated from local industrial activity.
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3.0 APPROACH AND METHODS
3.1 SAMPLING RATIONALE AND STRATEGY
The approach to sampling design for water chemistry in the River
Raisin - Monroe Harbor estuary was based on the need to address multiple
objectives (as defined In the previous section) with limited resources.
Spatial and temporal gradients In water chemistry were viewed as important
elements in sampling designed to provide data for:
1) An Integrated approach among physics, chemistry, and biology;
2) A mass balance of various chemicals;
3) An assessment of water quality during critical events.
The strategy for sampling, then, was to attempt to obtain this gradient
information on various surveys throughout the study in ways that would meet
as many of these objectives as possible.
All of the surveys were designed with the integrated approach In mind.
Water chemistry samples were taken simultaneously with water movement
measurement and renewal water for biological testing. This ensured the
compatability of the data. The first few surveys were quite extensive In
space and time, allowing the needs of the integrated approach and the mass
balance to be met. As preliminary information from these surveys became
available, the sampling was tailored to the types of information still
lacking. For example, results from the first three surveys guided the next
three surveys In which the effects of critical events were defined. Thus,
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the strategy was a flexible one, in that it took advantage of knowledge
gained tn the previous surveys as well as seasonal changes at the sampling
site to address information gaps as the study progressed,
Over the course of the two years of the Monroe Harbor study, the
sampling strategies and locations re altered to reflect increasing
understanding of the ecosystem, and to account for seasonal changes in water
flow and discharge (see Tables 3.1 and 3.2). These different approaches are
described below.
Surveys I and II (July 12—17 and September 13—18, 1983)
The purpose of these surveys was to investigate the presumed existence
of a contaminant/toxicity gradient within the lower River Raisin ecosystem.
Total and dissolved metals and organics were sampled at five river stations,
one tributary (Mason Run) and one Lake Erie station. In addition, total and
dissolved metals and total organics were collected from four potential point
sources (see Figures 3.1 and 3.2). DurIng Survey 1, daily grab (once/day)
and composite (three times/day, and combined) samples were collected at all
stations. During Survey II, composite samples were collected at selected
stations, which changed each day. In addition, grab samples were collected
at half of the stations each day, with the locations changing so that each
station was sampled every other day.
Survey III (October 25-28, 1983)
Based on the results of the Cerlodaphnia and fathead minnow toxicity
tests associated with Surveys I and II, attention was focused on the effluent
plume of the Monroe Waste Water Treatment Plant (WWTP), from its discharge
pipe downstream to the turning basin (see Figure 3.3). The purpose of this
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plume study was to sample a stronger, more well—defined gradient of water
quality and toxicity for correlation analysts.
Daily grab samples, for total and dissolved metals and total organics,
were collected at all plume stations, and dissolved organics samples were
collected from a subset of the plume stations and from Lake Erie. To provide
continuity with previous work, on the first day of the survey composite total
and dissolved metals and organics samples were also collected from all of the
stations used in Surveys I and II.
Survey IV (April 2-5, 1984)
With this survey, the scope of the Monroe Harbor project was expanded
to Include the nearshore zone of western Lake Erie. Aerial observation
showed that the runoff-fed, highly turbid and discrete River Raisin plume
extended out into Lake Erie, with Its exact direction and extent largely
determined by prevailing wind patterns.
On April 4, 1984, subsurface samples for total and dissolved metals
and total and particulate organics were collected at eight river stations,
two tributaries, one potential point source (WbETP), and ten nearshore Lake
Erie stations. In addition, similar samples were collected from a depth of
three meters at four of the river stations. See Figures 3.4A and 3.4B.
Survey V (May 9, 1984)
Like Survey IV, this survey Included an evaluation of the contaminant
gradient In the River Raisin plume as It was diluted and dissipated in the
nearshore zone of Lake Erie.
Seven stations were positioned in Lake Erie along a temperature!—
conductivity gradient established on the day of the survey. Total and
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dissolved metals grab samples were collected at these stations and also at
one tributary, one point source, and three river stations. Total and
particulate organics grab samples only were collected fran two river
stations, 1 and 4. See Figures 3.5A and 3.5B.
Surveys VI, VII, VIII, IX and X (May 30, June 12, July 10, July 25 and
August 1, 1984)
These surveys were Intended to evaluate the temporal variability of
contaminant concentrations and their associated toxicities within the River
Raisin. Total and particulate organics grab samples were collected at two
river stations, 1 and 4. Total and dissolved metals samples were collected
at these stations, at the mouth of the river (26) and at the mouth of the
Detroit Edison power plant coolant water discharge canal (29). See Figure
3.6 for details.
3.2 COLLECTIONS
Any project of this scope requires a sampling strategy that will provide
a maximum amount of Information while still taking personnel and analytical
constraints Into account. With this In mind, the water sampling efforts were
divided between two sample types:
— Grab samples, that provided uSnapShOtSu of contaminant
concentrations at a specific Instant In time; and
— Composite samples, that gave an average, Integrated value
of contaminant concentration over a known length of tine.
Organics and metals grab samples were collected on all surveys, as
described in Section II of this report. Sample volumes for organics varied;
4 1 for Surveys I and II, 8 1 for Survey III, and 12 1 for the r naining
surveys. This reflected our estimation of expected contaminant levels.
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Composite samples were collected only on Surveys I, II and III.
Every eight hours (0800, 1600 and 2400 hours) on each day of the survey,
water was collected, returned to the USEPA RIY Bluewater and processed as
described in Sections 3.l.A and B. For organics analysis, solvent extracts
from each part of the composite (1 1) were collected in the same bottle,
resulting in a 3 1 composite sample representing one 24—hour period. For
metals analysis, splits of each part of the composite were also combined in
the same bottle.
In addition to collecting both grab and composite samples, the whole
water was often fractionated Into dissolved constituents and particulates.
Details of the processing of these fractions are described below.
3.2.1 Total (Whole) Water
Organics
Sample volumes varied depending on survey number and sample type.
Each 1 1 sample was collected in a 1—gallon (3.8 1) amber glass jug (empty
Burdick & Jackson pesticide—grade solvent bottle). Near-surface samples
were collected by submerging the bottles by hand. Sub—surface water was
collected by a portable peristaltic pump equipped with silicone pump tubing
and Tygon® (polyvinyl chloride, PVC) sampling hose.
The bottles were returned to the USEPA R/V Bluewater, which was
anchored near Station 4. One hundred milliliters (mL) of dichloroniethane
(DCM) was added to each bottle, and they were shaken vigorously for three
minutes. After waiting two hours for the solvent to settle, the D 1I layer
was drawn off using a one liter separatory funnel. An additional 100 mL 0CM
was added to the sample, which was again shaken for three minutes; after a
brief settling period, the D M was added to the first extract via the
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separatory funnel. The water was discarded, and the jug rinsed with 50 mL
DCM. This rinse also was added to the extract. This solvent extract was
stored in a 1—gallon amber glass jug In the dark at room temperature until
further processing occurred at LIRS, as described In Section 3.3.
Metals
Trace metal samples were collected In new wIde-mouth 500 ml
Nalgene® linear polyethylene (IPE) bottles washed with hot water In a
dishwater, rinsed with deionized water, with 30% v/v nitric acid, and again
with deionized water; bottles were then soaked tn 2% v/v nitric acid for two
weeks, rinsed six times with deionized water, and dried in an oven (105°C)
with the caps ajar.
Near—shore river samples were collected by hand. The bottle was
quickly lowered below the water surface and filled, after a prior rinse with
station water. On several occasions, Station 4 was sampled near the bottom.
Sampling these lower levels required a peristaltic pump equipped with
silicone pump tubing and a TYGON® sampling hose.
Effluents and tributaries were sampled by several methods. Mason Run
was sampled from a bridge (Station 8) by lowering a half gallon LPE
wide—mouth Nalgene® bottle fixed to a polypropylene rope with stainless
steel clamps. The bottle was weighted from below with lead, and the bottle
mouth was sheltered with a plastic awning or lid suspended from the rope just
above It. The purpose of the lid was to keep out debris as the sample was
pulled up. Before sampling, the bottle was rinsed with station water. This
technique was also used when the Ford intake (Station 10) was sampled. Hand
dipping was the method used to collect water at Ford’s polishing lagoon
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(StatIon 9). The Monroe Wastewater Treatment Plant (Station 7) was sampled
with the peristaltic pump apparatus.
All total metal samples were acid-spiked and stored In 500 ml
polyethyl ene bottl es.
3.2.2 Filtered Water (Dissolved Fraction)
Organics
Bottles of raw water were returned from the field to the R/Y
Bluewater, and the water was pumped (Cole-Palmer 1/3 h.p. peristaltic pump;
5/16 inch (f.d.) silicone and Teflon® tubing) through a 1,000 pm
stainless steel prefilter and a prebaked (482°C) Whatman GF/F glass fiber
filter (4.25 cm diameter; 0.7 pm porosity) into a 1—gallon amber glass
bottle. Filters were changed when the back pressure reached 10 to 15
p.s.I. One to six filters were used per sample. The pump was purged
thoroughly with sample water between samples. One hundred ml of D M was
added to each filtered sample. The sample was extracted as described above
for whole water. Volumes filtered ranged from 3 to 8 1.
These filtered water extracts were stored as per the total water
extracts.
Metals
A 100 ml portion of the unacidified total metal sample was filtered
through a 045 pm Sartorius cellulose acetate filter. The filtering
apparatus was a Miulipore polycarbonate Sterifil® filtration system.
Before use, the system was soaked In 4% v/v HNO 3 , then rinsed well with
deionized water. The filter was set In place and 50 mL of deionized water
was filtered, then discarded. Fifty niL of sample was then ft1 tered and
discarded. Sample water was filtered until the filter began to clog. Before
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filling a 175 ml LPE bottle with filtrate, the first 50 mL of filtrate was
used to rinse ft out.
When filtering was complete, both the total and dissolved samples were
preserved with ULTREX® nitric acid by adding 3 ml per liter of sample.
Samples were refrigerated at 7°C until analyzed.
3.2.3 Particulates
Organic s
After Survey III (the last survey of 1983), it was realized that the
collection of filtered water by the method described above presented a number
of difficulties. First, frequent filter changes required by the high
turbidity at some stations increased the level of background contamination.
Also, the small sample volume necessitated by time and equipment constraints
sometimes did not provide adequate contaminant levels for analysis.
Consequently, the amount of dissolved PCB was calculated Indirectly, by
collection and analysis of the suspended particulates and whole water, rather
than directly by analysis of the filtrate.
In this procedure, whole water was collected in glass jugs as in
previous surveys, and transported back to LLRS. The water, pumped by a
peristaltic pump equipped with silicone rubber pump tubing and approximately
1.5 m of 9 nm (i.d.) Teflon® sample tubing, was passed through a
stainless steel filter-holding apparatus containing a 1,000 urn prefilter and
a 0.7 urn-porosity, 293 inn-diameter Whatinan GF/F glass microfiber filter
(prebaked at 482°C). The filtrate was collected for volume determination.
Filtration was stopped when the back pressure reached approximately 10 p.s.l.
(70 kpa). The filter was removed, folded, and placed In a clean (soap and
water; acetone, DCM and hexane rinse) flint glass jar containIng 150 mL
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acetone. Jars were stored In the dark at 8°C until extraction. Between
samples, the apparatus was purged with water from the next sample for
approximately 30 seconds. Separate filtration equipment was used for river.
point source and Lake Erie samples to minimize ucarry_overa contamination.
Volumes filtered ranged fran 4 1 to 16 L, depending on particulate
concentrations.
3.3 SAMPLE EXTRACTION
3.3.1 Total and Filtered Water
The solvent extracts collected in the field were returned to LLRS.
The extract was poured from the bottle into a one-liter separatory funnel,
passed through an anhydrous sodium sulfate column and Into a 500 ml
kuderna-Danish (KD)/lower tube assembly. When half full, the KD and a Snyder
column were placed on a steam bath and the solvent was concentrated to
approximately 50 ml. This concentration was repeated until all of the D M
extract had been reduced to approximately 50 ml. A rinse of 250 ml n—hexane
was then run through the separatory funnel and sulfate column and into the
KD, and the solvent was then boiled down to less than 10 ml.
The concentrated hexane extract was transferred to a 10 ml graduated
tube and then evaporated In a water bath under nitrogen gas to 0.5 ml. This
was then diluted to 2.0 mL with hexane.
The extract was then either left in the graduated tube for cleanup
with concentrated sulfuric acid, or pipetted into an ampule, sealed and
stored for Florisil® cleanup (SectIon 3.4).
System blanks consisted of a volume of D M equal to that used to
extract the largest sample of each set.
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3.3.2 Particulates
The contents of the jar (filter and acetone) were placed in the
Soxhiet apparatus (Soxhlet, 500 ml rouridbottom flask and condenser) and
extracted with 150 mL n—hexane and 150 ml acetone for six hours on a heating
mantle. Extract was poured from the roundbottoni flask into a 1W flask and
concentrated to 50 ml on a steam bath. n—Hexane (100 ml) was added to the
1W, and again concentrated to 50 mL. The extract was poured Into a
separatory funnel, as was an n—hexane rinse of the 1W. Any lower water layer
was drained off and discarded, and the extract was passed through an
anhydrous sodium sulfate column Into the 1W. Another 100 ml of hexane was
passed through the same separatory funnel and sulfate column and Into the 1W.
The extract was finally concentrated to less than 10 ml on the steam bath.
The extract was then transferred to a 10 mL graduated tube and
evaporated In a water bath under N 2 gas to 0.5 mL. n—Hexane was added to
restore it to 2.0 ml.
Extract cleanup was as described below.
System blanks consisted of unused filters placed (in the field) in a
clean jar with acetone, and processed as per the sample filters.
3.4 CLEAN-UP (ORGANICs)
All organic total water, filtered water, and particulate sample
extracts were acid cleaned. Four mIs of concentrated H 2 S0 4 (Baker
Instra_Analyzed®) was added to the graduated tubes containing the
extract, shaken, and allowed to sit overnight. The following morning the
graduated tubes were placed in an acetone/dry ice bath until the acid layer
froze, at which time the upper n—hexane layer was pipetted off, placed in an
ampule and sealed.
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In addition to acid clean—up, some total water and all particulate
samples from Survey 4 required further clean—up with Florisil®.
Clean—up columns were dry packed with 20 grams of Florisil ® which
had been baked at 650°C for two hours and stored until needed in a 130°C
drying oven.
After an Initial 50 ml rinse of the column with n-hexane, 1 ml of
sample extract was injected onto the column followed by 250 mL of 4% D M in
hexane.
The eluant was collected in a KD flask, concentrated to less than 10
ml on a steam bath, and transferred to a 10 ml graduated tube. A stream of
N 2 gas was used to evaporate the eluant down to 0.5 mL, after which It was
brought up to 2 ml with hexane, transferred to an ampule and sealed.
A blank and a PCB standard were processed with each florisil
group and were treated as samples with the following exceptions: 1) no
initial extract was Injected onto the column for the blanks; 2) 2 ml of PCB
standard was Injected onto the column; 3) 200 pL of of internal standard was
added to both the blank and the standard before the final volume was adjusted
to 2 mL with n—hexane.
In addition, 2 mL of PCR standard solution obtained from the same
batch as the standards eluted through the column, was evaporated to 0.5 mL
with nitrogen, 200 pL of internal standard was added and the final volume
was adjusted to 2 mL with n—hexane.
3.5 ANALYSIS AND QUANTITATION
3.5.1 Organics
High resolution fused silica capillary gas chromatography was
performed on a VARIAN Model 3700 gas chroratograph equipped with a 63 Ni
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electron capture detector (ECD). A 50 in fused silica column (0.2 n n i.d.)
coated with SE-54 (Hewlett-Packard) was used to separate the PCB congeners.
The oven temperature was progranuned at a rate of 1.0°C m1n 1 from 100 to
270°C and held at 270°C for ten minutes. The injector and detector
temperatures were 270°C and 320°C, respectively. The sample volume, 4.5 zI,
was Injected by an automatic sampler using a splitless injection technique
(10:1 split ratio, vented from 0.75 to 1.75 mm). The hydrogen carrier gas
was held at a constant pressure of 2.25 kg cm 2 to give the optimized
velocity (ul at 100°C of 50 cm sec .
The chroniatograpPiic data were acquired using a Hewlett-Packard 3354
Laboratory Automation System (LAS) and transferred to a Digital PDP—1l/45
computer via magnetic tape.
Once transferred, each raw file was subjected to a series of programs
for data analysis:
(1) Attenuate (AN) — Expands the scale of the chromatogram.
(2) PLOT (PIT) — Establishes a chromatogram base line.
(3) PEAKS (PKS) — Determines peak height.
(4) Mean Standard Deviation (MSD) — Determines baseline noise mean
and the standard deviation used in the ‘Peaks’ program.
(5) PUP - Compares the sample file to a library file for retention
tiii e and names PCB or Pesticide peaks detected.
(6) UPDATE (UPD) — Updates the library with the calibrating standard.
(7) Sample Final Concentration (SFC) — Gives the total PCB or
Pesticide sample concentration, the number of peaks accepted tn
the analysis and the honiolog distribution
(8) COMSTAR (cMS) — A multiple regression program that fits observed
congeners in sample with a linear combination or Aroclors. Any
peaks not fit are considered outliers and marked for rejection.
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Once the analysis was completed, the data were stored tn a final data
base and archived on magnetic tapes.
3.5.2 Metals
Because suspended particulates were present, all total metals samples
were nitric acid digested using a method adapted from USEPA (1971).
Copper and chromium were analyzed with a Perkin—Elmer 460 AtomIc
Absorption Spectrophotometer fitted with a graphite furnace, a HGA-220
controller and AS—i Auto Sampler. Analytical conditions were determined by
applying the methods In Perkin-Elmer (1977).
Duplicate injections and analyses were performed on each sample,
blank, and standard. The mean peak height was used to calculate the
concentration.
Zinc, because of its higher concentrations, was analyzed using a
Perkin—Elmer 603 Atomic Absorption Spectrophotometer In the flame mode.
Standard grade acetylene and air were used to support the flame. Analytical
conditions were taken directly from the Perkin—Elmer 603 Methods Manual.
After absorbance readings or peak heights were measured, the data were
processed automatically using a computer program which was written to correct
for blanks, perform linear regressions, plot the standards, and determine the
concentration of the samples.
Detection limits for the metals analyzed are reported in Table 3.3.
3.6 QUALITY ASSURANCE
The quality assurance program was designed to control and evaluate
the quality of field and laboratory work with respect to: (a) accuracy ,
through analysis of blanks and standards, intercomparison and sample recovery
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studies; and (b) py ecision , through replicate and between-run analyses. The
specific uses of these quality control measures are described below.
3.6.1 Metals
Any analytical procedure should address accuracy and precision of the
measurement. Trace metal analyses are subject to various sources of error,
which complicates Interpretation of the final results. Not knowing the
precision of measurements limits the usefulness of the data set.
To insure accuracy, blanks were quantified at various steps in the
analytical process (Table 3.4). The filtering process In the field was
monitored by filtering deionized water. This sample served as a filter
blank. Sample bottles used in the study were tested for blank levels by
filling them with deionized water and preserving and storing them with the
field samples. The metals digestion process was monitored by digesting
three deionized water blanks for every 20 samples. These blanks were used
to correct the sample concentration results as shown In Section 4.6.
Accuracy of the results was also insured by use of intercomparison
samples (Table 3.5). These samples were received from the United States
Environmental Monitoring and Support Laboratory, Cincinnati. Intercomparison
samples helped insure accuracy by comparing our analytical results to outside
measurements.
Standard additions were used to quantify samples whenever recovery of
the added metal was not close to 100%. Some metal analyses, such as for
lead, are more prone to recovery problems in the laboratory than are others.
The approach taken in this project was to assume that recovery would be a
problem whenever samples frcin a new study site were received. Therefore,
all samples were quantified Initially by the standard addition method.
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After a number of analyses were performed, the recoveries were evaluated
(Table 3.6). Standard additions were continued for any metal analyses with
persistent recovery problems. Metal analyses without recovery problems were
measured by directly comparing analytical absorbance signals to a standard
cu rye.
Precision was estimated at various stages of the analytical process.
Duplicate samples were collected in the field. Analytical results from these
duplicates provided the data user with an estimate of overall variability In
the analytical process, which Included variability in the medium sampled
(Tables 3.7, 3.8). Analytical/Instrumental variability Included variability
of sample handling in the laboratory and uncertainty from analytical
Instrumentation. This analytical/instrumental precision was estimated by
using between-run sample replicates, defined as the standard deviation of a
sample analyzed each for some period (Table 3.9).
In order to detennine contamination Introduced In the filtering
process, two filter blanks were taken during each eight—hour shift in the
field. This involved filtering a sample-sized volume of deionized water. An
unfiltered sample of deionized water was also taken at the same time. The
unfiltered sample (batch blank) served two purposes: as a bottle blank, and
as a reference for the filter blank. The analytical results of the batch
blank and filter blank were compared; if equal, they were then no filter
contamination was recorded. Equality here was confirmed by a 1-test (Table
3.4).
3.6.2 Drganics
A quality assurance plan was designed and used here to address iiieL uu
Interference, particulate extraction efficiency, precision and accuracy.
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Method Interference
The preparation of organic samples for gas chromatographic analysis
Is a complex process involving many steps. An effort was made not only to
monitor overall method Interference but also to determine at what processing
step(s) Interferences were introduced when they did occur.
The figure below shows the steps monitored by each type of method
interference check blank.
Sample collect. Sample flltr. Sample extrac. Sample clean—up Sample anal .
(Particulate fractions)
Filter Blanks
System Blanks
Florisil Blanks
A filter blank consisted of an unused filter stored In a clean jar to
which 150 nil of acetone was added. The filter blank was then processed along
with particulate samples.
Each extraction group had an associated system blank which represented
a volume of D M equal to that used to extract the largest sample. This blank
was then processed as a sample.
florisil blanks were used to monitor possible contamination from
the Florisil clean—up procedure. Florisil © blanks were processed
along with each clean—up group and were treated as samples with the exception
that no Initial extract was injected onto the columns.
Comparison of filter blanks) system blanks and Florisil® blanks
Indicate at which point in the process and at what levels method
Interferences occurred.
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In order to evaluate filter extraction efficiency, four particulate
filters were extracted for six hours, the solvent was changed, and the
filters were extracted for an additional sixteen hours. Both first and
second extracts were analyzed. Efficiency of extraction was calculated by
dividing the value of the first extract by the sum of the values of the
first and second extracts and multiplying the result by 100 (Table 3.10).
Ar assumption was made that extraction for a total of 22 hours removed all
of the extractable material.
Precision
Precision was estimated for the entire measurement system using
collocated duplicate samples (Table 3.11).
Analytical precision was estimated by repetitive analysis of PCB
calibration standards analyzed as samples (Table 3.12).
Accuracy
Instrumental accuracy was assessed by analyzing Aroclor mixtures
1221, 1016, 1254 and 1262, obtained from the U.S. Environmental Protection
Agency’s Monitoring and Support Lab (EMSL), Cincinnati, Ohio (Tabl e 3.13).
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4.0 RESULTS AND DISCUSSION
Results are presented in terms of spatial and temporal profiles of PCB
concentrations in whole water and particulate samples, and of chromium,
copper and zinc concentrations in whole water and filtrate samples (Figures
4.1 - 4.41). The numerical values plotted in the profiles are also given in
Tables 4.1 — 4.9, along with P18 analysis blanks. In the metals data, blank
values have already been subtracted from sample measur ents. PCB analysis
was performed at the level of specific congeners and homologs, but only the
total PCB results are reported here. Calculations of dissolved PCB and
5 partlculate’ metals concentrations can be made from these data. The same
applies to the metals data.
The organochlorjne analysis Included other selected compounds:
pentachlorobenzene, al pha—BHC, hexachi orobenzene, ganm a—BHC, heptachi or,
alpha-chlordene, aidrin, ganina—chiordene, heptachior epoxide, oxychiordane,
gamma—chiordarie, alpha—chlordane, trans—nonachior, dieldrin, 4,4’—DDE,
endrin, cis—nonacpilor, 4,4’—DDD, 4,4’—DDT and methoxychior. Since
concentrations of these were not exceptional, the results are not Included
in this report.
Spatial profiles reflect gradients of PCB or metal concentrations in
the water column along a series of stations from the upstream boundary of the
study area (Station 1) to the nearshore waters of Lake Erie (Station 11).
As indicated on the maps (Figures 2.1 — 2.6), the stations include point
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sources of contaminants, surface and bottom water samples at StatIon 4, and
plume gradients. The mean concentrations given below for each survey
represent both composfte and grab samples, and duplicate samples that were
collected tn some cases over several days.
Temporal profiles show seasonal variations of PCB or metal
concentrations in the water column at only two locations, Station 1 at the
upstream boundary, and Station 4 just downstream from the turning basin
(Figure 2.1). Ten surveys were conducted during July 1983 through August
1984. Profiles of river flow conditions during the surveys are shown in
Appendix A (Figures A.1 - A.lO).
Quality control results are given at the end of the separate
discussions of organics and metals.
4.1 SPATIAL PROFILES, PCBs
For Survey 1 (July 12-17, 1983) a comparison of whole water data for
composite and grab samples Is presented in Figure 4.1. Each plot of mean,
standard deviation and range represents five days of samples (generally five
composite samples and two grab samples). Both profiles reflect similar
gradients of total PCB concentrations which occurred at Station 8 and 4 near
the turning basin. The actual values for composite and grab samples are
given fri Table 41. For most of the 24-hour periods, the composite sample
value was slightly higher than Its grab sample counterpart (average of 33 vs.
30 ng/L). All composite and grab sample values during Survey 1 have been
combined for each station as shown at the bottom of Table 4.1. The mean
values indicate that total PCB concentrations near the upstream boundary
(Station 1) were on the order of 7—9 ng/L. The discharge water from the
Monroe Waste Water Trea ent Plant (Station 7) was markedly higher at 34
32
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ng/L. Apparently, this effluent level was reduced to 8.9 ng/L by dilution
just downstream froni the plant at Station 3. Mean PCB concentrations furthe
downstream were dramatically higher at 147 ng/L In the mouth of Mason Run
(Station 8) and at 51 ng/L just below the turning basin (Station 4). High
variability at these stations Indicates some episodic effect on PCB
concentrations. Levels were elevated to 57 ng/L also at the water Intake of
a large automotive plant (StatIon 10) nearby. However, in Lake Erie near the
River Raisin mouth (Station 6), the PCB level of 14 ng/L was much reduced,
and was near the boundary condition level of 9 ng/L at Station 11
approximately 5 km offshore. Additional samples from Stations 7, 9 and 5
required further clean-up before analysis, and these results are not yet
available.
Results from some corresponding composite filtrate samples (Figure and
Table 4.2) indicate first, that in most cases the filtrate values were
unrealistically higher than the totals and were, therefore, contaminated.
Because of later concern about contamination in the filtering process and the
likelihood of low filtrate values being near detection limits, particulate
fractions were collected Instead of filtrate after the first three surveys.
In Survey 2 (September 13-17, 1983), the sampling plan differed
somewhat. Station 2 was dropped because ft seemed to duplicate conditions at
Station 1. No results are available for Station 7. Station 4 was sampled at
1 in and 1 in above the bottom in order to evaluate any effects of
stratification. The results of Survey 2 (Figure and Table 4.3) indicate a
similar spatial pattern of PCB distribution except that concentrations were
much higher relative to boundary conditions of 10 ng/L. PCB levels in
lower river and nearshore lake were approximately double those In the
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previous survey. At Station 4, the PCB level In surface water was sane 30%
higher than that near the bottom. As In Survey 1, filtrate samples were
contaminated by the filtering process and did not yield reliable results.
Survey 3 (October 25-27, 1983) involved two different strategies.
Results of the first phase consist of a composite sample profile of the same
station as used in Survey 1 and 2 (Figure and Table 4.4). The station
profile of PCB is again similar to that In previous surveys except for an
anomalous value of 220 ng/L In offshore Lake Erie (Station 11) whole water.
The comparable filtrate value (9.2 ngIL) Is more realistic. Filtrate values
as a fraction of whole water PCB are shown in Table 4.4(8). Not counting the
upper and lower extremes, the average of flltrate/wtiole water PCB was 53%.
In the second phase of the survey, PCB profiles were recorded over three days
by daily grab samples taken at seven new stations within the Monroe WWTP
effluent plume (Figure 2.3). The results (Figure and Table 4.5) defined a
downstream gradient of PCB that was generally weak but more pronounced along
the south shore of the river. Sharp rises in concentration observed at
Station 19 on days 1 and 3 of the survey probably indicated the influence of
much higher levels seen In the turning basin during the first phase,
especially in surface waters. Within the plume group of samples, several of
the filtrate values exceeded those of whole water (Figure and Table 4.6).
In Survey 4 (Apr11 2—5, 1984) whole water and particulate grab samples
were collected at most of the original and some additional stations as well
(Figure and Table 4.7). The new stations were established to monitor the
dispersion of contaminants within the river plume in nearshore Lake Erie
during a period of high runoff and river flow. However, most of the lake
samples required further clean—up, and the results were not available here.
34
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In the river profile PCB levels exhibited the usual increases in the area of
the turni ng basin and declines toward the river mouth and Into Lake Erie.
The Edison Power Plant inlet In the lower river (Station 24) and outlet In
the lake (Station 29) had similar concentrations of whole water PCB at 17 and
19 ng/L. Although particulate PCB values were approximately half that of
whole water in most cases they exceeded whole water values in four samples.
Most significantly in Survey 4, the PCB concentrations at StatIons 8 (Mason
Run) and 4 (below turning basin) were much lower than in previous low—water
surveys. Most values in this area (at 13-31 ng/L) were not markedly higher
than the upstream boundary or lake concentrations; this suggests a greater
dilution effect with increased flows.
In Survey 5 (May 9, 1984) the sampling strategy of Survey 4 was
repeated on the lower river and its plume in nearshore Lake Erie. Although
metals analysis was conducted on all samples, PCB analysis was limited to
whole water and particulate samples from Stations I and 4 only. These two
stations represented the upstream boundary condition and outflow from the
turning basin, respectively. Due to analytical constraints on PCB analysis,
this approach was continued throughout the remaining surveys. Surveys 6-10
were conducted on May 30, June 12, July 10, July 25 and August 1, 1984. On
these latter five surveys, Stations 1, 4, 26 and 29 were sampled for whole
water and dissolved metals. Only Station 1 and 4 were sampled for whole
water and particulate PCB.
4.2 TEMPORAL PROFILES, PCB
The PCB results for Surveys 5—10 (Figures and Tables 4.8 and 4.9) are
presented here as a temporal profile of concentrations at Station 1 and 4.
Concentrations In river water entering the study area at Station 1 appeared
35
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to reach a maximum of 13 ngfL in late May, and declined steadily to a season
low of 4.3-4.6 by August 1. Particulate PCB levels averaged slightly less
than half of those in whole water. In contrast, PCB concentrations at
Station 4 showed an opposite tendency to reach a minimum of 7—14 ng/L tn May
and June, and increased to a maximum value of 210 ng/L on August 1. These
trends suggest that the levels of PCBs below the turning basin may be
inversely related to concentrations upstream.
Other temporal profiles for Stations 1 and 4 (Figures 4.10 and 4.11)
represent all of the grab and composite sample data for ten surveys in
1983-84. The results for Station 1 indicate fairly consistent levels of PCB,
mostly in the range of 5—15 ng/I., during the fall and spring. The lowest
concentration of “3 ng/L occurred in early October, 1983 (Survey 3). This
was In a period of low flow (‘ ‘5 cm/sec), as were the highest concentrations
of 13 ng/L during Survey 2. At Station 4, however, the highest levels of 600
ng/L In Survey 2 at low flow were 3—fold greater than any values observed
during similar low flow conditions in Surveys 8-10. Since concentrations do
not seem well correlated to flows or upstream PCB levels, this suggests some
change in the sources of PCB in Station 4 water between fall 1983 and spring
1984. One possible influence is the maintenance dredging that occurred
during this period, or a change in external loadings to the turning basin.
A summary of PCB data from selected stations for all 10 surveys Is
shown in Table 4.20.
4.3 ORGANICS QC
Blank values have not been subtracted from the organics data, but are
presented separately here.
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Method Interference
System blanks, filter blanks and florisil blanks are reported as
the percent the blank value was of the associated sample values (Tables 4.3,
4.4, 4.5, 4.6, 4.7, 4.8, and 4.9).
Of 156 total water composite and grab samples analyzed with associated
system blanks, 85% had system blanks <10% of the total sample values, and
only 4% had system blank values in excess of 50% of the associated sample
values.
All of the system blank values exceeding 50% of the corresponding
sample values were composite samples from Survey 3.
Ninety—five percent of filtrate water samples analyzed with associated
-blanks had system blanks <10% of the total sample values while 81% of
particulate samples had filter blanks <10% of the corresponding sample
values.
Thirteen particulate samples from Survey 4 were florisil® cleaned
and thus had associated Florisil® blanks. All 13 samples had
Florisil ® blanks which were 11% of the associated sample values.
Particulate Extraction Efficiency
Four particulate samples were processed and analyzed to determine
particulate extraction efficiency. The results indicate that the extraction
was both highly efficient and reproducible (Table 3.8).
Preci sion
Results of the analysis of collocated duplicate samples are shown in
Table 3.9.
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Although one of every ten samples was collected in duplicate, due to
sample selection for analyses, instrument and processing problems, less th t
ten percent of the samples analyzed were duplicates.
The replicate analysis of PCB calibration standards for analytical
precision showed mean values within + 10% of the true concentrations (Table
3.10).
Accuracy
Instrumental accuracy was monitored by analyzing Aroclor mixtures
(Table 3.11). Aroclor mixtures 1016 and 1262 consistently showed values
higher than the true concentrations.
4.4 SPATIAL PROFILES, METALS
Results for copper, chromium and zinc, as totals and dissolved
fractions in water, are presented as a series of spatial profiles
representing the river and lake stations discussed earlier (FIgures 4.12-4.39
and Tables 4.10—4.19). The following general observations pertain to the
results of each survey.
In Survey 1 (Figures 4.12—4.14, Table 4.10), mean zinc concentrations
were particularly high at Station 7 (43.4 pg/L) and Station 9 (80.3 pg/I).
The latter represented effluent water discharged by a large automotive plant.
Copper and chromium levels (42 pg/I and 32 pg/I) were also relatively high
at Station 9. By comparison, the upstream boundary mean concentrations of
copper, chromium and zinc at Station 1 were 3.87, 1.59 and 4.14 pg/I,
respectively. The open lake values at Station 11 were still lower at 2.75,
.933 and 3.17 pg/L, respectively. Slightly elevated levels of all three
metals were also observed at Station 8 (Mason Run) and Station 10 (the auto
plant water Intake).
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In Survey 2 (Figures 4.15—4.17, Table 4.11), the zinc level at Station
7 and all three metal concentrations at Station 9 were less elevated with
respect to boundary levels. Chromium results were anomalous in that the mean
values for total and dissolved metal were the same at 14.7 iig/L and standard
deviations, however, were much greater for total chromium. Chromium levels
were also elevated (total, 4.44 pg/L) at Station 5, which represents the auto
plant outfall in the lower river.
In Survey 3 (Figures 4.18—4.20, Table 4.12), a similar distribution
pattern was seen for the main river stations. In the Monroe WWTP plume
(Stations 13-19) zinc levels declined with increasing distance from the
outfall, whereas copper and chromium levels increased slightly toward the
turning basin. The WWTP was clearly a primary source of zinc. In both
Surveys 2 and 3, bottom water at Station 4 appears to be slightly enriched
with respect to all three metals.
Survey 4 results (Figures 4.21—4.23, Table 4.13), whIch included a
river plume study In Lake Erie, indicate that chroumium levels generally
increased downstream in the river and along the lake shore within the
plume. However, lake concentrations at 4-7 pg/I were still far less than
those in Station 9 effluent. Copper and zinc levels were also about
two—fold higher in general than most river values. Zinc concentrations in
Station 7 effluent were still somewhat higher. The zinc concentration at
the power plant discharge (Station 29) In Lake Erie was notably higher (33
pg/L) than that In lake water (15 pg/L).
Survey 5 results (Figures 4.24—4.26, Table 4.14) also represent a
river plume gradient in Lake Erie, originating largely at Station 29 (power
plant outfall). The dilution gradient Is most apparent for total and
39
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dissolved copper (Figure 4.25). Station 7 was, again, a dominant source of
high zinc concentrations (32 pg/L).
In Surveys 6—10 (Figures 4.27—4.41, Tables 4.15—4.19) only four
stations were sampled for metals: Stations 1, 4 and 26 in the river, and
Station 29 near the power plant outfall. Its intake in the river was near
Station 5, the auto plant outfall. In all of these surveys, copper
concentrations were notably elevated 2 to 3—fold at Station 29 relative to
levels at the river stations. In general, zinc concentrations at Station 4
(turning basin) were not markedly higher than at Station 1 despite zinc
loadings from Station 7 (WWTP) between them. In most cases, chromium levels
were slightly higher at Station 4 than at Station 1.
4.5 TEMPORAL PROFILES, METALS
Temporal profiles for all surveys (1—10) at Station 1 (Figures
4.42-4.44) indicate that average concentrations of all three metals (except
possibly zinc) were not very different in the fall (1983) and spring (1984).
However, variability was greatly increased under high flow conditions in the
spring. Average zinc levels appear to have been somewhat higher In the
spring.
Temporal profiles for Station 4 (Figures 4.45—4.47) indicate a more
constant variability for concentrations of all three metals in the fall and
spring. In general, copper and chromium concentrations were similar at
Stations 1 and 4 throughout the year. Zinc concentrations approximately
2—fold higher at Station 4.
A summary of metals data from selected stations for all 10 surveys is
shown in Table 4.20.
40
-------
4.6 METALS QC
In the case of metals, the results of bottle, filter, and digestion
blanks analysis are already subtracted from the sample data presented here.
Detection limits for all three metals analyzed are given in Table 3.1.
Table 3.2 shows that no correction was required for the filtering
process In any of the surveys. Furthermore, since the batch blanks were
below the detection limits for all metals, bottle blanks were assumed to be
negligible for all surveys. Only filter blanks were collected In Survey 2.
These blanks were below the detection limit and, therefore, were considered
negligible.
Results of several intercomparison studies are presented in Table 3.3.
The LLRS results (actual) were compared with the QC sample data from EPA,
Cincinnati, represented by the true valuesb. The is their mean recovery.
The 95% confidence level Is their mean recovery + two standard deviations.
In both of these series, the LLRS results fell within the 95% confidence
Interval (mean recovery + two standard deviations).
No chemical interferences were found when analyzing copper and zinc,
as indicated by the recovery data (Table 3.4). The concentrations were
calculated directly from a linear regression of synthetically prepared
standard solutions. However, the analyses still Included a standard
addition determination on every fifth sample in order to monitor recovery
throughout the study. Recovery here was defined as the slope of the
standard addition calculation for a sample x 100, divided by the mean slope
of the standard addition for the standard.
In contrast, the mean recovery for dissolved and total chromium was
well above 100% (Table 3.4). This indicates interferences were present
41
-------
which enhanced the analytical signal and, therefore, standard additions was
used to determine the concentration of this metal. There was no need to
correct the reported chromium data to reflect this enhancement. This was
accomplished by calculating the concentration of each sample using the
method of standard additions.
Every tenth sample collected in the field included a duplicate, which
was processed in the same way as any other sample collected. The standard
deviation calculated for samples and their duplicates gives an estimate of
the overall precision, Including both field and Instrumental variations
(Table 3.5).
The following equation was used to calculate the standard deviation:
Standard deviation = / 2 where, d = difference between the sample
/ Ed and Its duplicate.
V
k = number of duplicates.
Ideally, the standard deviation for a set of samples and duplicates
should be the same. Three sample-duplicate data sets were created for water
samples: river, lake, and the Monroe Wastewater Treatment Plant. Table 5
shows the results. Differences between duplicates collected during a storm
event on Lake Erie during Survey IV (Table 3.6) seems to suggest that the
storm had a rather large impact on the overall variability In the samples
collected during this cruise. These samples were not included with other
Lake Erie samples because of their probable different standard deviation due
to the high solids concentrations in these samples.
Certain samples were analyzed once a day for a number of days as
ubetweenrunu replicates. The observed variability of these replicates
(Table 37) was assumed to be due to laboratory and instrumental procedures
42
-------
only. The field duplicates mentioned earlier were potentially more variable
since there was additional uncertain related to field conditions; i.e.,
bottle blanks, filtering and possible non—honiogenity of the water samples.
The standard deviations in Table 3.5 do not appear to be much higher than
the standard deviations in Table 3.7. This suggests that the variability of
our reported results for copper, zinc, and chromium was mainly due to
laboratory arid instrumental procedures.
43
-------
5.0 REFERENCES CITED
Cole, Richard A. 1978. Entrainment at a once-through cooling system on
western Lake Erie. Institute of Water Research and Departhent of
Fisheries and Wildlife — Michigan State University. EPA-600/3-78—070.
pp. 1—10.
Filkins, J.C.., M.D. Mullin, LI. Richardson, V.E. Smith, J.E. Rathbun, S.G.
Rood, ICR. Rygwelski, and T. Kipp. 1985. A report on the surficial
and vertical distribution of polychiorinated biphenyls in the sediments
of the lower River Raisin, Monroe Harbor, Michigan - 1983 and 1984.
Report to the USEPA Large Lakes Research Station, Grosse lie, Michigan.
International Joint Commission, Science Advisory Board. November 1980. A
Perspective on the Problem of Hazardous Substances In the Great Lakes
Basin Ecosystem. Great Lakes Science Advisory Board Report to the
International Joint Commission. pp. 1—70.
International Joint Commission, Toxic Substances Committee. November 1980.
First Report of the Toxic Substances Committee. Windsor, Ontario.
94 pp.
International Joint Commission, Water Quality Board. November 1983. 1983
Report on Great Lakes Water Quality. Windsor, Ontario. 97 pp.
International Joint Commission, Water Quality Board. November 1983. 1983
Annual Report of the Committee on the Assessment of Human Health
Effects of Great Lakes Water Quality. Windsor, Ontario. 34 pp.
Jones, JO. 1983. Personal communication. University of Michigan, Ann
Arbor, Michigan.
Mathews, Susan H. 1985. Bioassay methodoloqies for Monroe Harbor Project,
1983—1984. Report to the LJSEPA Large Lakes Research Station, Grosse
lie, Michigan.
Michigan Depar iient of Natural Resources, Water Quality Division, Biology
Section. 1979. River quality in the River Raisin basin. pp. 3—4.
Michigan Deparbnent of Natural Resources. 1982. Report of a municipal waste
water survey conducted at Monroe Wastewater Treatment Plant, Monroe
County, Monroe, Michigan, June 7-8, 1982. Michigan Depar nent of
Natural Resources, Environmental Protection Bureau, Point Source
Studies Section, Lansing, Michigan. 9 p.
44
-------
Michigan Deparbnent of Natural Resources. 1983. Personal communication;
memos by E. Evans (12/2/76) and D. Batchelor (5/16/78).
Michigan Deparbnent of Public Health and the Michigan Water Resources
Commission. 1969. The River Raisin basin. p. 74.
Monroe County Drain Commission. 1984. Environmental assessment — Monroe
metropolitan area. pp. 1—6.
Mount, D.I. and T.J. Norberg. 1984. A seven—day life cycle cladoceran
toxicity test. Environ. Toxicol. Chem., 3: 425-434.
Mozola, Andrew J. 1970. Geology for environmental planning in Monroe
County, Michigan — report investigation 13. Geological Survey
Division, Deparbnent of Natural Resources. pp. 1—8.
Perkin—Elmer. 1977. Analytical Methods for Atomic Absorption Spectroscopy
Using the HGA Graphite Furnace.
Petty, Steven M. 1984. Personal coninunicati on. City of Monroe.
US. Environmental Protection Agency. 1971. Methods for Chemical Analysis
of Water and Wastes. Water Quality Office, Analytical Quality Control
Laboratory. p. 88.
U.S. Environmental Protection Agency. 1975. Monroe, Michigan. Report on
the degree of pollution of bottom sediments. 1975 Harbor Sediment
Sampling Program, April 9, 1975. U.S. Environmental Protection Agency,
Region 5, Great Lakes Surveillance Branch, ChIcago. 9 p.
U.S. Environmental Protection Agency. 1976. Monroe Harbor, Michigan.
Report on the degree of pollution of bottom sediments. Sampled:
October 18, 1976. U.S. Environmental Protection Agency, Region 5,
Great Lakes Surveillance Branch, Chicago. 9 p.
U.S. Environmental Protection Agency. 1976. Quality Criteria for Water.
Washington, D.C. 501 pp.
U.S. Geological Survey. 1982. Water resources data — Michigan water year
1981. Water Data Report MI-81-1. p. 435.
45
-------
APPENDIX
RIVER RAISIN FLOW DATA DURING SURVEYS 1-10
46
-------
SURVEY I
JULY 12-17, 1983
i i i i i i I I I I 1 1 1 I 1
1 2 3 4 5 6 7 8 9 101 11213141S1G1718I 0 12e23242S2s2?2829 e3132
DAYS
C
M
100
80.
60.
40.
20.
0
-n
• -1
CD
-J
a.
CD
-1
C,
—I.
-a.
0
U,
C,
1
0
CD
0
- ‘S
-a.
v)
C
1
CD
-a
-------
SURVEY 2
SEPTEMBER 13-18,1983
I III 1111111 I I I 111111 11111111
1 2 3 4 5 6 7 8 910111213141516171819202122232425262728293031
DAYS
T1
-4 .
•1
CD
-4.
CD
-
-4.
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-J
0
z
(I - ,
.
0
CD
a-
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10
8.
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-------
SURVEY 3
OCTOBER 25—28, i 83
10.
-TI
0
1
(D
8.
-I.
CD
II I I I I I I I I I III I I I I I I I I I I I 1111
I 2 3 4 5 6 7 8 91011121314151617181920212223242S262728293031
DAYS
-------
SURVEY 4
APRiL 2—5k 1984
1 2 3 4 5 6 7 8 91 0111213141 516 17181920212223242 526V28293 03 132
lee
80
60
40
C
11
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T1
to
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DAYS
-------
SURVEY S
MAY 3—9, 1984
50.
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• -1
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40.
—J.
CD
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30.
C
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20.
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0
CD
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Io . a.
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I I I I I I
2 3 4 5 6 7 8 9 10
DAYS
-------
SURVEY 6
MAY 24—30, 1984
C
M
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100
80
60
40
20
0
-Il
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C
1
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-s
a.
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0
0
0.
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•1
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- 5
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0 .
22
26
28 30
DAYS
-------
I I I I - 1
5 6 7 8
9 10 11 12 13 14 15
SURVEY 7
JUNE 6-12, 1984
C
M
U,
50
40
30.
2@
10
0
-
‘a
CD
a.
CD
w
-S.
-I )
In
0
CD
a.
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DAYS
-------
SURUEV 8
JULY 4-10, 1984
10
‘•1
CD
cc
CD
1
6.
-1.
1
C
-,
-1
0
4_
0
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2 4 6 B 10
DAYS
-------
SURVEY 9
JULV lg-25, 1984
10
-Ti
-4
CD
8.
-4.
18 2’; 2 2 2 26
DAYS
-------
SURVEY 10
JULY 26—AUGUST 1, 1984
10 _________________________
-n
o.
C
(D
8
9
m
DAYS
-------
0
00
I. ... .......
......•••••j•••.. .....
‘ ,, ‘
Ova
0,, :: .
\ •i••• ti1 &..v cr 1 j , ,q a,r /‘
:i’ J / / / /
•CIC .0 SItIS
F j j r
. q .... —
Figure 2.1. River Raisin drainage basin. (Taken from: Water Resources - Conditions and Uses - In
the River Raisin Basin; Michigan Water Resources Comission, 1965.)
LUC*”ON 0*0
LI S *0000 00500*0 00 ,151
500* ? tI015-,tI,u00. Slob SS I. .*oasv
Ua Sta ø Vt0 5* 1 10
-------
5000.
JPN FED NRA RPA Nfl)’ JUN JUL RUG SEP OCT NOV DEC
GflGC: O’1 176 500
RIVER RAISIN
NEAR PIONRUE.
ilYr. Average flows (197040)
‘1000.
3000.
2000.
1000.
0.
IIICH.
Figure 2.2.
Raisin River 11-year average daily flow (cfs) 12 km upstream from Lake Erie (USGS data).
-------
GAGE: 04176500
PEAK FLOWS IN THOUSANDS OF CFS
Figure 2.3. Peak flows in the River Raisin at Monroe since 1938.
(Data from the U.S.G.S.)
F
R
E
Q
U
E
N
C
V
14
12
10
8
6
4
2
0
0 2 4 6 8 10 12
14
-------
1976 1977 1978
1979 1980 1981 1982 1983
YE 9
LI
A
lb
E
R
S
1’
A
C
E
F
E
E
I
C . ’
CD
574
573
572
571
570
569
568
567
Figure 2.4. Lake Erie level at gage 3087.
Data is from NOAA.
-------
Figure 2.5. The Monroe Harbor Study Area. Points A and B are reference
points for the depth profile map in Figure 6.
Lake Erie
—a
Mason Run
Turning Basin
A
-------
LAKE ERIE
Figure 2.6. River Raisin depth profiles (feet). Depths are referred to International Great Lakes Datum (1955)
for Lake Erie elevation 568.6 ft. above mean water level at Father Point, Quebec. Data from
Computer Sciences Corporation at the EPA Large Lakes Research Station, August 7, 1984.
18
-------
Figure 2.6 (Cont’d.)
3
(A)
-------
14
1R
19A
21
20A
2O
19E
13
T2 1
Figure 2.6 (Cont’d.)
-------
Consol ic’ ed
Packagir. Corp.
North Plant
Detroit Stoker
Compa fly
Union Camp
Ford Motor Company
Consolidated
Packaging Corp.
South Plant
Monroe
Wastewater
Treatment Plant
Figure 2.7.
Detroit Edison
Power Plant
a. ’
( T1
Industries in the Monroe Harbor Study Area.
-------
Figure 2.8. The P’bnroe Power Plant cooling intake and discharge.
Also shown are results of a heated effluent plume study.
(Cole, 1978).
DETROIT
RIVER
AISIN
I
‘k&’j MEt
B.&Y
66
-------
Fiq. 3.1
Stations sampled ‘
(July l 2 -i
Ing Monroe Harbor Survey 1
,, 1983).
1 •
I.
I , .
I—
.1
I.
S.
• t.
.0
WWTP
FORD
:
:
LAKE ERIE
D1 SON
-------
Fiq. 3.2. Stations sampled
(September
ing Monroe Harbor
1 -l8, 1983).
, ..... . ..
FORD
..l..
OETE O1T
Dt&ON
Survey 2
It
•t.
co
‘F
‘It
LAKE ERIE
-------
Fig. 3.3. Stations sampled ‘ 1 rinq Monroe Harbor Survey 3
(October 25 - November , 1983), includIng the
Waste Water Treatment Plume.
FORD MOTOR CO.
cø 4 o’(
DETROIT
EDISON
LAKE ERIE
116
1
-------
Fiq. 3.4a. Stations samp1 iuring Monroe Harbor Survey 4
(April 2-5, 1 , ): River stations.
FORD
LAKE ERIE
DF TROtT
•1’
1’.
-------
Fig. 3.4b.
MICHIGAN
Stations sampled
(April 2-5, 1984):
during ttnroe Harbor Survey 4
Lake Erie stations.
LAKE ERIE
S®
71
.- •1
-------
hg. i.5a. Stations samp1e’
(May 9, 198L.
FORD
I.
during Monroe Harbor
River stations.
I ,
‘ t I..
DEIPO 1T
DI OP’1
Survey 5
I .
wwTp
1 .
LAKE
ERIE
-------
Survey 5
LAKE ERIE
I I J. -.JU. Ldi1OflS sarnpiea Gurini,
( 1984); ake Er € tations.
wwTP
FORD
DETROIT
ED! SON
..,
-------
Fig. 3.6. Stations sampled during nroe Harbor Survey 6 (May 30, 1984),
Survey 7 (June 12), Survey d (July 10), Survey 9 (July 2S)
and Survey 10 (August 1).
wWTP
FORD
LAKE ERIE
DE TROll
IDt ON
-------
Figure 4.1.
grab (b)
Spatial profile of total PCB
whole water samples. Monroe
(‘See map, Figure 2.1).
a
11
in composite (a) and
Harbor, Survey 1.
I
0
c i i
2
a
03
0
V
-a
g
0
6
0 1
—
cu
w
a
0
75
-------
MH1 DISSOLVED PCB
0
0
0 0
—I
0 i
0
Vim-
5.
01 02 03 05 10
STATION
Figure 4.2. Spatial profile of total PCB In composite filtrate water samples.
Moniroe Harbor, Survey 1. (See map, FIgure 2.1).
-------
Q ccIdP t
Figure 4.3.
grab (b)
03
Spatial profile of total PCB
whole water samples. Monroe
(See map, Figure 2.2).
77
in composite (a) and
Harbor 1 Survey 2.
LJ
a
01
KEY:
2
a 54
é
01
c i
a
5’.’
11
-------
N
A
N
0
G
R
A
‘1
S
P
E
R
I
I
E
R
250
200
150
tee
50
0
Figure 4.4.
TOTA.. PCBj RIVER STATIONS
SURVEY 3j 25 OCT 85
1 3 8 45 4B 10 6 11
STATION
Spatial profile of total PCB in composite whole water and filtrate water.
Monroe Harbor, Survey 3. (See map, Figure 2.3).
-------
I I
13 *4
UIIOLI WATER TOTAL PCB Tp PLU
SURVEY 3
I I I I
15 16 17 18 19
STAT ION
KEY.
2
Figure 4.5. Spatial profile
Monroe Harbor WWTP plume,
station averages
a
of total PCB in grab whole water samples.
Survey 3; daily concentrations (a) and
(b). (See map, Figure 2.3).
5 1.
41.
30 .
20
10
N
A
N
G
p
S
P
E
R
L
I
I
£
P
26 OCT 83
27 OCT 83
28 OCT 83
kJflw flfl A
40
30
I
0
A
a
a
‘7
a
79
-------
N
A
N
0
G
R
A
P 1
S
14
12
10
8
P
o:i E
R 6
4
2
0
L
:i
T
E
R
FILTERED WATER TOTAL PCB; WWTP PLUME
SURVEY 3
STATION
Figure 4.6. Spatial profile of total PCB in grab filtrate water samples.
Monroe Harbor. Survey 3. (See map, Figure 2.3).
13 14 15 16 17 18 19
-------
TOTAL PCB
SURVEY 4
STATION
28 26 11 29
Spatial profile of total PCB in
Monroe Harbor, Survey 4.
whole water particulate grab samples.
(See map, Figure 2.4).
N
A
N
0
G
R
A
11
S
P
L
I
T
E
R
60
50
40
30
20
10
0
1 7 21 20 8 4$ 4B 2223S23B24
Figure 4.7.
-------
a.
o -
C.
-
D 0
-a,
(ups
Lfl -J
—. D
(I,
(D 0
rD (J) -
—J
a.
00
o n -.,
I_•,) -n
a. a
• 0
C
- a’
-v
• -, c_)
0
- b
a,
1
c,- -
00 .’
-i a
Co
- .a
U1 (D
I -c
0i
0.
N
A
4
0
G
R
A
P1
S
p
E
R
L
I
T
E
R
14
12
10
8
6
4
2
0
TOTAL PCB AT STATION 1
SURVEY
5 6 7 8 9
10
-------
TOTAL PCB AT STATION 4
-n
.
0)
.1-s
c CD
—I.
C D
-4
D 0
—a -5
(DOl
U) —
—S )
CD
CD & -+
. .a.
—00
T1
( ) .a. . .p
(0- 0
-S Q
-
• S C-)
00
— CD
• a.
- (0
D 5
0 a
1 D
(n-
1 -
-------
STA ON 1 TOTAL PCB 1983
14-
o 0 0
0 0
o 0
10-
_.1 0
0 0
: 0
%U AUG SEP ocr *W DEC N FEB MAR APR MAY JIWI JUL MJG SEP
MONTh
Figure 4.10. Temporal profile of total PCB in all grab and composite whole
samples at Station 1. Monroe Harbor, Surveys 1-10.
-------
STA11ON 4 TOTAL PCB 1983
0
600 o
0
cP
co
4OO
8
2OO - 0
0 o o
0
0
0•
JUL AUG SEP OCT NOV DEC JAN FEB MAR APR MAY JUN JUL AUG SEP
MONTh
Figure 4.11. Temporal profile of total PCB in all grab and composite whole water
samples at Station 4. Monroe Harbor, Surveys 1-10.
-------
1 TOTAL O POML*4
$
ao
2
I
I
I
0 -
I
EY
LaN
07
03
}
0804
SWCN
06
t
09
06
1
41 DISSOLY O-ROM’L
L5
t5’
3
I.
0 - C.
01 07 03 08 06 II
SWK o
a
Figure 4.12. Spatial
grab and composite
profile of total and dissolved
water samples. Monroe Harbor,
(See map, Figure 2.1).
chromium in
Survey 1.
86
-------
I
D SSOLVD
a
I II T
C
01 02 07 03 Oe 04 09 Of ’ 06
St&TC
Figure 4.13. Spatial profile of tQtal and dissolved copper in
grab and composite water samples. Monroe Harbor, Survey L
(See map, Figure 2.1).
87
-------
MH1T tA NC
1
KEY. ii
WR1 D SOLV ZINC
30
I’
C, ________________
WO3O804OO to’ ti
Figure 4.14. Spatial profile of total and dissolved zinc in
grab and composite water samples. Monroe Harbor, Survey 1.
(See map, Figure 2.1).
88
-------
Figure 4.15. Spatial profile of total and dissolved chromium in
grab and composite water samples. tknroe Harbor 3 Survey 2.
(See map 3 Figure 2.2).
IOtAL O1PO tJM
I
* DcsOL W c o i
40
El
Os
S4 &41
09
89
-------
TO1*
rr
40
8
KEY.
V
01
07
03
08
S4
B4
8
0
C. - . -
C l 07 03 08 Si 84 OS 05 06 11
I
Figure 4.16. Spatial profile of total and dissolved copper in
grab and composite :ater sar’ples. t bnroe Harbor, Survey 2.
(See map, Figure 2.2).
90
-------
Q TOt&L Th C
7
i jili ,1•
Figure 4.17. Spatial profile of total and dissolved zinc in
grab and composite water samples. Monroe Harbor, Survey 2.
(See map, Figure 2.2).
Sc
50
01 O7030 S4
06 11
k4- 2 DtSSc*..v Jc
S
*
0 1
07030634 R
09O5 06
91
-------
MH 3 TOTAL O1RO 4L A
0
S 30
o o
a
2-
V y.,,,Ir. u. . ..
KEY: oe
AThON
PLAN
MH3 DtSSOLY O 4 UM
1.5
1 0 5
i
0-_____________
S1A OH
Figure 4.18. Spatial profile of total and dissolved chromium in
grab and composite water samples. bnroe Harbor, Survey 3.
(See map, Figure 2.3).
92
-------
MH3 TOTh OPFER
M .
‘I
I0•
0-
ON
0
0
0
0
0
MH3 D SSO O R
0
5
00
‘p
0
I—
S
Figure 4.19. Spatial profile of total and dissolved copper in
grab and composite water samples. Monroe Harbor, Survey 3.
(See map, Figure 2.3).
93
-------
I& 3 TOTAL ZP C
c.
so
0
40•
_ 00 0O * IP ç
S ON
& 3 D1SSO1V ZPC
M I.
3O
0
. 00 000 i
d d d
Figure 4.20. Spatial profile of total and dissolved zinc In
grab and composite water samples. Monroe Harbor, Survey 3.
(See map, Figure 2.3).
94
-------
Figure 4.21. Spatial profile of total and dissolved chromium in
grab and composite water samples. Monroe Harbor, Survey 4.
(See map, Figure 2.4).
1144 TOTAL C ROhflU 4
S.
‘a
0
4.
0
0
0
0
00
2
0
0
0
0
o0
0
0.
0
0
0
4 4 4D4,9
0
ON
0 . .
k1H4 DISSOLVED CHROIUM
0
04
0
0
00
0
0
0
02
00
0
0000
0
0
0
0
0
0
95
-------
0
0
MH4 TOTAL COPPER
I D
.e.
4.
2
SrA ON
0 0
0
0
0
0
0
0
0
0
0
0
0
Oe
4 DSSOLVED COPPER
4
3.
I
0
2
0
0
0
0
0
0
0
0
0
0
1•
E
0
0
0
0
0
0
0
0
0
0
0
4 4 pA 9
SIAT)OH
Figure 4.22. Spatial profile of total and dissolved copper in
grab and composite water samples. Monroe Harbor, Survey 4.
(See rndp, Figure 2.4).
96
-------
0
h4H4 TOTAL ZINC
30•
0
0
0
0
0
0
00
0
0
0
0
0
0
0
C
0
0
0
ON
0
AH4 D SSOLVW ZINC
40
30
0-
0
0 0 0
0
0
0
0
0
0
0
0
0 0o
00
0
0
Figure 4.23. Spatial profile of total and dissolved zinc in
grab and composite water samples. Monroe Harbor, Survey 4.
(See map, Figure 2.4).
97
-------
14 - 15 TOTAL CHROh4 UM
0
0
0
0 0
0 0 000
0
0
0
dIc7O80 S2941424344 46V
1415 DISSOLVE O1 OI FLJM
0.4 0 0 0
0 0 0
5 0
02 0 0 0 0 0
o 0
0107 0 O4 11252629414243444546 V
STATOP
Figure 4.24. Spatial profile of total and dissolved chromiun ‘in
grab and composite water samples. Monroe Harbor 1 Survey 5.
(See map, Figure 2.5).
98
-------
0
Figure 4.25. Spatial profile of total and dissolved copper in
grab and composite water samples. Monroe Narbor, Survey 5.
(See map, Figure 2.5).
M 5 T t6L
0
0
0
8
0
5.
0
0
0
0
0
00
0
0
0
.0
01070804 11 2526 4ICL344d546V
STA 0 4
4
* D SOLV P R
3.
0
00
8
C
0
0
0
0
0
0
1•
o0
0
00
0
0107080411 262941 C 4344154647
99
-------
MH5 1OTAL ZJ C
0
30-
o
0
: 0 0 0 0
-E.
01 07 08 04 II 25 26 29 41 C 43 .44 46 47
STAT W
145 D SOLVED 4C
0
0
o 0
0 000 o 0
0 0 0
0
0
010708041125252941 C 4344 s 4547
1ON
Figure 4.26. Spatial profile of total and dissolved zinc in
grab and composite water samples. Monroe Harbor, Survey 5.
(See map, Figure 2.5).
100
-------
MH6 TOTAL C POP1 A
C
46 D Y D C O UP
504.
D
02
0 .0
01 04 26 29
0
0
0
Figure 4.27. Spatial profile of total and dissolved chromium in
grab and composite water samples. Monroe Harbor, Survey 6.
(See map, Figure 2.6).
101
-------
M-$6 TOTAL COPP(R
1
S AflON
a 6 D SO VED COPPER
—
0
5
Figure 4.28. Spatial profile of total and dissolved copper in
grab and composite water samples. t4Dnroe Harbor, Survey 6.
(See rriap, Figure 2.6).
102
-------
M 46 1 1rAL ic
0
0
0
0
5,
0•
01 04 26 29
STATIOH
5.
0
3.
0
C
I
0 -.
01 04 26 29
Figure 4.29. Spatial profile of total and dissolved zinc in
grab and composite water samples. bnroe Harbor, Survey 6.
(See map, Figure 2.6).
103
-------
and dissolved
Monroe Harbor,
2.6).
chromium 1n
Survey 7.
MH7 TOTAL CHRO$P&L
a
S.
4.
E
E
E
E
01
04
MH7 DSSOLVED MROh&
0
S OP4
Figure 4.30. Spatial profile of total
grab and composite water samples.
(See map, Figure
104
-------
M47 T OP R
a
r
8
0
0
01 04 26
I 47 D SOLV Oc R
5.
0
a.
8
0 0
0
1
01 0 ’ 2 6
Figure 4.31. Spatial profile of tota’ and dissolved copper in
grab and composite water samples. Monroe Harbor, Survey 7.
(See map, Figure 2.6).
105
-------
1M47 TOT4L Z 4C
C
0
C
2
C
0
01 26 29
STATION
M47 D SO 4C
7 -s
I.
0•
—1-
01 04 26 29
Figure 4.32. Spatial profile of total and dissolved zinc in
grab and composite water samples. Mnroe Harbor, Survey 7.
(See map, Figure 2.6).
106
-------
MH8 TOTAL c o iw
t5 o
0
0
I.
03
0•
01 04 26
S1* ON
0 0 0
C D
0 .00
01 04 26 29
TAr1OPI
Figure 4.33. Spatial profile of total and dissolved chromium in
grab and composite water samples. Monroe Harbor, Survey 8.
(See map, Figure 2.6).
107
-------
MHB TUT’AL OP R
ON
0
MHB D$SSOLYED cO ’tR
3
f2.
01 04 29
0
0
0
Figure 4.34. Spatial profile of total and dissolved copper in
grab and composite water samples. Monroe Harbor, Survey 8.
(See map, Figure 2.6).
108
-------
M-18 TOTAL ZPC
0
0
f 4.
2
r i
01 04 26 29
SlAl1OP4
MI48 DGSOLV ZPC
0
4 0
2
0
0
—2-
01 04 26 29
S1A O 4
Figure 4.35. Spatial profile of total and dissolved zinc in
grab and composite water samples. nroe Harbor, Survey 8.
(See map, Figure 2.6).
109
-------
M}49 TOTAL cHRo auM
3
<2
C,
I )
t.
0
0
0 0
01
0
STATiON
29
MH9 D OLV c 1Ro.Aw
5
C)
01 26 29
STATiON
Figure 4.36. Spatial
grab and composite
profile of total
water samples.
(See map, Figure
and dissolved chromium in
Monroe Harbor, Survey 9.
2.6).
110
-------
C
TOTAL COP R
V.
8
4.
0-
01 0 26 29
0
0
0
Figure 4.37. Spatial profile of total and dissolved copper in
grab and composite water samples. Monroe Harbor, Survey 9.
(See map, Figure 2.6).
111
-------
Figure 4.38. Spatial profile of total and dissolved zinc in
grab and composite water samples. ttnroe Rarbor, Survey 9.
(See map, Figure 2.6).
1.4-19 TOTAL D C
01 04
26
STA ON
29
2
1149 D1SSOLY D
I.
0
03
01
04
26
STAT N
29
112
-------
Figure 4.39. Spatial profile of tota’ and dissolved chromium in
grab and composite water samples. Monroe Harbor, Survey 10.
(See map, Figure 2.6).
bJ
Mc DGSOLYED OOI LI
0.2-
5
0
0
0.1•
0
01
04
26
st&now
29
113
-------
0
I&(X TOTAL. COPPER
8
4.
2
di
S1A1 ON
0
0
0
DGSOLYED COPPER
2
C
0
I
0
0
04
26
29
Figure 4.40. Spatial profile of total and dissolved copper in
grab and composite water samples. Monroe Harbor, Survey 10.
(See map, Figure 2.6).
114
-------
cx ICTAL ThIC
r
-j
0
C
0•
0 04 26 29
II- D SSOL W D C
A.
3. 0
I,
0•
01 04 26 29
STAT
Figure 4.41. Spatial profile of total and dissolved zinc in
grab and composite water samples. Monroe Harbor Survey 10.
(See map, Figure 2.6).
115
-------
STATION 1 TOTA.L I O41PJM
I
0
S.
L
2 0 0
0
o 0 0
0•
.U. AUG OCT NOV DEC N1 FEB MAR APR MAY .R.W4 AL AUG
1983 WONTH 1984
STAT)ON I D SS. acoMu 4
0. 5
0 o
0 0 o
0 0
0
0 0
0 0 000 00
AL AUG SEP OCT NOV DEC .W4 FEB MAP AP MAN’ A)N AlL AUG SCP
1Q MQ iT
Figure 4.42. Temporal profiles of total and dissolved chroniium at
Station 1; Monroe Harbor, Surveys 1-10.
116
-------
STAnON 1 TOTAL COP
S.
S
4.
2
0
0
C
0
0
8
o C
o 8
8
0
RM RI& Y
1983 MONTH
wjIAuc
19&
szp
STA1)ON 1 DfSS. cOP
0
5
0
0
0
0
8
2
8
0
0
0
AL AVG
0
pocT
1 3
0
0
e8
0
rte
MONTH
Figure 4.43.
APR
AY .ftJN ,U. AUG
I
SEP
Temporal profiles of total and dissolved copper at
Station 1; & nroe Harbor, Surveys 1—10.
117
-------
S
STAT1ON 1 TOTAL ZPIIC
vu
0
0 0
‘ -5
AL AUG P OCT sOS ’ 0CC JAN FEB MAR APR MAY .PJN .U.. AUG SEP
3983 MONTH 1984
2 0
0
‘ -4 -r
AL AUG &P OCT NOV
F 1
Figure 4.44. Temporal profiles of total and dissolved zinc at
Station 1; nroe Harbor, Surveys 1-10.
0
0
0
o 0
0
o 0
o o • 00
0 0
• 0 0
o o 0
5.
STATiON 1 DISS. ZINC
0
0
0
0
00
.
0
lb
0
0
0
lb
—2
0
0
MONTH
DCC JAN FEB MAR PR MAY )JN JJL AUG SCP
118
-------
STA1)ON 4 TOTAL CHROMiUM
0
a
0
o0
2 S
-J 0
0
0
000
0
o 0
a
2 0 O o& 0
r o°° 9
0
1983 MONTH 1984
STATION 4 D6SOWW CHROMIUM
Ca. .
0.4
0 0 0
o 0 0 0
• 0 0 000
0.0-0 0
0
p p p p . T P
J.L JG P OCT N 0CC JAN FEB MAR
1983 OHT)4
Figure 4.45. Temporal profiies of total and dissolved chromium
at Station 4; ftrnroe Harbor, Surveys 1—10.
119
-------
P T NOV
19R3
Figure 4.46. Temporal profiles of total ana dissolved copper
at Station 4; ftnroe Harbor 1 Surveys 1-10.
STAT)ON 4 TOTAL COPPER
STA1)ON 4 DISSOLVED COPPER
0
5
0
0
3.
0
0
0
0
2
0
0
0
AL AUG
0
0
0
0
0
AN FEB
APR
NAY JUN
1934
AL
AUG
SEP
120
-------
STATION 4 TOTAL C
C
0
o 0
: 0 00
Oo 00 0:
oo,& oo 0
8 o 0 0
0
‘ f
19 3 MOPiTH
STAT)OP1 4 DISS, Z C
0
0
0 0 0 0
40 0 0
o 0 0
2 0 0
o o 0
V
—2 -‘
.U. AUG P OCT MCW D(t .MN FEe MAR APR MAY .A) Jj_ AUG S P
MO (TH 19 .1
Figure 4.47. Temporal profiles of total and dissolved zinc at
Station 4; ?tnroe Harbor, Surveys 1-10.
121
-------
TABLE 3.1. SURVEY SAMPLING STRATEGY
Total organics
Dissolved organics
Particulate organics
= Total metals
= Dissolved metals
-J
Survey
Date
Stations
Sampled
Sample
Typec Collected
Comments
Grab
Composite
I
July 12-17, 1983
Fig. 3.1
TO,
TM, DM
TO, DO, TM, ON
No DO on StatIons 7,
8, 4 or 10
II
September 13-18
Fig. 3.2
TO,
TM, DM
TO, DO, iN, DN
Ill
Oct. 25 — Nov. 1
Fig. 3.3
TO,
DO, TM,
DM
TO, DO, iN, D I I
DO only on Stations
11, 14, 17,
A 19
IV
Apr11 2—5, 1984
Fig. 3.4
TO,
P0, TN,
I)M
Not Collected
V
May 9
Fig. 3.5
TO,
Pa, TN,
ON
Not Collected
TO and PU only from
StatIons 1 &
4
VI
May 30
Fig. 3.6
TO,
P0, TM,
D I I
IJot Collected
TO and P0 only from
Stations 1 & 4
VII
June 12
Fig. 3.6
TO,
P0, TM,
DM
Plot Collected
TO and P0 only from
Stations 1 & 4
VIII
July 10
Fig. 3.6
TO,
P0, TN,
OM
Plot Collected
TO and P0 only from
Stations 1 & 4
IX
July 25
Fig. 3.6
TO,
PD, TM,
DM
Not Collected
TO and P0 only from
Stations 1 & 4
X
August 1
Fig. 3.6
10,
P0, 114,
D I I
Not Collected
TO and P0 only from
StatIons 1 & 4
TO
DO
P0
N
DM
-------
TABLE 3.2. STATION DESCRIPTIONS
Station No. Description
1 Farthest upstream; by Winchester Road Bridge
2 Off of connercial marina
3 Off of WWTP outfall
4 At downstream edge of turning basin
S Of I of Ford Motor Company outfall
6 Just off of river mouth
7 WbITP; post—chlorination well
8 Tributary; Mason Run
9 Ford Motor Company outfall; just after settling lagoon
10 Ford Motor Company intake, of Lake Erie water
11 Lake Erie
12 Control site for biological projects; not reported here
13 WWTP plume staticrn; Survey II ! only
14 WWTP plume station; Survey III only
15 WWTP plume station; Survey III only
16 WTP plume station; Survey I I I only
17 WWTP plume station; Survey III only
18 WWTP plume station; Survey III only
19 WWTP plume station; Survey HI only
20 Upstream of tributary; Mason Run; Survey IV only
21 Between WVTP and turning basin; Survey IV only
22 Between turning basin and Detroit Edison intake, Survey IV only
23 Between turning basin and Detroit Edison intake, Survey IV only
24 Detroit Edison intake; Survey IV only
25 Monroe City drinking water intake
26 River mouth
28 Between Detroit Edison Intake and river mouth
29 Detro It Edison discharge canal
30 Nearshore Lake Erie; Survey IV only
31 Nearshore Lake Erie; Survey IV only
32 Nearshore Lake Erie; Survey I I ’ only
33 Nearshore Lake Erie; Survey IV only
34 Nearshore Lake Erie; Survey IV only
35 Nearshore Lake Erie; Survey IV only
36 Plearshore Lake Erie; Survey IV only
37 Nearshore Lake Erie; Survey IV only
38 Pdearshore Lake Erie; Survey IV only
39 ToxicIty test control water; Port Huron pump station
40 Toxicity test control water; Reconstituted water
4) Nearshore Lake Erie; Survey V only
42 Pdearshore Lake Erie; Survey V only
43 Nearshore Lake Erie; Survey V only
44 Nearshore Lake Erie; Survey V only
45 t4earshore Lake Erie; Survey V only
46 Nearshore Lake Erie; Survey V only
47 Nearshore Lake Erie; Survey V only
123
-------
TABLE 3.3. DETECTION LIMITS — METALS
Detection Limit (pg/I) Analytical
.25 Perkf n-Elmer 460
Absorption using
.31 Perkin-Elner 460
Absorption using
4 PerkI n—Elmer 603
Absorpti on
Metal
Chromi urn
Copper
Zinc
Method
flameless Atomic
50 iL
Flameless Atomic
50 pL
Flame Atomic
124
-------
TABLE 3.4. MONROE HARBOR STUDIES SAMPLE BLANKS - METALS
(Note: B.B. = Batch Blank and F.B. = Filter Blank)
Metal
Monroe
Harbor
Survey
#
No. Samples
(B.B., F.B.)
Mean pg/L
(B.B., F.B.)
Standard
Deviation
pg/L
(B.B., F.B.)
T—Test
Result
Copper
Copper
Copper
Copper
Copper
Copper
1
2
3
[ 4,5,6]
[ 9, X l
[ Z]
[ 12, 12)
[ 18, 17)
[ 8, 8]
[ 9, 9)
[ 3, 3]
[ —, 4]
[ W.16, .72]
ET.31, 1.31]
[ W.16, T.31]
[ W.16, T.31]
[ T.31, T.31)
[ —, W.16]
[ T.31, 1.02]
[ .44, .51]
[ W.l6, W.16]
[ .59, .60]
[ .45, .36]
[ —, W.16]
*Salpe
Same
Same
Same
Same
Same
Chromium
Chromium
Chromium
Chromium
Chromium
Chromium
1
2
3
[ 4,5,6)
[ 9, XJ
EZ]
[ 11, 12]
[ 18, 18)
[ 8, 8]
[ 9, 9]
[ 3, 3]
[ —, 4]
[ W.12, W.12]
[ W.12, W.12]
[ W.l2, W.12]
[ 11.12, W.12]
[ 11.12, 11.12]
[ —, 11.12]
[ W.12, W.l2]
[ 1.25, W.12]
[ W.l2, 11.12]
[ 11.12, 11.12]
[ 11.12, 11.12]
1—, 11.12]
Same
Same
Same
Same
Same
Same
Zinc
Zinc
Zinc
Zinc
Zinc
Zinc
1
3
5
[ 4,5,6)
[ 9, X)
[ Z]
[ 12, 12]
[ 18, 18]
[ 8, 8]
[ 9, 9)
[ 3, 3]
1—, 4]
[ 112, 112]
[ 112, 112]
[ 112, 112]
[ 112, 112)
[ 112, 112]
[ —, 112]
[ 112, 112]
tW2, 112]
[ T4, 112]
[ 14, 14]
[ 112, 112]
1—, 112]
Same
Same
Same
Same
Same
Same
*At the 95% confidence level, the mean batch blanks and filter blanks were
equal; therefore, no blank correction was needed for the filtering process.
Results less than the detection limit but greater than or equal to half the
detection limit are preceded by UTW. The detection limit follows the UTU.
Results less than half the detection limit are preceded by a UWD. One-half the
detection limit follows the .11”.
125
-------
TABLE 3.5. INTERCOMPARISON WITH IJSEPA ENVIRONMENTAL MONITORING
AND SUPPORT LABORATORY, CINCINNATI
(Concentrations In pg/L)
Mean
Measured Mean
Recovery
Recovery
QC True
+ 2 Standard
Theviations
LIPS
Reported by
EPA
Value
(95%
Metal :Series
Result
X
(Designed)
Level)
Copper: WP475 (#4)
11
11.3
11
6.1
16.5
Copper: WP475 (#6)
328
346
350
—
311 - 381
Chromium: WP475 (#6)
234
242
250
196
288
Chromium: WP475 (#4)
10
10.2
10
-
Chromium: WS378 (#2)
19
18.2
18
— 12.4
(15.1
Chromium: WS378 (#13)
50
46.0
46
-
(38.9 - 53.1)
Zinc: WP475 (#4)
13
17.1
16
9.7
24.5
Zinc: WP475 (#6)
393
396
400
—
352 - 440
126
-------
TABLE 3.6. PERCENT RECOVERIES CALCULATED FROM STANDARD ADDITIONS ON
SAMPLES FROM THE MONROE HARBOR STUDY
Metal
Number of
Samples
Mean
Percent
Recovery
Standard
Deviation
Dissolved Copper
87
101
28
Total Copper
127
108
27
Dissolved Zinc
89
104
22
Total Zinc
139
104
14
Dissolved Chrcii ium
357
139
20
Total Chromium
127
-------
TABLE 3.7. RESULTS OF FIELD DUPLICATES, MONROE HARBOR STUDY,
1983-1984
WWTP Samples
River Samples Lake Samples ( Station 7 )
Number Standard Number Standard Number Standard
Metal of Deviation of Deviation of Deviation
Pairs ( igfL) Pairs (pg/L) Pairs (pgfL)
Dissolved Zinc
16
3
—
-
4
1
Total Zinc
15
3
4
3
—
—
Dissolved Chromium
12
.05
5
.13
5
.60
Total Chromium
15
.34
4
.20
4
.14
Dissolved Copper
9
.36
4
.26
—
—
Total Copper
11
.47
-
—
—
-
Detection Limits ( .igIL), Zinc = 4, ChromIum = .25, Copper =
.31
TABLE 3.8. VARIATION OF DUPLICATES FROM LAKE
ERIE DURING
STORM CONDITIONS (SURVEY IV)
Metal
Station 35
Station 38
— C 1 )
( g/L)
- C 2 )
(pg/L)
Dissolved ZInc
8
1
Total Zinc
3
15
Dissolved Chromium
.03
.08
Total Chromium
3.6
1.5
Dissolved Copper
1.1
2,1
Total Copper
-
—
*f 1 is the first measur nent
C 2 is the second measurBnent
128
-------
Sample Name*
Source
Chr nium (pg/I)
Copper (ugh.)
Zinc (pgfL)
Plumber, Mean,
Standard Deviation
Number, Mean,
Standard Deviation
Number, Mean,
Standard Deviation
MHQCTOO1
MHQCTOO2
MFIQCTOO3
River Raisin Water
(Total)
Monroe WTP
(Total)
Nearshore Lake Erie
(Total)
6, 2.0, .32
4, 2.2, .58
7, 2.3, .58
7, 3.8, .96
4, 9.6, 1.60
6, 4.4, .79
7, 5, 4
4, 41, 2
6, 10, 6
MHQCDOO I
MHQC0002
River Raisin Water
(Dissolved)
Monroe WWTP
(Dissolved)
3, .27, .09
3, .19, .10
-
—
4, 2, 4
-
*These samples were composites of samples and were prepared in the laboratory for Q.C. purposes
only.
TABLE 3.9. MONROE HARBOR BETWEEN RUN SAMPLE REPLICATES
-J
to
-------
TABLE 3.10. EXTRACTION EFFICIENCY OF PARTICULATE FILTERS
SAJIPLE ID.
1ST EXTRACTION
(ngfL)
2ND EXTRACTION
(ng/L)
% EFFICIENCY
MH4006PTS4N1
MH4OO6PTS4N2
PIH4007PTB4N1
MH4 009PT26N 1
9.8
11
14
17
1.3
0.15
020
0.34
88
99
99
98
1 30
-------
TABLE 3.11. DUPLICATE SAMPLE ANALYSIS
SURVEY
SAMPLE 1.0.
TOTAL PCB (ngfL)
STANDARD
DEVIATION
(ng/L)
COEFFICIENT
OF
VARIATION
MEAN
RANGE
1
MH1OO2’ 1TO1C1
MH 1O13WTO4C1
MK1 51 9WTO8C1
12
34.5
310
11—13
32—37
300-320
1.4
3.9
0.98
0.12
0.11
0.0034
2
MH2002WTO1C1
PIH2O16WTS4C1
MH2O1 7WTB4C1
MH2O31WTO6C1
MH2O87WTS4N1
MH2O88WTB4N1
11
255
325
32
545
300
10—12
250-260
310-340
24—40
460-630
270-330
1.2
10
22
11
1 20
47
0.11
0.04
0.068
0.35
0.21
0.16
3
MH3002WTO3C1
MH3002WFO3C1
MH3009WTO3N1
MH3O2OWFO1N1
MH3O42WT15NI
15.5
13.5
4.35
3.35
4.0
9-22
11-16
4.2-4.5
3.1—3.6
3.8-4.2
9.1
3.7
0.19
0.36
0.27
0.59
0.28
0.043
0.11
0.068
4
MH4006WTS4N1
MH4006PTS4N1
16
10.4
13-19
9.8-11
4. 2
0.7
0.27
0.068
8
MH8 0 02WTO4N1
MH8002PT O4N1
85
70.5
50-1 20
63-78
48
79
0.57
0.16
10
MHXOD1WT O1N1
4.45
4.3—4.6
0.19
0.042
131
-------
TABLE 3.12. REPLICATE ANALYSIS OF PCB QC STANDARDS
True Standard Coefficient
Concentration Mean Range Deviation of
Number (ng/nL) (ng/mL) (ng/mL) (ngfmL) Variation
6
107.6
HO
100-120
8.2
0.076
22
245
240
160-300
31
0.13
3
258.3
240
220-260
23
0.093
58
270
250
190-300
27
0.11
TABLE 3.13. REPLICATE ANALYSIS OF AROCLOR MIXTURES
Aroclor
Mixture
Number
True
Concentration
(rig/mL)
Mean
(ng/mL)
Range
(ngfmL)
Standard
Deviation
(ng/mL)
Coefficient
of
Variation
1221
12
129.6
130
86-160
26
0.20
1016
6
26.2
29
27-31
1.6
0.055
1016
3
63.0
78
76-81
3
0.038
1254
8
16.2
15
14—17
1.3
0.086
1254
11
43.2
45
39—58
6.3
0.14
1262
10
36.8
54
42-78
11
.-
0.20
1 32
-------
TABLE 4.1. TOTAL PCB IN COMPOSITE AND GRAB WHOLE WATER SAMPLES,
MONROE HARBOR, SURVEY 1
OAT(
-
AT
N V
pp
It
F
SNIP1.E NIM EPS
1
2
7
3
8
4
9
10
5 —
6
11
J
012
L
Total PCB ny/I
C
T
11/13
5.2
6.6
86
35
64
6.0
7•a
USyitem Blank
T
T-1f( -I
T- J
1—)
[ -J
(-1
t—)
1-1
-‘
.1
U 13
I
V
Total PCB ng/L
C
•1 —
8.3
3.T
7.4
3.3
34
31
5.)
B.T
80
140
32/37
7
67
U
14
P.c
Systein WIenl
T
r—
(-)
(2)
T41
1—)
(3)
(0)
T3)
1—)
10)
(11
UJ1(TJ
( J
U)
f—)
(11
(1)
J
(ff14
1
‘
Total PCB ngft
C
12
11
13
96
20
66
76
T
T .R
1 Sy3tem STank
T
i
C
(zj
[ 3)
-
—ru ;
3
u
(37]
U I!
(1)
J
U 15
I
V
—
Total PCB ny/L
12
1.
19
71
71
14
1
6.U
7.4
8.7
7 I
74
c i i
v i
O 7
5ystemBTank
T
[ 71)
J41}
1-)
(7)
(-)
1’,
r
T}
3)
(1)
(ii
ti)
1)
jnj
nj
J Total PC8 ny/I C
U16
I ‘ystem Blani r
V
T0TA1 PCB ICIG)
MEAN + S.D. 4RANGE)
7.3
1.7
8.6
320/100
210
60
4.7
) l .7
(4)
-
(o)_
1—)f -)
(a)
1 (J)
171
nn
9.3+3.2
13.1:13)
—
1.0+7.6
(3.311)
34
8.9+2.0
(5.1-13)
141+103
(7 3?O)
51+66
(20710)
67.10
(44:71)
11+6. I
(4:26)
4.7
-a
C • Co pos1te Sample
C • Grab Sample
-------
-J
(.J
TABLE 4.2. TOTAL PCB IN COMPOSITE FILTRATE WATER SAMPLES,
MONROE HARBOR, SURVEY 1
DATE
STATIO) NIN8ERS
1
2
7
3
8
4
9
10
5
H
J
U 12
I-
Y
Total PCB ng/L
23
22
19
20
16
16
11
1 Systa. Blank
(5)
(5)
(6)
(3)
(1)
(2)
(5)
J
1113
I
Y
Total PCB mg/I
6.3
11
% Systetn Blank
(- )
(4)
-------
-I
U,
TABLE 4.3.
TOTAL PCB IN COMPOSITE AND GRAB WHOLE WATER S1 MPLES,
MONROE HARBOR, SURVEY 2
DATE
-
AT
N V
pp
LE
E
STATION NtM 1(RS
1
7
3
8
S4
84
9
10
5
6
11
S
E 13
P
T
Total PC8 ng/L
C
10/12
100
340
450
280
160
10
730
-
470
67
40
78
5 5ystem Blank
T—
T
C
j 7)f(5 )
(3)
(7F
iiF
11)
(1)
in
ni
111
r
u i
S
[ 14
P
r
Total PCB ng/L
12
170
290
510
170
70
17
740
7 1 )
5Syste. Blank
(26)
181
(1)
(51
(4)
(31
(171
(1)
______
(31
S
( 15
P
r
Total PCB ng/L.
C
10
130
210
250/260
340/110
62
41
.9
460
210
170
‘110
71
5 Syst Blank
T
T
J301
[ 4f ”
(6)
uT
(OL
T61J14T
(3)/(3 )
( f l
( 1 ) 1
(3)
117)
IV
ill
S
E 16
P
T
Total PCO ngfL
C
8.2
60
410
130
3 0
57
21
IW
44
S S ste Blent
T•
(8)
( lT
(0)
______
(7 )
(1)
(0)
(11
171
S
E 17
P
T
Total PCB ng/L
C
5.0
68
590
240
55
24/40
460f630
270/330
74
4?
5 System Blank
T
1
(12)
115F
(0)
(0)
11)f10) ,
(0)
(0)/Fof
(7)
r . 1—
[ TI/TO)
(S 1
TOTAL PCB (CIG)
MEAJI • S.D. (RNdGE)
10+2.5
(6’’ 12)
112+75
(60:240)
407+181
(21U-730)
388.179
(130:630)
293.40
(170:470)
82+36
3 .lfl
111:44)
37+11
(20:441
C • Composite Sample
G • Grab Sample
-------
Filtrate/Whole
PCB
TABLE 44. TOTAL PCB IN COMPOSITE WHOLE (A) AND FILTRATE (B),
MONROE HARBOR, OCTOBER 25, SURVE? 3
(A)
-J
STATION NUMBERS
1
3
-
8
4S
4B
10
6
11
Total PCB ng/L
11
22/9
—
220
140
—
17
220
% System Blank
(140)
(85/118)
—
(17)
(18)
—
(77)
(20)
(B)
STATION NUMBERS
1
3
8
4S
4B
10
6
11
Total PCB ng/L
6.3
16/11
56
110
73
21
6.3
9.2
% System Blank
(0)
(0) 1(0)
(7)
(0)
(0)
(9)
(6)
(22)
0.57
0.73/1.22
0.52
0.52
0.37
0.44
-------
TABLE 4.5. TOTAL PCB IN GRAB WHOLE WATER SAMPLES,
MONROE HARBOR, WWTP PLUME, SURVEY 3
—I
DATE
STATION NUMBERS
13
14
15
16
17
18
19
0
C 26
T
Total PCB ng/L
—
6
6
5.6
4.7
6.2
17
% System Blank
—
(11)
(8)
(5)
(9)
(3)
(1)
0
C 27
T
Total PCB ng/L
—
46
4
7.7
8.3
8.4
7.8
System Blank
-
—
—
0
C 28
T
Total PCB ng/L
23
2.1
3.8/4.2
3.7
8.5
4.2
48
% System Blank
(1)
(0)
(6)1(11)
(4)
(1)
(1)
(5)
Total PCB
23
18+24
(2.146)
4.5+1.0
(3. —4)
5.7+2.0
(3.17.7)
7.2+2.1
(4.78.5)
6.3+2.1
(4.28.4)
24.3+71
(7.848)
-------
TABLE 4.6. TOTAL PCB IN GRAB FILTRATE WATER SAMPLES,
MONROE HARBOR, WWTP PLUME, SURVEY 3
DATE
STATION NUMBERS
13
14
15
16
17
18
1
0
C 26
T
Total PCB ng/L
-
6.2
-
-
2.2
—
3.6
% System Blank
—
.
(6)
—
—
(5)
—
(4)
0
C 27
T
Total PCB ng/L
-
4.4
-
-
14
—
10
% System Blank
-
(6)
—
—
(10)
—
(4)
0
C 28
T
Total PCB ngfL
-
6.6
—
—
2.7
—
9.3
% System Blank
—
(1)
—
—
(5)
—
(4)
Total PCB
5.7+1.2
6.3+6.7
7.6+3.5
(4.46.6)
(2.2’14)
(3.6’lO)
-------
-J
0
TABLE 4.7. TOTAL PCB IN GRAB WHOLE WATER (A) AND PARTICULATE (B) SAMPLES,
MONROE HARBOR, SURVEY 4
(A)
STATION NU nFRS
1
7
21
20
8
45
48_ 2?
225
?3
24
?R
?
11
Total PCB ng/L
12
8.9
12
14
19
19/13
26
21
2
3)
17
—
A
1A
1
1Apr11 I. 1984)
% System Blank
—
(11)
(5)
(8)
(1)
(31/—
(2)
(0)
(3)
(2)
—
—
(3)
(41
(1)
(3).
% Florisli blank.
(B)
STATION NtIMBtRS
1 7
21
20
8
45
48
22
225
238
24
28
26
II
?Q
Total PCB ng/L
4.1
4.1
5.3
36
13
9.8/11
14
26
17
28
22
17
17
11
2Q
(April 4, 1984)
S System Blank
(6)
(6)
-
(2)
(4)
(2)/(3)
(2)
-
-
—
—
-
(1)
-
-
S FlorisIl
(9)
(6)
(11)
(3)
(6)
—/—
—
(6)
(6)
(6)
(c)
( )
(4)
(7)
( )
Blank
Partlculate/—
0.34 0.46 0.44
2.57
0.68 0. 2/-
0.54
0.51
0.68
0.00
1.29
—
2.1
0.61
1 .l
Whole PCH
0.85
-------
TABLE 4.8. TOTAL PCB IN GRAB WHOLE WATER (A) AND
PARTICULATE (B) SAMPLES AT STATION 1,
MONROE HARBOR, SURVEYS 5-10
(3)
(7)
—
(8)1(6)
STATION
1
SURVEY
5
6
7
8
9
10
A
Total PCB ng/L
5.9
13
8.4
6.9
4.9
4.6/4.3
% System Blank
(3)
(6)
(6)
(6)
(13)
(28)/(10)
B
Total PCB ng/L
1.8
8.4
2.7
2.4
—
-
% System Blank
(29)
(14)
(20)
(3)
—
—
TABLE 4.9. TOTAL PCB IN GRAB WHOLE WATER
PARTICULATE (B) SAMPLES AT STATION
MONROE HARBOR, SURVEYS 5-10
(A) AND
4,
STATION
4
SURVEY
5
6
7
8
9
10
A
Total PCB ng/L
110
14
6.7
120/50
93
210
% System Blank
(1)
(3)
(8)
(3)1(5)
(3)
(1)
B
Total PCB ng/L 110
% System Blank
63/78
72
140
-------
TABLE 4.10. SPATIAL PROFILES OF 0 OLVED AND TOTAL METALS (pg/L), SURVEY 1
STATION
COPPER
CHROMIUM
ZIPU
DISSOLVED
TOTAL
DISSOLVED
TOTAL
DISSOLVED
TOTAL
1 2.26 + 0.225 3.87 + 0.783 0.221 + 0.057 1.59 + 0.488 2.36 + 1.18 4.14 + 3.98
(2.00 2.55) (2.90: 5.20) (0.15: 0.30) (0.9: 2.4) (1.0: 4.0) (-2.0: 11.0)
2 2.87 + 1.44 3.56 + 0.614 0.200 + 0.082 1.24 + 0,35 2.71 + 1.11 4.37 + 6eSfl
(1.80:5.50) (2.70—4.30) (0.1:0.3) (0.6:1.8) (1.0: 4.0) (—3.0:13.0)
7 4.12 + 0.564 7.46 + 5.94 0.407 + 0.084 2.36 + 2.09 22.6 + 7.14 43.4 + 15.7
(3.60: 5.30) (2.10 21.20) (0.3: 0.5) (0.7:6.8) (14.0: 38.0) (27.0: 75.5)
3 2.15 + 0.176 3.83 + 1.04 0.183 + 0.117 1.63 + 0.596 3.83 + 2.14 3.86 + 8.21
(2.00 — 2.40) (2.70 — 5.60) (0.1 — 0.4) (0.8 — 2.3) (0.0 — 6.0) (—12.0 — 15.0)
8 3.28 + 1.26 6.66 + 2.46 0.264 + 0.103 3.24 + 0.78 1.21 + 1.78 8.63 + 7.85
(2.10: 5.55) (4.50 12. 30) (0.1 0.4) (2.1 4.25) 1—1.0 4.0) ( 1.0: 26.0)
4 3.27 + 1.43 4.03 + 0.918 0.186 + 0.204 1.96 + 0.793 3.29 + 1.25 4.37 + 5.34
(2.00 5.60) (2.60: 5.40) (0.0: 0.6) (0.95 3.30) (1.0: 5.0) (—5.0: 12.0)
9 14.6 + 5.28 42.0 + 21.0 15.2 + 9.97 32.0 + 21.3 16.0 + 5.16 80.3 + 75.2
(8.9 — 21.6) (18.5 — 72.2) (7.2 — 29.7) (10.0 — 60.2) (6.0 — 23.0) (31.0 — 2c1.0)
5 2.54 + 1.24 5.36 + 1.56 0.736 + 0.673 2.76 + 1.16 1.57 + 1.27 5.81 + 5.69
(1.3:5.1) (3.6:8.6) (0.2: 2.15) (1.5:4.45) (—1.0 3.0) (_2.5:15.O)
10 1.93 + 0.55 6.33 + 0.595 0.129 + 0.076 3.89 + 1.11 1.14 + 2.41 13.9 + 753
(1.5:3.1) (5.5:7.1) (0.0: 0.2) (2.7:6.4) (_1.O : s.O) (7.0: 28.0)
6 1.83 + 0.294 334 + 0.866 0.25 + 0.187 1.19 + 0.441 2.50 + 1.05 3.43 + 6.90
(1.52.3) (2.34.9) (O.O 0.5) (O.61.8) (1.O4.O) (—9.O11.O)
11 2.33 + 0.263 2.75 + 1.17 0.10 + 0.00 0.933 + 0.423 025 + 1.26 3.17 + 2.32
(2.1 2.6) (1.0 4.2) (0.10 0.10) (0.5:1.7) (—1.0 2.0) (0.0: 7.0)
-------
TABLE 4.11. SPATIAL PROFILES OF DI )LVED AND TOTAL METALS (pg/I), SURVEY 2
STATIO 1I
COPPER
CHROMIUM
ZINC
DISSOLVED
TOTAL
DISSOLVED
TOTAL
DISSOLVED
TOTAL
1 2.31 + 1.46 4.23 + 1.67 0.093 + 0.148 1.64 + 0.415 0.786 + 2.16 6.07 + 1.92
(1.5 5.6) (2.5= 7.6) (0,0 0.4) (1.2: 2.2) (-.2.0= 5.0) (3.0 9.0)
7 3.14 + 2.07 4.71 + 2.18 0.80 + 0.373 0.533 + 0.225 20.4 + 2.87 77,7 + 3.27
(1.36.7) (2.95 —8.80) (0.3:1.35) (0.3:0.9) (16.0: 23.0) (2?.o : 31.0)
3 1.88 + 0.343 3.77 + 0.476 0.167 + 0.103 1.45 + 0.493 1.33 + 3.33 9.17 + 1.72
(1.22.1) (3.24.5) (0.1: 0.3) (1.0:2.4) (-.3.0:7.0) (6.0:11.0)
8 2.07 + 0.632 7.80 + 2.05 0.343 + 0.151 2.67 + 0.582 1.86 + 1.86 10.0 + 1.15
(1.2 — 3.0) (5.4 — 10.8) (0.2 — 0.6) (2.0 — 3.8) (—1.0 — 5.0) (8.0 — 11.0)
S4 1.74 + 0.327 4.13 + 0.575 0.068 + 0.149 2.01 + 0.477 1.63 + 2.26 8.63 + 2.26
(1.2 — 2.25) (3.5 — 5.3) (—0.1 — 0.3) (1.55 — 2.8) (—2.0 — 5.0) (4.0 — 11.0)
84 1.59 + 0.543 4.64 + 0.748 0.1 + 0.131 2.35 + 0.878 1.06 + 1.94 9.50 + 1.93
(1.1 : 2.8) (3.45 5.7) (0.0: 0.4) (1.1 3.5) (-.1.0: 4.0) (6.0 :13.0)
9 9.99 + 2.18 32.2 + 15.3 14.7 + 9.03 14.7 + 18,5 17.6 + 4.31 41.6 + 6.9
(6.4: 12.7) (18.3 54.8) (6.5 32.7) (0.0: 50.6) (12.0: 24.0) (31.0: 53.0)
5 2.17 + 0.894 7.51 + 4.20 1.04 + 0.439 4.44 + 1.54 1.71 + 2.81 11.4 + 4.04
(1.0: 3.7) (4.0:15.3) (0.3: 1.6) (2.2:6.0) ( 3.0: 4.0) (0.0: 20.0)
1.66 + 0.484 6.28 + 1.66 0.763 + 0.288 2.21 + 1.31 2.5 + 2.0 8.25 + 2.cS
(1.1 2.4) (4.3 8.8) (0.0: 0.8) (0.0:4.1) (0.0: 6.0) (5.0: 13.0)
6 1.24 + 0.207 4.49 + 2.71 0.019 + 0.092 2.14 + 1.29 0.00 + 2.20 8.75 + 2.95
(0.9 1.6) (1.6 10.5) (-0.1 0.2) (0.8:4.8) (—3.0 3.0) (6.0: 14.0)
11 1.70 + 0.678 2.73 + 0.955 0.15 + 0.058 2.04 + 1.42 -0,5 + 1.73 7.0 + 1.87
(1.2: 2.7) (2.1 4.4) (0.1 0.2) (1.0:4.5) (—2.0 2.0) (5.0 9.0)
-------
TABLE 4.12. SPATIAL PROFILES OF ISSOLVED AND TOTAL METALS ( .igfL) SURVEY 3
2.63 + 0.812
(1.6: 37)
1.16 + 0.743
(0.6 2.2)
1.43 + 0.106
(1.35 1.50)
1.94 + 1.24
(1.0: 3.7)
1.0 + 0.0
(1.0=1.0)
0.9 + 0.0
(0.9 0.9)
18.5 + 0.0
(18.5 18.5)
1.4 + 0.0
(1.4 1.4)
0.6 + 0.0
(0.6 0.6)
0.8 + 0.0
(0.8 0.8)
2.7 + 1.79
(1.1 •:
2.99 + 0.986
(1.9: 4.2)
7.01 + 4.10
(3.7 — 12.2)
3.08 + 0.106
(3.0: 3.15)
9.18 + 3.32
(6.0 :• 14.5)
2.5 + 0.0
(2.5: 2.5)
3.7 + 0.0
(3.7 3.7)
39.6 + 0.0
(39.6 : 39.6)
5.8 + 0.0
(5.8 5.8)
8.3+ 0.0
(8.3: 8.3)
3.1 + 0.0
(3.1 3.1)
2.08 + 1.16
(0.8 3.6)
0.35 + 0.278
(0.0: 0.75)
0.15 + 0.058
(01 0.2)
0.325 + 0.177
(0.2: 0.45)
0.16 + 0.182
(0.0: 0.4)
0.0 + 0.0
(0.0 0.0)
-0.1 + 0.0
(-0.1 •: -0.1)
20.0 + 0.0
(20.0 20.0)
1.0 + 0.0
(1.0 1.01
0.1 + 0.0
(0.1 0.1)
0.1 + 0.0
(0.1 0.1)
0.1 + 0.082
(0.0: 0.2)
1.64 + 0.351
(1.3:2.2)
1.44 + 0.095
(1.3 — 1.5)
1.73 + 0.241
(1.55:1.90)
5.42 + 1.72
(3.5:7.6)
2.9 + 0.0
(2.9: 2.9)
3.4 + 0.0
(3 4: 34)
38.9 + 0.0
(20.0: 20.0)
3.8 + 0.0
(3.8 3.8)
3.8 + 0.0
(3.8: 3.8)
2.9 + 0.0
(2.9 2.9)
2.7 + 1.51
(1.3:4.7)
1.7 + 0.447
(1.0: 2.0)
32.9 + 2.78
(29.0 :
3.25 + 2.47
(1.5 5.0)
3.0 + 2.45
(0.0: 6.0)
2.0 + 0.0
(2.0 2.0)
-2.0 + 0.0
(—2.0 -2.0)
25.0 + 0.0
(25.0 25.0)
2.0 + 0.0
(2.0:2.0)
1.0 + 0.0
(1.0: 1.0)
2.0 + 0.0
(2.0 2.0)
3.25 + 1.26
(2.0 5.0)
5.2 + 1.3
(3.0 ‘: 6.0)
59.0 + 18.1
(48.0 86.0)
8.75 + 0.354
(8.5 9.0)
17.2 + 2.77
(14.0:21.0)
10.0 + 0.0
(10.0 10.0)
12 + 0.0
(12 :• 1?)
48.0 + 0.0
(48.0 48.0)
16.0 + 0.0
(16.0: 16.0)
12.0 + 0.0
(12.0: 12.01
17.0 + 0.0
(1?.0 12.0)
10.8 + 9.54
(4.0 - 25.0)
STATION
COPPER
CHROMIUM
7 INC
DISSOLVED
TOTAL
DISSOLVED
TOTAL
DISSOLVED
TOTAL
-J
1
7
3
8
S4
9
5
10
6
11
-------
TABLE 4.12 (CONT’D)
STATION
COPPER
CHROMIUM
ZINC
DISSOLVED
TOTAL
DISSOLVED
TOTAL
DISSOLVED
TOTAL
13 1.03 + 0.153 3.13 + 1.32 0.233 + 0.058 1.17 + 0.153 25.0 + 3.61 38.7 + 1.53
(0.9 1.2) (1.7 4.3) (0.2 0.3) (1.0=1.3) (22.0= 29.0) (37.0: 40.0)
14 2.23 + 0.321 3.83 + 2.58 0.333 + 0.153 1.73 + 0.321 867 + 321 15.7 + 6.51
(2.0 2.6) (2.1 — 6.8) (0.2 0,5) (1.5: 2.1) (5.0 11.0) (p .0 22.0)
15 2.18 + 0.077 2.8 + 0.624 0.367 + 0.252 1.7 + 0.1 6.5 + 1.8 11.5 + 1.37
(2.1 — 2.25) (2.1 — 3.3) (0.1 — 0.6) (1.6 — 1.8) (4.5 — 8.0) (10.5 — 13.0)
16 4.23 + 3.00 3.27 + 0.814 0.533 + 0.551 1.73 + 0.586 7.33 + 6.56 13.0 + 3.0
(2.4 = 7.7) (2.7: 4.2) (0.0: 1.1) (1.3: 2.4) (3.0 : 15.0) (10.0: 16.0)
17 2.7 + 0.781 4,9 + 1.92 0.467 + 0.404 2.3 + 0.52 4.67 + 1.53 74.0 + 1.0
-p (2.2 : 3.6) (3.6: 7.1) (0.1 0.9) (1.7= 2.6) (3.0 6.0) (13.0= 15.0)
18 2.23 + 0.058 3.2 + 1.04 0.467 + 0.503 2.13 + 0.416 4.33 + ?.08 10.0 + 2.65
(2.2: 2.3) (2.6: 4.4) (0.0 1.0) (1.8: 2.6) (2.0 6.0) (7.0 1 ?.0)
19 2.43 + 0.306 4.33 + 1.48 0.4 + 0.3 2.5 + 0.819 333 + 3.21 5.67 + 1.53
(2.1 2.7) (2.7 5.6) (0.1 0.7) (1.8 3.4) (1.0 7.0) (5,0 8.0)
-------
TABLE 4.13. SPATIAL PROFILES OF DIsSOLVED ANI) TOTAL METALS (ugh), SURVEY 4
STATION
COPPER
CHROMIUM
ZINC
DISSOLVED
TOTAL
DISSOLVED
TOTAL
DISSOLVED
TOTAL
1 1.4 1.3 0.4 2.1 5.0 7.0
7 0.7 2.9 0.2 0.Q 35.0 39.0
8 1.5 1.4 0.2 1.8 3.0 5.0
4 1.52 + 0.318 1.70 + 0.1 0.15 + 0.07 1.75 + 0.07 5.0 + 0.0 a•75 + 1.77
(1.3: 1.75) (1.6 1.8) (0.1 : 0.2) (1.7:1.8) (5.0= 5.0) (3.5 :6.01
11 0.6 4.9 0.2 2.5 1.0 10.0
20 1.4 4.8 0.1 2.8 6.0 15.0
21 1.7 2.6 0.4 1.9 5.0 5.0
0 ,
22 0.9 3.7 0.2 2.4 3.0 4.0
23 1.75 + 0.354 4.0 + 3.11 4.0 + 0.0 2.75 + 0.212 4.0 + 1.41 11.5 + 778
(1.5: 2.0) (1.8 6.2) (4.0 = 4.0) (2.6 2.9) (3.0 5.0) (6.0 17.0)
24 0.5 2.7 2.2 2.2 4.0 11.0
25 1.5 2.1 0.4 3.6 7.0 16.0
26 2.4 1.9 0.2 3.1 10.0 15.0
28 2.2 3.4 0.7 2.6 4.0 19.0
29 3.1 8.4 0.5 3.8 11.0 33.0
30 2.4 9.0 0,5 3.8 4.0 15.0
-------
TABLE 4.13 (CONT’D)
STATION
COPPER
CHROMIUM
ZINC
DISSOLVED
TOTAL
DISSOLVED
TOTAL
DISSOLVED
TOTAL
31
32
33
34
35
35
38
2.2
2.3
3.2
2.5
2.75
2.2
1.75
10.7
9.7
5.2
7.2
5.35
3.8
4.55
0.3
0.3
0.3
0.3
0.2
0.3
0.25
7.9
4.2
55
7,4
39
4.1
5.25
3.0
5.0
5.0
3.0
8.0
19.0
4.5
28.0
2O.O•
17.0
24.0
19.5
12.0
14.5
-J
-------
TABLE 4.14. SPATIAL PROFILES OF DISSOLVED AND TOTAL METALS (pgfL), SURVEY S
STATION
COPPER
CHROMIUM
7DJC
DISSOLVED
TOTAL
DISSOLVED
TOTAL
DISSOLVED
TOTAL
1 1.7 2.5 0.1 1.55 2.5 —1.5
7 0.9 2.0 0.4 0.6 32.0 32.0
8 1.2 11.3 0,1 8.3 4.0 19.0
4 1.3 6.4 0.2 4.1 7.0 11.0
U 1.6 3.2 0.2 3.1 6.0 8.0
25 1.4 3.3 0.2 0.2 5.0 2.0
26 2.3 5.5 0.2 4.3 6.0 12.0
29 3.5 10.9 0.5 4.8 3.0 21.0
41 3.2 12.1 0.4 7.3 5.0 15.0
42 3.2 9.1 0.3 3.7 -1.0 18.0
43 2.5 7.8 0.3 14.4 12.0 9.0
44 2.7 6.8 0.3 4.2 1.0 9.0
45 2.3 5.3 0.2 3.8 2.0 1?.O
46 2.1 4.7 0.4 4.1 8.0 3.0
47 2.2 5.6 0.25 5.1 S.5 18.c
-------
TABLE 4.15. SPATIAL PROFILES OF DISSOLVED AND TOTAL METALS (pg/I), SURVEY 6
STATION
COPPER
CHROMIUM
ZINC
DISSOLVED
TOTAL
DISSOLVED
TOTAL
DISSOLVED
TOTAL
1
4
26
29
2.8
2.7
2.6
5.4
8.9
9.4
7.25
13.6
0.1
0.1
0.65
0.3
7,1
7.4
5.7
6.2
5.0
.O
2.5
4.0
1.O
10.0
2.O
20.0
-------
TABLE 4.16. SPATIAL PROFILES OF DISSOLVED AND TOTAL METALS t ig/L), SURVEY 7
STATION
1
4
COPPER
CHROMIUM
ZINC
DISSOLVED
2.1
2.0
TOTAL
5.8
5.2
DISSOLVED
0.1
0.1
TOTAL
3.8
1.8
DISSOLVED
2.0
0.0
TOTAL
11.0
1.0
26
29
2.0
4.7
8.2
14.1
0.1
0.2
3,8
3.0
2.0
-1.0
10.0
0.0
-------
TABLE 4.17. SPATIAL PROFILES OF DISSOLVER AND TOTAL METALS lug/I), SUPVEY R
-J
STATION
1
4
COPPER
CHROMIUM
ZINC
DISSOLVED
1.8
2.1
TOTAL
4.7
6.05
DISSOLVED
0.1
0.15
TOTAL
1.5
1.55
DISSOLVED
4.0
5.5
TOTAL
6.0
R.O
26
29
1.6
3.8
4.6
9.8
0.1
0.1
1.1
1.3
0.0
-1.0
10.0
6.0
-------
TABLE 4.18. SPATIAL PROFILES OF DISSOLVED AND TOTAL METALS (pg/I.), SURVEY 9
STATION
COPPER
CHROMIUM
ZINC
DISSOLVED
TOTAL
DISSOLVED
TOTAL
DISSOLVED
TOTAL
1
4
26
29
1.6
0,3
1.3
?.9
3.1
2.8
2.7
10.8
0.7
1.0
0.0
0.2
1.0
5.0
1.0
1.9
0,0
1.0
0.0
2.0
6.0
9.0
6.0
11.0
-J
U,
-------
TABLE 4.19. SPATIAL PROFILES OF DISSOLVED AND TOTAL METALS (pg/I), SURVEY 10
STATION
COPPER
CHROMIUM
ZINC
DISSOLVED
TOTAL
DISSOLVED
TOTAL
DISSOLVED
TOTAL
1
4
26
29
1.85
1.1
1.3
2.8
3.85
4.3
1.9
9.5
0.15
0.0
0.1
0.3
0.55
1.9
0.5
1.9
4.0
0.0
3,0
-1.0
15.0
9.0
2.0
4.0
2
0 ’
N)
-------
TABLE 4.20.
SUMMARY OF DATA FROM SELECTED STATIONS FOR 10 SURVEYS
(1983-1984).
OF MONROE HARBOR
SURVEY
TOTAL PCBs n
/L
TOTAl._ HPOIl1UM fL
TOTAL COPPER
pq/1.
‘TOTAL 7TN
1 ,qfL
5Th. 1
STA.
STA. 6
STA. I
5TA. 4
TA. 6 (26)
STA. 1
5TA. 4
6 (2 J*
5Th. 1
‘T 4
TA. S
1
9.3
51
14
1.6
2.0
1.2
3.9
4.0
3•3
4.1
4 4
34
2
10
388
32
1.6
2.0
2.1
4.2
4.1
4.5
6.1
.6
.P
3
11
220
17
1.6
2.9
2.9
3.0
2.5
3.1
5.2
10.0
1?
4
12
16
8
2.1
1.8
3.1
1.3
1.7
1.9
7.0
4.8
15
S
5.9
110
•
1.6
4.1
4.3
2.5
6.4
5.5
—1.5
11
12
6
13
14
—
7.1
7.4
5.7
9.9
9.1
7.3
21
10
V
7
8.4
6.7
—
3.8
1.8
3.8
5.8
5.2
8.2
11
1
10
8
6.9
85
.
1.5
1.6
1.1
4.7
6.1
4.6
6
8
10
9
4.9
93
-
1.0
5.0
1.0
3.1
2.8
2.7
6
q
6
10
4.5
210
-
0.6
1.9
0.5
3.9
4.3
1.9
15
9
TOTALS
8.6.3.0
(4.c 13)
1194121
(6.7 388)
18.10
c8 32)
2.3+1.9
(O. 7.11
3.1+1.9
(1.61.4)
2.6+1.7
(O.5 S.7)
4.1+2.1
(1. 8.9)
4.7.2.3
(1.19.4 )
4.5+2.3
(1.Q8.2)
8.3+5.8
1 —1. 21)
8. ’ 4.P
ti19)
10.146.R
( ??)
-J
*For metals data, Ste. 6 used In Surveys 1—3; Ste. 26 in Surveys 4-10.
------- |